Epoxy resin composition containing perfluoroalkyl epoxide

An epoxy resin composition which comprises: PA1 (1) a monoepoxide having at least one perfluoroalkyl group in one molecule; and PA1 (2) an epoxy resin having two or more epoxy groups in one molecule, the weight ratio of (1):(2) being 0.05:99.95 to 50:50. The composition can be cured with a curing agent to give a cured product having improved water-proof, oil-resistance and anti-contamination properties.

The present invention relates to an epoxy resin composition, and more 
particularly, to an epoxy resin composition which can be cured to give a 
cured product. 
An epoxy resin is one kind of pre-polymer and a curable composition thereof 
with a curing agent has excellent adherent properties to various 
materials. Therefore, such a curable composition can be used as a paint or 
an adhesion. Further, cured products thereof are used as materials for 
laminated structures, materials for civil engineering and construction, 
materials for electric goods and the like. 
However, since the cured product, which is the final product from the 
curable composition, contains a functional group such as amino, hydroxy 
and the like, the water-proof properties, oil-resistance properties and/or 
anti-contamination properties thereof are generally inferior. 
The main object of the present invention is to provide an epoxy resin 
composition which can be cured with a curing agent to give a cured product 
having improved water-proof properties, oil-resistance properties and 
anti-contamination properties. This object as well as other objects and 
advantages of the present invention will become apparent to those skilled 
in the art from the following description. 
According to the present invention, these objects can be generally 
accomplished by providing an epoxy resin composition, which comprises: 
(1) a monoepoxide having at least one perfluoroalkyl group in one molecule; 
and 
(2) an epoxy resin having two or more epoxy groups in one molecule, the 
weight ratio of (1):(2) being 0.05:99.95 to 50:50. 
Upon curing with a curing agent, the composition of the present invention 
forms a hardened coating film or a hardened molded product, the surface of 
which has excellent water- and oil-repellancy. 
It is necessary that the monoepoxide (1) used in the present invention 
should have at least one perfluoroalkyl group, in the molecule thereof. 
When the monoepoxide contains no perfluoroalkyl groups, it is difficult to 
obtain a cured product having water- and oil-repellancy. 
As a monoepoxide (1), a compound of the formula: 
##STR1## 
wherein R.sub.f is a perfluoroalkyl group having 1 to 18 carbon atoms; m 
is 0 or an integer from 1 to 3; and n is 0 or 1, or a mixture thereof may 
be employed. Preferred examples of the above compounds are those of the 
formula: 
##STR2## 
The above monoepoxide can be prepared by a known method. For example, the 
monoepoxide can be prepared according to the following reaction: 
##STR3## 
The epoxy resin (2) used in the present invention has two or more epoxy 
groups, particularly, two to four epoxy groups, in the molecule thereof. 
It is difficult to obtain a rigid cured product by curing an epoxy resin 
composition mixed with a curing agent unless the epoxy resin to be used 
has two or more epoxy groups. 
As an epoxy resin (2), a compound of the formula: 
##STR4## 
wherein j is 0 or an integer from 1 to 15, preferably 0, 1 or 2; and R is 
C.sub.k H.sub.2k (wherein k is an integer from 2 to 8), (CH2).sub.y 
(CF.sub.2).sub.p (CH.sub.2).sub.y (wherein y is 1 or 2 and p is an integer 
from 2 to 10) or a group of the formula: 
##STR5## 
(wherein R.sub.f ' is a perfluoroalkyl group having 3 to 10 carbon atoms), 
or a mixture thereof may be employed. Preferred examples of the above 
compounds are those of the formula: 
##STR6## 
wherein p' is an integer from 4 to 10, or 
##STR7## 
wherein p" is an integer from 3 to 10. The above epoxy resin can be 
prepared by a known method. 
The epoxy resin composition of the present invention contains 0.05 to 50% 
by weight, preferably, 1 to 30% by weight of the monoepoxide (1) and 99.95 
to 50% by weight, preferably, 99 to 70% by weight of the epoxy resin (2) 
based on the total weight of the composition. That is, in the epoxy resin 
composition of the present invention, the weight ratio of the monoepoxide 
(1) to the epoxy resin (2) is 0.05:99.95 to 50:50, preferably, 1:99 to 
30:70. When the amount of the monoepoxide (1) is less than 0.05% by 
weight, the desired results can hardly be obtained. On the other hand, 
when the amount thereof is more than 50% by weight, a remarkable 
improvement in the quality of the cured product can hardly be expected and 
the mechanical properties thereof become inferior. 
The epoxy resin composition of the present invention can be prepared by 
mixing the above monoepoxide (1) and the above epoxy resin (2) according 
to a conventional technique. 
The epoxy resin composition of the present invention can be cured according 
to a known method for curing a conventional epoxy resin. For example, the 
epoxy resin composition can be cured by adding a curing agent such as an 
alkylene diamine having 1 to 12 carbon atoms in the alkylene moiety (e.g. 
ethylene diamine, propylene diamine etc.), a polyethylene polyamine (e.g. 
diethylene triamine, triethylene tetramine, tetraethylene pentamine etc.), 
diphenyldiaminomethane, a tertiary alkylamine having 1 to 6 carbon atoms 
in the alkyl moiety (e.g. trimethylamine, triethylamine, tripropylamine 
etc.), an acid anhydride (e.g. phthalic anhydride, hexahydrophthalic 
anhydride, dodecenyl succinic anhydride etc.) or a boron trifluoride-amine 
complex 
##STR8## 
and reacting at room temperature or with heating to about 200.degree. C. 
The amount of curing agent to be added to the epoxy resin composition is 
not critical, but when the boron trifluoride-amide complex or tertiary 
alkylamine is used, it is usually used in an amount of 0.5 to 5% by weight 
based on the weight of the epoxy resin composition, and when the alkylene 
diamine, polyethylene polyamine, diphenyldiaminomethane or acid anhydride 
is used, it is usually used in an amount of 0.8 to 1.2 equivalent per 1 
equivalent of epoxy group of the epoxy resin. A curable composition 
prepared by mixing the above epoxy resin composition with a curing agent 
is also included in the scope of the present invention. Optionally, the 
curable composition may contain other additives such as alumina, silica, 
titanium dioxide, glass fiber, and the like.

The following examples further illustrate the present invention in detail 
but are not to be construed to limit the scope thereof. In the examples, 
all "parts" are by weight unless otherwise stated. 
EXAMPLE 1 
To 100 parts of the compound of the formula: 
##STR9## 
there was added the compound of the formula: 
##STR10## 
wherein n is 0 or 1, in the amounts shown in Table 1 and also 3 parts of 
the curing agent, BF.sub.3 C.sub.2 H.sub.5 NH.sub.2, to obtain a solution. 
The resulting solution was applied on a clean aluminum plate and cured at 
110.degree. C. for 2 hours. The contact angles of water and n-hexadecane 
against the cured coating film thus obtained were determined. 
The results are shown in Table 1. 
TABLE 1 
______________________________________ 
Amount Contact angle (degrees) 
n (parts) Water n-Hexadecane 
______________________________________ 
0 10 58 56 
3 56 56 
1 55 49 
0.1 51 31 
1 30 74 57 
15 64 56 
10 66 56 
5 61 56 
1 58 52 
0.1 51 36 
Without addition 50 .ltoreq.20 
______________________________________ 
EXAMPLE 2 
To 100 parts of the compound of the formula: 
##STR11## 
there was added the compound of the formula: 
##STR12## 
wherein n is 2, 3 or 4, in the amounts shown in Table 2 and also 3 parts 
of the curing agent, BF.sub.3 C.sub.2 H.sub.5 NH.sub.2, to obtain a 
solution. The resulting solution was applied on an aluminum plate and 
cured at 150.degree. C. for 2 hours. The contact angles of water and 
n-hexadecane against the cured coating film thus obtained were determined. 
The results are shown in Table 2. 
TABLE 2 
______________________________________ 
Amount Contact angle (degrees) 
n (parts) Water n-Hexadecane 
______________________________________ 
2 15 88 33 
10 88 30 
5 87 25 
1 83 27 
0.1 81 19 
3 15 96 40 
10 96 41 
5 96 37 
1 90 32 
0.1 80 20 
0.01 89 .ltoreq.20 
0.001 80 .ltoreq.20 
4 10 114 74 
5 112 70 
1 100 61 
0.1 91 31 
0.01 90 20 
0.001 86 20 
Without addition 79 .ltoreq.20 
______________________________________ 
EXAMPLE 3 
To 100 parts of the compound of the formula: 
##STR13## 
there was added 5 parts of the compound of the formula: 
##STR14## 
The resulting epoxy resin composition was cured on an aluminum plate by 
adding a curing agent thereto as shown in Table 3. The contact angles of 
water and n-hexadecane against the curing coating film thus obtained were 
determined. 
The results are shown in Table 3. 
TABLE 3 
______________________________________ 
Curing Contact 
condition angle (degrees) 
Temp. n-Hexa- 
Curing agent 
Parts (.degree.C.) 
Time Water decane 
______________________________________ 
Ethylenediamine 
8 Room 4 days 
104 59 
temp. 
Diaminodiphenyl- 
26 150 2 hrs. 
105 65 
methane 
Tetraethylene 
14 80 2 hrs. 
102 58 
pentamine 
Dodecenyl 130 150 20 hrs. 
98 52 
succinic 
anhydride 
______________________________________ 
EXAMPLE 4 
To one part of the compound of the formula: 
##STR15## 
there was added 0.1 part of the compound of the formula: 
##STR16## 
and the resultant was mixed homogeneously to obtain a liquid epoxy resin 
composition. To the resulting composition, there was added 0.14 part of 
tetraethylene pentamine, and the mixture was stirred for a while until it 
became homogeneous. The mixture was applied on an aluminum plate and cured 
at 80.degree. C. for 13 hours. The contact angles of water and 
n-hexadecane against the cured coating film thus obtained were determined. 
The results are shown in Table 4 hereinafter. 
Then, the cured coating film was dipped into ethanol for 3 hours. After 
washing with acetone, the film was dried at 80.degree. C. for 8 hours and 
the contact angles of water and n-hexadecane against the film were 
determined. 
The results are shown in Table 5 hereinafter. 
COMATIVE EXAMPLE 1 
The same procedure as described in Example 4 was repeated except that 
(CF.sub.3).sub.2 CF(CF.sub.2 CF.sub.2).sub.3 CH.sub.2 CH.sub.2 OH was 
substituted for 
##STR17## 
to obtain a cured coating film. In this case, although phase separation of 
the resulting homogeneous mixture was observed as curing progressed, the 
same procedure was carried out. The contact angles of water and 
n-hexadecane against the resulting cured coating film were determined 
before and after the same treatments as described above, i.e. dipping into 
ethanol, washing with acetone and drying. 
The results are also shown in Tables 4 and 5 hereinafter. 
COMATIVE EXAMPLE 2 
The same procedure as described in Example 4 was repeated except that 
##STR18## 
was not added to obtain a cured coating film. Likewise, the contact angles 
of water and n-hexadecane against the resulting coating film were 
determined before and after the same treatments with ethanol and acetone. 
The results are also shown in Tables 4 and 5. 
TABLE 4 
______________________________________ 
Contact angle (degrees) 
Examples Water n-Hexadecane 
______________________________________ 
Example 4 96 43 
Comparative 99 57 
Example 1 
Comparative 52 21 
Example 2 
______________________________________ 
TABLE 5 
______________________________________ 
Contact angle (degrees) 
Examples Water n-Hexadecane 
______________________________________ 
Example 4 96 41 
Comparative 78 26 
Example 1 
Comparative 76 22 
Example 2 
______________________________________ 
The present invention being thus described, it will be obvious that the 
same may be varied in many ways. Such modifications are not to be regarded 
as a departure from the spirit and scope of the present invention, and all 
such modifications are intended to be included within the scope of the 
following claims.