Fluorine-modified thermosetting resin and thermosetting resin composition

Fluorine-modified thermosetting reins are available as phenolic or epoxy resins having trifluoromethyl groups and a naphthalene skeleton in a molecule. They are useful as components of resin compositions or resin modifiers and cure to products having low water pickup, low coefficient of thermal expansion, and adhesion as well as heat resistance and mechanical strength. Thermosetting resin compositions having such a thermosetting resin blended therein are useful in semiconductor element packaging.

This invention relates to a fluorine-modified thermosetting resin which is 
a useful epoxy resin or phenolic resin for use as components of various 
resin compositions or modifiers for various resins. It also relates to a 
thermosetting resin composition having the thermosetting resin blended 
therein. 
BACKGROUND OF THE INVENTION 
Thermosetting resins are widely used in a variety of electric and 
structural materials which are subject to casting, impregnation, 
lamination and molding. More rigorous requirements are now imposed on 
these materials in various applications. In particular, heat resistance 
and low moisture absorption are important factors for such materials. 
Among prior art thermosetting resins, epoxy resins and phenolic resins were 
most useful. Known polyepoxy compounds for heat resistance purposes 
include phenol novolak epoxidized compounds (e.g., Epikote 154 
commercially available from Yuka Shell Epoxy K. K.), cresol novolak 
epoxidized compounds (e.g., EOCN commercially available from Nippon Kayaku 
K. K.), methylenedianiline tetraepoxide, and epoxidized tri- and 
tetra(hydroxyphenyl)alkane compounds. Also known phenolic resins include 
phenol novolak resins, ortho-cresol novolak resins, resins of bisphenol-A 
and triphenolmethane, etc. 
Cured products resulting from these resins exhibit heat resistance which is 
relatively high, but not fully satisfactory. Also, such resins undesirably 
require high temperature and long heating time in order to acquire a 
practically acceptable strength and are not satisfactorily easy to 
process. For semiconductor encapsulation purposes, not only are heat 
resistance, low moisture absorption and good processability required, but 
low coefficients of thermal expansion and firm adhesion are also needed. 
In the prior art, thermosetting resin compositions comprising an epoxy 
resin, a phenolic resin as a curing agent for the epoxy resin, and an 
inorganic filler have been used for semiconductor packaging. A number of 
problems must be overcome in order to meet the recent requirement of 
thickness reduction of semiconductor packages. For example, when flat 
packages are mounted on printed wiring boards, the packages are immersed 
in a solder bath at elevated temperature. On solder immersion, cracks can 
occur in packages of conventional thermosetting resin compositions due to 
thermal shocks. If the flat packages have absorbed moisture before 
mounting on printed wiring boards, steam explosion can occur in the 
packages upon immersion in a hot solder bath, also inducing cracks. 
Approaches for overcoming such problems are taken from both the frame and 
packaging resin aspects. As to the resin, improvements are needed in 
moisture absorption, coefficient of thermal expansion, and adhesion to 
frames as 7ell as mechanical strength and glass transition temperature. 
SUMMARY OF THE INVENTION 
Therefore, an object of the present invention is to provide a thermosetting 
resin which is a useful epoxy resin or phenolic resin for use as a 
component of various resin compositions or a modifier for various resins 
and which is easy to process and cures to products having heat resistance, 
high mechanical strength, high glass transition temperature, low 
coefficients of thermal expansion, low moisture absorption and improved 
adhesion. 
Another object of the present invention is to provide a thermosetting resin 
composition which cures to products having high mechanical strength, high 
glass transition temperature, low coefficients of thermal expansion, low 
moisture absorption and improved adhesion. 
A further object is to provide such cured products. 
According to a first aspect of the present invention, there is provided a 
thermosetting resin of the following general formula (1) or (2): 
##STR1## 
wherein R.sup.1 is 
##STR2## 
R.sup.4 is --H or a monovalent organic group having 1 to 20 carbon atoms, 
R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are independently 
##STR3## 
with the proviso that at least one of R.sup.5, R.sup.6, R.sup.7, and 
R.sup.8 is 
##STR4## 
R.sup.9 and R.sup.10 are independently 
##STR5## 
and 
n is 0 or an integer of from 1 to 7. 
According to a second aspect of the present invention, there is provided a 
thermosetting resin composition comprising the fluorine-modified resin of 
formula (1) or (2). More particularly, the composition includes an epoxy 
resin, a phenolic resin, an inorganic filler, and a fluorine-modified 
resin of formula (1) or (2) as an epoxy resin and/or phenolic resin. Cured 
products obtained by thermosetting the thermosetting resin composition are 
also contemplated. 
The thermosetting resin of the invention is easy to process and highly 
reactive with other epoxy resins, phenolic resins or the like, and itself 
cures to products having heat resistance over a long term, high mechanical 
strength at elevated temperature, high hardness, low coefficients of 
thermal expansion, low moisture absorption and improved adhesion. 
Therefore, the thermosetting resin is a useful epoxy resin or phenolic 
resin for use as a component of various resin compositions or a modifier 
for various resins. 
Due to the inclusion of such a thermosetting resin, the thermosetting resin 
composition of the invention cures to products having low moisture 
absorption, low coefficients of thermal expansion, and improved adhesion 
while retaining the glass transition temperature of the epoxy resin. 
Therefore, the composition may find best use in semiconductor packaging.

DETAILED DESCRIPTION OF THE INVENTION 
The thermosetting resin of the present invention is of the following 
general formula (1) or (2). 
##STR6## 
In the formulae, R.sup.1 is 
##STR7## 
R.sup.4 is --H or a monovalent organic group having 1 to 20 carbon atoms, 
preferably 1 to 10 carbon atoms, for example, methyl, phenyl, and 
o-hydroxyphenyl groups. 
R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are independently 
##STR8## 
with the proviso that at least one or R.sup.5, R.sup.6, R.sup.7, and 
R.sup.8 is 
##STR9## 
R.sup.9 and R.sup.10 are independently 
##STR10## 
wherein R.sup.4 to R.sup.8 are as defined above. 
Letter n is 0 or an integer of from 1 to 7. 
The thermosetting resin of the present invention can be readily synthesized 
by using a fluorine-modified bisphenol-A of the following general formula 
(3) and a mono-, di-, tri- or tetrahydroxynaphthalene of the following 
general formula (4), interacting them with an aldehyde compound in the 
presence of a catalyst, thereby obtaining a novolak type phenolic resin. 
##STR11## 
In the formulae, R.sup.1 to R.sup.10 are as defined above, and R.sup.11, 
R.sup.12, R.sup.13 and R.sup.14 are independently --H or --OH, with the 
proviso that at least one of R.sup.11 and R.sup.14 is --OH. 
The starting reactants, fluorine-modified bisphenol-A and 
hydroxynaphthalene, are commercially available and may be used in any 
desired proportion. Preferably the fluorine-modified bisphenol-A and 
hydroxynaphthalene are used in a molar ratio of from about 0.01 to about 
100, more preferably from about 0.1 to about 10. 
The aldehyde compound may be formaldehyde and salicylaldehyde, for example. 
The amount of aldehyde compound used is not particularly limited although 
the molar ratio of aldehyde compound to phenolic compound preferably 
ranges from about 0.05 to about 1, more preferably from about 0.11 to 
about 0.7. A molar ratio of aldehyde compound to phenolic compound of less 
than 0.05 would sometimes result in a polymer having a smaller molecular 
weight whereas a molar ratio in excess of 1 would sometimes cause 
gelation. 
The catalyst used herein may be selected from well-known alkali and acid 
catalysts, for example, such alkali catalysts as KOH and NaOH and such 
acid catalysts as hydrochloric acid, sulfuric acid, nitric acid, oxalic 
acid, paratoluenesulfonic acid, acetic acid, butyric acid, and propionic 
acid. The alkali or acid catalyst may be used in a catalytic amount, often 
in an amount of about 0.5 to 2% by weight based on the phenolic compound. 
The conditions under which reaction to form novolak type polymers takes 
place are not particularly limited. Preferably, the fluorine-modified 
resin and aldehyde compound are combined in an alkaline aqueous solution 
to form a resol, which is made acidic. The hydroxynaphthalene is then 
added to the resol. Reaction is allowed to proceed at about 100.degree. to 
150.degree. C. for about 4 to 8 hours, obtaining a novolak polymer. 
Phenolic resins according to the present invention are produced in this way 
and if necessary, then epoxidized into epoxy resins which also fall within 
the scope of the present invention. 
According to the second aspect of the present invention, the thermosetting 
resin composition is comprised of an epoxy resin, a phenolic resin, an 
inorganic filler, and a fluorine-modified resin of formula (1) or (2) or 
resin containing fluorine atoms and a naphthalene skeleton. 
The resin containing fluorine atoms and a naphthalene skeleton of formula 
(1) or (2) is an epoxy or phenolic resin having water repellency 
attributable to the fluorine atoms and high rigidity and hydrophobic 
nature attributable to the naphthalene skeleton. Preferred examples of the 
resin of formula (1) or (2) used in the present composition are those 
having the following structural formulae. 
##STR12## 
In the composition of the invention, an epoxy resin and a phenolic resin 
are blended in addition to the fluorine-modified resin and they may be 
ones commonly used in conventional semiconductor packaging compositions. 
More particularly, the epoxy resin (other than the fluorine-modified resin 
of the invention) may be selected from those resins having at least two 
epoxy groups in a molecule, for example, bisphenol-A epoxy resins, novolak 
type epoxy resins, cycloaliphatic epoxy resins, glycidyl ester type epoxy 
resins, and preferably polyfunctional epoxy resins and naphthalene 
ring-containing epoxy resins, alone or in admixture of two or more. These 
epoxy resins should preferably have a softening point of 50.degree. to 
100.degree. C. and an epoxy equivalent of 100 to 400. Use of brominated 
epoxy resins is also useful if flame retardancy is desired. 
The phenolic resin serves as a curing agent for the epoxy resin. The 
phenolic resin (other than the fluorine-modified resin of the invention) 
may be selected from phenol novolak resins, cresol novolak resins, and 
those having two or more phenolic hydroxyl groups such as 
triphenolmethane. The phenolic resins should preferably have a softening 
point of 60.degree. to 120.degree. C. and a hydroxyl equivalent of 90 to 
150. 
The phenolic resin may be used in such amounts as to provide an equivalent 
ratio of epoxy group/hydroxyl group between 0.5 to 2 in the thermosetting 
resin composition. Often about 30 to 70 parts by weight of the phenolic 
resin is used per 100 parts by weight of the epoxy resin. The amount of 
fluorine-modified phenolic resin plus conventional phenolic resin blended 
should preferably be adjusted to such a range. Less than 30 parts of the 
phenolic resins would sometimes be too small to provide strength whereas 
more than 70 parts would sometimes result in a lowering of moisture 
resistance. 
The fluorine-modified resin of formula (1) or (2) is preferably used in an 
amount of about 20 to 100%, more preferably about 50 to 80% by weight 
based on the total weight (100%) of the epoxy resins and phenolic resins 
combined. The fluorine-modified epoxy resin among the fluorine-modified 
resins of formula (1) or (2) is preferably used in an amount of about 0 to 
100%, more preferably about 50 to 80% by weight based on the total weight 
of the epoxy resin(s). The fluorine-modified phenolic resin among the 
fluorine-modified resins of formula (1) or (2) is preferably used in an 
amount of about 0 to 100%, more preferably about 50 to 80% by weight based 
on the total weight of the phenolic resin(s). 
The inorganic filler is blended in the present composition for the purpose 
of reducing the coefficient of thermal expansion of cured products, 
thereby alleviating the stresses on semiconductor elements. For example, 
fused silica and crystalline silica in pulverized or spherical form are 
often used. Alumina, silicon nitride and aluminum nitride are also useful. 
Mixtures of pulverized and spherical forms are preferred as well as 
principally spherical form fillers. 
The inorganic fillers should preferably have a mean particle size of about 
5 to 20 .mu.m and be blended in an amount of about 200 to 1600 parts, more 
preferably about 300 to 1200 parts by weight per 100 parts by weight of 
the epoxy resin. Less than 200 parts of the filler would sometimes result 
in cured products having a higher coefficient of thermal expansion to 
apply substantial stresses to semiconductor elements, degrading the 
element properties. Compositions containing more than 1600 parts of the 
filler would be too viscous during molding. Desirably, the inorganic 
fillers are previously surface treated with silane coupling agents. 
In addition to the above-mentioned components, the thermosetting resin 
composition of the invention may contain silicone series plasticizers or 
thermoplastic resins for stress reducing purposes. Examples include 
silicone rubber powder, silicone gel, organic resin-silicone block 
polymers MBS resins, and SEBS. It is also useful to surface treat the 
inorganic filler with a two part type silicone rubber or silicone gel 
before addition. 
These stress reducing agents are desirably used in an amount of about 0.5 
to 10% by weight, especially about 1 to 5% by weight based on the entire 
thermosetting resin composition. Less than 0.5% of the stress reducing 
agent would be less effective for imparting thermal shock resistance 
whereas more than 10% would sometimes result in a lowering of mechanical 
strength. 
If desired, the thermosetting resin composition of the present invention 
may contain curing promoters such as imidazole or its derivatives, 
phosphine derivatives, and cycloamidine derivatives; mold release agents 
such as carnauba wax, higher fatty acids, and waxes; and silane coupling 
agents, antimony oxide, phosphorus compounds, bromine and 
chlorine-containing compounds, all in their commonly used amounts. 
The thermosetting resin composition of the invention may be prepared by 
uniformly melting and milling the above-mentioned components in a roll 
mill, kneader or continuous extruder preheated at about 80.degree. to 
100.degree. C. The order of addition of the components is not critical. 
The thermosetting resin and thermosetting resin composition according to 
the present invention are useful for semiconductor packages including DIP, 
flat pack, PLCC, and SO types. Any conventional molding technique may 
used, for example, transfer molding, injection molding and casting. The 
composition is often molded at a temperature of 150.degree. to 180.degree. 
C. and post cured at 150.degree. to 180.degree. C. for about 2 to 16 
hours. 
EXAMPLE 
Examples of the present invention are given below by way of illustration 
and not by way of limitation. All parts and percents are by weight unless 
otherwise stated. G represents 
##STR13## 
EXAMPLE 1 
A 1-liter four-necked flask equipped with a condenser, thermometer and 
stirrer was charged with 168 grams of 
2,2-bis(4-hydroxy-phenylhexafluoropropane, 48.7 grams of 37% formaldehyde 
aqueous solution and 100 grams of water in a nitrogen atmosphere. With 
stirring, 1.0 gram of potassium hydroxide was added to the flask and 
reaction was carried out for 6 hours under reflux. After cooling, 3.3 
grams of oxalic acid, 140 grams of toluene, and 80 grams of 
2,6-dihydroxynaphthalene were added to the flask. The mixture was heated 
to remove water for 2 hours under toluene reflux. After a further 2 hours 
of reaction, the toluene was removed under vacuum and reaction was carried 
out at 150.degree. C. for one hour. Thereafter, the reaction mixture was 
cooled, diluted with methyl isobutyl ketone, and washed with water. Upon 
removal of the solvent by distillation, there was obtained 218 grams 
(yield 85.9%) of Compound A having a OH equivalent of 131 (theory 127). 
Compound A was identified by NMR and IR analysis. 
##STR14## 
Next, a 1-liter four-necked flask equipped with a condenser, thermometer 
and stirrer was charged with 197 grams of Compound A, 800 grams of 
epichlorohydrin, and 1.5 grams of cetyltrimethylammonium. The mixture was 
stirred for 3 hours under reflux. Then 120 grams of 50% sodium hydroxide 
aqueous solution was added dropwise to the flask in a vacuum 
(80.degree.-90.degree. C./100-130 mmHg). After the completion of dropwise 
addition, the mixture was aged for 3 hours, filtered, and removed of the 
solvent. Further, hydrolyzable chlorine was removed with 10% sodium 
hydroxide aqueous solution. Water washing left 250 grams (yield 91%) of 
Compound B having an epoxy equivalent of 189 (theory 183). 
##STR15## 
EXAMPLE 2 
A 1-liter four-necked flask equipped with a condenser, thermometer and 
stirrer was charged with 168 grams of 
2,2-bis(4-hydroxyphenyl)hexafluoropropane, 48.7 grams of 37% formaldehyde 
aqueous solution and 100 grams of water in a nitrogen atmosphere. With 
stirring, 1.0 gram of potassium hydroxide was added to the flask and 
reaction was carried out for 6 hours under reflux. After cooling, 3.3 
grams of oxalic acid, 140 grams of toluene, and 72 grams of 
.alpha.-naphthol were added to the flask. The mixture was heated to remove 
water for 2 hours under toluene reflux. After a further 2 hours of 
reaction, the toluene was removed under vacuum and reaction was carried 
out at 150.degree. C. for one hour. Thereafter, the reaction mixture was 
cooled, diluted with methyl isobutyl ketone, and washed with water. Upon 
removal of the solvent by distillation, there was obtained 214 grams 
(yield 87.0%) of Compound C having a OH equivalent of 169 (theory 164). 
Compound C was identified by NMR and IR analysis. 
##STR16## 
Next, a 1-liter four-necked flask equipped with a condenser, thermometer 
and stirrer was charged with 177 grams of Compound C, 800 grams of 
epichlorohydrin, and 1.5 grams of cetyltrimethylammonium. The mixture was 
stirred for 3 hours under reflux. Then 120 grams of 50% sodium hydroxide 
aqueous solution was added dropwise to the flask in a vacuum 
(80.degree.-90.degree. C./100-130 mmHg). After the completion of dropwise 
addition, the mixture was aged for 3 hours, filtered, and removed of the 
solvent. Further, hydrolyzable chlorine was removed with 10% sodium 
hydroxide aqueous solution. Water washing left 236 grams (yield 90.5%) of 
Compound D having an epoxy equivalent of 228 (theory 220). 
##STR17## 
IR spectra of Compounds A to D are shown in FIGS. 1 to 4. NMR peaks of 
Compounds A to D have the following ascription. 
.sup.1 H NMR solvent: (CD.sub.3).sub.2 CO 
ppm (.delta.) 
##STR18## 
EXAMPLE 3 
A 1-liter four-necked flask equipped with a condenser, thermometer and 
stirrer was charged with 168 grams of 
2,2-bis(4-hydroxyphenyl)hexafluoropropane, 48.7 grams of 37% formaldehyde 
aqueous solution and 100 grams of water in a nitrogen atmosphere. With 
stirring, 1.0 gram of potassium hydroxide was added to the flask and 
reaction was carried out for 6 hours under reflux. Separately, but by the 
same procedure, a mixture of 84 grams of 
2,2-bis(hydroxyphenyl)hexafluoropropane, 48.7 grams of 37% formaldehyde 
aqueous solution, 100 grams of water, and 1.0 gram of potassium hydroxide 
was subject to reaction. After cooling, these two reaction mixtures were 
combined in a 2-liter flask, to which 6.6 grams of oxalic acid, 300 grams 
of toluene, and 160 grams of 2,6-dihydroxynaphthalene were added. The 
mixture was heated to remove water for 2 hours under toluene reflux. After 
a further 2 hours of reaction, the toluene was removed under vacuum and 
reaction was carried out at 150.degree. C. for one hour. Thereafter, the 
reaction mixture was cooled, diluted with methyl isobutyl ketone, and 
washed with water. Upon removal of the solvent by distillation, there was 
obtained 395 grams (yield 84.5%) of Compound E having a OH equivalent of 
144 (theory 138). Compound E was identified by NMR and IR analysis. 
##STR19## 
Next, a 1-liter four-necked flask equipped with a condenser, thermometer 
and stirrer was charged with 216 grams of Compound E, 800 grams of 
epichlorohydrin, and 1.5 grams of cetyltrimethylammonium. The mixture was 
stirred for 3 hours under reflux. Then 120 grams of 50% sodium hydroxide 
aqueous solution was added dropwise to the flask in a vacuum 
(80.degree.-90.degree. C./100-130 mmHg). After the completion of dropwise 
addition, the mixture was aged for 3 hours, filtered, and removed of the 
solvent. Further, hydrolyzable chlorine was removed with 10% sodium 
hydroxide aqueous solution. Water washing left 265 grams (yield 88.5%) of 
Compound F having an epoxy equivalent of 205 (theory 194). 
##STR20## 
Examples 4-6 & Comparative Example 1 
Three thermosetting resin compositions were prepared by blending 
fluorine-modified epoxy resins B, D, F and fluorine-modified phenolic 
resins A, C, E synthesized in Examples 1 to 3, curing catalyst, ground 
quartz, and flame retardant in the amounts shown in Table 1 and uniformly 
melting and milling the blend in a hot two-roll mill. 
For comparison purpose, a thermosetting resin composition was similarly 
prepared using the phenol novolak resin (Compound G) and epoxidized 
ortho-cresol novolak resin (Compound H). 
##STR21## 
These thermosetting resin compositions were examined by the following tests 
(i) to (iv). 
(i) Spiral flow 
The spiral flow was measured at 175.degree. C. and 70 kg/cm.sup.2 using a 
mold according to the EMMI standard. 
(ii) Mechanical strength (flexural strength and flexural modulus) 
A tensile test bar of 10.times.4.times.100 mm according to JIS K-6911 was 
molded from the composition at 180.degree. C. and 70 kg/cm.sup.2 for 2 
minutes and post cured at 180.degree. C. for 4 hours. The bar 7as measured 
for flexural strength and flexural modulus at room temperature. 
(iii) Coefficient of expansion and glass transition temperature 
A test piece of 5.times.5.times.15 mm was molded at 180.degree. C. and 70 
kg/cm.sup.2 for 2 minutes and post cured at 180.degree. C. for 4 hours. 
The test piece was measured for coefficient of expansion and glass 
transition temperature (Tg) using a dilatometer while it was heated at a 
rate of 5.degree. C./min. 
(iv) Water pickup 
A disk having a diameter of 50 mm and a thickness of 3 mm was molded at 
180.degree. C. and 70 kg/cm.sup.2 for 2 minutes and post cured at 
180.degree. C. for 4 hours. It was allowed to stand for 24 hours in a 
121.degree. C./100% RH atmosphere and then measured for water pickup. 
TABLE 1 
__________________________________________________________________________ 
Comparative 
Example Example 
4 5 6 1 
__________________________________________________________________________ 
Composition (pbw) 
Phenolic resin A 38.7 
Phenolic resin C 40.7 
Phenolic resin E 39.2 
Phenolic resin G 33.5 
Epoxy resin B 52.8 
Epoxy resin D 50.8 
Epoxy resin F 52.3 
Epoxy resin H 58.0 
Flame retardant 8.5 8.5 8.5 8.5 
Triphenylphosphine 1.0 1.0 1.0 1.0 
Silane coupling agent* 
1.0 1.0 1.0 1.0 
Ground quartz 500.0 
500.0 
500.0 
500.0 
Co-flame retardant (SbO.sub.3) 
8.0 8.0 8.0 8.0 
Mold release agent** 0.8 0.8 0.8 0.8 
Carbon black 1.0 1.0 1.0 1.0 
Properties 
Spiral flow (cm) 62.0 65.0 58.0 63.0 
Flexural strength (kg/mm.sup.2) 
12.9 13.4 13.7 12.8 
Flexural modulus (kg/mm.sup.2) 
1970 1880 2040 1850 
Tg (.degree.C.) 192 173 188 162 
Coefficient of linear expansion (10.sup.-5 /.degree.C.) 
.alpha. 1 
0.91 1.02 1.11 1.58 
.alpha. 2 
2.98 3.85 3.96 6.93 
Water pickup (%) 0.55 0.49 0.52 0.72 
__________________________________________________________________________ 
*Silane coupling agent = glycidoxypropyltrimethoxysilane 
**Mold release agent = carnauba wax 
It is evident from Table 1 that the thermosetting resin compositions using 
the thermosetting resins within the scope of the present invention present 
cured products having high flexural strength and flexural modulus, 
especially high Tg, a low coefficient of linear expansion and low water 
pickup as compared with the composition using conventional orthocresol 
novolak epoxy resin and phenol novolak resin. 
EXAMPLES 7-20 & COMATIVE EXAMPLES 2-6 
Nineteen thermosetting resin compositions were prepared by blending the 
components shown in Tables 2-4, 1.5 parts of 
.gamma.-glycidoxypropyltrimethoxysilane, 1.5 parts of wax E, 1.0 part of 
carbon black, 0.8 parts of triphenylphosphine and uniformly melting and 
milling the blend in a hot two-roll mill. 
These thermosetting resin compositions were examined by the following tests 
(i) to (v). 
(i) Spiral flow 
The spiral flow was measured at 175.degree. C. and 70 kg/cm.sup.2 using a 
mold according to the EMMI standard. 
(ii) Mechanical strength (flexural strength and flexural modulus) 
A tensile test bar of 10.times.4.times.100 mm according to JIS K-6911 was 
molded from the composition at 180.degree. C. and 70 kg/cm.sup.2 for 2 
minutes and post cured at 180.degree. C. for 4 hours. The base was 
measured for flexural strength and flexural modulus at 215.degree. C. 
(iii) Coefficient of expansion and Tg 
A test piece having a diameter of 4 mm and a height of 15 mm was measured 
for coefficient of expansion and Tg using a dilatometer while it was 
heated at a rate of 5.degree. C./min. 
(iv) Water pickup 
A disk having a diameter of 30 mm and a thickness of 3 mm was molded at 
175.degree. C. for 2 minutes and post cured at 180.degree. C. for 4 hours. 
It was allowed to stand for 24 hours in a 85.degree. C./85% RH atmosphere 
and then measured for water pickup. 
(v) Adhesion 
A cylindrical button having a diameter of 15 mm and a height of 5 mm was 
molded on a 42-alloy plate of 17.times.17.times.1 mm thick at 175.degree. 
C. for 2 minutes and post cured at 180.degree. C. for 4 hours. Using a 
push-pull gage, the force required to separate the molded button from the 
42-alloy plate was measured (average of 8 samples). 
TABLE 2 
__________________________________________________________________________ 
Example 
7 8 9 10 11 2 13 14 15 
__________________________________________________________________________ 
Composition (pbw) 
Epoxy resin (Ib) 
52.8 -- -- 56.8 -- -- -- -- -- 
Epoxy resin (IIb) 
-- 51.1 -- -- 60.5 -- -- -- -- 
Epoxy resin (IIIb) 
-- -- 52.9 -- -- 58.5 -- -- -- 
Epoxy resin (IVb) 
-- -- -- -- -- -- -- -- -- 
EOCN 1020 (65) 1) 
-- -- -- -- -- -- 54.0 48.3 52.3 
Phenolic resin (Ia) 
38.7 -- -- -- -- -- 37.5 -- -- 
Phenolic resin (IIa) 
-- 40.4 -- -- -- -- -- 43.2 -- 
Phenolic resin (IIIa) 
-- -- 38.6 -- -- -- -- -- 39.2 
Phenolic resin (IVa) 
-- -- -- -- -- -- -- -- -- 
TD-2093 2) -- -- -- 34.7 31.0 33.0 -- -- -- 
Brominated epoxy resin 3) 
8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 
Silica 500 500 500 500 500 500 500 500 500 
Properties 
Spiral flow (cm) 
22 23 20 24 25 22 21 22 21 
Flexural strength (kg/mm.sup.2) 
12.5 12.7 13.1 12.3 12.4 12.8 13.1 12.4 13.4 
Flexural modulus (kg/mm.sup.2) 
1820 1860 1810 1920 1880 1790 1810 1830 1830 
Tg (.degree.C.) 181 182 179 174 182 185 179 178 180 
Coefficient of linear expansion 
0.91 0.95 1.0 1.1 1.0 0.9 0.9 1.0 1.1 
(10.sup.-5 /.degree.C., .alpha. 1) 
Water pickup (%) 
0.55 0.49 0.50 0.52 0.51 0.49 0.48 0.50 0.51 
Adhesion (kg) 22 27 31 30 23 31 32 33 31 
__________________________________________________________________________ 
TABLE 3 
__________________________________________________________________________ 
Example 
16 17 18 19 20 
__________________________________________________________________________ 
Composition (pbw) 
Epoxy resin (Ib) 28.7 29.6 -- -- 29.2 
Epoxy resin (IIb) -- -- -- 29.8 -- 
Epoxy resin (IIIb) -- -- -- 29.8 -- 
Epoxy resin (IVb) -- 29.6 -- -- 29.2 
EOCN 1020 (65) 1) 28.7 -- 51.1 -- -- 
Phenolic resin (Ia) -- -- 20.0 -- -- 
Phenolic resin (IIa) -- -- -- -- -- 
Phenolic resin (IIIa) -- -- -- -- -- 
Phenolic resin (IVa) -- -- 20.2 -- -- 
TD-2093 2) 34.1 32.3 -- 32.0 33.0 
Brominated epoxy resin 3) 
8.5 8.5 8.5 8.5 8.5 
Silica 500 500 500 500 500 
Properties 
Spiral flow (cm) 22 24 20 20 21 
Flexural strength (kg/mm.sup.2) 
12.5 12.8 12.5 12.4 12.5 
Flexural modulus (kg/mm.sup.2) 
1810 1850 1800 1820 1840 
Tg (.degree.C.) 181 181 179 176 175 
Coefficient of linear expansion (10.sup.-5 /.degree.C., 
1.1pha. 1) 
1.2 0.9 1.0 1.1 
Water pickup (%) 0.49 0.48 0.50 0.51 0.51 
Adhesion (kg) 28 27 30 31 32 
__________________________________________________________________________ 
TABLE 4 
__________________________________________________________________________ 
Comparative Example 
2 3 4 5 6 
__________________________________________________________________________ 
Composition (pbw) 
Epoxy resin (Ib) -- -- -- -- -- 
Epoxy resin (IIb) -- -- -- -- -- 
Epoxy resin (IIIb) -- -- -- -- -- 
Epoxy resin (IVb) -- 29.5 -- 50.1 27.3 
EOCN 1020 (65) 1) 58.8 29.5 47.7 -- 27.3 
Phenolic resin (Ia) -- -- -- -- -- 
Phenolic resin (IIa) -- -- -- -- -- 
Phenolic resin (IIIa) -- -- -- -- -- 
Phenolic resin (IVa) -- -- 43.8 41.4 18.4 
TD-2093 2) 33.5 32.5 -- -- 18.4 
Brominated epoxy resin 3) 
8.5 8.5 8.5 8.5 8.5 
Silica 500 500 500 500 500 
Properties 
Spiral flow (cm) 21 22 21 22 21 
Flexural strength (kg/mm.sup.2) 
12.7 12.9 13.1 12.8 13.1 
Flexural modulus (kg/mm.sup.2) 
1820 1840 1810 1830 1820 
Tg (.degree.C.) 162 165 164 163 162 
Coefficient of linear expansion (10.sup.-5 /.degree.C., 
1.5pha. 1) 
1.4 1.3 1.3 1.4 
Water pickup (%) 0.72 0.75 0.71 0.69 0.70 
Adhesion (kg) 10 11 12 13 11 
__________________________________________________________________________ 
The epoxy resins and phenolic resins used herein are shown below. 
##STR22## 
(Ia) R.dbd.H, OH equiv. 131, SP 95.degree. C. (Ib) R.dbd.G, Epoxy equiv. 
189, SP 83.degree. C. 
##STR23## 
(IIa) R.dbd.H, OH equip. 169, SP 85.degree. C. 
(IIb) R.dbd.G, Epoxy equiv. 228, SP 73.degree. C. 
##STR24## 
(IIIa) R.dbd.H, OH equip. 144, SP 105.degree. C. (IIIb) R.dbd.G, Epoxy 
equiv. 206, SP 97.degree. C. 
##STR25## 
(IVa) R.dbd.H, OH equip. 171, SP 95.degree. C. (IVb) R.dbd.G, Epoxy equiv. 
224, SP 85.degree. C. 
Note 
1) ortho-cresol novolak type epoxy resin (softening point 65.degree. C., 
epoxy equiv. 200) tradename EOCN 1020(65) manufactured by Nippon Kayaku K. 
K. 
2) phenol novolak type epoxy resin (softening point 100.degree. C., OH 
equiv. 110) tradename TD2093 manufactured by Dai-Nihon Ink K.K. 
3) brominated phenol novolak type epoxy resin (softening point 85.degree. 
C., epoxy equiv. 280) tradename BREN-S manufactured by Nippon Kayaku K.K. 
It is evident from Tables 2 to 4 that the thermosetting resin compositions 
comprising epoxy resin, phenolic resin, inorganic filler and a phenolic or 
epoxy resin having fluorine atoms and a naphthalene skeleton within the 
scope of the present invention present cured products retaining mechanical 
strength such as high flexural strength and flexural modulus and 
exhibiting high Tg, a low coefficient of linear expansion and low water 
pickup and firm adhesion as compared with the composition free of a 
phenolic or epoxy resin having fluorine atoms and a naphthalene skeleton.