JP3527605B2 - Curable composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable composition containing a saturated hydrocarbon polymer which is cured by a hydrosilylation reaction.

[0002]

2. Description of the Related Art Conventionally, various curable liquid compositions which produce a rubber-like substance upon curing have been developed. Among them, as a curing system excellent in deep-curing property, an organopolysiloxane having an average of two or more vinyl groups in one molecule at the end or in the molecular chain is averaged, and a hydrogen atom bonded to a silicon atom is averaged in one molecule. One which is crosslinked with an organohydrogenpolysiloxane having two or more has been developed, and it is used as a silicone-based sealing material or potting material by utilizing its excellent weather resistance, heat resistance and water resistance. However, this curing system is high in cost, poor in adhesiveness, and easy to cause mold, etc.
Its use is limited. On the other hand, as a system which does not use such an expensive organopolysiloxane, a saturated hydrocarbon polymer having at least one alkenyl group in the molecule is cured having two hydrogen atoms bonded to two silicon atoms in the molecule. A curable composition that is cross-linked with an agent is disclosed in JP-A-2-
No. 75644 and Japanese Patent Laid-Open No. 3-181565. The cured product of this composition has excellent weather resistance, heat resistance, low moisture permeability, and the like, and is expected to be used in a wide range of applications. However, although the curable composition in which the polymer is a saturated hydrocarbon polymer has excellent curability and mechanical properties as rubber, it has insufficient adhesiveness to metals and plastic materials. Further, an adhesive composition obtained by adding a silane coupling agent to the above composition for the purpose of improving the adhesiveness thereof is disclosed in Japanese Patent Application Laid-Open No. 4-185687, but it has an effect of improving the adhesiveness, but is insufficient. It was something. Japanese Patent Application No. 8-134729 discloses an adhesive composition containing an organoaluminum compound and / or an organotitanium compound in addition to a silane coupling agent as a composition exhibiting excellent adhesiveness.

[0003]

The object of the present invention is to provide a saturated hydrocarbon polymer excellent in low moisture permeability, low hygroscopicity, low gas permeability, heat resistance, weather resistance, electrical insulation and vibration absorption. In a curable composition that can be cured by addition-type curing using, the adhesiveness is further improved.

[0004]

The present inventors have found that when a saturated hydrocarbon polymer represented by isobutylene is applied to an addition type curing system, a silane coupling agent, an organoaluminum compound and / or an organotitanium. It has been found that a saturated hydrocarbon-based cured product having excellent adhesiveness can be obtained by adding the compound and the polyvalent alkoxysilane and / or its condensate.

That is, the present invention provides (A) an isobutylene polymer containing at least one hydrosilylation-reactive alkenyl group in the molecule (B) a curing agent containing at least two hydrosilyl groups. (C) Hydrosilylation catalyst (D) Silane coupling agent (E) Organoaluminum compound and / or organotitanium compound (F) Polyfunctional alkoxysilane and / or a curable composition containing a condensate thereof.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) used in the present invention is a saturated hydrocarbon polymer having at least one alkenyl group capable of hydrosilylation reaction in the molecule. 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, the repeating unit constituting the main chain except the alkenyl group It is meant to be composed of saturated hydrocarbons.
Moreover, the alkenyl group capable of hydrosilylation reaction is not particularly limited as long as it is a group containing a carbon-carbon double bond that is active in hydrosilylation reaction. As the alkenyl group, an aliphatic unsaturated hydrocarbon group such as vinyl group, allyl group, methylvinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group And other cyclic unsaturated hydrocarbon groups. In the present invention, the component (A) preferably has 1 to 10 alkenyl groups in one molecule. Furthermore, in the component (A) in the present invention, it is desirable that the alkenyl group capable of hydrosilylation reaction be introduced at the polymer terminal. In this way, when the alkenyl group is at the polymer terminal, the effective amount of network chains of the cured product finally formed is large, and it becomes easy to obtain a rubber-like cured product having high strength and high elongation. preferable. The polymer forming the skeleton of the saturated hydrocarbon polymer as the component (A) is (1) ethylene,
Propylene, 1-butene, isobutylene, and other olefinic compounds having 1 to 6 carbon atoms are polymerized as main monomers, (2) butadiene, isoprene, and other diene-based compounds are homopolymerized, and It can be obtained by a method such as copolymerizing with a diene compound and then hydrogenating, but it is easy to introduce a functional group at the terminal, easy to control the molecular weight, and the number of terminal functional groups can be increased. From the viewpoints of the above, an isobutylene-based polymer, a hydrogenated polybutadiene-based polymer, or a hydrogenated polyisoprene-based polymer is preferable.

In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, and the monomer units having copolymerizability with isobutylene are preferably contained in the isobutylene-based polymer in an amount of 50% ( % By weight, the same applies hereinafter), more preferably 30% or less, particularly preferably 20% or less. Examples of such a monomer component include olefins having 4 to 12 carbon atoms,
Examples thereof include vinyl ether, 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, 4-methyl-1-pentene, hexene,
Vinyl cyclohexane, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methyl styrene, dimethyl styrene, pt-
Butoxystyrene, p-hexenyloxystyrene, p
-Allyloxystyrene, p-hydroxystyrene, β-
Pinene, indene, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,
3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxy Examples include silane.

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 main monomer unit,
Other monomer units may be contained. Further, in the saturated hydrocarbon polymer used as the component (A) in the present invention, a single bond such as a polyene compound such as butadiene or isoprene having a double bond remaining after the polymerization is used as long as the object of the present invention is achieved. The monomer unit may be contained in a small amount, preferably in the range of 10% or less.

The number average molecular weight (GPC method, polystyrene conversion) of the saturated hydrocarbon polymer, preferably isobutylene polymer, hydrogenated polyisoprene or hydrogenated polybutadiene polymer is 100,000 or less, more preferably 500 to 1
It is preferably about 00000, particularly 1000 to 4
It is preferable that the liquid substance has a fluidity of about 0000 and that it has fluidity from the viewpoint of easy handling.

Further, as the method for producing the component (A) of the present invention, there are disclosed in JP-A-3-152164 and JP-A-7-30490.
9 A method of introducing an unsaturated group into a polymer by reacting a polymer having a functional group such as a hydroxyl group with a compound having an unsaturated group as disclosed in each of the publications can be mentioned. Further, in order to introduce an unsaturated group into a polymer having a halogen atom, a method of carrying out a Friedel-Crafts reaction with an alkenylphenyl ether, a method of carrying out a substitution reaction with allyltrimethylsilane in the presence of a Lewis acid, various phenols and Friedel Examples include a method of introducing a hydroxyl group by carrying out a Kraftz reaction and then using the above-mentioned alkenyl group introduction method together. Further, U.S. Pat. No. 4,316,973 and JP-A-63-105.
A method of introducing an unsaturated group at the time of polymerizing a monomer as disclosed in Japanese Patent Laid-Open No. 005/1985 and Japanese Patent Application Laid-Open No. 4-288309 is also possible.

The curing agent which is the component (B) of the present invention is not limited as long as it has at least two hydrosilyl groups in the molecule. Here, one hydrosilyl group means one SiH group. Therefore, when two hydrogen atoms are bonded to the same Si, it is calculated as two hydrosilyl groups. As the component (B), organohydrogenpolysiloxane is one of the preferable ones. The organohydrogenpolysiloxane referred to here is
It refers to a polysiloxane having a hydrocarbon group or a hydrogen atom on the Si atom, and when its structure is specifically shown,

[0012]

[Chemical 1]

Examples thereof include chain-like and cyclic ones. Considering that among the various hydrosilyl group-containing groups described above, the compatibility of the hydrosilyl group-containing curing agent which is the component (B) of the present invention with various organic polymers such as the component (A) is less likely to be impaired. The following are particularly preferable.

[0014]

[Chemical 2]

The number of hydrosilyl groups contained in the component (B) may be at least 2 in one molecule, but is preferably 2 to 40. 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. Further, when the number of the hydrosilyl groups is more than 40, the stability of the curing agent as the component (B) is deteriorated, and moreover, a large amount of the hydrosilyl groups remains in the cured product even after curing, causing voids and cracks. Becomes

Hydrosilylation which is the component (C) of the present invention
The catalyst is not particularly limited, and any one can be used.
Wear. Specifically, chloroplatinic acid, a simple substance of platinum,
Solid white on carriers such as alumina, silica, carbon black, etc.
Gold supported; platinum-vinyl siloxane complex {Example
For example, Pt_n(ViMe₂SiOSiMe₂Vi)_n, Pt
[(MeViSiO) _Four]_m}; Platinum-phosphine complex
{For example, Pt (PPh₃)_Four, Pt (PBu₃)_Four};White
Gold-phosphite complex {for example, Pt [P (OP
h)₃]_Four, Pt [P (OBu)₃]_Four(In the formula, Me is methyl
Group, Bu is butyl group, Vi is vinyl group, Ph is phenyl group
Group, n and m are integers), Pt (acac)
₂See also US Pat. No. 3,159,601 to Ashby et al.
And platinum-carbonized water described in US Pat. No. 3,159,662.
Elementary composites, as well as Lamoreaux et al., US Pat.
220972 Platinum alcoholate described in the specification
A catalyst is also included.

As an example of a catalyst other than the platinum compound,
Is RhCl (PPh₃)₃, RhCl ₃, Rh / Al
₂O₃, RuCl₃, IrCl₃, FeCl₃, AlCl₃,
PdCl₂・ 2H₂O, NiCl₂, TiCl_Four, Etc.
To be These catalysts may be used alone or in combination of two or more.
You may use together. From the point of catalytic activity, chloroplatinic acid,
Platinum-olefin complex, platinum-vinylsiloxane complex,
Pt (acac)₂Etc. are preferred. Especially as the amount of catalyst
There is no limitation, but to 1 mol of the alkenyl group in the component (A)
To 10^-1-10^-8It is preferable to use it in the range of mol.
Preferably 10^-2-10^-6It should be used in the mol range
Yes. Also, hydrosilylation catalysts are generally expensive and corrosive.
In addition, a large amount of hydrogen gas is generated and the cured product foams.
It may be done so 10^-1Not use more than mol
Good.

In the present invention, since the curable composition is cured by the addition reaction of the Si—H group to the alkenyl group using the noble metal catalyst, the curing rate is very fast, which is convenient for line production. The silane coupling agent which is the component (D) of the present invention includes at least one functional group selected from an epoxy group, a methacrylic group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group and a carbamate group in the molecule. A silane coupling agent having a silicon atom-bonded alkoxy group is preferable. Regarding the functional group, it is particularly preferable that the molecule has an epoxy group, a methacryl group, or an acryl group in terms of curability and adhesiveness. Specifically, examples of the organosilicon compound having an epoxy functional group and a silicon atom-bonded alkoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxy. Examples thereof include cyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane. Also,
Examples of the organosilicon compound having a methacryl group or an acryl group and a silicon atom-bonded alkoxy group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyl. Triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane,
Examples thereof include acryloxymethyltrimethoxysilane and acryloxymethyltriethoxysilane.

The organoaluminum compound which is the component (E) of the present invention is preferably a chelate organic compound which is a useful catalyst for the hydrolysis and condensation reaction of alkoxysilyl groups. Specific examples include aluminum acetylacetonate and the like. Moreover, as the organotitanium compound which is the component (E) of the present invention, an organotitanium compound having a Ti—O—C bond, which is a useful catalyst for the hydrolysis and condensation reaction of an alkoxysilyl group, is preferable. Specific examples thereof include tetraalkoxytitanium such as tetraisopropoxytitanium and tetrabutoxytitanium, as well as general titanate coupling agents such as those having a residue such as oxyacetic acid and ethylene glycol.

Various alkoxysilanes can be used as the polyvalent alkoxysilane which is the component (F) of the present invention. These alkoxysilanes are alkoxysilanes having no functional groups such as epoxy group, methacrylic group, acryl group, isocyanate group, isocyanurate group, vinyl group and carbamate group in the molecule. Specifically, tetramethoxysilane, tetraethoxysilane, tetra (n-propyl) silane, tetra (n-butyl) silane and other tetraalkoxysilanes and condensates thereof or trialkoxy such as methyltriethoxysilane and ethyltriethoxysilane. Silane and its condensates can be used.
Among these, tetraalkoxysilane, trialkoxysilane substituted with a saturated alkyl group such as methyl group, or a condensate thereof is preferable.

Further, various plasticizers and various inorganic fillers may be added to the curable composition of the present invention depending on the purpose. The plasticizer is added to improve the fluidity of the present composition, and a commonly used plasticizer can be used, but it is compatible with the saturated hydrocarbon polymer used in the present invention. Good ones are preferred. Specific examples of the plasticizer include polybutene, hydrogenated polybutene, α
-Methylstyrene oligomer, liquid polybutadiene, hydrogenated liquid polybutadiene, paraffin oil, naphthene oil, atactic polypropylene, and the like, but among them, hydrogenated polybutene containing no unsaturated bond, hydrogenated liquid polybutadiene, paraffin oil is preferable. Hydrocarbon compounds such as naphthenic oil and atactic polypropylene are preferred.

As the inorganic filler, various inorganic fillers such as calcium carbonate, talc, silica and carbon black can be used. However, since the curable composition of the present invention utilizes curing by hydrosilylation reaction,
In using it, consideration should be given to the presence or absence of inhibition for the hydrosilylation reaction, for example, when the composition contains a large amount of water, a side reaction may occur during the curing reaction.

Further, a storage stability improver can be used for the purpose of improving the storage stability of the curable composition of the present invention. This storage stability improver is a conventional stabilizer known as a storage stabilizer for the component (B) of the present invention, and may be any one that achieves the intended purpose, and is not particularly limited. is not. Specifically, a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, an organic peroxide and the like can be preferably used. More specifically, 2-benzothiazolyl sulfide, benzothiazole, thiazole, dimethylacetylene dicarboxylate, diethyl acetylene dicarboxylate, BHT, butylhydroxyanisole, vitamin E, 2 -(4-Morphodinyldithio) benzothiazole, 3-methyl-1
-Butene-3-ol, acetylenically unsaturated group-containing organosiloxane, acetylene alcohol, 3-methyl-
1-butyl-3-ol, diallyl fumarate, diallyl maleate, diethyl fumarate, diethyl maleate
G, dimethyl maleate, 2-pentene nitrile, 2,
3-dichloropropene and the like can be mentioned, and thiazole and benzothiazole are preferable in view of compatibility of pot life / rapid curability, but the invention is not limited thereto.

Furthermore, the curable composition of the present invention comprises
Other fillers, antioxidants, ultraviolet absorbers, pigments, surfactants and the like can be added as required.
Specific examples of this filler include titanium oxide, zinc oxide, and barium sulfate. The composition of the present invention has low moisture permeability, low hygroscopicity, low gas permeability, heat resistance,
A curable composition that uses a saturated hydrocarbon polymer that has excellent weather resistance, electrical insulation, and vibration absorption properties and that can be cured by addition-type curing. Curable composition.

Among the various characteristics described above, for example, with regard to low moisture permeability, excellent moisture permeability coefficient of about 1 × 10 ⁻¹¹ · cm / cm ² · sec · cmHg is exhibited. Further, regarding heat resistance, it exhibits excellent characteristics that no melting is observed on the surface even under a severe condition of 130 ° C. for 300 days, and further, regarding electric insulation, it exhibits an excellent dielectric constant of about 2.44.

Due to such characteristics, the composition of the present invention can be used in a wide range of application fields such as sealing materials for electric and electronic parts, various coating materials, gasket materials, sealing materials, molding materials, paints and adhesives. Hereinafter, the present invention will be described in more detail with reference to Examples.

[0027]

EXAMPLE The molecular weight of the compound A shown in this example is GP.
It was measured by C, ¹ H-NMR. GPC analysis: system; system manufactured by Waters (pump 600E, differential refractometer 401), column; Shodex K-804 manufactured by Showa Denko KK, mobile phase: chloroform, ¹ H-NMR in which number average molecular weight is expressed in terms of polystyrene : Varian Gemini-30
0, measuring solvent; carbon tetrachloride + heavy acetone Also, the pressure cooker process is Hirayama Seisakusho MOD
EL PC422R (serial No. 90127
0620) was used.

Example 1 Compound A which is a component (A) having the following structure and synthesized by the method described in JP-A-63-105005 (analytical values are shown in Table 1).

[0029]

[Chemical 3]

[0030]

[Table 1]

And a compound B which is a component (B) having the structure shown below:

[0032]

[Chemical 4]

The amount of alkenyl groups in component (A) and (B)
Weighed so that the ratio of the amount of Si-H groups in the minute is 1: 1.2
In addition, Irganox 1010 (
(Made by Ba Geigy) with respect to 100 parts by weight of the component (A)
1 part by weight was weighed, and this was kneaded with a roll three times. Continued
(D) as component 3-glycidoxypropyltrimetho
Xysilane (manufactured by Nippon Unicar Co., Ltd., trade name: A-18)
7) 4.4 parts by weight per 100 parts by weight of component (A),
Aluminum acetylacetonate as component (E)
0.2 parts by weight per 100 parts by weight of component (A),
As a component, tetraethoxysilane (Shin-Etsu Chemical Co., Ltd., L
S-2430) is 2.0 per 100 parts by weight of component (A).
Parts by weight were weighed and mixed. Furthermore, as a storage stability improver,
30 molar equivalents of methylmalate to platinum and (C) formation
Minute catalyst bis (1,3-divinyl-1,1,3,3
3-Tetramethyldisiloxane) platinum complex catalyst (8.3
× 10 ^-Fivemmol / μl, xylene solution)
5 × 10 with respect to the number of moles of the amount of alkenyl groups in the component (A)
^-FourWeighed so as to be equivalent and mixed uniformly. The composition
In addition to examining the curability of the
A test piece was prepared and heated at 150 ° C. for 1 hour to be cured.

Example 2 As in Example 1, except that the addition amount of tetraethoxysilane condensate (Colcoat Co., Ltd., trade name: ethyl silicate 40) as component (F) was changed to 100 parts by weight of component (A). On the other hand, a test piece was prepared in an amount of 2.3 parts by weight. Example 3 Same as Example 1, except that titanium tetrabutoxide was added as the component (E) to 100 parts by weight of the component (A).
2 parts by weight, a condensate of tetraethoxysilane as component (F) (Colcoat Co., Ltd., trade name: ethyl silicate 4
0) is added in an amount of 2.3 with respect to 100 parts by weight of the component (A).
A test piece was prepared as a part by weight.

Example 4 Same as Example 1, except that titanium tetrabutoxide as the component (E) was added to 100 parts by weight of the component (A).
2 parts by weight, a condensate of tetraethoxysilane as component (F) (Colcoat Co., Ltd., trade name: ethyl silicate 4
0) is added to 1.2 parts with respect to 100 parts by weight of the component (A).
A test piece was prepared as a part by weight.

Comparative Example 1 A test piece was prepared in the same manner as in Example 1 except that the component (F) was not added. Comparative Example 2 As in Example 1, except that titanium tetrabutoxide was used as the component (E) per 100 parts by weight of the component (A).
A test piece was prepared by adding 0 part by weight and not adding the component (F). Table 2 summarizes each formulation.

[0037]

[Table 2]

For the evaluation of the adhesiveness, the test piece obtained as described above was tested for the adhesive strength after normal condition and pressure cooker (PCT) treatment (121 ° C., 2 atmospheric pressure, 20 hours treatment) according to JIS K 6850 tensile strength. The shear strength or cross-cut tape method was used for evaluation. Aluminum (thickness 1.6 mm) was used as the base material. Further, glass (thickness 2.8 mm) was evaluated by a cross-cut tape method. The evaluation results of the adhesiveness are shown in Tables 3 and 4.

[0039]

[Table 3]

From Table 3, it can be seen that if the component (F) is not added, the interface will be destroyed and the adhesive force to the substrate will be small.

[0041]

[Table 4]

The numerical values in Table 4 represent the number remaining when 25 pieces of 2 mm square were cut into the cured product and peeled off with a tape. 25/25 represents the number of pieces that were not peeled at all, and 0/25 represents that all were peeled. It can be seen from Table 4 that the adhesive force to the substrate is small when the component (F) is not added. Example 5 Amount of alkenyl group in component (A) and Si-H in component (B)
Weighed so that the ratio of the base amount is 1: 2.0, and further process oil (made by Idemitsu Kosan, trade name: PS-
32) to 50 parts by weight of 100 parts by weight of component (A),
Furthermore, as an antioxidant, MARK AO-50 (ADEKA
3 parts by weight of Argus Chemical Co., Ltd. (100 parts by weight of component (A)) and 100 parts by weight of fused silica (made by Tatsumori Co., Ltd.) of 100 parts by weight of component (A) were weighed.
This was kneaded with a roll three times. Subsequently, as component (D), 3-glycidoxypropyltrimethoxysilane (manufactured by Nippon Unicar Co., Ltd., trade name: A-187) was added in an amount of 4.3 parts by weight per 100 parts by weight of component (A), and (E). Titanium tetrabutoxide as a component is 0.2 parts by weight with respect to 100 parts by weight of the component (A), and tetraethoxysilane (LS-2430 manufactured by Shin-Etsu Chemical Co., Ltd.) as the component (F) is 100 parts by weight of the component (A). 1.9 parts by weight were mixed and weighed. Further, dimethyl maleate was used as a storage stability improver in an amount of 30 molar equivalents with respect to platinum, and bis (1,
3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst (8.3 × 10 ⁻⁵ mmol / μl,
The xylene solution) was weighed so that platinum was 5 × 10 ⁻⁴ equivalent with respect to the number of moles of the alkenyl group of the component (A), and mixed uniformly. The curability of the composition was examined, and the composition was applied onto various base materials to prepare test pieces, which were heated at 150 ° C. for 1 hour to be cured.

Example 6 A test piece was prepared in the same manner as in Example 5, except that the addition amount of tetraethoxysilane as the component (F) was 1.0 part by weight with respect to 100 parts by weight of the component (A). Example 7 In the same manner as in Example 5, except that the amount of the tetraethoxysilane condensate (Colcoat Co., Ltd., trade name: ethyl silicate 40) added as the component (F) was 100 parts by weight of the component (A). A test piece was prepared as 2.3 parts by weight.

Example 8 The same procedure as in Example 5 was carried out, except that the addition amount of tetraethoxysilane condensate (Colcoat Co., Ltd., trade name: ethyl silicate 40) as the component (F) was changed to 100 parts by weight of the component (A). To 1.1 parts by weight to prepare a test piece. Comparative Example 3 A test piece was prepared in the same manner as in Example 5, except that the component (F) was not added. Table 5 shows the results of the adhesion evaluation for each formulation, and Tables 6 and 7 show the results of the adhesiveness evaluation.

[0045]

[Table 5]

[0046]

[Table 6]

[0047]

[Table 7]

The numerical values in Table 7 represent the number of pieces left when 25 pieces of 2 mm square were cut in the cured product and peeled off with a tape. 25/25 represents the number of pieces that were not peeled at all, and 0/25 represents that all were peeled. It can be seen from Table 7 that the adhesive force to the substrate is small when the component (F) is not added. From the results shown in Tables 3, 4, 6 and 7, the following facts were clarified. By adding a small amount of an organoaluminum compound or organotitanium compound as the component (E) and a small amount of tetraalkoxysilane or a condensate thereof as the component (F), the durable adhesion and durable adhesive strength of the cured product are improved. Particularly effective for glass.

As described above, the curable composition according to the present invention has a wider range of application than conventional and has improved adhesiveness.

[0050]

EFFECTS OF THE INVENTION According to the present invention, as is clear from the examples, in the addition type curing system using a saturated hydrocarbon polymer, it is possible to improve the adhesiveness without impairing the curability. . In particular, addition type cured products using saturated hydrocarbon polymers are excellent in various characteristics such as low moisture permeability, low moisture absorption, low gas permeability, heat resistance, weather resistance, electrical insulation, and vibration absorption. It is a rubber-like elastic body, and by combining it with adhesiveness, it is used in fields where adhesiveness is essential, such as sealing materials for electric and electronic parts, various coating materials, sealing materials, paints, adhesives, etc. The reliability of can be increased.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08L 83/05 C08L 83/05 (56) References JP-A-8-311342 (JP, A) JP-A-6-200123 (JP , A) JP-A-4-185687 (JP, A) JP-A-8-134165 (JP, A) JP-A-6-279691 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB) Name) C08L 9/00-21/00 C08L 23/00-23/36 C08L 83/05

Claims (10)

(57) [Claims] 1. The following components (A), (B), (C),
Curable composition containing (D), (E) and (F); (A) at least one in the molecule of an isobutylene polymer (B) containing at least one alkenyl group capable of hydrosilylation reaction in the molecule. Curing agent (C) hydrosilylation catalyst (D) silane coupling agent (E) organoaluminum compound and / or organotitanium compound (F) polyvalent alkoxysilane and / or condensate thereof containing two hydrosilyl groups 2. The curable composition according to claim 1, wherein the polymer as the component (A) is a polymer having at least one alkenyl group introduced at the end of the polymer chain. 3. The curable composition according to claim 1, wherein the polymer as the component (A) is a polymer in which the total amount of repeating units derived from isobutylene is 50% by weight or more. 4. The curable composition according to claim 1, wherein the polymer as the component (A) is a polymer in which the total amount of repeating units derived from isobutylene is 80% by weight or more. 5. The curable composition according to claim 1, wherein the curing agent as the component (B) is a polyorganohydrogenpolysiloxane containing at least two hydrosilyl groups in the molecule. 6. The silane coupling agent as the component (D) comprises at least one functional group selected from an epoxy group, a methacrylic group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group and a carbamate group in the molecule and silicon. The curable composition according to claim 1, which is a compound having an alkoxy group bonded to an atom. 7. The silane coupling agent as the component (D) is a compound having in the molecule at least one functional group selected from an epoxy group, a methacryl group and an acryl group and an alkoxy group bonded to a silicon atom. 1. The curable composition according to 1. 8. The curable composition according to claim 1, wherein the organoaluminum compound as the component (E) is an aluminum chelate compound. 9. The curable composition according to claim 1, wherein the organotitanium compound as the component (E) is an organotitanium compound having a Ti—O—C bond. 10. The curable composition according to claim 1, wherein the polyvalent alkoxysilane as the component (F) is tetraalkoxysilane and / or its condensate or trialkoxysilane and / or its condensate.