Curing resin composition and its cured product

This invention discloses a curing resin composition comprising (a) an organic resin containing no less than 2 alkenyl groups per molecule, and having a number average molecular weight of 500-100,000. (b) an organohydrogen-polysiloxane containing no less than 2 Si--H bonds per molecule, and (c) a platinum catalyst. It is desired that the organic resin of component (a) is at least one type chosen from acrylic, polyester and epoxy. The preferable amount of component (b) is such that there are 0.8-4 hydrogen atoms bonded to silicon atoms per alkenyl group of component (a).

FIELD OF THE INVENTION 
This invention concerns a curing resin composition, and in particular, a 
curing resin composition with excellent weatherability and physical 
properties. 
BACKGROUND OF THE INVENTION 
In the prior art, curing resin compositions are known comprising a hydroxyl 
group-containing resin such as an acrylic resin or polyester resin, 
blended with a melamine resin or polyfunctional isocyanate compound as a 
curing agent. However, in such melamine curing systems, curing requires a 
high temperature of 150.degree.-230.degree. C. resulting in poor 
workability and economic viability. They also lose lower alcohols with a 
corresponding loss of volume. Further, they suffer from the disadvantage 
of poor weatherability due to the triazine skeleton, and in the case of 
isocyanate curing systems, there was also the problem of toxicity and 
decline of weatherability. 
Methods have been reported to improve weatherability by condensation 
crosslinkage at room temperature of acrylic resins wherein alkoxysilyl 
groups are introduced into the molecule (e.g., Japanese Kokai Koho 
(Unexamined Publication) Nos. 57-36109 and 58-55666), but as their curing 
rate was slow, contamination occurred due to hydrolysis of remaining 
alkoxysilyl groups and they also had poor anti-corrosion properties. Other 
curing systems have been reported which make use of the reactivity of 
alkoxysilyl groups and hydroxyl groups in organic resins (e.g., Japanese 
Kokoku Koho (Examined Publication) No. 63-33512); however, not only their 
thermocuring rate was slow, but also their resistance to salt water was 
poor. 
On the other hand, systems where a vinylpolysiloxane and 
organohydrogenpolysiloxane were cured in the presence of a platinum 
catalyst have been known for many years. 
However, the cured product swells up in solvents and therefore has poor 
solvent resistance. In addition, it has poor alkali resistance and as it 
also has poor recoatability, its use in the paint field has been very 
limited. 
The improvement of recoatability by using alkoxysiloxane-modified 
polyesters containing propyl groups (e.g., Japanese Patent Kokai Koho No. 
62-263265), and crosslinking methods by using polysiloxanes containing 
alkoxysilylalkyl groups (e.g., Japanese Kokai Koho Nos. 57-139123 and 
61-127733), have been proposed. Even using these methods; however, a 
curing composition which is satisfactory from the viewpoints of mechanical 
strength, compatibility with other resins and recoatability, has still not 
been found. 
Further, in recent years, paints which contain organic solvents have been 
cited as factors responsible for atmospheric pollution. 
The inventors carried out intensive studies to resolve these disadvantages 
in the prior art and found that by crosslinking an organic resin 
containing unsaturated groups using the addition reaction of an 
organohydrogenpolysiloxane, the weatherability and physical properties, 
i.e., solvent resistance, alkali resistance, acid resistance, water 
resistance, salt water resistance, anti-corrosion properties and 
contamination resistance, could be improved. In addition, recoatability 
was satisfactory, and when the composition was used as a paint, there was 
not necessarily any need to use organic solvents. 
SUMMARY OF THE INVENTION 
The first object of this invention is therefore to provide a curing resin 
composition with excellent weatherability. 
A second object of this invention is to provide a curing resin composition 
which cures at low temperature, does not undergo any shrinkage after 
curing, and can thus be used as a molding resin. 
A third object of this invention is to provide a curing resin composition 
with excellent humidity resistance, water resistance and salt water 
resistance. 
A fourth object of this invention is to provide a curing resin composition 
with excellent solvent resistance, alkali resistance, acid resistance and 
recoatability. 
A fifth object of this invention is to provide a solvent-free or high solid 
type curing resin composition which does not cause atmospheric pollution 
due to organic solvent. 
The above objects are attained by a composition comprising (a) at least one 
type of resin chosen from the group acrylic, polyester or epoxy, having no 
less than 2 organic groups containing alkenyl groups per molecule, and 
having a number average molecular weight of 500-100,000; (b) an 
organohydrogenpolysiloxane containing no less than 2 Si-H bonds per 
molecule; and (c) a catalytically effective amount of platinum compound. 
The curing reaction in the composition proceeds at low temperature, and 
there is practically no shrinkage after curing. Moreover, as the curing is 
a crosslinking reaction which involves the formation of Si--C bonds, the 
cured product has very good weatherability, water resistance and solvent 
resistance. Consequently, it has good recoatability, and its 
weatherability is further enhanced.

DETAILED DESCRIPTION OF THE INVENTION 
The alkenyl group in the resin used as component (a) of this invention may 
for example be vinyl, allyl, methylvinyl, dimethylvinyl, cyclohexenyl or 
butenyl. 
The acrylic resin containing alkenyl groups is obtained by copolymerization 
of an acrylic monomer containing alkenyl groups such as allyl 
(metha)acrylate or cyclohexenylmethyl methacrylate with another 
polymerizable monomer. 
The acrylic monomer containing alkenyl groups may be obtained for example 
by a reaction involving the elimination of hydrochloric acid from 
methacrylic acid chloride and an alkenylic alcohol, a reaction involving 
the elimination of alcohol from a lower ester of methacrylic acid and an 
alkenylic alcohol, or an addition reaction of an acrylic monomer 
containing isocyanate with an alkenylic alcohol. 
Of other polymerizable monomers, acrylic monomers are particularly to be 
preferred. The acrylic monomer may for example be methyl (metha) acrylate, 
ethyl (metha) n-butyl (metha)acrylate, i-butyl (metha)acrylate, 
t-butyl(metha)acrylate, 2-ethylhexyl(metha)acrylate, 
lauryl(metha)acrylate, phenyl(metha)acrylate, benzyl(metha)acrylate, 
2-hydroxyethyl(metha)acrylate, 2-hydroxypropyl(metha)acrylate, 
4-hydroxybutyl(metha)acrylate, the addition product of 
2-hydroxyethyl(metha)acrylate and .epsilon.-caprolactone (e.g., Placcel 
FM1 (commercial name) manufactured by Daicell Kagaku Kogyo Inc.), glycidyl 
(metha)acrylate, 3-trimethoxysilylpropyl(metha)acrylate, 
3-triethoxysilylpropyl-(metha)acrylate, 
3-triethoxysilylpropyl-(metha)acrylate, 
3-dimethoxymethylsilylpropyl-(metha)acrylate, 
2-acrylamide-2-methylpropanesulfonic acid (metha)acrylate, acid 
phosphoxypropyl (metha)acrylate, tributyltin(metha)acrylate, 
(metha)acrylamide, (metha)acryloyl isocyanate, or 2-isocyanate ethyl 
(metha)acrylate. 
In this invention, in addition to the above, a non-acrylic .alpha., 
.beta.-unsaturated monomer such as styrene, .alpha.-methylstyrene, 
itaconic acid, maleic acid, vinyl acetate, allyl acetate, vinyl 
trimethoxysilane, vinyl triethoxysilane, vinyl methyl-dimethoxysilane or 
vinyl methyl-diethoxysilane, can also be copolymerized. It is however 
preferable that the proportion of said monomer is no more than 50 wt %. 
Other methods of synthesizing the acrylic resin containing alkenyl groups 
are for example, the addition reaction of an acrylic resin containing 
hydroxyl groups with an alkenylic isocyanate compound and/or anhydride of 
a carboxylic acid containing alkenyl groups; addition reaction of an 
acrylic resin containing isocyanate with an alkenylic alcohol; addition 
reaction of an acrylic resin containing carboxyl groups with an epoxy 
compound containing alkenyl groups; and addition reaction of an acrylic 
resin containing epoxy groups with a carboxylic acid containing alkenyl 
groups. 
The acrylic resin containing hydroxyl groups may be obtained by 
copolymerization of an acrylic monomer containing hydroxyl groups such as 
2-hydroxylethyl-(metha)acrylate, 2-hydroxypropyl-(metha)acrylate, 
4-hydroxybutyl-(metha)acrylate, the addition product of 
2-hydroxyethyl-(metha)acrylate and .epsilon.-caprolactone (e.g. the 
Placcel FM series) with another acrylic monomer, or with a non-acrylic 
.alpha., .beta.-unsaturated monomer in a proportion of no more than 50 wt 
%, or by homopolymerization of an acrylic monomer containing hydroxyl 
groups. The alkenylic isocyanate may for example be allyl isocyanate, 
(metha)acryloyl isocyanate, or 2-isocyanate ethyl (metha)acrylate. 
The anhydride of the carboxylic acid containing alkenyl groups may be 
itaconic anhydride, maleic anhydride or tetrahydrophthalic anhydride. 
The acrylic resin containing isocyanate may be obtained by copolymerization 
of an acrylic monomer containing isocyanate such as (metha)acryloyl 
isocyanate or 2-isocyanate ethyl (metha)acrylate with another acrylic 
monomer, or with a non-acrylic .alpha., .beta.-unsaturated monomer in a 
proportion of no more than 50 wt %, or by homopolymerization of an acrylic 
monomer containing isocyanate. 
The alkenylic alcohol may for example be allyl alcohol, vinyl alcohol, 
3-butene-1-ol, 2-(allyloxy)ethanol, glycerine diallyl ether, 
tetrahydrobenzyl alcohol, 3-methyl-2-butene-1-ol, 3-methyl-3-butene-1-ol, 
2-methyl-3-butene-2-ol, oleyl alcohol and crotyl alcohol. 
The acrylic resin containing carboxyl groups may be obtained by 
copolymerization of an acrylic monomer containing carboxyl groups such as 
(metha)acrylic acid and/or an acrylic monomer containing carboxyl groups 
into which an .alpha., .beta.-unsaturated monomer with carboxyl groups 
such as itaconic acid or maleic acid has been incorporated with another 
acrylic monomer and/or a non-acrylic .alpha., .beta.-unsaturated monomer, 
the proportion of .alpha., .beta.-unsaturated monomer in the product being 
no more than 50 wt %, or by homopolymerization of an acrylic monomer 
containing carboxyl groups. 
The epoxy compound containing alkenyl groups may for example be allyl 
glycidyl ether. 
The acrylic resin containing epoxy groups may be obtained for example by 
copolymerization of an acrylic monomer containing epoxy groups such as 
glycidyl (metha)acrylate with another acrylic monomer, or with a 
non-acrylic .alpha., .beta.-unsaturated monomer in a proportion of no more 
than 50 wt %, or by homopolymerization of an acrylic monomer containing 
epoxy groups. 
The carboxylic acid containing alkenyl groups may for example be allyl 
acetate, (metha)acrylic acid, 2-butenonic acid, 3-butenonic acid, crotonic 
acid, 10-undeconoic acid or linoleic acid. 
Further, the polyester resin containing no less than 2 alkenylic organic 
groups per molecule may be easily manufactured by condensation 
polymerization of the above alkenylic alcohols and a polyfunctional 
alcohol with a polybasic acid. 
The polyfunctional alcohol may for example be ethylene glycol, propylene 
glycol, 1,6-hexane diol, diethylene glycol, neopentyl glycol, 
hydroxypivalic acid neopentyl glycol ester, trimethylolpropane or a 
dimethylsiloxane containing alcoholic hydroxyl groups at both ends. The 
polybasic acid may for example be phthalic anhydride, isophthalic acid, 
terephthalic acid, adipic acid, azelaic acid or trimellitic acid. Further, 
some monofunctional alcohol or monobasic acid may also be used if 
necessary. Other methods of synthesizing polyester resins containing 
alkenyl groups are for example, an addition reaction of the carboxyl 
groups of the polyester resin obtained by condensation polymerization of 
said polyfunctional alcohols and polybasic acids, with said epoxy 
compounds containing alkenyl groups, and an addition reaction of the 
hydroxyl groups of the polyester resin obtained by condensation 
polymerization of polyfunctional alcohols and polybasic acids with said 
alkenylic isocyanates and/or the anhydrides of carboxylic acids containing 
alkenyl groups. 
The epoxy resin containing no less than 2 alkenylic organic groups per 
molecule may, with the exception of said acrylic resins containing epoxy 
groups, be easily manufactured for example by the addition reaction of 
bisphenyl A diglycidyl ether and said carboxylic acids containing alkenyl 
groups, or by the addition reaction of the hydroxyl groups of an epoxy 
resin, prepared by the condensation polymerization reaction of 
epichlorohydrin and bisphenol A, and said alkenylic isocyanates and/or 
anhydrides of carboxylic acids containing alkenyl groups. 
The molecular weight of these acrylic resins, polyester resins or epoxy 
resins is preferably 500-100,000, but more preferably 2,000-50,000. 
If the organic resin containing alkenyl groups has a molecular weight of 
less than 500, it has poor film-forming properties and the film is weak; 
conversely, if its molecular weight is greater than 100,000, the resin is 
highly viscous, has poor workability and is unsuitable as a high solid 
type resin composition--that is, a proportion of non-volatiles is high. 
Component (b) of this invention is an organohydrogenpolysiloxane containing 
no less than 2 Si--H bonds per molecule. It crosslinks the alkenyl groups 
of component (a) by hydrosilylation. 
The organohydrogenpolysiloxane of component (b) may be represented by the 
following general formulae (1)-(3): 
##STR1## 
Where R.sup.1 and R.sup.2 are pheny or alkyl groups with 1-6 carbon atoms, 
a is an integer in the range 0.ltoreq.a.ltoreq.100, and b is an integer in 
the range 2.ltoreq.b&lt;.ltoreq.100. 
##STR2## 
Where R.sup.2 and R.sup.3 are phenyl or alkyl groups with 1-6 carbon atoms, 
c is an integer in the range 0.ltoreq.c.ltoreq.8, d is an integer in the 
range 2.ltoreq.d.ltoreq.10, and 3.ltoreq.c+d.ltoreq.10. 
##STR3## 
Where R.sup.1 and R.sup.2 are phenyl or alkyl groups with 1-6 carbon atoms, 
e is an integer in the range 2.ltoreq.e.ltoreq.100, an f is an integer in 
the range 0.ltoreq.f.ltoreq.100. 
The alkyl groups with 1-6 carbon atoms, R.sup.1, R.sup.2 and R.sup.3, may 
be methyl, ethyl, propyl or butyl, but from an industrial viewpoint, 
methyl and propyl are to be preferred. Further, the degree of 
polymerization is specified by a-f. For siloxanes with a higher degree of 
polymerization than those given by the above ranges, viscosity increases, 
workability is poor and compatibility with component (a) declines. From 
the viewpoint of improving compatibility, compounds which include phenyl 
as the organic group are to be preferred. 
Examples of component (b) which are particularly to be preferred are, 
therefore, methylphenyl hydrogenpolysiloxane and 
methylpropylhydrogenpolysiloxane. 
We give below some specific examples of component (b), but this invention 
is by no means limited to these examples. 
##STR4## 
The amount of component (b) added is preferably such that there are 0.8-4, 
but more preferably 1.0-1.5, hydrogen atoms bonded to silicon per alkenyl 
group of component (a). Hence, by adjusting the amount of component (b) 
which is added, a cured product with excellent weatherability, luster and 
pliability can be obtained. If the number of hydrogen atoms is less than 
0.8 or more than 4, the resin or coating film deteriorates due to reaction 
of residual alkenyl groups or hydrogen atoms with moisture or 
contaminants, or due to the action of ultraviolet light. 
Component (c) of this invention is a catalyst intended to cure components 
(a) and (b). For this purpose, platinum with valency 0 or 4 may be used, 
but from an industrial viewpoint chloroplatinic acid is to be preferred. 
The curing reaction then proceeds at low temperature such as 
80.degree.-180.degree. C., and there is practically no shrinkage after 
curing. 
The amount of platinum atoms is preferably 5-1,000 ppm, but more preferably 
10-500 ppm, with respect to 100 parts by weight of a mixture of components 
(a) and (b). If it is less than 5 ppm curing properties are poor, while if 
it is greater than 1,000 ppm the composition tends to cure before 
application or molding which is undesirable. 
In this invention, in order to control reactivity, a substance which slows 
curing by coordinating with the platinum catalyst, for example, an 
acetylenic compound, may also be added in a suitable proportion. This 
retarding agent should preferably be such that it volatilizes outside the 
system when vaporized, or such that it is present in a closed system and 
evaporates when the system is opened so as to activate the platinum 
catalyst. Examples of such retarding agents are ethynyl alcohol, 
3-ol-propine, 3-ol-3, 3-dimethylpropine, 3-trimethylsiloxypropine, and 
3-trimethylsiloxy-3, 3-dimethylpropine. 
The mixture of components (a), (b) and (c) is cured either without a 
solvent or after dissolving in an organic solvent at room temperature or 
by heating. The preferable curing temperature is 80.degree.-180.degree. C. 
The crosslinkages formed by the curing reaction are Si--C bonds, unlike 
the case of the curing reaction which takes place by condensation of 
silanols and alcohols or alkoxy groups. The cured product therefore has 
excellent moisture resistance, water resistance and salt water resistance. 
Further, as the product is cured by crosslinking, it has quite good 
solvent resistance, alkali resistance and recoatability. 
Further, pigments and additives may be added to the resin composition of 
this invention if desired, but the addition of substances or compounds 
which interfere with the hydrosilylation reaction, for example substances 
containing elements such as nitrogen, phosphorus and arsenic, is 
undesirable. 
By applying to metals such as ion and alumina, inorganic materials such as 
slate, concrete and tile or resins such as epoxy resin, acrylic resin, 
urethane resin and silicone resin and curing the composition of this 
invention, a paint film with high durability, weatherability and water 
resistance is obtained. Further, by molding and curing the composition, a 
cured product with excellent mechanical properties and pliability is 
obtained. The composition may therefore be used as for example an external 
finish for paints, protective coating, electrical insulation material, 
anti-soiling topcoat and molding resin. Further, by using the composition 
of this invention, a high solid paint of low viscosity can also be 
obtained. 
EXAMPLES 
We shall now describe this invention in more detail by means of specific 
examples, but it should be understood that the invention is in no way 
limited to them. All proportions are parts by weight. 
MANUFACTURING EXAMPLE 1 
70 parts of xylene and 20 parts of butanol were introduced into a reaction 
vessel. After raising the temperature to 110.degree. C. while introducing 
nitrogen gas, a mixed solution comprising 10 parts styrene, 10.7 parts 
methacrylic acid, 16.7 parts 2-ethylhexyl methacrylate, 40.l parts 
methylmethacrylate, 22.5 parts ethyl acrylate and 1. 2 parts t-butylperoxy 
2-ethylhexanoate was dripped in over 3 hours. After the addition was 
complete, the mixture was aged at 105.degree. C. for 1 hour, 10 parts 
xylene and 0.2 parts t-butylperoxy 2-ethylhexanoate were dripped in over 
30 minutes, and the mixture aged at 105.degree. C. for a further 2 hours. 
The reaction temperature was then raised to 120.degree. C., then 13 parts 
of allyl glycidyl ether and 0.2 parts of dimethylbenzylamine were each 
dripped in over 30 minutes. 
The yield of the addition reaction of carboxy groups to glycidyl groups was 
measured by means of acid titratione. After 2 hours, an acrylic resin 
solution [A] was obtained with a yield of 86%. Non-volatiles in the 
solution [A] accounted for 52.8 wt %. 
MANUFACTURING EXAMPLE 2 
80 parts of xylene were introduced into a reaction vessel while introducing 
nitrogen gas, and a mixed solution comprising 13.9 parts methacroyl 
isocyanate, 28.4 parts 2-ethylhexyl methacrylate, 34.6 parts methacrylate, 
23.2 parts ethyl acrylate and 1.2 parts t-butylperoxy 2-ethylhexanoate 
were dripped in over 3 hours. After the addition was complete, the mixture 
was aged at 105.degree. C. for 1 hour, 20 parts xylene and 0.5 parts 
t-butylperoxy 2-ethylhexanoate were dripped in over 30 minutes, and ageing 
carried out at 105.degree. C. for a further 2 hours. 20 parts butyl 
acetate were then added and after cooling to 50.degree. C. 7.2 parts of 
allyl alcohol were dripped in over 30 minutes. 
30 minutes after this addition was completed, the yield of the reaction 
between isocyanate and alcohol was measured by IR. It was found that the 
isocyanate absorption at 2,230 cm-1 had completely disappeared. The 
solution obtained will be referred to as acrylic resin solution [B]. 
Non-volatiles in the solution [B] accounted for 47.5 wt %. 
MANUFACTURING EXAMPLE 3 
53.4 parts isophthalic acid, 26.7 parts neopentyl glycol, 17.8 parts 
hydroxypivalic acid neopentyl glycol ester, 1.6 parts trimethylol propane 
and 0.05 parts dibutyltin oxide were introduced into a reaction vessel 
equipped with a dropping funnel. After raising the temperature to 
150.degree. C. the temperature was raised to 210.degree. C. over 10 hours, 
and a dehydration condensation reaction was carried out until the acidity 
was 5.0. The reaction temperature was then reduced to 120.degree. C., 17.1 
parts anhydrous trimellitic acid were introduced gradually, and the 
mixture aged for 1 hour. 10.2 parts allyl glycidyl ether, 31 parts xylol 
and 0.2 parts dimethylbenzylamine were then introduced to carry out the 
reaction. The reaction was terminated after 2 hours when the acidity of 
the solid fraction was 5.0. 54 parts xylol were introduced into the 
reaction product to give a polyester resin solution [A]. Non-volatiles in 
the solution [A] accounted for 58.3 wt %. 
MANUFACTURING EXAMPLE 4 
35.5 parts bisphenol A diglycidyl ether was introduced into a reaction 
vessel, and the temperature was raised to 120.degree. C. 17.2 parts 
butenonic acid and 0.1 parts dimethylbenzylamine were dripped in over 1 
hour, and after ageing for 2 hours, 30 parts of xylol and 5 parts 
methylisobutyl ketone were added to give an epoxy resin solution [A]. 
Non-volatiles in the solution [A] accounted for 60.1 wt %. 
MANUFACTURING EXAMPLE 5 
40 parts xylene and 20 parts butanol were introduced into a reaction 
vessel, and the temperature was raised to 110.degree. C. while introducing 
nitrogen gas. A mixed solution comprising 15 parts styrene, 3.1 parts 
methacrylic acid, 34.1 parts 2-ethylhexyl methacrylate, 31.6 parts methyl 
methacrylate, 16.2 parts 2-hydroxyethyl methacrylate and 1.2 parts 
t-butylperoxy 2-ethylhexanoate was then dripped in over 3 hours. After the 
addition was complete, the mixture was aged at 105.degree. C. for 1 hour, 
6.7 parts xylene and 0.2 parts t-butylperoxy 2-ethylhexanoate were dripped 
in over 30 minutes, and the mixture was aged at 105.degree. C. for 2 hours 
to give an acrylic resin solution [C]. Non-volatiles in the solution [C] 
accounted for 59.7 wt %. 
MANUFACTURING EXAMPLE 6 
53.4 parts isophthalic acid, 26.7 parts neopentyl glycol, 17.8 parts 
hydroxypivalic acid neopentyl glycol ester, 1.6 parts trimethylol propane 
and 0.05 parts dibutyltin oxide were introduced into a reaction vessel 
equipped with a dropping funnel. After raising the temperature to 
150.degree. C., the temperature was raised to 210.degree. C. over 10 
hours, and a dehydration condensation reaction was carried out until the 
acidity was 5.0 55 parts xylol were introduced into the reaction product 
to give a polyester resin solution [B]. Non-volatiles in the solution [B] 
accounted for 64.4 wt %. 
MANUFACTURING EXAMPLE 7 
60 parts xylene were introduced into a reaction vessel, and the temperature 
was raised to 110.degree. C. while introducing nitrogen gas. A mixed 
solution comprising 30 parts styrene, 30 parts 2-ethylhexyl methacrylate, 
40 parts cyclohexenylmethyl methacrylate, and 2.0 parts 
azobis-isobutyronitrile was then dripped in over 3 hours. After the 
addition was complete, the mixture was aged at 110.degree. C. for 1 hour, 
6.7 parts xylene and 0.2 parts t-butylperoxy 2-ethylhexanoate were dripped 
in over 30 minutes, and the mixture was aged at 110.degree. C. for a 
further 2 hours to give an acrylic resin solution [D]. Non-volatiles in 
the solution [D] accounted for 58.9 wt %. 
MANUFACTURING EXAMPLE 8 
61.8 parts terephthalic acid, 29.5 parts hydroxypivalic acid neopentyl 
glycol ester, 9.6 parts trimethylol propane and 0.05 parts dibutyltin 
oxide were introduced into a reaction vessel equipped with a dropping 
funnel. After raising the temperature to 150.degree. C., the temperature 
was raised to 210.degree. C. over 6 hours, and 20 ml of the mixture was 
distilled off. After cooling to 140.degree. C., 18.3 g of glycerine 
diallyl ether were introduced, the temperature was raised to 220.degree. 
C. over 5 hours, and having confirmed that 3.4 g of methanol had distilled 
off, the reaction was terminated. 67 parts xylol was then introduced into 
the reaction product to give a polyester resin solution [C]. Non-volatiles 
in the solution [C] accounted for 58.8 wt %. 
MANUFACTURING EXAMPLE 9 
60 parts xylene were introduced into a reaction vessel, and the temperature 
was raised to 110.degree. C. while introducing nitrogen gas. A mixed 
solution comprising 30 parts styrene, 20 parts 2-ethylhexyl methacrylate, 
50 parts cyclohexenylmethyl methacrylate, and 2.0 parts 
azobis-isobutyronitrile was then dripped in over 3 hours. After the 
addition was complete, the mixture was aged at 110.degree. C. for 1 hours, 
6.7 parts xylene and 0.2 parts t-butylperoxy 2-ethylhexanoate were dripped 
in over 30 minutes, and the mixture was aged at 110.degree. C. for a 
further 2 hours to give an acrylic resin solution [E]. Non-volatiles in 
the solution [E] accounted for 60.3 wt %. 
EXAMPLE 1 
80 parts of the acrylic resin solution [A], 20 parts of the compound: 
##STR5## 
and 0.1 parts of a 2% ethanolic solution of chloroplatinic acid were mixed 
well together, applied to an iron plate so as to form a dry film of 
thickness 20 .mu.m, and baked at 180.degree. C. for 20 minutes. The 
physical properties of the cured film are shown in Table 1. 
The values of physical properties were measured as follows. 
Pencil hardness: 
Measured according to JIS (Japan Industrial Standard) K 5400, paragraph 
6-14. 
Xylol rubbing test: 
The film was rubbed 50 times back and forth with a 1 cm.times.1 cm piece of 
cotton wool impregnated with xylene, and its external appearance was 
judged visually. 
Mandrel test: 
Measured according to JIS K 5400, paragraph 6-16. 
The external appearance of the film was judged visually using a 2 mm 
mandrel. 
Impact resistance test: 
Measured according to JIS K 5400, paragraph 6-13. 
A 300 g weight was dropped from a height of 50 cm, and the external 
appearance of the film was judged visually. 
Initial luster: 
Titanium oxide (commercial name:TIPAQUE R-820, Ishihara Industries K.K.), 
was added to each resin in the proportion of 40 parts based on 100 parts 
by weight of solid resin and dispersed by a Ball Mill. The resulting white 
paint was cured, and the 60 degree mirror surface luster (prior to 
weatherability test) was measured. The curing of the paint film of each 
Example and Comparative Example was carried out in the same way. 
Weatherability: 
Weatherability was measured by visually judging the retention of 60 degree 
mirror surface luster and external appearance after exposure to 2,000 hrs 
of sunshine weather meter. 
Acid resistance: 
0.2 cc of a 0.1N (normal) sulfuric acid solution was applied to each of the 
cured clear paint films. After leaving at 20.degree. C. and 75% humidity 
for one day and night, the films were dried at 60.degree. C. for 10 
minutes, and their deterioration was visually judged. 
.circleincircle.: excellent resistance 
.largecircle.: good resistance 
.DELTA.: some marks on film 
x: clouding of film 
Viscosity test: 
Each resin system was adjusted with xylol such that non-volatiles accounted 
for 55 wt %, and its viscosity was measured at 25.degree. C. by an E type 
viscometer. 
EXAMPLE 2 
80 parts of the acrylic resin solution [A], 20 parts of 
1,3,5,7-tetramethyl-1-propylcyclotetrasiloxane and 0.1 parts of a 2% 
ethanolic solution of chloroplatinic acid were mixed well together, 
applied to an iron plate so as to form a dry film of thickness 20 .mu.m, 
and baked at 180.degree. C. for 20 minutes. The physical properties of the 
cured film are shown in Table 1. 
EXAMPLE 3 
60 parts of the acrylic resin solution [B], 20 parts of the compound: 
##STR6## 
and 0.1 parts of a 2% ethanolic solution of chloroplatinic acid were mixed 
well together, applied to an iron plate so as to form a dry film of 
thickness 20 .mu.m, and baked at 180.degree. C. for 20 minutes. The 
physical properties of the cured film are shown in Table 1. 
EXAMPLE 4 
60 parts of the polyester resin solution [A], 20 parts of the compound: 
##STR7## 
and 0.1 parts of a 2% ethanolic solution of chloroplatinic acid were mixed 
well together, applied to an iron plate so as to form a dry film of 
thickness 20 .mu.m, and baked at 180.degree. C. for 20 minutes. The 
physical properties of the cured film are shown in Table 1. 
EXAMPLE 5 
80 parts of the epoxy resin solution [A], 20 parts of the compound: 
##STR8## 
and 0.1 parts of a 2% ethanolic solution of chloroplatinic acid were mixed 
well together, applied to an iron plate so as to form a dry film of 
thickness 20 .mu.m, and baked at 180.degree. C. for 20 minutes. The 
physical properties of the cured film are shown in Table 1. 
EXAMPLE 6 
100 parts of the acrylic resin solution [D], 30 parts of the compound: 
##STR9## 
and 0.1 parts of a 2% ethanolic solution of chloroplatinic acid were mixed 
well together, applied to an iron plate so as to form a dry film of 
thickness 20 .mu.m, and baked at 140.degree. C. for 25 minutes. The 
physical properties of the cured film are shown in Table 1. 
EXAMPLE 7 
100 parts of the polyester resin solution [C], 30 parts of the compound: 
##STR10## 
and 0.1 parts of a 2% ethanolic solution of chloroplatinic acid were mixed 
well together, applied to an iron plate so as to form a dry film of 
thickness 20 .mu.m, and baked at 180.degree. C. for 20 minutes. The 
physical properties of the cured film are shown in Table 1. 
EXAMPLE 8 
100 parts of the acrylic resin solution [E], 30 parts of the compound: 
##STR11## 
and 0.1 parts of a 2% ethanolic solution of chloroplatinic acid were mixed 
well together, applied to an iron plate so as to form a dry film of 
thickness 20 .mu.m, and baked at 140.degree. C. for 25 minutes. The 
physical properties of the cured film are shown in Table 1. 
COMATIVE EXAMPLE 1 
100 parts of acrylic resin (C) and 43 parts of SUPER BECKAMINE L-127 (a 
trade name of melamine resin manufactured by Dai Nippon Ink and Chemical 
Co.) were mixed well together, and cured as in Example 1. The measured 
physical properties are shown in Table 1. 
COMATIVE EXAMPLE 2 
100 parts of acrylic resin (C), 25 parts of BURNOCK D-950 (a trade name of 
polyisocyanate manufactured by Dai Nippon Ink and Chemical Co.) and 0.1 
parts of dibutyltin dilaurylate were mixed well together, applied to an 
iron plate, and cured at 25.degree. C. for 1 hour. The physical properties 
of the film are shown in Table 1. 
COMATIVE EXAMPLE 3 
100 parts of polyester resin [B] and 43 parts of SUPER BECKAMINE L-127 (a 
trade name of melamine resin manufactured by Dai Nippon Ink and Chemical 
Co.) were mixed well together, and cured as in Example 1. The measured 
physical properties are shown in Table 1. 
From the results in Table 1, it was confirmed that the curing resin 
composition of this invention is able to form a cured film which is 
particularly remarkable for its excellent luster and weatherability. 
TABLE 1 
__________________________________________________________________________ 
Example 1 
Example 2 
Example 3 
Example 4 
Example 5 
Example 6 
__________________________________________________________________________ 
Pencil hardness 
H H H H 2H H 
Xylol rubbing test 
no change 
no change 
no change 
no change 
no change 
no change 
Mandrel test no change 
no change 
no change 
no change 
no change 
no change 
Impact resistance test 
no change 
no change 
no change 
no change 
no change 
no change 
Initial lustre 
92 87 85 90 90 90 
Acid resistance 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
Viscosity (centi poise) 
350 480 310 280 240 95 
Weatherability 
90 85 88 80 72 90 
Lustre preservability (%) 
Film appearance 
no change 
no change 
no change 
no change 
no change 
no change 
__________________________________________________________________________ 
comparative 
comparative 
comparative 
Example 7 
Example 8 
example 1 
example 2 
example 3 
__________________________________________________________________________ 
Pencil hardness H 2H 2H H H 
Xylol rubbing test 
no change 
no change 
no change 
no change 
no change 
Mandrel test no change 
no change 
no change 
clack clack 
Impact resistance test 
no change 
no change 
no change 
no change 
clack 
Initial lustre 85 91 85 82 85 
Acid resistance .circleincircle. 
.circleincircle. 
X .DELTA. 
X 
Viscosity (centi poise) 
180 112 750 640 680 
Weatherability 82 92 48 60 40 
Lustre preservability (%) 
Film appearance no change 
no change 
partially 
partially 
partially 
chalking 
chalking 
chalking 
__________________________________________________________________________