JPH0995523A - Resin composition and method for preparing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a tough epoxy resin adhesive composition having excellent peeling strength without detriment to the shear adhesiveness and heat resistance of the constituent curable epoxy resin. SOLUTION: An adhesive composition comprising 95-70 pts.wt. curable epoxy resin and 5-30 pts.wt. polyether having at least one reactive silicone group in the molecule is provided. This composition contains 0.1-5 pts.wt. curing catalyst for the polyether and 1-20 pts.wt. silicone compound having a crosslinkable group represented by the general formula: SiR<1> (OR2 )2 or Si(OR<2> )3 (wherein R<1> and R<2> , which may be the same or different from each other, are each a 1-20C monovalent substituted or unsubstituted hydrocarbon group). Particles of a cured polyether are dispersed in the curable epoxy resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition and a method for producing the same, and more specifically, an epoxy resin resin composition having a high peel adhesive strength in which a silicone-containing polyether rubber is dispersed in an epoxy resin, and a method for producing the same. Regarding manufacturing method.

[0002]

BACKGROUND OF THE INVENTION Curable epoxy resins have excellent shear adhesive strength and heat resistance, and are widely used as adhesives and various composite materials, and also widely used as insulating materials for various electric and electronic parts. There is. However, since the cured product is hard and brittle, it has a problem of weak peel adhesion when used as an adhesive.

As a composition for improving the drawbacks of such a curable epoxy resin, a composition in which an epoxy resin is dispersed in a silicone crosslinkable elastomer has been proposed in recent years (for example, JP-A-4-33981). , 4-2
92616, JP-A-61-148225, etc.). However, although these compositions have excellent peel adhesive strength because the cured product is a rubber elastic body at room temperature, when viewed as an epoxy adhesive, the epoxy resin has excellent inherent properties such as hardness and rigidity. However, there is a drawback that the heat resistance and the shear adhesive strength are impaired due to the lack of heat resistance. Further, these compositions also include compositions in which a silane crosslinkable elastomer is added to an excess amount of an epoxy resin, but a cured product obtained from this composition has a low deterioration in high temperature characteristics, The compatibility between the resin and the elastomer is poor, and a reaction injection molding (RIM) method must be adopted to obtain a cured product, and it is difficult to use such a composition as an adhesive.

As a method for mixing and stabilizing two originally incompatible polymer compounds, there is a method of curing by reacting an organopolysiloxane in an epoxy resin in the presence of a catalyst (Japanese Patent Publication No. No. 18986). In this method, after mixing both components, the elastomer is reacted with vigorous stirring, and as a result, the elastomer phase is 1 to 2
This results in a spherical dispersion having a wide particle size distribution of 0 μm. Therefore, the homogeneity of the cured product is not always sufficient, and a step of vacuum degassing after stirring is required,
There was a drawback.

Further, as a component for improving the brittleness of the epoxy resin, a carboxyl group-terminated liquid nitrile rubber (CTB) is used.
N) is well known. When CTBN is added to the epoxy resin, the CT will increase as the epoxy resin cures.
Since BN takes a dispersed form in the epoxy resin, there is a drawback that the physical properties vary depending on the curing conditions.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a tough epoxy resin adhesive which is excellent in peel adhesive strength without impairing the shear adhesive strength and heat resistance of the curable epoxy resin. .

[0007]

Therefore, the present invention provides (a)
An adhesive composition comprising 95 to 70 parts by weight of a curable epoxy resin and (b) 5 to 30 parts by weight of a polyether containing at least one reactive silicone group in the molecule, which comprises (c) 0.1 to 5 parts by weight of a curing catalyst of the polyether (b) and (d) a functional group capable of reacting with an epoxy group, and a general formula: —SiR ¹ (OR ² ) ₂ or —Si (OR ² ) ₃ (formula Wherein R ¹ and R ² are the same or different and each represents a substituted or unsubstituted monovalent hydrocarbon having 1 to 20 carbon atoms.)
1 to 20 having a crosslinkable group represented by
An adhesive composition containing a part by weight of the curable epoxy resin (a), in which cured particles of the polyether (b) are dispersed, and the curable epoxy resin (a) 95-
An adhesive composition comprising 70 parts by weight and 5 to 30 parts by weight of the above polyether (b), 0.1 to 5 parts by weight of the above polyether curing catalyst (c) and the above silicone compound
(d) 1 to 20 parts by weight of polyether (b) is added to cure catalyst
Provided is a method for producing an adhesive composition, characterized in that the cured particles of the polyether (b) are formed in a curable epoxy resin by being cured by (c).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the epoxy resin (a) can be selected from a wide range of ordinary epoxy resins. Specific examples thereof include a bisphenol A-type epoxy resin obtained by reacting bisphenol A, bisphenol AD, biphenyl and the like with epichlorohydrin, a bisphenol AD type epoxy resin, a biphenyl type epoxy resin and the like, a hydrogenated epoxy resin, and glycidyl. Examples thereof include ester type epoxy resins, novolac type epoxy resins, urethane modified epoxy resins having urethane bonds, and rubber modified epoxy resins containing polybutadiene or NBR.

The polyether (b) has at least one reactive silicone group in the molecule. A typical example of the reactive silicone group is represented by the general formula: —SiR ¹ (OR ² ) ₂ (wherein R ¹
And R ² are as defined above. ) Is a hydrolyzable silicon functional group. Normally reactive silicone groups are
Although it is present at the terminal of the molecule, it may be present at other than the terminal. The polyether backbone may be a conventional polyether. Specific examples of the polyether include poly (methyldimethoxysilyl ether) and the like, and commercially available products can be used. These polyether polymers may be used alone or in combination of two or more.

As the silicone compound (d), a usual silane coupling agent is preferably used, and specific examples thereof include γ-aminopropyltrimethoxysilane, β-aminoethyltrimethoxysilane, γ-aminopropyldimethoxysilane, Examples include γ- [β-aminoethylaminopropyl] trimethoxysilane, β-phenylaminopropyltrimethoxysilane, and γ-cyclohexylaminopropyltrimethoxysilane.

As the polyether curing catalyst (c) contained in the composition of the present invention, a commonly used polyether curing catalyst can be used. For example, metal organic carboxylates such as tin octylate, tin stearate, tin naphthenate, tin octylate, organotins such as di-n-butyltin dilaurate, di-n-butyltin diphthalate, alkyl titanates, etc. Can be used alone or in combination.

The amount of each of the components (a) to (d) used is 5 to 30 parts by weight, preferably 10 to 30 parts by weight of the polyether (b) with respect to 95 to 70 parts by weight of the curable epoxy resin (a). Parts by weight, more preferably 15 to 25 parts by weight, the polyether curing catalyst (c) is 0.1 to 5 parts by weight, preferably 1 to 5 parts by weight.
The amount of the silicone compound (d) is 1 to 20 parts by weight, preferably 3 to 10 parts by weight.

The catalyst (c) mainly acts as a curing catalyst for the reactive silicone-containing polyether. When the amount of the catalyst (c) used does not reach the above-mentioned predetermined amount, the curing speed tends to be slow, and when it is more than the predetermined amount, the pot life tends to be shortened. If the amount of the polyether (b) used is less than 5 parts by weight, the modifying effect cannot be obtained, and if it exceeds 30 parts by weight, the entire resin is in a gel state.

To prepare the composition of the present invention, these components (a) to (d) are blended in predetermined amounts and mixed with stirring. The crosslinking (curing) reaction of the polyether by such stirring and mixing may be carried out at room temperature, but if necessary, at an appropriate temperature (for example, 40 to 8).
The reaction time can be shortened by heating to 0 ° C.) or adding a cocatalyst (laurylamine, tertiary amine compound, water, etc.) to accelerate the crosslinking reaction.

Agitation may be performed gently, and the change in particle size due to agitation efficiency is small. The spherically-formed reactive silicone-containing polyether particles can be stably and uniformly dispersed in the epoxy resin matrix by a stirring action, and a liquid or solid composition of the present invention can be obtained.

[0016]

The present invention is characterized in that the reactive silicone group-containing polyether is uniformly dispersed in the epoxy resin under extremely easy conditions, whereby the heat resistance of the epoxy resin can be improved by using a conventional stirring device. The flexibility of the composition is improved and the composition having desired peel adhesion and toughness can be obtained without lowering the adhesiveness and shear adhesive strength.

The composition of the present invention is cured in the presence of a usual epoxy resin curing agent and the like. Since the composition of the present invention has high toughness and flexibility, it can be used, for example, in various coating agents, adhesives, prepregs and the like.

Next, the present invention will be described more specifically with reference to examples. Examples 1 to 4 and Comparative Example 1 A predetermined amount of each predetermined component shown in the following Table 1 was reacted according to the production method described below, and a predetermined amount of modified polyamidoamine was added thereto, and the mixture was reacted at 100 ° C. for 6 hours. An epoxy resin cured product was produced. All quantities are given in parts by weight. The adhesive performance and the glass transition temperature of the obtained composition were measured. The results are shown in Table 1.

[0019]

[Table 1]

Production method (Example 1) To 100 parts by weight of a bisphenol A type epoxy resin (Epicote 828 manufactured by Yuka Shell Epoxy Co., Ltd.) was added 5 parts by weight of a reactive silicone group-containing polyether (Cyryl SAT30 manufactured by Kanegafuchi Chemical Co., Ltd.). , Γ-aminopropyltrimethoxysilane (A110 manufactured by Unicar Japan)
0) 1 part by weight was added, and 0.1 part by weight of dibutyltin laurate was added thereto while stirring at 80 ° C., and stirring was continued for further 8 hours. The reaction mixture becomes a milky white liquid.

After completion of the reaction, the mixture is left to cool at room temperature to obtain an epoxy resin composition in which the reactive silicone group-containing polyether resin particles are uniformly dispersed in the epoxy resin. As a result of observation with a scanning electron microscope, the particle size of the silicone resin is 0.5.
Was about 2 μm.

(Example 2) Bisphenol A type epoxy resin (Epicote 828, manufactured by Yuka Shell Epoxy Co., Ltd.) 10
To 0 parts by weight, 10 parts by weight of a reactive silicone group-containing polyether (Cyryl SAT30 manufactured by Kanegafuchi Chemical Co., Ltd.) was added, 1 part by weight of γ-aminopropyltrimethoxysilane (A1100 manufactured by Nippon Unicar) was added, and the mixture was stirred at 80 ° C. While adding 0.1 parts by weight of dibutyltin laurate,
Continue stirring for another 8 hours. The reaction mixture becomes a milky white liquid.

After completion of the reaction, the mixture is left to cool at room temperature to obtain an epoxy resin composition in which reactive silicone group-containing polyether resin particles are uniformly dispersed in the epoxy resin. As a result of observation with a scanning electron microscope, the particle size of the silicone resin is 0.5.
Was about 2.5 μm.

(Example 3) Bisphenol A type epoxy resin (Epicote 828, manufactured by Yuka Shell Epoxy Co., Ltd.) 10
20 parts by weight of a reactive silicone group-containing polyether (Cyryl SAT30 manufactured by Kanegafuchi Chemical Co., Ltd.) was added to 0 parts by weight, 1 part by weight of γ-aminopropyltrimethoxysilane (A1100 manufactured by Nippon Unicar) was added, and the mixture was stirred at 80 ° C. While adding 0.1 parts by weight of dibutyltin laurate,
Continue stirring for another 8 hours. The reaction mixture becomes a milky white liquid.

After the completion of the reaction, the mixture is left to cool at room temperature to obtain an epoxy resin composition in which the reactive silicone group-containing polyether resin particles are uniformly dispersed in the epoxy resin. As a result of observation with a scanning electron microscope, the particle size of the silicone resin is 0.5.
Was about 1.0 μm.

Example 4 Bisphenol A type epoxy resin (Epicote 828, manufactured by Yuka Shell Epoxy Co., Ltd.) 10
To 0 parts by weight, 30 parts by weight of a reactive silicone group-containing polyether (Cyryl SAT30 manufactured by Kanegafuchi Chemical Co., Ltd.) was added, and further 1 part by weight of γ-aminopropyltrimethoxysilane (A1100 manufactured by Nippon Unicar) was added, and the mixture was stirred at 80 ° C. While adding 0.1 parts by weight of dibutyltin laurate,
Continue stirring for another 8 hours. The reaction mixture becomes a milky white liquid.

After completion of the reaction, the mixture is allowed to cool at room temperature to obtain an epoxy resin composition in which reactive silicone group-containing polyether resin particles are uniformly dispersed in the epoxy resin. As a result of scanning electron microscope observation, the silicone resin particle size is 1.0.
˜5.0 μm.

Comparative Example 1 A bisphenol A type epoxy resin (Epicote 828 manufactured by Yuka Shell Epoxy Co., Ltd.) was used alone.

Examples 5 to 7 Epoxy resins were prepared according to Example 3 and reacted under the curing conditions shown in Table 2 below to obtain cured products, and the T-type peel adhesive strength at 20 ° C. was measured.

Comparative Examples 2 to 4 ) 100 parts by weight of a bisphenol A type epoxy resin (Epicote 828, manufactured by Yuka Shell Epoxy Co., Ltd.) was used as a carboxyl group-terminated liquid nitrile rubber [Hycar CTBN] 20 manufactured by Goodrich. 10 parts by weight of modified polyamidoamine was added to prepare a cured product under the reaction curing conditions shown in Table 2, and the T-type peel adhesive strength at 20 ° C. was measured. Table 2 shows the results.

[0031]

[Table 2]

In the evaluation of the adhesive strength of the above composition, a mild steel plate (SS-41, 25 mm × 100 mm × 1.6 mm) was used for measuring the tensile shear adhesive strength in accordance with JIS K6850.
Is used as an adherend, and the T-type peeling adhesive force is measured by JIS
Aluminum according to K6854 (A1050 25mm × 3
(00 mm × 0.3 mm) was used as the adherend.

Claims (2)

[Claims] 1. An adhesive composition comprising (a) 95 to 70 parts by weight of a curable epoxy resin and (b) 5 to 30 parts by weight of a polyether containing at least one reactive silicone group in the molecule. And (c) 0.1 to 5 parts by weight of a curing catalyst of the polyether (b) and (d) a functional group capable of reacting with an epoxy group, and a general formula: —SiR ¹ (OR ² ) ₂ or — Si (OR ² ) ₃ (In the formula, R ¹ and R ² are the same or different and each represents a substituted or unsubstituted monovalent hydrocarbon having 1 to 20 carbon atoms.)
1 to 20 having a crosslinkable group represented by
An adhesive composition comprising a part by weight of which particles of the polyether (b) cured by the curing catalyst (c) are dispersed in the curable epoxy resin (a). 2. An adhesive composition comprising (a) 95 to 70 parts by weight of a curable epoxy resin and (b) 5 to 30 parts by weight of a polyether containing at least one reactive silicone group in the molecule. And (c) 0.1 to 5 parts by weight of a curing catalyst of the polyether (b) and (d) a functional group capable of reacting with an epoxy group, and a compound represented by the general formula: —SiR ¹ (OR ² ) ₂ or —Si ( OR ² ) ₃ (In the formula, R ¹ and R ² are the same or different and each represents a substituted or unsubstituted monovalent hydrocarbon having 1 to 20 carbon atoms.)
1 to 20 having a crosslinkable group represented by
An adhesive composition, characterized in that, by adding parts by weight, the polyether (b) is cured by the curing catalyst (c) to form cured particles of the polyether (b) in the curable epoxy resin. Manufacturing method.