JP3205914B2 - Epoxy resin composition - 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 ethoxy resin composition, and more particularly to an epoxy resin composition having excellent mechanical strength and adhesion to metal.

[0002]

2. Description of the Related Art Conventionally, epoxy resin cured products have been widely used for paints, civil engineering, adhesives, electric / electronic materials, composite materials, etc. due to their excellent mechanical properties, electrical properties, chemical properties, and thermal properties. It is used in many fields. At present, epoxy resin curing agents generally used include aminos,
It is roughly divided into polyaminoamide compounds and acid anhydrides.

[0003] Among those using amines as a curing agent, epoxy resin compositions using an aliphatic amine as a curing agent cure quickly at a low temperature, but have a short pot life, have an unpleasant odor, and have an unpleasant odor in the air. It has a disadvantage that it is easily affected by carbon dioxide gas. On the other hand, an epoxy resin curing agent using an aromatic amine as a curing agent exhibits relatively well-balanced properties such as heat resistance, mechanical properties, and chemical resistance. However, this epoxy resin composition cures slowly and has a mechanical strength of, for example, 1000 to 1300 kg / c in bending strength.
m ² , and further improvement in physical strength is desired to further expand the application.

A cured product obtained from an epoxy resin composition using a polyaminoamide compound as a curing agent differs in the type of the polyaminoamide compound used, but has excellent electrical properties and adhesiveness, but has a bending strength of 1000 kg.
/ Cm ² or less, tensile strength of 200 to 700 kg / cm ²
And the mechanical strength is insufficient.

[0005] Epoxy resin cured products using an acid anhydride as a curing agent are said to have excellent electrical and mechanical properties among epoxy resins, and are used in large quantities mainly in electric insulating materials. ing. However, its mechanical strength
For example, its bending strength is 600 to 1400 kg / c.
m ² , and the tensile strength was 400 to 800 kg / cm ² , which was not sufficient for use as a structural member or the like.

[0006] Therefore, none of the conventional curing agents have sufficient mechanical strength and can further expand the use as a structural member.

[0007]

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 having excellent mechanical strength of a cured epoxy resin and good adhesion to metal. It is intended to provide a composition.

[0008]

According to the present invention, a primary grade of 0.2 to 20 parts by weight per 100 parts by weight of epoxy resin (A), polybasic acid anhydride (B) and epoxy resin (A). and / or from aminocarboxylic having a secondary amino group
An epoxy resin composition comprising a metal salt of an acid (C) is provided .

That is, the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that an epoxy resin comprising an epoxy resin, a polybasic acid anhydride and an amino compound having a primary and / or secondary amino group. The composition was found to have extremely high mechanical strength when cured, as compared with conventional epoxy resin cured products, and the present invention has been achieved.

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. Used epoxy resin is used.

Examples of the polybasic anhydride (B) include dodecenyl succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride,
Examples include methylhexahydrophthalic anhydride, methylhymic anhydride, head acid anhydride, tetrabromophthalic anhydride, maleic anhydride, and phthalic anhydride. The molar ratio of the epoxy group of the epoxy resin (A) to the anhydride group of the polybasic acid anhydride (B) is 1.0: 0.7 to 1.4. Is preferably within the range. If the mixing ratio of the polybasic acid anhydride (B) is lower than this or if it is higher than this, curing is poor, and the mechanical strength and electrical properties of the obtained cured product are undesirably reduced.

The metal salt of an aminocarboxylic acid (C) includes one or more metal salt portions of a carboxylic acid (a) in one molecule.
On-bond) and a compound having a primary and / or secondary amino group, for example, aminobenzoic acid, aminochlorobenzoic acid, aminomethylbenzoic acid, glycine,
Metal salts such as aminocaproic acid, aminocabrylic acid, aminoundecanoic acid and aminovaleric acid are used. As 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.

Epoxy resin (A), polybasic acid anhydride
(B) and 100 parts by weight of the epoxy resin (A)
0.2 to 20 parts by weight of aminoMetal salts of carboxylic acids
(C) obtained from the epoxy resin composition of the present invention.
Cured products have high mechanical strength, especially bending strength and tensile strength.
This has the effect of significantly increasing the degree. This is d
Epoxy resin consisting of oxy resin and polybasic acid anhydride
Amino in the compositionMetal salts of carboxylic acidsBy blending
An amide bond is formed, and the amide bond is formed in the cured product.
Hydrogen bond between amide bond and ester bond
It is considered that the internal cohesion due to the combination increases.

The compounding ratio of the metal salt of aminocarboxylic acid (C) having a primary and / or secondary amino group is as follows:
The amount is 0.2 to 20 parts by weight based on 100 parts by weight of the epoxy resin, but when the compounding ratio of the metal salt of aminocarboxylic acid (C) is less than this , the metal of aminocarboxylic acid
There is almost no effect of adding the salt, and if the amount is more than this, the heat resistance and workability of the obtained cured product are undesirably reduced.

Further, aminoMetal salt of carboxylic acid (C)
Was compoundedEpoxy resin composition has good adhesion to metal
Not only is it favorable, but the ionic bond
It significantly accelerates the curing of the epoxy resin, and the cured product
Improves thermal properties.Metal salts of aminocarboxylic acids(C)
If the proportion of is less than this,TheAdd the compound
Has little effectMetal salts of aminocarboxylic acids
If the compounding ratio of (C) is higher than this,As mentioned above
ToDue to the high viscosity of the obtained epoxy resin composition,
The workability decreases, and the heat resistance of the obtained cured product also decreases.
Not preferred.

As the curing accelerator, tertiary amines, i.
Epoxy such as midazoles, dicyandiamide, Lewis acids, etc.
Using a material that is usually used as a curing accelerator for silicone resin
Can be These accelerators can be used as needed.
The amount of addition may be epoxy resin (A),
Basic acid anhydride (B) and aminoMetal salts of carboxylic acids
0.01 to 3.0% by weight based on the total amount of (C) is preferred.
No.

Further, the epoxy resin composition of the present invention may contain additives, such as a plasticizer, a filler, a colorant, a reinforcing agent, and other modifiers having various purposes, which are used in ordinary epoxy resin compositions. May be blended.

As a general method for preparing the epoxy resin composition of the present invention, a polybasic acid anhydride (B) and a metal salt of an aminocarboxylic acid (C) are mixed and mixed at room temperature or under heating. It can be obtained by mixing and making uniform, then adding and mixing the epoxy resin (A) and, if necessary, a curing accelerator.

[0019]

Next, the present invention will be specifically described by way of examples. Parts in Examples are parts by weight. The contents of the components used below are as follows. Epoxy resin a: Epomic R-139 (manufactured by Mitsui Petrochemical Industries, Inc., bisphenol-type epoxy resin having an epoxy equivalent of 183) Epoxy resin b: Epicoat 191 (manufactured by Shell Chemical Co., Ltd.)
Bisphenol-type epoxy resin having an epoxy equivalent of 162) polybasic anhydride a: hexahydrophthalic anhydride polybasic anhydride b: methylhymic anhydride amino compound a: aniline amino compound b: 4,4′-diaminodiphenylmethane amino compound c: 3,3′-diaminodiphenyl sulfone amino compound d: 4,4′-diaminodiphenyl ether amino compound e: hexamethylenediamine amino compound f: magnesium salt of p-aminobenzoic acid amino compound g: m-aminobenzoic acid Potassium salt Amino compound h: Calcium salt of ε-aminocaproic acid Curing accelerator a: N, N-dimethylbenzylamine Curing accelerator b: 2-ethylimidazole

The flexural strength and tensile strength were measured according to ASTM D790-81 and ASTM D638, respectively.
Measured according to -82. The adhesive force to the copper plate was determined by applying the epoxy resin composition to a copper plate having a thickness of 1.5,
For 3 hours and further at 180 ° C. for 4 hours.
It was evaluated by measuring the tensile shear strength at ° C. The glass transition temperature was measured using a torsional free damping type viscoelasticity measuring device (manufactured by Resca) at a frequency of 0.1 to 3.0 Hz.
It was determined based on the result measured at a temperature rising rate of 2 ° C./min.

Embodiment 1(Reference example)  82 parts of polybasic acid anhydride a and 2.5 parts of amino compound a
Was mixed at 120 ° C to make it uniform, and then cooled to 80 ° C.
100 parts of epoxy resin a and 0.09 parts of curing accelerator a
The mixture was added and mixed to obtain an epoxy resin composition of the present invention. This
Pour the epoxy resin composition of
In the evening, further post-cured at 180 ° C for 4 hours.
A fat cured product was obtained. Flexural strength of this cured product is 1640kg
/ Cm^Two, Tensile strength is 790kg / cm^TwoAnd extremely good
Exhibited mechanical properties.

Examples 2 to 4(Reference example)  Mix polybasic acid anhydride a and amino compound at 120 ° C
After cooling to 80 ° C, the epoxy resin a and
And a curing accelerator a, and mix the epoxy resin of the present invention.
A composition was obtained. Pour this epoxy resin composition into a mold
After curing at 130 ° C overnight and then at 180 ° C for 4 hours
Then, an epoxy resin cured product was obtained. Song of the obtained cured product
Table 1 shows the breaking strength and the tensile strength.

Comparative Example 1 Polybasic acid anhydride a was melted at 80 ° C., and 100 parts of epoxy resin a and 0.1 part of curing accelerator a were added and mixed.
An epoxy resin composition was obtained. The epoxy resin composition was poured into a mold and post-cured at 130 ° C. overnight and further at 180 ° C. for 4 hours to obtain a cured epoxy resin. The bending strength and tensile strength of the obtained cured product are shown in Table 1 together.

[0024]

[Table 1]

Comparative Example 2 An epoxy resin composition was obtained by adding 27 parts of the amino compound b to 100 parts of the epoxy resin a and uniformly dissolving it at 70 ° C. The epoxy resin composition was poured into a mold and post-cured at 80 ° C. overnight and further at 140 ° C. for 5 hours to obtain a cured epoxy resin. The cured product has a bending strength of 1300 kg / cm ² and a tensile strength of 640 kg / cm ² .
cm ² .

Examples 5 to 6(Reference example)  Polybasic anhydride b and amino compound are mixed at 120 ° C.
After homogenizing, the mixture was cooled to 80 ° C., and epoxy resin b and
The curing accelerator a is added and mixed, and the epoxy resin set of the present invention is mixed.
A product was obtained. Pour this epoxy resin composition into a mold
After curing at 130 ° C overnight and then at 180 ° C for 4 hours
Then, an epoxy resin cured product was obtained. Song of the obtained cured product
Table 2 shows the breaking strength and the tensile strength.

Comparative Example 3 110 parts of polybasic acid anhydride b, 100 parts of epoxy resin b and 0.1 part of curing accelerator a were added and mixed at 80 ° C. to obtain an epoxy resin composition. The epoxy resin composition was poured into a mold and allowed to stand at 130 ° C. overnight and at 180 ° C. for 4 hours.
After curing for an hour, an epoxy resin cured product was obtained. The bending strength and tensile strength of the obtained cured product are also shown in Table 2.

[0028]

[Table 2]

Examples 7-9 Metal salts of polybasic acid anhydrides and aminocarboxylic acids were
After mixing at 0 ° C. to make uniform, the mixture was cooled to 80 ° C., and then an epoxy resin was added and mixed to obtain an epoxy resin composition of the present invention. The epoxy resin composition was post-cured at 130 ° C. overnight and further at 180 ° C. for 4 hours to obtain a cured epoxy resin. Table 3 shows the glass transition temperature of the obtained cured product. Further, Table 3 shows the tensile shear strength of the epoxy resin composition with respect to the copper plate.

Comparative Example 4 After melting 82 parts of polybasic acid anhydride a at 80 ° C., 100 parts of epoxy resin a and 1.4 parts of curing accelerator b were added.
By mixing, an epoxy resin composition was obtained. The epoxy resin composition was post-cured at 130 ° C. overnight and further at 180 ° C. for 4 hours to obtain a cured epoxy resin. Table 3 shows the glass transition temperature of the obtained cured product. Further, Table 3 also shows the tensile shear strength of the epoxy resin composition with respect to the copper plate.

Comparative Example 5 After heating 110 parts of polybasic acid anhydride b to 80 ° C., 100 parts of epoxy resin a and 0.1 part of curing accelerator b were added and mixed to obtain an epoxy resin composition. The epoxy resin composition was post-cured at 130 ° C. overnight and further at 180 ° C. for 4 hours to obtain a cured epoxy resin. Table 3 shows the glass transition temperature of the obtained cured product. Further, the tensile shear strength for the copper plate is also shown in Table 3.

[0032]

[Table 3]

[0033]

As described above, the cured product obtained from the epoxy resin composition of the present invention has significantly higher mechanical properties, particularly bending strength and tensile strength, than conventional epoxy resin cured products. The use of the epoxy resin as a structural member is expected to be further expanded by using the epoxy resin composition of the present invention. In addition,
The epoxy resin composition of the present invention obtained by using a metal salt of a minocarboxylic acid has a metal salt portion of a carboxylic acid (ionic bond).
) Has the effect of accelerating the curing of the epoxy resin,
It does not necessarily require a general accelerator and has excellent adhesion to metals. Therefore, the epoxy resin composition of the present invention is practically extremely useful.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 59/58 C08G 59/52

Claims (1)

(57) [Claims] An amino having a primary and / or secondary amino group of 0.2 to 20 parts by weight per 100 parts by weight of an epoxy resin (A), a polybasic acid anhydride (B), and an epoxy resin (A). An epoxy resin composition comprising a metal salt of a carboxylic acid (C).