JPS5818929B2 - epoxy resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an epoxy resin composition that has excellent curing properties and pot life, low viscosity, and good heat resistance of the cured product.

Conventionally, aromatic amines are well known as curing agents for epoxy resins, but when this type of compound is used as a curing agent, the cured product has excellent heat resistance and chemical resistance, but Curing time is generally long due to the presence of dust, steric hindrance of aromatic rings, etc., and it is necessary to improve the curing characteristics by adding a curing accelerator.

However, addition of a large amount of accelerator is not preferable because it has a negative effect on the heat resistance of the cured product, particularly on the thermal decomposition properties.

The present invention improves these drawbacks by using an epoxy resin as a curing agent together with poly-P-vinylphenol and aromatic amines selected from dihalogenated diaminodiphenylmethane and diaminodiphenylsulfone, and poly-IJ p-vinylphenol and poly-IJ p-vinylphenol. It is characterized by having an aromatic amine equivalent ratio of 2:8 to 5:5, and is used as a heat-resistant adhesive with excellent curing properties and pot life, as well as low viscosity and excellent heat resistance of the cured product. The present invention provides an epoxy resin composition used for.

Examples of the epoxy resin used in the present invention include bisphenol A diglycidyl ether type epoxy resin,
Butadiene diepoxide, 4,4'-cy(1,2-epoxyethyl)diphenyl ether, 4,4'-cy(epoxyethyl)biphenyl, diglycidyl ether of resorcin, diglycidyl ether of phloroglucin, P
- Triglycidyl ether of amine phenol, ■・3
・5-) IJ (1,2-epoxyethyl)benzene, 2,2',4,4'-tetraglycidoxybenzophenone, tetraglycidoxytetraphenylethane, polyglycidyl ether of phenol formaldehyde novolac, trimethylolpropane Triglycidyl ether of cresol formaldehyde novolak, triglycidyl ether of glycerin, diglycidyl ether type epoxy resin of halogenated bisphenol A, polyglycidyl ether of halogenated phenol formaldehyde sovolak, triglycidyl isocyanurate, hydantoin epoxy resin (Ciba Geigy product name XB-2793, XB-2818
)and so on.

When dihalogenated diphenylmethane or diaminodiphenylsulfone is used as a curing agent in a system that does not use a curing accelerator, the pot life is excellent, but when used alone, the curing properties are poor and it cannot be used practically.

In the present invention, an epoxy resin composition with excellent curing properties was obtained by using po'J-P-vinylphenol in a specific ratio in combination with the aromatic amine.

PolyP, a curing agent used in combination with these aromatic amines
-Vinylphenol has an average molecular weight of 3000 to 1ooo
A polymer compound of o having a hydroxyl equivalent of around 120 is preferable.

Furthermore, halogens such as bromine and chlorine or other substituents may be introduced onto the phenol nucleus.

These poly-IJ-P-vinylphenols are commercially available from Maruzen Sekiyu Co., Ltd. under the trade name Resin M Luzin MB (brominated poly-P,-vinylphenol).

The amounts of this type of curing agent, the aromatic amine and poly-P-vinylphenol used in the present invention range from 0.7 to 1.5 equivalents in total per equivalent of the epoxy resin.

Outside this range, the properties of the cured product will be poor.

Further, the equivalent ratio of these poly-P-vinylphenols and aromatic amines is 2:8 to 5:5.

If the ratio is less than this (2:8 to o:io), the curing properties and heat resistance will deteriorate.

If the ratio exceeds this ratio (5:5 to 10:0), the viscosity becomes too high and the adhesive strength decreases.

Furthermore, in the present invention, it is possible to use a solvent and a curing accelerator.

Solvents include acetone, methyl ethyl ketone, methyl selon, methyl imbutyl ketone, dimethyl formamide, etc., and curing accelerators include tertiary amines, imidazoles, aminotriazoles, boron trifluoride complex salts, and pyrazole. These include aminopyridines, aminoquinaldines, aminoquinolines, and aminopyrimidines.

The present invention will be explained in detail below with reference to examples.

However, the present invention is not limited to the following examples.

Example 1 Ciba Geigy brominated epoxy resin Araldai) 8
011 (Br content 21%, epoxy equivalent 490 g/eq
, 80% methyl ethyl ketone solution (melting point 71°C) 125
y, 20.4P of 33% methyl ethyl ketone solution of 3,3'-dichloro-4,4'-diaminodiphenylmethane
and Po'J-P-vinylphenol "Resin M" manufactured by Maruzen Sekiyu Co., Ltd. (average molecular weight approximately 5000, hydroxyl equivalent approximately 120 f
I/eq) 33% methyl ethyl ketone solution 36.6?
and stirred at room temperature.

(Solution A) In the above formulation, the equivalent ratio of these two types of curing agents is 1:1.

To this solution A, 1.0% of a 1% solution of 2-methylimidazole in methyl ethyl ketone was added as a curing accelerator, and the mixture was thoroughly stirred at room temperature until it became uniform.

The gelation time of this solution at 160°C was 290 seconds.

However, the gelation time was measured in accordance with JIS-C-2104.

Also, as a curing accelerator in solution A, 1.0 f? of a 10% methylceronlube solution of 3-amino-1-H-1.2.4-triazole was added instead of 2-methyl-imidazole. The gelation time of this solution was 210 seconds at 160°C.

Example 2 Araldai) 8011080% methyl ethyl ketone solution 125? 33% methyl ethyl ketone solution of 3,3'-dichloro-4,4'-diaminodiphenylmethane 28
．． 33% methyl ethyl solution of 5f and resin M 21.9S
' and stirred at room temperature.

(Solution B) In the above formulation, the equivalent ratio of these two types of curing agents is 3.3'
-Dichloro-4-4'-diaminodiphenylmethane:Resin M=7:3.

To this solution B, 1.0 l of a 1% solution of 2-methyl-imidazole in methyl ethyl ketone was added, and the mixture was sufficiently stirred at room temperature until it became homogeneous.

The gelation time of this solution at 160°C was 310 seconds.

Further, when a 10% methylceronlube solution i,off of 3-amino-1-H-1,2,4-triazole was added to solution B, the gelation time of this solution was 300 seconds.

Example 3 To 125 g of an 80% methyl ethyl ketone solution of Araldite 8011, 32 g of a 33% methyl ethyl ketone solution of 3,3'-dichloro-4,4'-diaminodiphenylmethane was added.
．． 7f and Resin M in 33% methyl ethyl ketone solution 14
．． 7fl was added and stirred at room temperature.

(Solution C) In the above formulation, the equivalent ratio of these two types of curing agents is 3,3'-dichloro-4,4'-diaminodiphenylmethane:Resin M=8:2.

To this solution C, add 1% solution of 2-methyl-imidazole in methyl ethyl ketone. Ov was added, and the mixture was sufficiently stirred at room temperature until the mixture became homogeneous.

The gelation time of this solution at 160°C was 420 seconds.

Furthermore, when 1.01 ml of a 10% methylseronolp solution of 3-amino-1-f(-1,2,4-triazole) was added to solution C, the gelation time of this solution at 160°C was 420 seconds. Ta.

Comparative Example 1 40.8 P of a 33% methyl ethyl ketone solution of 3,3'-dichloro-4,4/-diaminodiphenylmethane was added to 125 g of an 80% methyl ethyl ketone solution (Araldai) 80110, and the mixture was stirred at room temperature.

(Solution E) The gelation time of solution E at 160°C was 3600 seconds.

10% of 2-ethyl-4-methylimidazole in solution E
When 2.01 ml of methyl ethyl ketone solution was added, the gelation time of this solution at 160°C was 2050 seconds.

Further, when 15 g of a 10% methylceronlube solution of 3-amino-1-H-1,2,4-triazole was added to solution E, the gelation time of this solution at 160°C was 1200 seconds.

Examples 4-1 to 4-3 4-1 The gelation time of solution A at 160°C in Example 1 was 540 seconds.

Further, the viscosity of Solution A remained unchanged even after being left at room temperature for one week, and the pot life was excellent.

4-2 The gelation time of solution B in Example 2 at 160°C was 670 seconds.

4-3 The gelation time of solution C in Example 3 at 160°C was 940 seconds.

Example 5 The resin compounded in Example 1 using 2-methyl-imidazole as a curing accelerator was cured at 170°C for 2 hours,
The thermal decomposition temperature of this cured product was measured using a thermomechanical testing machine manufactured by Shinku Riko Co., Ltd., and was found to be 342°C.

Comparative Example 2 The resin composition of Comparative Example 1 using 2-ethyl-4-methylimidazole as a curing accelerator was cured at 170°C for 2 hours.

The thermal decomposition temperature of this cured product was 300°C.

Example 6 Epicor) 1001080% methyl ethyl ketone solution 1
3 of 3,3'-diaminodiphenylsulfone to 25P
3% methyl ethyl ketone solution 18.61 and resin M 3
36 g of 3% methyl ethyl ketone solution was added and stirred at room temperature.

(Solution G) In the above formulation, the equivalence of these two types of curing agents is 1:1.

Add 2.0% of a 1% methyl ethyl ketone solution of 2-ethyl-4-methyl-imidazole to this solution G as a curing accelerator.
1 and stirred thoroughly at room temperature until homogeneous.

The gelation time of this solution at 160°C was 337 seconds.

For comparison, only 37.2f of a 33% methyl ethyl ketone solution of 3,3'-diaminodiphenylsulfone was used as a curing agent instead of the above two combination curing agents, and 160
The gelation time at °C was measured to be 2100 seconds.

Example 7 Epicote 10010 80% methyl ethyl ketone solution 1
251, a 33% solution of 3,3'-dichloro-4,4'-diaminodiphenylmethane in methyl ethyl ketone 20
．． 15' and Resin M in 33% methyl ethyl ketone solution 3
6? and stirred at room temperature.

(Solution H) In the above formulation, the equivalent ratio of these two types of curing agents is 1:1.

Add 2.02% of a 1% solution of 2-ethyl-4-methylimidazole in methyl ethyl ketone to this solution H as a curing accelerator.
and stirred thoroughly at room temperature until homogeneous.

The gelation time of this solution at 160°C was 328 seconds.

For comparison, only 402 g of a 33% methyl ethyl ketone solution of 3,3'-dichloro-4,4'-diaminodiphenylmethane as a curing agent was used instead of the above two combination curing agents, and the gelation time at 160°C was 300 when measured
It was 0 seconds.

Example 8 Epicote 10010 80% methyl ethyl ketone solution 1
25 grams of 33% methyl-ethyl ketone solution of 3,37-dichloro-4,4'-diaminodiphenylmethane 20.
IP and resin MB (brominated poly-p-vinylphenol, average molecular weight about 8000, hydroxyl equivalent weight about 235
′? 70.5 f of a 33% methyl ethyl ketone solution of /eq, Br content 50%) was added, and the mixture was stirred at room temperature.

(Solution ■) In the above formulation, the equivalent ratio of these two types of curing agents is 1:1.

To this solution (1) was added 1.0 g of a 1% solution of 2-methyl-imidazole in methyl ethyl ketone as a curing accelerator, and the mixture was thoroughly stirred at room temperature until uniform.

The gelation time of this solution at 160°C was 614 seconds.

Comparative Example 3 In Example 5, instead of Resin M, novolak type phenol formaldehyde resin manufactured by Hitachi Chemical, trade name HP-60 was used.
7N (softening point: 85°C, hydroxyl equivalent: 106 g/eq) and 3,3'-dichloro-4,4'-diaminodiphenylmethane in an equivalent ratio of 1:1 at 170°C. It was allowed to cure for 2 hours.

The thermal decomposition temperature of this cured product was 320°C.

When compared with Example 5, resins M and 3.3' according to the invention
-Dichloro-4,4'-diaminodiphenylmethane was found to have a higher thermal decomposition temperature.

Comparative Example 4 73.2 g of a 33% methyl ethyl ketone solution of Resin M was added to 125 g of an 80% methyl ethyl ketone solution of Araldite 8011, and the mixture was stirred at room temperature.

(Solution J) The gelation time of Solution J at 160°C was 1440 seconds.

It was found that the curing properties of Resin M alone were poor.

Comparative Example 5 To the solution J of Comparative Example 4, 0.67 f of a 33% methyl ethyl ketone solution of 3,3'-dichloro-4,4'-diaminodiphenylmethane was added (0.22% based on the epoxy resin).
) Stirred at room temperature.

(Solution K) The gelation time of the solution at 160° C. was 1320 seconds.

Even when a small amount of 3,3'-dichloro-4,4'-diaminodiphenylmethane was added to Resin M, the curing properties were poor.

After evaporating the solvent with this resin formulation, it was cured at 170°C for 2 hours, and the thermal decomposition temperature of this cured product was measured to be 340°C.
It was ℃.

Comparative Example 6 33 of 4,4'-diaminodiphenylmethane in 8011080% methyl ethyl ketone solution 125P
% methyl ethyl ketone solution 15.3S' and 3 of Resin M
36.61 g of a 3% methyl ethyl ketone solution was added, and the mixture was stirred at room temperature.

In the above formulation, the equivalent ratio of these two types of curing agents is 1:1.

The gelation time of this solution at 160°C was 420 seconds, but when left at room temperature, it gelled after 3 days, indicating that the pot life was poor.

As explained above in the examples, it was found that the epoxy resin composition according to the present invention has excellent curing characteristics and pot life, and also has excellent heat resistance of the cured product.

Claims (1)

[Claims] 1 0.7 to 1 equivalent of epoxy resin to epoxy resin
In an epoxy resin composition containing 1.5 equivalents of a curing agent, poly-IJ-P-vinylphenol and an aromatic amine selected from dihalogenated diaminodiphenylmethane and diaminodiphenylsulfone are used together as a curing agent, and poly-P-vinyl An epoxy resin composition characterized in that the equivalent ratio of phenol to aromatic amine is 2:8 to 5:5.