JPH06279691A - Curable composition and sealant - Google Patents

Abstract

PURPOSE:To provide a curable composition excellent in weatherability, heat resistance, curing characteristics, low moisture permeability and one-pack stability, useful as a sealant, etc., essentially comprising each specific hydrocarbon- based curing agent, polymer, hydrosilylating catalyst and adhesion-imparting agent. CONSTITUTION:The objective composition essentially comprising (A) a hydrocarbon-based curing agent containing in the molecule at least two hydrosilyl groups, with a molecular weight of <=30000, (B) a saturated hydrocarbon polymer <=100000 in molecular weight, containing in one molecule at least one alkenyl group, with repeating units derived from isobutylene accounting for >=50wt.% of the polymer, (C) a hydrosilylating catalyst such as chloroplatinic acid and (D) an adhesion-imparting agent such as epoxy resin, and pref., furthermore, (E) a preservation stability improver. The weight ratio: (A+B+C)/D is pref. (100:10) to (100:200).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition and a sealing material, and more specifically, (A) a hydrocarbon system containing at least two hydrosilyl groups in a molecule and having a molecular weight of 30,000 or less. Curing agent (B) Saturated hydrocarbon polymer having at least one alkenyl group in the molecule and having a molecular weight of 100,000 or less (C) Hydrosilylation catalyst (D) Curability using an adhesiveness-imparting agent as an essential component The present invention relates to a composition and a sealing material obtained by curing the composition.

[0002]

2. Description of the Related Art Conventionally, various sealing materials have been used in the construction, automobile, electric field, etc. for the purpose of bonding between the same kind or different kinds of materials, or for reinforcing and supplementing during assembly processing. Therefore, various materials having different curing modes and main chain structures have been proposed so far according to each application. However, conventionally used sealing materials include (1) high weather resistance, (2) high heat resistance, (3) fast curing, (4) low moisture permeability, (5) inorganic and organic materials. There is no material that has various properties such as adhesiveness, and further, there is no material that also considers the properties of (6) One-liquid stability.

For example, an addition type curing type silicone sealing material satisfies various characteristics (1), (2), (3), (5) and, in some cases, (6).
When it is used as a sealant without the characteristic (4), anxiety factors such as contamination of the surroundings are also observed. Further, the material having a saturated hydrocarbon polymer as the main chain disclosed in JP-A-1-198673 also cannot satisfy the characteristic (3) because it is a condensation type curing system.
Therefore, in order to impart the characteristic (3) to the technique disclosed in JP-A-1-198673, a simple conversion to an addition type curing system was attempted, but a silane coupling such as aminosilane that could be used in the condensation type curing system was attempted. The agent induces hardening inhibition, resulting in the loss of the properties of (5).

In view of the current situation, the purpose of the present invention is to
It is to obtain a curable composition and a sealing material which have various properties (1) to (6) together and are excellent in mechanical properties.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive studies to achieve this object, the present inventors have adopted a curing mode different from the technique described in JP-A-1-198673. And (5) adhesiveness with inorganic materials,
(6) We have found a technique that also satisfies the characteristics of one-liquid property.
By this, a curable composition that can achieve the above object,
Further, a sealing material can be obtained, and the present invention has been completed.

That is, the present invention comprises (A) a hydrocarbon-based curing agent having at least two hydrosilyl groups in the molecule and having a molecular weight of 30,000 or less. (B) containing at least one alkenyl group in the molecule. Which relates to a curable composition comprising a saturated hydrocarbon polymer (C) having a molecular weight of 100,000 or less (C) a hydrosilylation catalyst (D) an adhesiveness-imparting agent as an essential component, and a sealing material obtained by curing the composition. In the case of further providing one-component property, a curable composition obtained by using a storage stability improving agent as an essential (E) component in combination with the above (A) to (D) components, And a sealing material obtained by curing the composition.

There are no particular restrictions on the structure of the hydrocarbon-based curing agent containing a hydrosilyl group, which is the component (A) of the present invention, but the formula (I) RX _a (I) (X is at least one hydrosilyl group , R is a monovalent to tetravalent hydrocarbon group having 2 to 150 carbon atoms, and a is 1 to 4
An integer selected from. A hydrocarbon-based curing agent containing a hydrosilyl group having a molecular weight of 30,000 or less can be preferably used.

In the formula (I), X represents a group containing at least one hydrosilyl group, and if it is specifically exemplified, --Si (H) _n (CH ₃ ) _3-n , --Si (H ) _N (C ₂ H
_{5) 3-n, -Si (} H) n (C 6 H 5) 3-n, (n = 1
To 3) a hydrosilyl group containing only one silicon atom such as —SiH ₂ (C ₆ H ₁₃ ),

[0009]

[Chemical 1]

A hydrosilyl group containing two or more silicon atoms, such as

[0011]

[Chemical 2]

[0012]

[Chemical 3]

[0013]

[Chemical 4]

Examples thereof include hydrosilyl groups derived from various linear, branched, or cyclic polyvalent hydrogen siloxanes represented by Of the various hydrosilyl groups described above, the hydrosilyl group is formed from the viewpoint that the compatibility of the hydrosilyl group-containing hydrocarbon-based curing agent that is the component (A) of the present invention with various organic polymers is less likely to deteriorate. The molecular weight of the part is preferably 500 or less,
Further, considering the reactivity of the hydrosilyl group, the following are preferable.

[0015]

[Chemical 5]

[0016]

[Chemical 6]

In the formula (I), R is 1 to 2 to 150 carbon atoms.
Represents a tetravalent hydrocarbon group. The number of hydrosilyl groups contained in the formula (I) may be at least 2 in at least one molecule, but is preferably 2 to 15 and particularly preferably 3 to 12. When the composition of the present invention is cured by a hydrosilylation reaction, if the number of the hydrosilyl groups is less than 2, the curing is slow and a curing failure often occurs. When the number of the hydrosilyl group is more than 15,
The stability of the curing agent as the component (A) becomes poor, and in addition, a large amount of hydrosilyl groups remain in the cured product even after curing, causing voids and cracks.

The method for producing the hydrosilyl group-containing hydrocarbon curing agent which is the component (A) of the present invention is not particularly limited, and any method may be used. For example, (i) a hydrocarbon-based curing agent having a Si—Cl group in the molecule is used as LiAl
A method of reducing Si—Cl groups in the curing agent to Si—H groups by treating with a reducing agent such as H ₄ and NaBH ₄ , and (ii) a hydrocarbon compound having a functional group X in the molecule and a molecule A method of reacting a functional group Y which reacts with the functional group X and a compound having a hydrosilyl group at the same time, and (iii) at least 2 for a hydrocarbon compound containing an alkenyl group.
Examples include a method of selectively hydrosilylating a polyhydrosilane compound having one hydrosilyl group so that the hydrosilyl group remains in the molecule of the hydrocarbon compound even after the reaction.

Of the above methods, the method (iii) can be preferably used because the manufacturing process is generally simple. In this case, two or more of the hydrosilyl groups of some polyhydrosilane compounds may react with the alkenyl groups of the hydrocarbon compound to increase the molecular weight, but such a hydrocarbon compound is used as the component (A). But it doesn't matter.

The component (B) used in the present invention has a molecular weight of 10000 having at least one alkenyl group in the molecule.
It is a saturated hydrocarbon polymer of 0 or less. Here, the saturated hydrocarbon-based polymer is a concept that means a polymer substantially containing no carbon-carbon unsaturated bond other than the aromatic ring,
It means that the repeating unit constituting the main chain excluding the alkenyl group is composed of a saturated hydrocarbon. Also,
The alkenyl group refers to a group having one carbon-carbon double bond. In the present invention, the component (B) preferably has 1 to 10 alkenyl groups in one molecule.

The polymer forming the skeleton of the saturated hydrocarbon polymer which is the component (B) is (1) ethylene, propylene, 1
-Chemically polymerizing an olefinic compound having 1 to 6 carbon atoms such as butene and isobutylene as a main monomer,
(2) It can be obtained by a method such as homopolymerization of a diene compound such as butadiene or isoprene, or copolymerization of the above olefin compound and a diene compound, followed by hydrogenation. It is easy to introduce a functional group into, the molecular weight can be easily controlled, the number of terminal functional groups can be increased, and so on, an isobutylene-based polymer, a hydrogenated polybutadiene-based polymer or a hydrogenated polyisoprene-based polymer is used. Preferably.

In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, and the monomer unit having copolymerizability with isobutylene is preferably contained in the isobutylene-based polymer in an amount of 50% ( % By weight, the same below), more preferably 30% or less, particularly preferably 10% or less.

Examples of such monomer components include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinylsilanes, allylsilanes and the like. Specific examples of such a copolymer component include, for example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene and 4-methyl-.
1-pentene, hexene, vinylcyclohexane, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, pt-butoxystyrene, p-hexenyloxystyrene, p-allyloxystyrene, p-hydroxy. Styrene, β-pinene, indene, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3
-Divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and the like can be mentioned.

In the hydrogenated polybutadiene-based polymer and other saturated hydrocarbon-based polymers as well as in the case of the isobutylene-based polymer, in addition to the monomer unit as the main component,
Other monomer units may be contained. Further, in the saturated hydrocarbon polymer used as the component (B) in the present invention, butadiene, isoprene, 1,13-tetradecadiene, 1,9-decadiene, 1,5 are included in the range in which the object of the present invention is achieved. -A small amount of a monomer unit such as a polyene compound such as hexadiene that leaves a double bond after the polymerization may be contained, preferably 10% or less.

The number average molecular weight of the saturated hydrocarbon polymer, preferably isobutylene polymer, hydrogenated polyisoprene or hydrogenated polybutadiene polymer is 500 to 1000.
It is preferably about 00, particularly 1000 to 4000
A liquid substance having a liquidity of about 0 to a liquid substance is preferable from the viewpoint of easy handling. Regarding the method of introducing the alkenyl group into the saturated hydrocarbon polymer of the component (B),
Although various proposals can be made, they can be roughly classified into a method of introducing an alkenyl group after polymerization and a method of introducing an alkenyl group during polymerization.

As a method for introducing an alkenyl group after polymerization, for example, a hydroxyl group at the terminal, main chain or side chain is
General formula (2) CH ₂ ═CH—R ³ —Y (2) after forming a group such as ONa or —OK (in the formula, Y is a halogen atom such as chlorine atom or iodine atom, R ³ is —R ⁴ — , -R ⁴ -OC (= O)-or -R
^4- C (= O)-(R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and preferable specific examples thereof include an alkylene group, a cycloalkylene group, an arylene group, and an aralkylene group). With a divalent organic group,

[0027]

[Chemical 7]

A divalent group selected from R ⁵ is a hydrocarbon group having 1 to 10 carbon atoms is particularly preferable], and a saturated hydrocarbon group having a terminal alkenyl group is obtained by reacting the organic halogen compound. A polymer is produced. Examples of the method for converting the terminal hydroxy group of the terminal hydroxy saturated hydrocarbon polymer into an oxymetal group include alkali metals such as Na and K: metal hydrides such as NaH; metal alkoxides such as NaOCH ₃ ; caustic soda such as caustic soda and caustic potash. And the like.

The above-mentioned method gives a saturated hydrocarbon polymer containing a terminal alkenyl group having a molecular weight almost the same as that of the terminal hydroxy saturated hydrocarbon polymer used as a starting material, but it is desired to obtain a polymer having a higher molecular weight. In this case, before reacting the organohalogen compound of the general formula (2), at least two halogen atoms are contained in one molecule such as methylene chloride, bis (chloromethyl) benzene and bis (chloromethyl) ether. The molecular weight can be increased by reacting with a polyvalent organic halogen compound, and then by reacting with the organic halogen compound represented by the general formula (2),
It is possible to obtain a hydrogenated polybutadiene-based polymer having a higher molecular weight and having an alkenyl group at the terminal.

Specific examples of the organic halogen compound represented by the general formula (2) include allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl ( Chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy)
Examples thereof include benzene and allyloxy (chloromethyl) benzene, but are not limited thereto. Of these, allyl chloride is preferable because it is inexpensive and easily reacts.

The method of introducing an alkenyl group into an isobutylene polymer having a covalently bonded Cl group is not particularly limited, but for example, a method of performing a Friedel-Crafts reaction of various alkenyl phenyl ethers and a Cl group, A method of performing a substitution reaction of allyltrimethylsilane or the like and a Cl group in the presence of a Lewis acid, and a Friedel-Crafts reaction of various phenols and a Cl group to introduce a hydroxyl group, and then further introducing the above alkenyl group Examples thereof include a method of using them in combination.

As a method of introducing an alkenyl group during polymerization, for example, a compound having a halogen atom as an initiator and a chain transfer agent, and a carbon atom to which the halogen atom is bonded is bonded to an aromatic ring carbon And / or a cationic polymerizable monomer containing an isobutylene having a halogen atom, wherein the carbon atom to which the halogen atom is bonded is a tertiary carbon atom, and a Lewis acid is used as a catalyst. In the polymerization, a method for producing an isobutylene-based polymer having an allyl terminal by adding allyltrimethylsilane to the polymerization system,
-A method for producing an isobutylene-based polymer having an alkenyl group at the end of the main chain or side chain by adding a non-conjugated diene such as decadiene or an alkenyloxystyrene such as p-hexenyloxystyrene to a polymerization system Can be mentioned.

The Lewis acid, which is a component used as a cationic polymerization catalyst, is represented by MX'n (M is a metal atom, X'is a halogen atom), for example, BCl ₃ , E.
t ₂ AlCl, EtAlCl ₂ , AlCl ₃ , SnCl
₄ , TiCl ₄ , VCl ₅ , FeCl ₃ , BF _{3 and the} like can be mentioned, but not limited to these. Of these Lewis acids, BCl ₃ , SnCl ₄ , BF _{3 and the} like are preferable, and TiCl ₄ is more preferable. The amount of the Lewis acid used is preferably 0.1 to 10 times, more preferably 2 to 5 times, the number of moles of the initiator chain transfer agent.

The molar ratio of the hydrosilyl group to the alkenyl group in the components (A) and (B) produced as described above is preferably 0.2 to 5.0, more preferably 0.4 to 2.
5 is particularly preferred. When the molar ratio is less than 0.2,
When the composition of the present invention is cured, only a cured product having insufficient curing and stickiness and low strength is obtained, and when the molar ratio is more than 5.0, an active hydrosilyl group remains in the cured product even after curing. Since a large amount remains, cracks and voids tend to occur, and a uniform and strong cured product tends not to be obtained.

The hydrosilylation catalyst which is the component (C) of the present invention is not particularly limited and any one can be used. Specifically, chloroplatinic acid, a simple substance of platinum,
Solid platinum supported on a carrier such as alumina, silica, carbon black; platinum-vinyl siloxane complex {eg, Pt _n (ViM
e ₂ SiOSiMe ₂ Vi) _m , Pt [(MeViSi
O) ₄ ] _m }; platinum-phosphine complex {eg, Pt
_{(PPh 3) 4, Pt (} PBu 3) 4}; platinum - phosphite complex {for example, Pt [P (OPh _{3] 4,} Pt
[P (OBu) ₃ ] ₄ } (in the formula, Me is a methyl group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and n and m are integers), Pt (acac) ₂ , Also, Ashby (Ash)
by) U.S. Pat. Nos. 3,159,601 and 3,159,662.
Platinum-hydrocarbon composites described in US Pat. No. 3,220,320 to Lamoreaux.
Mention may also be made of the platinum alcoholate catalysts described in 972.

Examples of catalysts other than platinum compounds include Rh / Al ₂ O _{3 and the} like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable. The amount of the catalyst is not particularly limited, but it is preferably used in the range of 10 ^-1 to 10 ^-8 mol with respect to ¹ mol of the alkenyl group in the component (B). Preferably 10 ⁻³ to 10 ⁻⁶ mo
It is preferable to use it in the range of 1.

Examples of the adhesion-imparting agent which is the component (D) of the present invention include the following compounds. That is, a compound having a polar functional group such as an epoxy group, a hydroxyl group, a carboxyl group, and the like, and a functional group involved in an addition type curing system such as an alkenyl group, a hydrosilyl group, and the like, which can be incorporated into the main chain during curing, or , A mixture of an epoxy resin and a non-amine type epoxy resin curing agent that can be incorporated into the main chain during curing.

Here, the main chain refers to a molecule produced during curing of the curable composition of the present invention, and the component (D) reacts with at least the components (A) and / or (B), Incorporated into the molecule. In the above compound, the polar functional group is involved in an addition type curing system such as an alkenyl group, a hydrosilyl group, etc. The addition type curing system is the component (A) and / or (B) in the present invention. Or may be a compound having an alkenyl group and / or a hydrosilyl group independent of them. In the latter case, the resulting compound must undergo a binding reaction with at least component (A) and / or component (B).

Further, the above-exemplified epoxy group / hydroxyl group /
Polar functional groups such as carboxyl group etc. have the same molecule and /
Alternatively, the heterologous molecule can have one or more polar functional groups. Specific examples of the above compounds include a hydroxyl group / alkenyl group represented by 9-decen-1-ol, an epoxy group / alkenyl group represented by allyl glycidyl ether, and a carboxyl group / alkenyl group represented by 10-undecylenic acid. Examples thereof include compounds having polar functional groups such as groups. Further, the component (A) used in the present invention, a hydrocarbon-based curing agent having at least two hydrosilyl groups in the molecule and having a molecular weight of 30,000 or less, or any chain other than the component (A) Obtained by a partial hydrosilylation reaction between a branched or cyclic polyvalent hydrogen siloxane and the above-mentioned compound having a polar functional group / alkenyl group such as an epoxy group, a hydroxyl group, a carboxyl group, or the like. Epoxy group / hydroxyl group /
Examples thereof include compounds having both polar functional groups such as carboxyl group / hydrosilyl group. The conditions for carrying out the partial hydrosilylation reaction are not particularly limited, and may be used after heating and mixing in the presence of a hydrosilylation catalyst to complete the reaction, and after purification and isolation, or,
It may be used as it is at room temperature without any solvent. However, in order to participate in the addition type curing system by the hydrosilylation reaction of the component (B) with the alkenyl group of the component (B) and to be incorporated into the main chain during curing, it is necessary to leave one or more hydrosilyl groups in the molecule. Is required, and in order to be involved in the addition type curing system by the hydrosilylation reaction with the hydrosilyl group of the component (A) and to be incorporated into the main chain during curing, one or more alkenyl groups remain in the molecule. It is necessary to let And the compound of
The binding reaction with both the component (A) and the component (B) may be performed.

As the polyvalent hydrogen siloxane other than the above-mentioned component (A), for example, cyclic LS-8600.
[Shin-Etsu Co., Ltd.], and in the linear form, various hydrogen polysiloxanes are exemplified. Further, among the above-mentioned examples of the adhesion imparting agent which is the component (D) of the present invention, that is, the mixture of the epoxy resin and the curing agent for the non-amine epoxy resin, the epoxy compound is, for example, epichlorohydrin-bisphenol A type epoxy Resin, epichlorohydrin-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 , P-oxybenzoic acid-glycidyl ether ester type epoxy resin, III-aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, N,
N-diglycidylaniline, N, N-diglycidyl-o
Glycidyl ethers of polyhydric alcohols such as toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycerin,
Examples thereof include epoxidized products of unsaturated polymers such as hydantoin-type epoxy resins and petroleum resins, but not limited to these, and generally known epoxy resins can be used. Among these epoxy resins the formula:

[0041]

[Chemical 8]

It is preferable that at least two epoxy groups represented by are contained in the molecule, and bisphenol A type epoxy resins, novolac type epoxy resins, and various alicyclic epoxy resins are more preferable. Further, as a non-amine type epoxy resin curing agent, for example, trifluoroboric acid compound: phthalic anhydride, hexahydrophthalic anhydride,
Carboxylic anhydrides such as tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic anhydride, and chlorenic anhydride: alcohols: phenols: carboxylic acids: aluminum isopropylate, aluminum sec-butyrate, Aluminum tert-butyrate, aluminum tris (ethylacetoacetate), trishexafluoroacetylacetonato aluminum, trisethylacetoacetate aluminum, tris (n-propylacetoacetate) aluminum, tris (iso-
Propyl acetoacetate) Aluminum, Tris (n
-Butyl acetoacetate) aluminum, tris salicylaldehyde aluminum, tris (2-ethoxycarbonylphenolato) aluminum, tris (acetylacetonato) aluminum, and other aluminum complexes:

The aluminum complex described above and diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldiacetoxysilane, diphenyldiphenoxysilane, triphenylmethoxysilane, triphenylethoxysilane, diphenylvinylethoxysilane, etc. Aluminum complex / alkoxysilane mixture which is a mixture with an alkoxysilane: An aluminum complex / organic silanol mixture which is a mixture of the above aluminum complex and an organic silanol such as diphenyldisilanol, diphenylmethylsilanol, trimethylsilanol, triphenylsilanol and the like: Tetramethyl zirconate, tetraethyl zirconate, tetraisopropyl zirconate, tetra-n-butyl zirconate Titanate, tetra isobutyl zirconate, tetra -tert- butyl zirconate, tetrakis (OKI The Rick A Sid) zirconium, tetrakis (acetylacetonate) zirconium, tetrakis (n-
Examples of such compounds include zirconium complexes such as propyl acetoacetate) zirconium, tetrakis (ethyl acetoacetate) zirconium, and tetrakis (salicylaldehyde) zirconium.

Among these non-amine type epoxy resin curing agents, an aluminum complex / alkoxysilane mixture and an aluminum complex / organic silanol mixture are preferable because the curing of the epoxy resin upon heating is fast. The amount of the non-amine-based curing agent used for the epoxy resin varies depending on the type of the epoxy resin and the curing agent. It may be used within the range of parts.

Further, in the present invention, a curing agent for epoxy resin which is generally used for curing an epoxy resin, such as triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, meta. Xylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, 2,
Amines such as 4,6-tris (dimethylaminomethyl) phenol: The use of a curing agent for amine-based epoxy resins such as tertiary amine salt (A) of the present invention,
It is not preferable because it inhibits the curing of the components (B) and (C) due to the hydrosilylation reaction. Further, the ratio (weight ratio) of [(A) component + (B) component + (C) component] / [(D) component] in the present invention may be properly selected according to the purpose of use, and is not particularly limited. However, for example, if only [(A) component + (B) component + (C) component] is required to have adhesiveness to various substrates, 100 / 0.1 to 100/20
(Weight ratio) is preferable, and if it is desired to further improve mechanical strength, 100/10 to 100/200 (weight ratio) is preferable.

Further, in the present invention, when the mixture of the epoxy resin and the curing agent for the non-amine type epoxy resin among the adhesion imparting agents of the component (D) is used, only the adhesiveness to various substrates is imparted. Not only that, it also has an effect of improving the recovery rate of the cured product after the compression / tensile durability test. Furthermore, in the present invention, it is desirable to use a storage stability improver as an essential component (E), if necessary.

Examples of the storage stability improver include 2-benzothiazolyl sulfide, benzothiazole, thiazole, dimethylacetylene dicarboxylate, diethyl acetylene dicarboxylate, BHT, butylhydroxyanisole, vitamin E, 2- (4 -Morphodinyldithio) benzothiazole, 3-methyl-1-
Controlling the catalytic activity of component (C) such as buten-3-ol, 3-methyl-1-butyl-3-ol, diallyl fumarate, diallyl maleate, diethyl fumarate, diethyl maleate only at room temperature storage Is desirable.
When the storage stability improver is used, the amount used is catalyst 1
0.1 to 1000 mol, preferably 1 to mol
It is 100 mol. When the amount of the storage stability improver used exceeds the upper limit of the above amount, not only curing delay occurs but also curing failure occurs, and the physical properties required for the cured product cannot be satisfied. On the contrary, when the amount of the storage stability improver used is less than the lower limit of the above amount, the purpose of improving the storage stability of the composition cannot be achieved.

(A), (B), (C), (D) of the present invention
In some cases, if the component (E) is mixed and cured, a uniform cured product having excellent deep curability can be obtained without causing phenomena such as foaming. The curing conditions are not particularly limited, but generally 0 to 200 ° C., preferably 30 to 15
It is preferable to cure at 0 ° C. for 10 seconds to 4 hours. Especially 80-1
At a high temperature of 50 ° C., a material that cures in a short time of about 10 seconds to 1 hour can be obtained. The properties of the cured product depend on the main chain skeleton and molecular weight of the components (A) and (B) used, but rubber-like to resin-like products can be prepared. In addition, the ratio of the total of the four essential components (A), (B), (C) and (D) to the composition when the composition is added to produce a cured product is 10% or more, and further 30
% Or more, and various components are added as necessary.

Examples of the components to be added include, for example, physical property adjusters, plasticizers, fillers, ultraviolet absorbers, lubricants, pigments, etc. for adjusting the tensile properties of the resulting cured product. As the plasticizer, a commonly used plasticizer can be used, but one having good compatibility with the saturated hydrocarbon polymer used in the present invention is preferable. Specific examples of the plasticizer include polybutene, hydrogenated polybutene, α-methylstyrene oligomer, biphenyl, triphenyl, triaryldimethane, alkylenetriphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyldiphenyl, and partially hydrogenated terpolymer. Hydrocarbon compounds such as phenyl, paraffin oil, naphthene oil, atactic polypropylene, and the like, among them, hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil, atactic polypropylene, etc., which preferably do not contain unsaturated bonds;
Dibutyl phthalate, diheptyl phthalate, di (2-
A phthalate ester adhesive such as ethylhexyl) phthalate, butylbenzyl phthalate, and butylphthalyl butyl glycolate, a silane coupling agent, and other compounds can be used. Specific examples of such compounds include phenol resins, epoxy resins, γ-aminopropyltrimethoxysilane, aminosilane compounds such as N- (β-aminoethyl) aminopropylmethyldimethoxysilane, epoxysilane compounds, coumarone-indene resins. , Rosin ester resin, terpene-phenol resin, α-methylstyrene-vinyltoluene copolymer, polyethylmethylstyrene, alkyl titanates, aromatic polyisocyanate and the like.

Specific examples of the filler include asbestos, glass fiber, carbon fiber, mica, graphite, diatomaceous earth, clay, fume silica, precipitated silica, silicic acid anhydride, carbon black, calcium carbonate,
Examples thereof include clay, talc, titanium oxide, magnesium carbonate, quartz, fine aluminum powder, flint powder and zinc dust. Among these fillers, precipitated silica, fume silica, fillers having thixotropic properties such as carbon black, calcium carbonate, titanium oxide,
Talc and the like are preferred. The amount of the filler used is 10 parts with respect to 100 parts of the saturated hydrocarbon polymer (B).
〜500 parts are preferred, and 20 ~ 300 parts are more preferred.

When the curable composition of the present invention is used as a sealing material, the applicable substrate is inorganic glass, organic glass, aluminum, iron, reinforced plastic,
It may be wood, mortar, concrete, etc., and exhibits stable adhesiveness to these substrates for a long period of time. Then, it rapidly cures under heating to become a rubber-like material having excellent mechanical properties as a sealing material.

The rubber-like material thus obtained has low moisture permeability, and has good weather resistance, weather resistant adhesiveness, heat resistance and electrical insulation. Moreover, since the sealing material of the present invention has good storage stability and is stable for a long time in a low temperature state, it can be used as a one-pack type sealing agent having good workability.

Furthermore, it is possible to obtain a fluid having an appropriate viscosity and structural viscosity (thixotropic property) at room temperature, and the workability and sprayability are good. Further, using the sealing material of the present invention, in the case of producing double glazing,
Since it cures quickly, the line speed can be increased and the conventional double seal can be converted into a single seal.

Needless to say, it can be used for a conventional double-sealed double-layered glass and also as a two-component sealing material. Furthermore, since the composition of the present invention is rapidly cured by heating and the cured product becomes a rubber-like elastic body, the difference in the coefficient of linear expansion from that of the chip or the lead frame as in the case of using the conventional sealing resin. Due to the thermal stress caused by the above, problems such as cracks in chips and breakage of bonding lines are unlikely to occur, and a highly reliable semi-dynamic component is manufactured. Furthermore, the sealing performance is, for example, a moisture permeability coefficient of 1 × 10 ⁻¹¹ g · cm / cm ² · sec.
・ Has excellent moisture barrier property of about cmHg, excellent adhesion to aluminum substrate of about 6 kg / 25 mm in T-shaped peeling, and melted on the surface even under severe conditions such as 130 ° C for 300 days. As is clear from the excellent heat resistance of no heat and the excellent electrical characteristics represented by the excellent dielectric constant of about 2.44, a very excellent material is provided.

When the composition of the present invention is applied as a sealing resin, potting may be carried out in the same manner as that for epoxy resin sealing resins which have been generally used in the past.

[0056]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto. Production Example 1 A 1-liter pressure-resistant glass autoclave was equipped with stirring blades, a three-way cock and a vacuum line, and the polymerization container was dried by heating at 100 ° C. for 1 hour while drawing a vacuum in the vacuum line, and after cooling to room temperature. The pressure was returned to normal pressure with nitrogen using a three-way cock.

Then, while flowing nitrogen from one of the three-way cocks, 40 ml of 1,1-dichloroethane as a main solvent dried by calcium hydride treatment was introduced into the autoclave using a syringe. Then, 5 mmol of distilled and purified allyltrimethylsilane was added, and
(10 mg of 1,1-dichloroethane solution in which 2 mmol of the following compound A) was dissolved was added.

Next, a pressure-resistant glass liquefied gas sampling tube with a needle valve containing 7 g of isobutylene dehydrated by passing through a column filled with barium oxide was connected to a three-way cock, and then the container body was kept at -70 ° C. It was immersed in a dry ice-acetone bath and cooled for 1 hour while stirring the inside of the polymerization container. After cooling, after decompressing the inside with a vacuum line, the needle valve was opened and isobutylene was introduced into the polymerization vessel from the pressure-resistant glass liquefied gas sampling tube. After that, the pressure was returned to normal pressure by flowing nitrogen from one of the three-way cocks, and cooling was continued for 1 hour with stirring, and the inside of the polymerization vessel was cooled to −
The temperature was raised to 10 ° C.

Next, 3.2 g (10 mmol) of TiCl ₄ was added from a three-way cock using a syringe to start polymerization, and when 60 minutes had passed, methanol which had been cooled to 0 ° C. or lower was added. The reaction was completed. Then, the reaction mixture was taken out into an eggplant-shaped flask, and unreacted isobutylene, 1,1-dichloroethane,
Allyltrimethylsilane and methanol were distilled off, the remaining polymer was dissolved in 100 ml of n-hexane, and this solution was repeatedly washed with water until it became neutral. Then, the n-hexane solution was concentrated to 20 ml, and the concentrated solution was poured into 300 ml of acetone to precipitate and separate the polymer.

The polymer thus obtained is reconstituted with 1
It was dissolved in 00 ml of n-hexane, dried over anhydrous magnesium sulfate, filtered, and n-hexane was distilled off under reduced pressure to obtain an isobutylene polymer. The structure of Compound A is as shown below.

[0061]

[Chemical 9]

Production Example 2 10 g of 5 g of the isobutylene polymer obtained in Production Example 1 was used.
It was dissolved in 0 ml of n-hexane, 2 g of aluminum silicate was added, and the mixture was stirred at room temperature for 24 hours, filtered, and n-hexane was distilled off under reduced pressure to obtain an isobutylene polymer. Production Example 3 A 100 ml pressure-resistant glass autoclave was equipped with a stirring blade, a three-way cock, and a vacuum line, and the polymerization container was dried by heating at 100 ° C. for 1 hour while pulling a vacuum on the vacuum line, and then cooled to room temperature on three sides. The pressure was returned to normal pressure with nitrogen using a cock.

Then, while flowing nitrogen from one of the three-way cocks, methylene chloride 4 which is a main solvent dried by calcium hydroxide treatment in an autoclave using a syringe was used.
0 ml was introduced. Then, 20 mmol of distilled and purified 1,9-decadiene was added, and further, a methylene chloride solution (10 ml) in which 3 mmol of tricumyl chloride (TCC) was dissolved was added.

Next, a pressure-resistant glass manufacturing liquefied gas sampling pipe with a needle valve containing 7 g of isobutylene dehydrated by passing through a barium oxide-focused column was connected to a three-way cock, and then the container body was kept at -70 ° C. It was immersed in a dry ice-acetone bath, and the inside of the polymerization container was cooled for 1 hour while stirring. After cooling, after decompressing the inside with a vacuum line, the needle valve was opened and isobutylene was introduced into the polymerization vessel from the pressure-resistant glass liquefied gas sampling tube. After that, the pressure was returned to normal pressure by flowing nitrogen from one of the three-way cocks, cooling was further continued for 1 hour with stirring, and the inside of the polymerization vessel was heated to -30 ° C.

Next, 3.2 g of TiCl ₄ (10 mmo
1) was added from a three-way cock using a syringe to start polymerization, and when 60 minutes had passed, methanol precooled to 0 ° C. or lower was added to complete the reaction. Then, the reaction mixture was taken out into an eggplant-shaped flask, and unreacted isobutylene, methylene chloride, 1,9-decadiene and methanol were distilled off, and the remaining polymer was separated into 1
After dissolving in 00 ml of n-hexane, this solution was repeatedly washed with water until it became neutral. Then, the n-hexane solution was concentrated to 20 ml, and the concentrated liquid was poured into 300 ml of acetone to precipitate and separate the polymer.

The polymer thus obtained is reconstituted with 1
It was dissolved in 00 ml of n-hexane, dried over anhydrous magnesium sulfate, filtered, and n-hexane was distilled off under reduced pressure to obtain an isobutylene polymer.

Production Example 4 A three-way cock was attached to a 200 ml pressure-resistant glass container, and the polymerization container was set to 100 while drawing a vacuum in a vacuum line.
It was dried by heating at ℃ for 1 hour, cooled to room temperature, and then returned to normal pressure with nitrogen using a three-way cock. Then, while flowing nitrogen from one of the three-way cocks, a solution prepared by dissolving 1 mmol of tricumyl chloride shown in the above chemical formula 9 in 40 ml of methylene chloride dried by calcium hydride treatment was added to the autoclave using a syringe.

Next, a pressure-resistant glass liquefied gas sampling pipe with a needle valve containing 5 g of isobutylene dehydrated by passing through a column filled with barium oxide was connected to a three-way cock, and then the container body was kept at -70 ° C. It was immersed in a dry ice-acetone bath and cooled for 1 hour while stirring the inside of the polymerization container. After cooling, after decompressing the inside with a vacuum line, the needle valve was opened and isobutylene was introduced into the polymerization vessel from the pressure-resistant glass liquefied gas sampling tube. After that, the pressure was returned to normal pressure by flowing nitrogen from one of the three-way cocks, and cooling was continued for 1 hour with stirring, and the inside of the polymerization vessel was cooled to −
Cooled to 70 ° C.

Next, a solution (-30 ° C.) obtained by diluting 10 mmol of tin tetrachloride with 20 ml of methylene chloride was added from a three-way cock using a syringe to initiate polymerization, and after 60 minutes, 10 mmol of allyl phenyl ether was added. Was added from a three-way cock using a syringe. Then, the reaction solution was stirred at room temperature for 6 hours and then shaken with 100 ml of a saturated aqueous sodium hydrogen carbonate solution, and the organic layer was mixed with water (1).
It was washed twice with 00 ml. Concentrate the organic layer to 10 ml,
The polymer was precipitated by adding it to 300 ml of acetone with stirring.

80 m of the polymer thus obtained
It was dissolved in 1 n-hexane, dried over anhydrous magnesium sulfate, filtered, and n-hexane was distilled off under reduced pressure to obtain an isobutylene polymer. The yield was calculated from the yield of the polymers obtained in Production Examples 1 to 4, and M
n and Mw / Mn were measured by GPC method, and the terminal structure was ¹ H
-Protons assigned to each structure by the NMR (300 MHz) method (initiator-derived aromatic protons: 6.5 to 7.5 ppm, and polymer terminal-derived vinyl protons: 4.5 to 5.9 p)
It was determined by measuring and comparing the intensity of the resonance signal of (pm). The chlorine content in the polymer was determined by elemental analysis.
The results are shown in Table 1.

[0071]

[Table 1]

Production Example 5 To 300 g of hydrogenated polyisoprene having hydroxyl groups on both ends (manufactured by Idemitsu Petrochemical Co., Ltd., trade name EPOL) was added 50 ml of toluene, and dehydration was carried out by azeotropic degassing. t-BuO
What melt | dissolved K48g in THF200ml was inject | poured. After reacting for 1 hour at 50 ° C., allyl chloride 4
7 ml was added dropwise over about 30 minutes. 50 ℃ after dropping
And reacted for 1 hour. After the reaction was completed, 30 g of aluminum silicate was added to the reaction solution to adsorb the generated salt, and the mixture was stirred at room temperature for 30 minutes. About 250 by filtration and purification
g of allyl-terminated hydrogenated polyisoprene was obtained as a viscous liquid. It was confirmed by 300 MHz ¹ H-NMR analysis that an allyl group was introduced at 92% of the ends. The number of moles of olefin determined from the iodine value was 0.1046 mol / 100 g. The chlorine content determined by elemental analysis was 0.1% or less.
The viscosity measured by an E-type viscometer was 302 poise (23 ° C).

* Representative physical properties of Epol (from technical data) Hydroxyl group content (meq / g) 0.90 Viscosity (poise / 30 ° C) 700 Average molecular weight (VPO measurement) 2500 Production Example 6 Stir bar, dropping funnel, thermometer A 300 ml four-necked flask equipped with a three-way cock and a cooling tube was prepared. Next, in a nitrogen atmosphere, the cyclic polysiloxane of Chemical formula 10

[0074]

[Chemical 10]

(LS8600, manufactured by Shin-Etsu Chemical Co., Ltd.) 3
1.5 g (0.131 mol) was charged into the flask. 50 g of hydrogenated polyisoprene having 92% of the molecular terminals allyl group synthesized in Preparation Example 5 (the number of moles of olefin is 0.0536 mol), 50 ml of toluene, and platinum catalyst solvent (Pt (acac) ₂ 1 g in 99 g of toluene) A toluene solution consisting of 60 μl of a dissolved solution) was placed in a dropping funnel. The flask was heated to 70 ° C., and the toluene solution was added dropwise over about 2 hours. After dropping, 80 ℃
After stirring for about 5 hours at room temperature, the residual allyl group in the reaction solution was quantified by IR spectrum analysis.
It was confirmed that the carbon-carbon double bond at 5 cm ^-1 had disappeared. Next, in order to remove the catalyst remaining in the reaction system, silica gel (Wako Gel C, Wako Pure Chemical Industries, Ltd.)
-200) 5 g was added at room temperature, stirred for 2 hours and filtered using a flash column. To remove toluene and excess cyclic polysiloxane, the filtrate was evaporated and further degassed under reduced pressure at 80 ° C. for 3 hours to obtain a colorless transparent viscous liquid. The viscosity measured by an E-type viscometer was 514 poise (23 ° C.). The hydrosilyl group in the hydrogenated polyisoprene was confirmed as a strong absorption at 2150 cm ^{-1 in} the IR spectrum. The peak of the Si- H in NMR spectra of 300MHz and SiC H ₃ and SiC H ₂ -
By comparing the intensities of the combined peaks, it was found that an average of 1.2 hydrosilyl groups reacted per molecule of the cyclic polysiloxane. That is, the polymer is hydrogenated polyisoprene having a molecular end represented by the following formula 11 in which the molecular weight is partially increased by the cyclic hydrogen polysiloxane.

[0076]

[Chemical 11]

Production Example 7 The polymer obtained in Production Example 2 was used in place of the polymer obtained in Production Example 5, the amount of the polymer was 50 g, and LS-860 was used.
Manufactured in the same manner as in Manufacturing Example 6 except that the amount of 0 was changed to 16 g.

Production Example 8 A 200 ml four-necked flask was equipped with a condenser tube with a three-way cock, a pressure-equalizing dropping funnel, a thermometer, a magnetic chip,
Prepared with a glass stopper attached. 12.03 g (50 mmo) of the cyclic polysiloxane shown in Chemical formula 10 (LS8600 manufactured by Shin-Etsu Chemical Co., Ltd.) under a nitrogen atmosphere.
1) and 20 ml of toluene were charged into the flask.
A dropping funnel was charged with 2.76 g (20 mmol) of 1,9-decadiene and 200 μl of a platinum catalyst solution (a solution of 1 g of Pt (acac) ₂ dissolved in 99 g of toluene) dissolved in 30 ml of toluene. The flask was placed in an oil bath at 50 ° C., and the toluene solution was dropped into the flask over 2 hours under a nitrogen atmosphere. 50 ℃ after dropping
When the IR spectrum was measured at the time of the reaction for another 1 hour, the absorption of the olefin near 1640 cm ^-1 had completely disappeared, so the reaction was terminated at this time. After the reaction, the toluene solution was added to a saturated aqueous solution of ammonium chloride (100 ml × 2) and exchanged water (100 ml × 2).
After washing with 1), it was dried with Na ₂ SO ₄ . Na ₂ SO ₄
Was removed by filtration, the volatile matter was removed by evaporation, and then degassed under reduced pressure at 80 ° C. to obtain 9.11 g of a colorless transparent liquid. The hydrosilyl group in the hydrocarbon-based curing agent was confirmed as a strong absorption at 2170 cm ^-1 . In addition, the peak of Si-H and Si-
By comparing the intensity ratio of protons with CH ₃ (actually measured value 0.216) and the calculated intensity ratio, the curing agent has, on average, the structure of the formula shown below (n = 1 (Mw =
998) is 53% and n = 2 (Mw = 1377) is 47
%] Mixture. Based on this, the number of Si-H groups in the unit weight was calculated to be 0.769 mol.
It was / 100 g.

[0079]

[Chemical 12]

Production Example 9 In a 500 ml four-necked eggplant flask, a pressure-equalizing dropping funnel,
A thermometer, a stirring propeller, and a three-way cock attached were prepared. 20 g (50 of the cyclic polysiloxane (LS8600, manufactured by Shin-Etsu Chemical Co., Ltd.) shown in Chemical Formula 10 above under a nitrogen atmosphere.
mmol) and 50 ml of toluene were charged into the flask. 19 g of allyl glycidyl ether, platinum-vinylsiloxane complex solution (8.3 × 10 ⁻⁵ mmol / μl) 4
A solution obtained by mixing 00 μl and 50 ml of toluene was charged into a dropping funnel. The flask was placed in a water bath at 15 ° C, and the above solution was added dropwise in about 30 minutes while stirring under a nitrogen atmosphere.
Then, stirring was further continued at room temperature for 4 hours. During the dropping, the temperature of the solution in the flask was raised to about 25 ° C. I
From the R spectrum, it was confirmed that the absorption of the olefin around 1640 cm ^-1 had disappeared, so the reaction was terminated at this point. For the purpose of stabilizing the reaction product, 100 μl of benzothiazole was added, followed by vacuum concentration under reduced pressure at 60 ° C. or lower to obtain the target product.

The structure of the thus obtained adhesiveness-imparting agent was examined by NMR in the same manner as in Production Example 8. As a result, a cyclic polysiloxane having about 2 epoxy groups and about 2 SiH groups in one molecule was obtained. It was confirmed that Production Example 10 In a 500 ml four-necked eggplant flask, a pressure-equalizing dropping funnel,
A thermometer, a stirring propeller, and a three-way cock attached were prepared. Under a nitrogen atmosphere, 50 g of the curing agent synthesized in Production Example 8 and 100 ml of toluene were placed in a flask. Allyl glycidyl ether 22 g, platinum-vinyl siloxane complex solution (8.3 × 10 ⁻⁵ mmol / μl) 500 μ
A solution obtained by mixing 1 and 100 ml of toluene was charged into a dropping funnel. The flask was placed in a water bath at 15 ° C., the above solution was added dropwise to the solution in a nitrogen atmosphere with stirring for about 30 minutes, and then stirring was further continued at room temperature for 4 hours. During the dropping, the temperature of the solution in the flask was raised to about 28 ° C. The IR spectrum confirmed that the absorption of the olefin around 1640 cm ^-1 had disappeared, so the reaction was terminated at this point. For the purpose of stabilizing the reaction product, 100 μl of benzothiazole was added, followed by vacuum concentration under reduced pressure at 60 ° C. or lower to obtain the target product.

The structure of the thus obtained adhesiveness-imparting agent was examined by NMR in the same manner as in Production Examples 8 and 9. As a result, a compound having about 3 epoxy groups and about 3 SiH groups in one molecule was obtained. It was confirmed that Based on this, the number of SiH groups in the unit weight was calculated to be 0.382 mol / 10
It was 0 g. Production Example 11 In a 500 ml four-necked eggplant flask, a pressure-equalizing dropping funnel,
A thermometer, a stirring propeller, and a three-way cock attached were prepared. Under a nitrogen atmosphere, 50 g of the curing agent synthesized in Production Example 8 and 100 ml of toluene were placed in a flask. 9-
30 g of decen-1-ol, 500 μl of platinum-vinylsiloxane complex solution (8.3 × 10 ⁻⁵ mmol / μl),
A solution obtained by mixing 100 ml of toluene was placed in a dropping funnel. The flask was placed in a water bath at 15 ° C., the above solution was added dropwise to the solution in a nitrogen atmosphere with stirring for about 30 minutes, and then stirring was further continued at room temperature for 4 hours. During the dropping, the temperature of the solution in the flask was raised to about 22 ° C. The IR spectrum confirmed that the absorption of the olefin around 1640 cm ^-1 had disappeared, so the reaction was terminated at this point. For the purpose of stabilizing the reaction product, 100 μl of benzothiazole was added, followed by vacuum concentration under reduced pressure at 60 ° C. or lower to obtain the target product.

The structure of the thus obtained adhesiveness-imparting agent was examined by NMR in the same manner as in Production Examples 8, 9 and 10, and it was found that about 3 epoxy groups and about 3 SiH were contained in one molecule.
It was confirmed to be a compound having a group. Based on this, the number of SiH groups in the unit weight was calculated to be 0.365 mo
It was 1/100 g. Examples 1 to 10 Various Pt catalyst solutions as representatives of the component (A) obtained in Production Examples 6 to 8, the component (B) obtained in Production Examples 1 to 5 and the component (C), Production Examples 9 to 11 Using the component (D) obtained in (1) and other compounds, after compounding and curing, various properties were evaluated. However, Si of component (A)
H group: (B) component alkenyl group: (C) component Pt content = 1.1: 1.0: 5 × 10 ⁻⁴ (molar ratio). The formulation and evaluation results are shown in Table 2.
It was shown to. The amount of component (D) used in the table is [(A)
Component + (B) component] is described as 100 parts by weight.
The amount of the component (E) used is described as a mol ratio with respect to the Pt content of the component (C).

Tests and Evaluation Methods 1) Gelation time test method: A part of the compound was put on a gelation tester (manufactured by Nisshin Kagaku Co., Ltd.) and snap up time (at rubber elasticity) at 120 ° C. Time). 2) Dumbbell tensile test method: The composition was defoamed by centrifugation, poured into a Teflon mold to form a uniform sheet having a thickness of about 2 mm, and defoamed again under reduced pressure at room temperature. A cured product was produced under predetermined curing conditions (in an oven).
A No. 3 dumbbell conforming to JIS K6301 was punched out from the cured sheet, and a tensile test was performed at a tensile speed of 200 mm / min.

M ₅₀ (Kg / cm ² ): Strength at 50% elongation (modulus) M ₁₀₀ (Kg / cm ² ): Strength at 100% elongation (modulus) TB (Kg / cm ² ): Breaking strength EB (%): Elongation at break 3) Adhesion evaluation method: Place the compound defoamed by centrifugation on various base materials (glass, aluminum, mortar) in an oval shape with a thickness of about 5 mm and cure under prescribed curing conditions. Let After returning to room temperature, a peeling force is applied sideways while pressing from above with a finger to peel off the cured product from the substrate. At this time, it was judged that those that undergo interfacial peeling are x, those that undergo mixed failure are Δ, and those that undergo complete cohesive failure are o. 4) Thickening rate (%) The thickening rate of the compound after storage at room temperature for 2 weeks.

Comparative Examples 1 and 2 The same procedures as in Examples 2 and 10 were carried out except that the component (D) was not used. The evaluation results are also shown in Table 2.

[0087]

[Table 2]

Examples 11 to 16 The following raw materials were further added to the compounding system of Comparative Example 2 and kneaded 3 times with three paint rolls to obtain a composition for a sealing material. (The compounding system of Comparative Example 2 is described as 100 parts by weight) CCR (calcium carbonate): Shiraishi Industry Co., Ltd .: 100 parts by weight Polybutene OH: Idemitsu Petroleum Co., Ltd .: 90 parts by weight Irganox 1010: Ciba Geigy: 1 part by weight Carbon black # 30: Mitsubishi Kasei Co., Ltd .: 5 parts by weight Titanium oxide R-8200: Ishihara Sangyo Co., Ltd .: 7 parts by weight Various (D) components (listed in Table 3) in these compositions.
After being evenly mixed, a cured product was prepared and various properties were evaluated. The formulation and the evaluation results are shown in Table 3.
Except for the glass / aluminum H-type tensile properties, the same procedure as above was performed.

Test / Evaluation Method Glass / Aluminum H-type Tensile Test Method: According to the preparation of JIS A5758 durability test specimens, the composition was filled and cured under predetermined curing conditions, and then the tensile speed was 50 mm / min.
The tensile test was conducted at. Comparative Example 3 The procedure of Examples 11 to 16 was repeated, except that the component (D) was not used. The evaluation results are also shown in Table 3.

[0090]

[Table 3]

Examples 17 to 21 The glass / aluminum H-shaped samples prepared in Examples 11 to 15 were subjected to a sunshine carbon bomb arc weather meter (120 minute cycle, spraying 18 minutes) for 2000 hours.
After conducting the r test, the tensile test was conducted again,
All samples showed cohesive failure.

[0092]

As is clear from the results of Examples 1 to 21, the curable composition and sealing material of the present invention are
(1) High weather resistance, (2) High heat resistance, (3) Fast curing,
It can be seen that it is an excellent material having various properties such as (4) low moisture permeability, (5) adhesiveness with inorganic and organic materials, and (6) one-liquid stability.

By utilizing these characteristics, it is a material which can be suitably used for various purposes. For example, sealing material applications such as glass sealing materials, multi-layer glass sealing materials applications, automotive and electrical sealing material applications, and a wide variety of elastic adhesive applications that can be widely and suitably used and also utilize their adhesive properties, It is also suitable for use as an encapsulant around electric and electronic parts that makes use of saturated hydrocarbon-based electric insulation. In addition, it can be a suitable material as a base resin such as paint and adhesive.

Claims (5)

[Claims] 1. A curable composition comprising the following components (A), (B), (C) and (D) as essential components; (A) a molecular weight containing at least two hydrosilyl groups in a molecule. Saturated hydrocarbon polymer having a molecular weight of 100,000 or less, containing at least one alkenyl group in the molecule (C) Hydrosilylation catalyst (D) Adhesion imparting Agent 2. The curable composition according to claim 1, wherein the total amount of repeating units derived from isobutylene in the polymer as the component (B) is 50% by weight or more. 3. A sealing material comprising the following components (A), (B), (C) and (D) as essential components; (A) a molecule having at least two hydrosilyl groups and having a molecular weight of 30,000. The following hydrocarbon-based curing agents (B) Saturated hydrocarbon-based polymers containing at least one alkenyl group in the molecule and having a molecular weight of 100,000 or less (C) Hydrosilylation catalyst (D) Adhesion-imparting agent 4. The sealing material according to claim 3, wherein the total amount of repeating units derived from isobutylene in the polymer as the component (B) is 50% by weight or more. 5. The sealing material according to claim 4, which further contains a storage stability improver as an essential component (E).