JP3205915B2 - Metal-containing epoxy resin composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel metal-containing epoxy resin composition and a method for producing the same, and more particularly to a metal-containing epoxy resin composition having excellent adhesion to metals and a method for producing the same. .

[0002]

2. Description of the Related Art Conventionally, epoxy resin cured products have been widely used for paints, civil engineering, adhesives, electric / electronic materials and composite materials because of their excellent mechanical properties, electrical properties, chemical properties and thermal properties. It is used in the direction. To cure an epoxy resin, a method using an amine compound that reacts with an epoxy group, a curing agent such as an acid anhydride, a method using a curing accelerator that promotes a reaction between an epoxy group and these curing agents, or a method using an epoxy resin It is roughly classified into a method using a curing agent such as a tertiary amine, an imidazole, or a Lewis acid which promotes a polymerization reaction of a group. Of these, when a curing agent that reacts with an epoxy group such as an amine compound or an acid anhydride is used for curing the epoxy resin, curing will be insufficient if the blending ratio of the epoxy resin and the curing agent is not strictly controlled. Performance cannot be obtained.

On the other hand, when a curing agent that promotes the polymerization reaction of the epoxy group is used for curing the epoxy resin, there is an advantage that it is not necessary to control the compounding ratio of the curing agent so strictly. And recently, among these curing agents, imidazole derivatives capable of obtaining a cured product having excellent characteristics are widely used. However, although a cured product using an imidazole derivative as a curing agent has excellent properties, its adhesion to metal, for example, tensile shear strength on a copper plate is 100 k.
g / cm ² , and further improvement in adhesion is desired.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and an object of the present invention is to provide an epoxy resin composition having good adhesion to metal and a method for producing the same. .

[0005]

According to the present invention SUMMARY OF], such blended in the epoxy resin by the addition of a metal salt of an amino acid (B) and the epoxy resin (A) and the curing agent Rukoto A metal-containing epoxy resin composition characterized by comprising: an epoxy resin (A) and a metal salt of aminobenzoic acid (B)
With respect to 1 equivalent of epoxy group in the epoxy resin (A).
And the amino group in the metal salt of aminobenzoic acid (B) is
The solvent is blended so as to be 0.005 to 0.20 equivalent.
The epoxy resin (A) and the aminobenzoic acid in the presence of gold
There is provided a method for producing a metal-containing epoxy resin composition, wherein the solvent is distilled off after an addition reaction with the genus salt (B) .

That is, in a metal-containing epoxy resin composition using a metal salt of aminobenzoic acid and an epoxy resin as a curing agent, when heated, the ionic bonds contained in the epoxy resin composition become epoxy groups. The present invention has been found to act as a catalyst for the polymerization reaction of, and to be quickly cured, and to have an extremely large adhesive force to a metal as compared with a conventional epoxy resin composition.

The epoxy resin (A) used in the present invention is not particularly limited in molecular structure, molecular weight, etc. as long as it is a compound having two or more epoxy groups in the molecule. For example, bisphenol A type epoxy resin, bisphenol F Normally used epoxy resin, glycidyl dimer ester epoxy resin, polyalkylene ether epoxy resin, phenol novolak epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, diglycidyl epoxy resin, brominated epoxy resin, etc. Epoxy resin can be used.

The metal salt of aminobenzoic acid (B) has an amino group active to an epoxy group in the molecule and an ionic bond, and converts a carboxyl group in aminobenzoic acid into an alkali metal or an alkaline earth metal. Or by neutralizing with a metal ion generator such as an oxide, hydroxide or carbonate of a transition metal. As the kind of the metal, an alkali metal such as lithium, sodium, and potassium, an alkaline earth metal such as magnesium and calcium, and a transition metal such as zinc, nickel, aluminum, chromium, and iron are used.

The curing agent used in the present invention is an adduct of the metal salt of aminobenzoic acid (B) and the epoxy resin (A), and the metal salt of aminobenzoic acid (B) is added to the molecule of the epoxy resin (B). A) is obtained by adding-molecules or more.

Production of the metal-containing epoxy resin composition of the present invention
The mixing ratio of the metal salt of aminobenzoic acid (B) in the method is such that the amino group in the metal salt of aminobenzoic acid is 0.005 to 0.2 per 1 equivalent of the epoxy group in the epoxy resin (A).
Adjust to 0 equivalent . When the compounding ratio of the metal salt of aminobenzoic acid is less than this, the epoxy resin composition does not cure sufficiently, and when it is too large, the metal content in the composition increases, and the cured product becomes brittle. Absent.

The solvent used for producing the composition of the present invention includes, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, methanol, ethanol, water and the like. They can be used alone or as a mixture. The amount of these solvents used in the present invention varies depending on the type, but it may be an amount in which the metal salt of aminobenzoic acid and the epoxy resin are uniformly dissolved. However, it is not economically preferable.

Further, the epoxy resin composition of the present invention may further contain additives used in ordinary epoxy resin compositions,
For example, a plasticizer, a filler, a colorant, a reinforcing agent, and other modifiers having various purposes may be added.

In the production of the epoxy resin composition of the present invention, the epoxy resin and the metal salt of aminobenzoic acid are first dissolved in a solvent. It can be carried out. When the solvent used in the production of the metal-containing epoxy resin composition and the solvent that produces the metal salt of aminobenzoic acid using the metal ion generator are the same, put the aminobenzoic acid and the metal ion generator in the solvent. The reaction is carried out at room temperature or under heating for 5 minutes to 10 hours to form a solution of a metal salt of aminobenzoic acid, and an epoxy resin is added thereto and dissolved. After that, at least 40 ° C,
An adduct of a metal salt of aminobenzoic acid and an epoxy resin is formed in the solution by heating and reacting at a temperature lower than the boiling point of the solvent used and lower than the curing temperature. Preferred heating temperature is 60 ° C to 120 ° C, and heating time is 10 minutes to
10 hours. When the temperature is lower than 40 ° C., it takes a long time for the reaction, which is not preferable. When the heating time is 10 minutes or less, the addition reaction between the metal salt of aminobenzoic acid and the epoxy resin is insufficient. Conversely, when the reaction time is 10 hours or more, the addition reaction with the metal salt of aminobenzoic acid is insufficient. It is not preferable because not only an addition reaction with an epoxy resin but also a polymerization reaction of an epoxy group occurs.

Next, the solvent is distilled off. The solvent may be distilled off at normal pressure or under reduced pressure. Thus, the metal-containing epoxy resin composition of the present invention can be obtained. The metal salt of aminobenzoic acid is insoluble in an epoxy resin as it is, for example, 150
It does not dissolve in epoxy resin at all even at a temperature of ° C.
Further, even if both are dissolved in a solvent and the solvent is distilled off without heating after heating, a metal salt of aminobenzoic acid is deposited. However, according to the production method of the present invention, the metal salt of aminobenzoic acid does not precipitate even after the solvent is distilled off, and a uniform composition can be obtained.

The metal-containing epoxy resin composition thus obtained can be cured usually at a temperature of 100 ° C. or higher. At this time, some of the epoxy groups in the epoxy resin react with the amino groups in the metal salt of aminobenzoic acid, and the remaining epoxy groups promote the polymerization based on the etherification reaction due to the ionic bonds contained in the composition. The curing reaction proceeds. At that time, the cured product shows excellent adhesion to metals and the like. The catalytic effect of ionic bonding differs depending on the type of metal ion used, and the curing temperature and speed can be adjusted by changing the type and amount of the metal ion.

[0016]

Next, the present invention will be described in detail with reference to examples. The contents of the components used below are
It is as follows. Epoxy resin a: Epicoat 191 (manufactured by Shell Chemical Co., Ltd.
Bisphenol A type epoxy resin having an epoxy equivalent of 162) Epoxy resin b: Epomic R-139 (manufactured by Mitsui Petrochemical Industries, Ltd., bisphenol A type epoxy resin having an epoxy equivalent of 183) Metal salt a: Magnesium salt of p-aminobenzoic acid Metal salt b: Calcium salt of p-aminobenzoic acid Metal salt c: Magnesium salt of m-aminobenzoic acid Metal salt d: Lithium salt of p-aminobenzoic acid Metal salt e: Potassium salt of p-aminobenzoic acid Solvent a: N , N-dimethylformamide Solvent b: ethanol Solvent c: N, N-dimethylformamide and water = 10: 1
(Weight ratio) mixed solvent

The gelation time was as follows. After putting 10 g of a sample into a test tube having an inner diameter of 18 mm, inserting a rotor having an outer diameter of 10 mm, measuring the change in torque at 150 ° C., and measuring the change in torque until the torque became 3 g · cm. Time. The adhesive strength to the copper plate was evaluated by applying the epoxy resin composition to a copper plate having a thickness of 1.5 mm, after-curing at 130 ° C. overnight and further at 18 ° C. for 4 hours, and measuring the tensile shear strength at 23 ° C. did. The glass transition temperature was measured at a frequency of 0.
It was determined based on the results measured at 1 to 3.0 Hz and at a heating rate of 2 ° C./min.

Example 1 4.6 g (15.5 mmol) of a metal salt a was dissolved in a solvent a46.
g, and then melt the epoxy resin a 100 g (309 mmo).
l) was added and the mixture was heated at 80 ° C for 2 hours. Thereafter, the solvent was distilled off under reduced pressure to obtain a metal-containing epoxy resin composition of the present invention. The tensile shear strength when a copper plate was bonded with this composition was 158 kg / cm ² . The reaction rate of the epoxy group in this cured product was 95%.

Examples 2 to 5 After dissolving a metal salt of aminobenzoic acid in a solvent, an epoxy resin b was added and the mixture was heated at 80 ° C. for 2 hours. Thereafter, the solvent was distilled off under reduced pressure to obtain a metal-containing epoxy resin composition of the present invention. Table 1 shows the charged amounts of these compositions, the gel time at 150 ° C., the adhesive strength to a copper plate, and the glass transition temperature.
Shown in

Comparative Example 1 To 100 g (273 mmol) of epoxy resin b, 0.5 g of 2-ethylimidazole was added to obtain a uniform epoxy resin composition. The amount of the composition, the adhesive strength to a copper plate, the gel time at 150 ° C., and the glass transition temperature are also shown in Table 1.

[0021]

[Table 1]

Examples 6 and 7 After dissolving a metal salt of aminobenzoic acid in a solvent, an epoxy resin a was added and the mixture was heated at 100 ° C. for 1 hour. Thereafter, the solvent was distilled off under reduced pressure to obtain a metal-containing epoxy resin composition of the present invention. Table 2 shows the charged amounts of these compositions, the gel time at 150 ° C., the adhesive strength to a copper plate, and the glass transition temperature.
Shown in

Comparative Example 2 N, N was added to 100 g (309 mmol) of epoxy resin a.
-1.5 g of dimethylbenzylamine was added to make the mixture uniform to obtain an epoxy resin composition. Table 2 shows the preparation amounts of these compositions, the adhesive strength to a copper plate, the gel time at 150 ° C., and the glass transition temperature.

[0024]

[Table 2]

Example 8 0.8 g (5.6 mmol) of metal salt d was added to 62 g of solvent a.
And dissolved in 100 g of epoxy resin a (309 mmo).
l) was added and the mixture was heated at 100 ° C. for 1.5 hours. Thereafter, the solvent was distilled off under reduced pressure to obtain a metal-containing epoxy resin composition. The tensile shear strength when a copper plate was bonded with this composition was 142 kg / cm ² . The reaction rate of the epoxy group in this cured product was 94%.

Example 9 After dissolving 1.1 g (6.3 mmol) of metal salt e in 68 parts of solvent c, 100 g of epoxy resin a (309 mmol) was used.
l) was added and the mixture was heated at 80 ° C for 2 hours. Thereafter, the solvent was distilled off under reduced pressure to obtain a metal-containing epoxy resin composition. Tensile shear strength when a copper plate was bonded with this composition was 13
It was 7 kg / cm ² . The reaction rate of the epoxy group in this cured product was 98%.

[0027]

As described above, the metal-containing epoxy resin composition of the present invention remarkably promotes the ether reaction of the epoxy group by the ionic bond contained in the composition.
Even if a curing agent, a curing accelerator, a polymerization catalyst, etc. are not used again, the composition is quickly cured by heating and exhibits excellent adhesion to metals and the like. Further, the ionic bond showing the catalytic action is firmly bonded to the cured product via a chemical bond, and there is no danger of bleeding. In addition, this cured product has a high glass transition temperature due to ionic bonding, and therefore has improved heat resistance, and can be expected to be applied to a wide range of fields such as paints, adhesives, and sealing materials. Is high.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-49-105900 (JP, A) JP-A-49-76995 (JP, A) JP-A-57-2377 (JP, A) 120798 (JP, A) JP-A-50-68981 (JP, A) JP-A-5-70564 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59 / 50-59 / 52 C08G 59/14 C08G 59/40

Claims (2)

(57) [Claims] 1. A epoxy resin with a metal salt of an amino acid (B) and a curing agent adducts of the epoxy resin (A)
Metal-containing epoxy resin composition characterized Rukoto such blended in. 2. The epoxy resin (A) and the metal salt of aminobenzoic acid (B) are combined with the epoxy resin in the epoxy resin (A).
In the metal salt (B) of the aminobenzoic acid per 1 equivalent of the silane group
In such a manner that the amino group of
In combination, the epoxy resin (A) and the amino
A method for producing a metal-containing epoxy resin composition, which comprises subjecting an addition reaction with a metal salt (B) of benzoic acid, followed by distilling off the solvent.