Curable mixtures based on diglycidyl compounds and metal complex compounds

Curable mixtures, containing, PA0 (a) at least one bisphenol diglycidyl ether based on bisphenol A, hydrogenated bisphenol A or bisphenol F, PA0 (b) as a curing catalyst, a colorless or slightly yellow solution of a metal complex compound of the formula I EQU ]Me(H.sub.2 O).sub.x (Lm).sub.y ].sup.2+ (A.sup..crclbar.).sub.2 (I), PA0 in which PA1 Me is a divalent metal from the group comprising Zn, Cd, Sn, Pb, Ca or Mg, PA1 Lm is a saturated cyclic ether having 5 to 7 ring atoms, a linear or cyclic saturated aliphatic ether compound or a mixture of the ether and the ether compound, the ether and the ether compound having a boiling point of at least 60.degree. C., and PA1 A is an anion of the formula BF.sub.4.sup..crclbar., PF.sub.6.sup..crclbar., AsF.sub.6.sup..crclbar. or SbF.sub.6 .sup..crclbar., PA1 x is the number 4, 5 or 6 and y is zero or the number 1 or 2, the sum of x and y always being 6, the complex being dissolved in an excess of the corresponding ether or the corresponding ether compound, PA0 (c) a sterically hindered mononuclear or polynuclear phenol, a phosphite of the formula II or III ##STR1## in which R.sub.1, R.sub.2 and R.sub.3 independently of one another are each phenyl, alkyl-substituted phenyl having 1-12 carbon atoms in the alkyl radical or alkyl having 1 to 20 carbon atoms, or a mixture of a sterically hindered mononuclear or polynuclear phenol and a phosphite of the formula II or III and, if appropriate, PA0 (d) as a reactive diluent, up to 25 parts by weight, relative to 100 parts by weight (a), of at least one diglycidyl ether of 1,4-butanediol, 1,6-hexanediol or neopentyl glycol or a cresol glycidyl ether and, if appropriate, PA0 (e) as an adhesion promoter, an organic silane, titanate or zirconate, can be cured rapidly and give transparent mouldings which are resistant to yellowing. They are particularly suitable for sheathing or embedding opto-electronic components.

The present invention relates to curable mixtures based on certain 
diglycidyl compounds and metal complex compounds and to their use as 
transparent molding and coating compositions, in particular for sheathing 
or embedding opto-electronic components. 
Transparent casting resin compositions based on diglycidyl compounds for 
opto-electronic components are known, for example from German 
Offenlegungsschriften Nos. 3,016,097, 3,016,103 and 3,151,540. The casting 
resin compositions disclosed therein represent anhydride-curable epoxide 
resin compositions which have been provided with a curing accelerator. For 
certain applications, in particular for machine processing, such casting 
resin systems sometimes leave something to be desired with respect to mold 
occupation times. 
It has now been found that casting resin compositions of certain bisphenol 
diglycidyl ethers and certain metal complex compounds can, on the one 
hand, be fully cured very rapidly, i.e. they have shorter gelling and 
initial curing times and thus allow very short mould occupation times, 
and, on the other hand, do not yellow either on curing or on storage. 
The present invention thus relates to curable mixtures which contain 
(a) at least one bisphenol diglycidyl ether based on bisphenol A, 
hydrogenated bisphenol A or bisphenol F, 
(b) as a curing catalyst, a colorless or slightly yellow solution of a 
metal complex compound of the formula I 
EQU [Me(H.sub.2 O).sub.x (Lm).sub.y ].sup.2+ (A.sup..crclbar.).sub.2 (I), 
in which 
Me is a divalent metal from the group comprising Zn, Cd, Sn, Pb, Ca or Mg, 
Lm is a saturated cyclic ether having 5 to 7 ring atoms, a linear or cyclic 
saturated aliphatic ether compound or a mixture of the ether and the ether 
compound, the ether and the ether compound having a boiling point of at 
least 60.degree. C., and 
A is an anion of the formula BF.sub.4.sup..crclbar., 
PF.sub.6.sup..crclbar., AsF.sub.6.sup..crclbar. or 
SbF.sub.6.sup..crclbar., 
x is the number 4, 5 or 6 and y is zero or the number 1 or 2, the sum of x 
and y always being 6, the complex being dissolved in an excess of the 
corresponding ether or the corresponding ether compound, 
(c) a sterically hindered mononuclear or polynuclear phenol, a phosphite of 
the formula II or III 
##STR2## 
in which R.sub.1, R.sub.2 and R.sub.3 independently of one another are 
each phenyl, alkyl-substituted phenyl having 1-12 carbon atoms in the 
alkyl radical or alkyl having 1 to 20 carbon atoms, or a mixture of a 
sterically hindered mononuclear or polynuclear phenol and a phosphite of 
the formula II or III and, if appropriate, 
(d) as a reactive diluent, up to 25 parts by weight, relative to 100 parts 
by weight of (a), of at least one diglycidyl ether of 1,4-butanediol, 
1,6-hexanediol or neopentyl glycol or a cresol glycidyl ether and, if 
appropriate, 
(e) as an adhesion promoter, an organic silane, titanate or zirconate. 
Preferably, the mixtures according to the invention contain, as the 
component (c) a sterically hindered mononuclear or polynuclear phenol and, 
as the reactive diluent (d), 15 parts by weight, relative to 100 parts by 
weight of (a), of at least one diglycidyl ether of 1,4-butanediol, 
1,6-hexanediol or neopentyl glycol. 
Moreover, the mixtures according to the invention preferably contain the 
components (a), (b), (c) and (d). 
The component (a) in the mixtures according to the invention is preferably 
a bisphenol A diglycidyl ether, a hydrogenated bisphenol A diglycidyl 
ether or a mixture of a bisphenol A diglycidyl ether and a bisphenol F 
diglycidyl ether, in particular a bisphenol A diglycidyl ether or a 
mixture of bisphenol A and bisphenol F diglycidyl ethers. 
As the metal complex compound (b), the mixtures according to the invention 
preferably contain those in which, in the formula I, Me is Zn and A is 
BF.sup..crclbar.4. 
In the formula I, examples of suitable saturated cyclic ethers having 5 to 
7 ring atoms are tetrahydrofuran, tetrahydropyran, 1,3-dioxolane or 
hexamethylene oxide. 
Examples of suitable linear saturated aliphatic ether compounds are 
diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl 
ether, diethylene glycol di-n-butyl ether, triethylene glycol dimethyl 
ether (triglyme), triethylene glycol diethyl ether, triethylene glycol 
di-n-butyl ether, tetraethylene glycol dimethyl ether (tetraglyme), 
2-ethoxyethanol, and examples of suitable cyclic saturated ether compounds 
are tetrahydrofurfuryl alcohol, bis-tetrahydrofurfuryl ether and 
2-tetrahydrofurfuryloxy-tetrahydropyran. 
Preferably, Lm in the formula I is a saturated cyclic ether or a linear 
saturated aliphatic ether compound, and in particular Lm is 
tetrahydrofuran, hexamethylene oxide or triglyme. 
Those complex compounds in which, in the formula I, x is 4 and y is 2, are 
also preferred in the mixtures according to the invention. 
The metal complex compounds, used as curing catalysts, of the formula I are 
usually employed in catalytic quantities. Preferably, the quantity used is 
0.01 to 5 parts by weight, in particular 0.05 to 3.5 parts by weight, per 
100 parts by weight of bisphenol diglycidyl ether (a). As a rule, the 
curing catalysts are used as a 1-10 percent by weight solution, preferably 
as a 5-10 percent by weight solution, the ether compound in the metal 
complex and the ether used as solvent being normally identical. 
The metal complex compounds of the formula I are known compounds and can be 
prepared analogously to the process disclosed in EP patent No. 0,028,583 
by, for example, reacting a metal fluoride with BF.sub.3, PF.sub.5, 
AsF.sub.5 or SbF.sub.5 in the presence of a stoichiometric quantity of 
water in a complexing ether or a complexing ether compound (Lm) at an 
elevated temperature. 
The following are examples of compounds which can be added as the 
sterically hindered mononuclear or polynuclear phenols (c) to the mixture 
according to the invention: 2,6-di-tert.-butyl-4-methylphenol, 
2-tert.-butyl-4,6-dimethylphenol, 2,6-di-tert.-butyl-4-ethylphenol, 
2,6-di-tert.-butyl-4-n-butylphenol, 2,6-di-tert.-butyl-4-isobutylphenol, 
2,6-dicyclopentyl-4-methylphenol, 
2-(.alpha.-methylcyclohexyl)-4,6-dimethylphenol, 
2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 
2,6-di-tert.-butyl-4-methoxymethylphenol, 
2,6-di-tert.-butyl-4-methoxyphenol, 2,6-diphenyl-4-octadecyloxyphenol, 
2,2'-thio-bis-(6-tert.-butyl4-methylphenol), 
2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert.-butyl-3-methylphenol 
), 4,4'-thio-bis-(6-tert.-butyl-2-methylphenol), 
2,2'-methylene-bis-(6-tert.-butyl-4-methylphenol), 
2,2'-methylene-bis-(6-tert.-butyl-4-ethylphenol), 
2,2'-methylene-bis-[4-methyl-6-(.alpha.-methylcyclohexyl)phenol], 
2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 
2,2'-methylene-bis-(6-nonyl-4-methylphenol), 
2,2-methylene-bis-(4,6-di-tert.-butylphenol), 
2,2'-ethylidene-bis-(4,6-di-tert.-butylphenol), 
2,2'-ethylidene-bis-(6-tert.-butyl-4-isobutylphenol), 
2,2'-methylene-bis-[6-(.alpha.-methylbenzyl)-4-nonylphenol], 
2,2'-methylene-bis-[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol], 
4,4'-methylene-bis-(2,6-di-tert.-butylphenol), 
4,4'-methylene-bis-(6-tert.-butyl-2-methylphenol), 
1,1-bis-(5-tert.-butyl-4-hydroxy-methylphenyl)-butane, 
2,6-di-(3-tert.-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 
1,1,3-tris-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 
1,1-bis-(5-tert. 
-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene 
glycol bis-[3,3-bis-(3'-tert.-butyl-4'-hydroxyphenyl)-butyrate], 
di-(3-tert.-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene, 
di-[2-(3'-tert.-butyl-2'-hydroxy 
-5'-methylbenzyl)-6-tert.-butyl-4-methylphenyl] terephthalate, 
1,3,5-tri(3,5-di-tert.-butyl-4-hydroxybenzyl)2,4,6-trimethylbenzene, 
di-(3,5-di-tert.-butyl-4-hydroxybenzyl) sulfide, isooctyl 
3,5-di-tert.-butyl-4-hydroxybenzyl-mercaptoacetate, 
bis-(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol-terephthalate, 
1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxybenzyl) isocyanurate, 
1,3,5-tris-(4-tert.-butyl -3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 
dioctadecyl 3,5-di-tert.-butyl-4-hydroxybenzylphosphonate, monoethyl 
3,5-di-tert.-butyl-4-hydroxybenzylphosphonate, 
2,4-bis-octylmercapto-6-(3,5-di-tert.-butyl-4-hydroxyanilino)-striazine, 
octyl N-2,5-di-tert.-butyl-4-hydroxyphenyl-carbamate and esters of 
.beta.-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid with monohydric 
or polyhydric alcohols such as methanol, octadecanol, 1,6-hexanediol, 
neopentyl glycol, diethylene glycol, triethylene glycol, pentaerythritol 
or tris-hydroxyethyl isocyanurate, for example pentaerythrityl 
tetrakis-[3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate], and also 
esters of .beta.-(5-tert.-butyl-4-hydroxy-3-methylphenyl)-propionic acid 
with monohydric or polyhydric alcohols. 
The above phenols are known compounds, some of which are commercially 
available. 
Preferably, those phenols are used in the mixtures according to the 
invention which carry a tert.-butyl group in each of the two 
ortho-positions to the phenolic hydroxyl group. Amongst such phenols, the 
polynuclear phenols containing tert.-butyl groups are particularly 
preferred phenols for the mixtures according to the invention. 
The sterically hindered phenols are added to the mixtures according to the 
invention in general in quantities of 0.2 to 5 parts by weight per 100 
parts by weight of bisphenol diglycidyl ether (a). Preferably, the 
quantity is 0.4 to 3 parts by weight, especially 0.5 to 2.5 parts by 
weight, of sterically hindered phenol per 100 parts of bisphenol 
diglycidyl ether (a). 
In place of the said phenols, the curable mixtures according to the 
invention can also contain phosphites of the formula II or mixtures of the 
said phenols and the phosphites of the formula II in the same quantities 
by weight, relative to component (a). 
As the phosphites of the formula II, the mixtures according to the 
invention contain, for example, triphenyl phosphite, 
tris-(2,4-di-tert.-butylphenyl) phosphite, tris-(p-nonylphenyl) phosphite, 
di-(hexyl) phenyl phosphite, di-(heptyl) phenyl phosphite, di-(octyl) 
phenyl phosphite, di-(nonyl) phenyl phosphite, di-(decyl) phenyl 
phosphite, di-(undecyl) phenyl phosphite or di-(dodecyl) phenyl phosphite, 
and examples of suitable phosphites of the formula III are distearyl 
pentaerythritol diphosphite and di-(di2,4,tert.-butylphenyl) 
pentaerythritol diphosphite. 
Those phosphites of the formula II are preferably used in which R.sub.1 is 
phenyl and R.sub.2 and R.sub.3 are each alkyl having 1 to 12 and 
especially 6 to 12 carbon atoms. 
The phosphites of the formula II and III are known compounds, and some of 
them are commercially available. 
The diglycidyl compounds which can be used as reactive diluents (d) in the 
mixtures according to the invention are known compounds and are preferably 
added to the curable compounds when their processing requires a viscosity 
of less than 1200 mPas for example for processing as an injection-molding 
compound. Preferably, hexanediol diglycidyl ether or butanediol diglycidyl 
ether, in particular hexanediol diglycidyl ether, are used as the reactive 
diluent. 
Examples of silanes which, if appropriate, can be added as adhesion 
promoters (e) to the mixtures according to the invention are: 
vinyltriethoxysilane, vinyltrimethoxysilane, 
vinyl-tris-(.beta.-methoxyethoxy)-silane, 
.gamma.-methacryloxypropyl-trimethoxysilane, 
.gamma.-methacryloxypropyl-tris-(2- methoxyethoxy)-silane, 
.beta.-(3,4-epoxycyclohexyl)-ethyl-trimethoxysilane, 
.gamma.-glycidoxypropyl-trimethoxysilane, vinyltriacetoxysilane, 
.gamma.-mercaptopropyl-trimethoxysilane, 
.gamma.-aminopropyl-triethoxysilane and 
N-(.beta.-aminoethyl)-.gamma.-aminopropyltrimethoxysilane. 
Such compounds are known and are commercially available as silane adhesion 
promoters from Union Carbide corporation. 
Examples of suitable inorganic titanates which can be added, if 
appropriate, as adhesion promoters (e) to the mixtures according to the 
invention are the following compounds: isopropyl triisostearoyl titanate, 
isopropyl dimethacryloyl isostearoyl titanate, isopropyl 
tri-(dodecylbenzenesulfonyl) titanate, isopropyl tri-(dioctylphosphato) 
titanate, isopropyl 4-aminobenzenesulfonyl di-(dodecylbenzenesulfonyl) 
titanate, alkoxy trimethacryl titanate, isopropyl 
tri-(dioctylpyrophosphato) titanate, alkoxy triacryl titanate, isopropyl 
tri-(N-ethylamino-ethylamino)-titanate, titanates of the oxyacetate 
chelate type, for example titanium di-(cumylphenylate) oxyacetate or 
titanium di-(dioctylpyrophosphate) oxyacetate, titanates of the ethylene 
chelate type, for example di-(dioctylphosphato) ethylene titanate or 
di-(dioctylpyrophosphato) ethylene titanate, or cyclic titanates, for 
example dicyclo-(dioctyl)-pyrophosphato dioctyl titanate or 
dicyclo-(dioctyl)-pyrophosphato titanate. 
The said titanates are also known compounds and are commercially available 
from Kenrich Petrochemicals. 
Examples of suitable organic zirconates which, if appropriate, can be added 
as adhesion promoters (e) to the mixtures according to the invention are 
neoalkoxy tris(neodecanoyl) zirconate, neoalkoxy 
tris-(dodecylbenzenesulfonyl) zirconate, neoalkoxy 
tris-(dioctyl)-phosphato zirconate, neoalkoxy tris-(dioctyl)-pyrophosphato 
zirconate, neoalkoxy tris-(ethylenediamino)-ethyl zirconate or neoalkoxy 
tris-(m-amino)-phenyl zirconate. Such compounds are likewise known and 
commercially available from Kenrich Petrochemicals. 
The adhesion promoters present, if appropriate, in the mixtures according 
to the invention are in general added in quantities of 0.05-0.5 part by 
weight, preferably 0.01-0.3 and especially 0.01-0.1 part by weight, per 
100 parts by weight of the bisphenol diglycidyl ether (a). Amongst the 
said adhesion promoters, the organic silanes are used preferably, in 
particular those which contain an epoxide group. 
Depending on the application, yet further additives can be added to the 
mixtures according to the invention, such as levelling agents to obtain 
better surfaces in coatings or so-called deaerators in order to remove 
occluded air bubbles from the curable mixture before curing. Levelling 
agents are commercially available for example under the name "Silwett 
L-77" or "L 76023" from UCC, "Fluorad FC-430" from 3M or "Additol XL 
490/100" from Vianova Kunstharz AG. Deaerating agents are likewise on the 
market, for example under the name "Silicone-SH" or "Silicone-SAG" from 
Wacker Chemie, "BYK 525" or "BYK A500" from BYK-Mallincrodt or 
"Anti-Mousse Rhodorsil 411" from Rhone Poulenc. 
Moreover, the mixtures according to the invention can be provided in the 
known manner with coloring pastes, which must not adversely affect the 
transparence of the opto-electronic molding materials prepared from these 
mixtures. For applications in the opto-electronics field, diffuser pastes 
can, if appropriate, also be added to the mixtures according to the 
invention, in order to obtain adequate light scattering in the 
opto-electronic molding materials. 
As mentioned at the outset, the mixtures according to the invention are 
transparent molding and coating compositions which in general can be cured 
in the temperature range from 100.degree.-140.degree. C. The gelling times 
of the mixtures according to the invention are between 5 and 30 seconds in 
this temperature range. Because of their transparence, yellowing 
resistance and processing properties, the mixtures according to the 
invention are particularly suitable for the production of opto-electronic 
components, such as light-emitting diodes, opto-couplers or displays. In 
this application, it is advantageous if the mixtures according to the 
invention have a color number of less than 2 on the Gardener scale before 
curing. 
The present invention therefore also relates to the use of the mixtures 
according to the invention as encapsulation compositions or potting 
compounds for the production of opto-electronic components, and to 
opto-electronic components encapsulated or potted with the mixtures 
according to the invention.

The invention is explained in more detail in the examples which follow. 
The test methods mentioned in the examples are carried out as follows. 
Moist storage test: The fully cured light-emitting diodes are stored for 
500 hours at 85.degree. C. and a relative humidity of 85%. The voltage 
applied to the diodes is 4 V. The rise in the inverse current is measured. 
A diode is regarded as having failed when the current intensity rises to 
values greater than 10 .mu.A. 
Temperature shock test: The fully cured light-emitting diodes are 
alternatingly immersed for 15 minutes each time into a liquid cooled to 
-10.degree. C. and then into a liquid warmed to 90.degree. C. 100 such 
cycles are carried out. Specimens have passed the test if no stress cracks 
appear in the fully cured molded material. 
Preparation of the zinc tetrafluoborate complex in tetrahydrofuran (THF) Zn 
(H.sub.2 O).sub.4 (THF).sub.2.sup.2+ (BF.sub.4).sub.2 
113.7 g of zinc fluoride (1 mol+10% excess) are dispersed at room 
temperature in 317.28 g of THF (4.4 mol) in a sulfonation flask provided 
with a thermometer, dropping funnel, stirrer and gas inlet tube. Under a 
slow stream of argon, 207.68 g of BF.sub.3.2H.sub.2 O (2 mol) are added 
dropwise in the course of 2 hours in such a way that the reaction 
temperature does not rise above 50.degree. C. Reaction is then allowed to 
continue in the reaction mixture for a further 2 hours. 20 g of filter aid 
are then added at 30.degree. C. with stirring, and the reaction mixture is 
filtered with suction over a soft filter, with argon blanketing. This 
gives the zinc complex in a light yellow, highly viscous solution in 91% 
yield. The zinc content is 101.2 mg of Zn per 1 g of solution. 
Preparation of the zinc tetrafluoborate complex in triethylene glycol 
dimethyl ether (triglyme) 
103.4 g (1 mol) of zinc fluoride are dispersed at room temperature by 
stirring in 178.22 g (1 mol) of triglyme in a sulfonation flask provided 
with a thermometer, dropping funnel, stirrer and gas inlet tube. Under a 
slow stream of argon, 206.68 g of BF.sub.3.2H.sub.2 O are added dropwise 
in the course of 4 hours in such a way that the reaction temperature does 
not exceed 60.degree. C. Reaction is then allowed to continue at 
50.degree. C. for a further 2 hours. The turbid suspension is filtered 
overnight over a small Al.sub.2 O.sub.3 column. 
This gives a clear liquid of medium viscosity with a zinc content of 126 mg 
of Zn per 1 g of solution. 
Preparation of the zinc tetrafluoborate complex in hexamethylene oxide 
99.2 g (0.96 mol) of zinc fluoride are dispersed at room temperature by 
stirring in 384.6 g (3.84 mol) of hexamethylene oxide in a sulfonation 
flask provided with a thermometer, dropping funnel, stirrer and gas inlet 
tube. Under a slow stream of argon, 199.3 g (1.92 mol) of 
BF.sub.3.2H.sub.2 O are added dropwise in such a way that the reaction 
temperature does not exceed 60.degree. C. The dropwise addition is 
complete after 4 hours, and the reaction solution is heated to 60.degree. 
C. and allowed to react for a further 2 hours. The brownish turbid 
solution is filtered over a short column with a layer of Al.sub.2 O.sub.3 
and active charcoal. 
This gives 470.42 g of a clear, yellow liquid of low viscosity. 
EXAMPLE 1 
100 parts by weight of a bisphenol A diglycidyl ether resin having an 
epoxide content of 5.6-5.7 equivalents/kg and 10 parts by weight of 
1,6-hexanediol diglycidyl ether having an epoxide content of 6.4-6.6 
equivalents/kg are mixed at room temperature by means of a laboratory 
stirrer. The temperature of this resin mixture is then raised to 
80.degree. C. and, at this temperature, one part by weight of 
pentaerythrityl 
tetrakis-[3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate] is stirred in 
over 20-30 minutes. The mixture is then allowed to cool again to room 
temperature. 
100 parts by weight of the previously prepared mixture are then mixed at 
room temperature with 2 parts by weight of a zinc tetrafluoborate complex 
in tetrahydrofuran (Zn content 101.2 mg/g of solution). The gelling time 
of this reaction mixture is about 10 minutes at room temperature. Within 
one minute, the reaction mixture is injected by means of a plastic syringe 
into 25 cavities, consisting of a poly(methylpentene) thermoplastic of 
high heat distortion point, for light-emitting diodes and gelled and 
incipiently cured at 120.degree. C. The gelling time is 20-25 seconds. 
After incipient curing for 1-2 minutes, the light-emitting diodes are 
removed from the cavities and then fully cured for a further 8 hours at 
120.degree. C. Colorless mouldings are then obtained which remain free of 
yellowing even after storage at 120.degree. C. for 100 hours and have a 
glass transition point of 130.degree.-140.degree. C. The fully cured 
moldings pass both the moist storage test at 85.degree. C./85% relative 
humidity for 500 hours and the temperature shock test (100 changes from 
-10.degree. to +90.degree. C.). 
EXAMPLE 2 
Example 1 is repeated, using the same quantity of 1,4-butanediol diglycidyl 
ether having an epoxide content of 8.9 equivalents/kg in place of the 
hexanediol diglycidyl ether. The properties of the mouldings obtained 
correspond to those of Example 1. 
EXAMPLE 3 
Example 1 is repeated, using the same quantity of neopentyl glycol 
diglycidyl ether having an epoxide content of 7.3 equivalents/kg in place 
of the hexanediol diglycidyl ether. The properties of the moldings 
obtained correspond to those of Example 1. 
EXAMPLE 4 
Example 1 is repeated, but with the difference that, in place of the 
bisphenol A diglycidyl ether resin having an epoxide content of 5.6/5.7 
equivalents/kg, such a resin having an epoxide content of 5.1-5.4 epoxide 
equivalents/kg is used. The moldings obtained have the same properties as 
the moldings obtained according to Example 1. 
EXAMPLE 5 
Example 4 is repeated, using the same quantity of butanediol diglycidyl 
ether in place of the hexanediol diglycidyl ether. The properties of the 
moldings obtained correspond to those of Example 4. 
EXAMPLE 6 
Example 4 is repeated, using the same quantity of neopentyl diglycidyl 
ether in place of the hexanediol diglycidyl ether. The properties of the 
moldings obtained correspond to those of Example 4. 
EXAMPLE 7 
Example 1 is repeated, using the same quantity of distilled bisphenol F 
diglycidyl ether resin having an epoxide content of 6.0-6.4 equivalents/kg 
in place of the bisphenol A diglycidyl ether resin. The properties of the 
moldings obtained correspond to those of Example 1. 
EXAMPLE 8 
Example 7 is repeated, using the same quantity of butanediol diglycidyl 
ether in place of the hexanediol diglycidyl ether. The properties of the 
moldings obtained correspond to those of Example 7. 
EXAMPLE 9 
Example 7 is repeated, using the same quantity of neopentyl glycol 
diglycidyl ether in place of hexanediol diglycidyl ether. The properties 
of the moldings obtained correspond to those of Example 7. 
EXAMPLE 10 
Example 1 is repeated, using the same quantity of hydrogenated bisphenol A 
diglycidyl ether resin having an epoxide content of 4.3-4.8 equivalents/kg 
in place of the bisphenol A diglycidyl ether resin. The properties of the 
moldings obtained correspond to those of Example 1. 
EXAMPLE 11 
Example 1 is repeated, using the same quantity of a mixture of 50 parts by 
weight of a bisphenol A diglycidyl ether resin having an epoxide content 
of 5.1-5.4 equivalents/kg and 50 parts by weight of a distilled bisphenol 
F diglycidyl ether resin having an epoxide content of 6.0-6.4 
equivalents/kg in place of the bisphenol A diglycidyl ether resin. The 
properties of the moldings obtained correspond to those of Example 1. 
EXAMPLE 12 
Example 1 is repeated, using the same quantity of a mixture of 50 parts by 
weight of a bisphenol A diglycidyl ether resin having an epoxide content 
of 5.1-5.4 equivalents/kg and 50 parts by weight of a hydrogenated 
bisphenol A diglycidyl ether resin having an epoxide content of 4.3-4.8 
equivalents/kg in place of the bisphenol A diglycidyl ether resin. The 
properties of the moldings obtained correspond to those of Example 1. 
EXAMPLE 13 
Example 1 is repeated, using a mixture of 55 parts by weight of a bisphenol 
A diglycidyl ether resin having an epoxide content of 5.1-5.4 
equivalents/kg, 30 parts by weight of a distilled bisphenol F diglycidyl 
ether resin having an epoxide content of 6.0-6.4 equivalents/kg and 14 
parts by weight of hexanediol diglycidyl ether in place of the bisphenol A 
diglycidyl ether resin and 10 parts by weight of hexanediol diglycidyl 
ether. The properties of the moldings correspond to those of Example 1. 
EXAMPLE 14 
Example 13 is repeated, 0.1 % by weight of 
.gamma.-glycidyloxypropyl-trimethoxysilane also being added to the curable 
mixture. The properties of the moldings obtained correspond to those of 
Example 1. 
EXAMPLE 15 
Example 13 is repeated, using 14 parts by weight of butanediol glycidyl 
ether in place of the hexanediol glycidyl ether. At the same time, 2 parts 
by weight of the bisphenol A diglycidyl ether resin are replaced by the 
same quantity of cresol glycidyl ether. The viscosity of the reaction 
mixture is 600 mPas. The properties of the moldings obtained correspond to 
those of Example 1. 
EXAMPLE 16 
Example 15 is repeated, replacing 3 parts by weight of the bisphenol A 
diglycidyl ether resin by the same quantity of didecyl phenyl phosphite, 
the gelling time of the curable mixture at room temperature being extended 
from 15 to 75 minutes. At 120.degree. C., the gelling and curing times 
correspond to those of Example 1. The moldings obtained have the same 
properties as those obtained according to Example 1. 
EXAMPLE 17 
Example 16 is repeated, using the same quantity of tris-(p-nonylphenyl) 
phosphite in place of didecyl phenyl phosphite. A 100 g batch of resin and 
curing agent gels at room temperature in 9 minutes. The gelling times at 
100.degree. and 120.degree. C. are 40 and 20 seconds respectively. With 
the curing times given in Example 1, moldings are obtained which have have 
the same properties as the moldings according to Example 1. 
EXAMPLE 18 
Example 16 is repeated, using the same quantity of 
tris-(2,4-di-tert.-butylphenyl) phosphite in place of didecyl phenyl 
phosphite. A 100 g batch of resin and curing agent gels at room 
temperature in 6 minutes. The gelling times at 100.degree. and 120.degree. 
C. are 27 and 17 seconds respectively. When applying the curing conditions 
given in Example 1, moldings are obtained which have the same properties 
as the moldings according to Example 1.