A one-pack type of curable composition comprising a blend consisting essentially of a silyl group containing resin having a backbone substantially comprising a vinyl type polymer chain and containing at least one silicon atom attached to a hydrolyzable group at a terminal or in a side chain of its molecule, a curing catalyst, and a solvent. This composition has excellent storage stability, excellent workability, excellent weather resistance, and excellent weather resistance after coating and curing, and high hardness of the coated surface after curing.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to compositions which are curable by exposure to 
ambient moisture, and more particularly to such compositions which 
comprise a blend of a silyl group containing resin and a curing catalyst. 
2. Description of the Prior Art 
There are known in the prior art various silicon compounds containing a 
silicon atom attached to a hydrolyzable group. These compounds have good 
adhesion to inorganic substances because of the action of their 
hydrolyzable silyl group. Also, there is cross linking at ambient 
temperatures upon exposure to moisture, especially atmospheric moisture to 
form cured products having excellent durability. These compounds are thus 
extensively employed as paints, coating agents, adhesives, sealants, 
silane coupling agents, and the like. 
However, when these silicon compounds containing a silicon atom attached to 
a hydrolyzable group are used without a curing catalyst, they are slow in 
curing speed at room temperature, or at a relatively moderately elevated 
temperature. Thus, when a coating of such compound is required to be cured 
at a high rate, a high degree of heating at a high temperature is 
required. Accordingly, in such an instance, an enormous amount of energy 
is needed. 
To cure this deficiency, it has been suggested to use a curing catalyst 
incorporated into the curable composition, immediately prior to use, to 
thereby enhance the curing speed of the coating at a relatively low 
temperature. However, disadvantageously, once a curing catalyst is added 
to such a composition, it cannot be stored for any length of time because 
the composition will cure in a short length of time. Thus, when a part of 
the composition, such as for example a paint composed of such composition, 
has been used, the unused remainder is essentially wasted. Such curable 
compositions are generally called a two-pack type of curable composition. 
On the other hand, a curable composition may include therein a curable 
catalyst, in which case, no other composition or catalyst need be added 
immediately prior to use. This type of curable composition is called a 
one-pack type of curable composition. One known as a one-pack type of 
composition comprises a blend of a curing catalyst and a silicon compound 
having a backbone of hydrolyzable silyl group and having siloxane bonds. 
This prior one-pack type of composition has been found to have some 
deficiencies, such as non-optimal hardness after during, insufficiently 
good storage stability, only average workability and weather resistance. 
Accordingly, there is still a need in the prior art for a one-pack type of 
curable composition which has excellent storage stability, high hardness 
of the cured surface, excellent workability and weather resistance. 
SUMMARY OF THE INVENTION 
Accordingly, an object of the invention is to overcome the aforementioned 
and other deficiencies and disadvantages of the prior art. 
Another object is to provide a one-pack type of curable composition which 
is curable at high speeds without application of large amounts of heat at 
high temperatures, and has excellent storage stability, and when cured has 
excellent hardness of the surface so obtained, and further has excellent 
workability and weather resistance. 
The foregoing and other objects and features of the invention are attained 
in this invention which encompasses a mixture or homogeneous blend 
consisting essentially of (A) a silyl group containing resin having a 
backbone substantially comprising a vinyl type polymer chain and 
containing a silicon atom attached to a hydrolyzable group in a side chain 
or at the terminal of its molecule, (B) a curing catalyst, and (C) a 
solvent. Advantageously, the inventive composition has excellent 
workability during its application, excellent weather resistance, and 
excellent weather resistance after coating and curing, and excellent 
hardness of the resulting coating, obtained after curing by exposure to 
the ambient moisture. 
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
The resin used in this invention has a backbone which substantially 
comprises a vinyl type polymer chain and contains at least one, and 
preferably 2 or more, silyl groups attached to hydrolyzable groups at the 
terminals or in side chains in its molecules. Most of the silyl groups 
used herein are represented the formula: 
##STR1## 
wherein X is a hydrolyzable group, R.sub.1 and R.sub.2 are each hydrogen 
or any alkyl group, aryl group or aralkyl group having 1 to 10 carbon 
atoms, and n is an integer of 1,2 or 3. 
Examples of the hydrolyzable group include halogen, alkoxy, acyloxy, 
ketoxymate, amino, acid amido, aminoxy, mercapto, alkenyloxy groups, and 
the like. 
Production of the silyl group containing vinyl type resin according to the 
invention, may be effected in various ways. For example, one process, 
herein called process (i), involves hydrosilylation reaction using a vinyl 
type resin having a carbon-carbon double bond and a hydrosilane. Another 
process (called process (ii)) involves a copolymerization of a vinyl type 
compound and a silyl compound having a polymerizable double bond. These 
processes are advantageous from an industrial standpoint, and will be 
described in further detail below: 
Process (i) 
The silyl group containing vinyl type resin of this invention may be easily 
produced by reaction of a hydrosilane compound with a vinyl type resin 
having a carbon-carbon double bond, in the presence of a catalyst of a 
Group VIII transition metal. The hydrosilane compound used in this 
invention has the following general formula: 
##STR2## 
wherein R.sub.1 is hydrogen, or a monovalent hydrocarbon group selected 
from the group consisting of an alkyl group, an aryl group and an aralkyl 
group having 1 to 10 carbon atoms; X is a hydrolyzable group and n is an 
integer of 1, 2, or 3. 
Specific examples of hydrosilane compounds within this general formula 
include halogenated silanes, such as, methyldichlorosilane, 
trichlorosilane, phenyldichlorosilane, etc; alkoxysilanes, such as, 
methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, 
trimethoxysilane, triethyoxysilane, etc; acyloxysilanes, such as, 
methyldiacetoxysilane, phenyldiacetoxysilane, triacetoxysilane, etc; and 
other various silanes, such as methyldiaminoxysilane, triaminoxysilane, 
methyldiaminosilane, triaminosilane, bis(dimethylketoxymate)methylsilane, 
bis(cyclohexylketoxymate)methylsilane, methyldiisopropenoxysilane, 
triisopropenoxysilane, etc. 
The amount of hydrosilane compound used, can be any suitable amount, but, 
is preferably from 0.5 to 2 moles per carbon-carbon double bond, contained 
in the vinyl type resin. Although use of hydrosilane compound in an amount 
above this range is not excluded, no substantial benefit is obtained 
thereby. The added amount will usually remain unreacted and may be 
recovered for reuse. 
Furthermore, a highly reactive halogenated silane, which is an inexpensive 
basic starting material, may easily be employed as the hydrosilane 
compound used in this invention. The silyl group containing vinyl type 
resin, obtained by using a halogenated silane, when exposed to moisture in 
the ambient atmosphere, rapidly cures at the ambient temperature, and, 
disadvantageously, emits hydrogen chloride. This results in such problems 
as generation of pungent odor, due to the hydrogen chloride, and corrosion 
of substances in contact with the resin or adjacent to the resin. Hence, 
this resin can only be employed in a limited number of practical 
applications. Thus, it is desirable to subsequently further convert the 
halogen function group to other hydrolyzable functional groups. For 
example, it may be converted to alkoxy, acryloxy, aminoxy, amido, acid 
amido, ketoxymate, mercapto and the like groups. One method of such 
conversion is disclosed, for example, in Japanese Laid-Open Patent 
Application No. 91546/1979. 
The vinyl type resin used in process (i), in this invention is not 
particularly limited, except that the vinyl type resin containing hydroxyl 
groups are excluded. A resin comprising, as the main component, a 
homopolymer or a copolymer selected from the following is suitable: 
acrylic acid or methacrylic acid esters, such as, methyl acrylate, methyl 
methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl 
methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, etc; 
carboxylic acids, such as, acrylic acid, methacrylic acid, itaconic acid 
fumaric acid, etc; acid anhydrides, such as, maleic anhydride, etc; epoxy 
compounds, such as, glycidyl acrylate, glycidyl methacrylate, etc; amino 
compounds, such as, diethylaminoethyl acrylate, diethylaminoethyl 
methacrylate, aminoethyl vinyl ether, etc; amide compounds, such as, 
acrylamide, methacrylamide, itaconic acid diamide, alpha ethylacrylamide, 
crotonamide, fumaric acid diamide, maleic acid diamide, 
N-butoxymethylacrylamide, N-butoxymethylmethacrylamide, etc; 
acrylonitrile; iminol methacrylate; styrene; alpha methylstyrene; vinyl 
chloride; vinyl acetate; vinyl propionate; etc. On producing a homopolymer 
or copolymer of these vinyl compounds, allyl acrylate, allyl methacrylate, 
diallyl phthalate or the like, may be partially radical copolymerized 
therewith to incorporate a carbon-carbon double bond into the vinyl type 
resin at the molecular terminal or in a side chain of the molecule, for 
the hydrosilyation reaction. The amount of monomer necessary for this can 
be determined depending on the number of silyl groups in the desired 
resin. Furthermore, the molecular weight may be modified by adding a chain 
transfer agent, such as n-dodecylmercaptan, t-dodecylmercaptan, etc. 
Polymerization of these vinyl compounds may be conducted either using or 
not using a solvent. If a solvent is used, a non-reactive solvent is 
preferred, such as an ether, hydrocarbon, acetic acid ester, etc. 
In this invention, a catalyst of a transition metal complex is used in the 
stage of reacting the hydrosilane compound with the carbon-carbon double 
bond. Effectively employed as the transition metal complex catalyst, is a 
complex of a Group VIII transition metal selected from platinum, rhodium, 
cobalt, palladium and nickel. This hydrosilyation reaction may be effected 
at any temperature of from 50.degree. C. to 150.degree. C., and the 
reaction time may be about from 1 to 10 hours. 
Process (ii) 
The other process used in the invention, comprises radical polymerization 
of various vinyl type compounds with silane compound of the formula: 
##STR3## 
wherein R.sub.1 is a monovalent hydrocarbon group selected from an alkyl 
group, an aryl group and an aralkyl group having 1 to 10 carbon atoms, 
R.sub.3 is an organic residue containing a polymerizable double bond, X is 
a hydrolyzable group, and n is an integer 1, 2 or 3. 
Examples of the silane compounds used in this invention include: 
##STR4## 
These silane compounds may be synthesized in various manners. For example, 
they may be produced by reacting acetylene, allyl acrylate, allyl 
methacrylate or diallyl phthalate with methyldimethoxysilane, 
methyldichlorosilane, trimethoxysilane or trichlorosilane, in the presence 
of a catalyst of a Group VIII transition metal. 
While the compounds used for the synthesis of the vinyl type resin in the 
above process (i) may be used as a vinyl type compound used in process 
(ii), there may also be employed vinyl type compounds containing a 
hydroxyl group, such as, 2-hydroxyethyl acrylate, 2-hydroxyethyl 
methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 
2-hydroxyvinyl ether, N-methylol acrylamide, ARONIX 5700 (produced by Toa 
Gosei Chemical Company, Inc.), and the like. 
The synthesis of a copolymer of such vinyl type compounds and silane 
compounds may be carried out by a conventional solution polymerization 
method. The vinyl type compound, the silane compound, a radicalinitiator, 
and a chain transfer agent, such as n-dodecylmercaptan, 
t-dodecylmercaptan, and the like, selected according to the molecular 
weight desired in the produced silyl group containing resin, are added and 
reacted at a temperature of from 50.degree. C. to 150.degree. C. A solvent 
may be optionally used. If a solvent is used, a non-reactive solvent is 
referred, such as for example, an ether, a hydrocarbon, an acetic acid 
ester, and the like. 
The silyl group containing vinyl type resin, thus obtained, may be 
subjected to, for example, a method for displacing the hydrolyzable group, 
such as disclosed in Japanese Laid-Open Patent Application No. 91546/1979. 
Thus, there is obtained a silyl group containing vinyl type resin in which 
the backbone substantially comprises a vinyl type polymer chain and 
contains at least one silicon atom attached to a hydrolyzable group at a 
terminal or in a side chain of its molecule. 
Although the molecular weight of the silyl group containing vinyl type 
resin used in this invention is not particularly restricted, it is 
preferred that the molecular weight be in the range of from 1,000 to 
30,000, in view of stability and physical properties desired of the cured 
product. Furthermore, it is possible to improve the adhesion of the silyl 
group containing vinyl type resin by incorporating the above discussed 
ethylenically unsaturated organic monomer or monomers, containing active 
hydrogen such as a carboxyl group, a hydroxyl group, an amino group, an 
amido group, and the like, as a copolymerization component. 
The curing catalyst used in this invention may be selected from compounds 
generally used as curing catalyst for hydrolyzable silyl group containing 
resins. For example, one or more of the following may be employed: alkyl 
titanic acid salts; acidic compounds, such as, phosphoric acid, 
p-toluenesulfonic acid, phtalic acid, and the like; amine compounds, such 
as, aliphatic diamines such as ethylenediamine, hexanediamine, etc; 
aliphatic polyamines, such as, diethylenetriamine, triethylenetetramine, 
tetraethylenepentamine, etc; alicyclic amines, such as, piperidine, 
piperazine, etc; aromatic amines, such as, metaphenylenediamine, etc; 
ethanolamines; triethylamine; and various modified amines, such as used as 
curing agents for epoxy resins; organic tin compounds, such as, carboxylic 
acid organic tin compounds, such as 
EQU (n--C.sub.4 H.sub.9).sub.2 Sn(OCOC.sub.11 H.sub.23 --n).sub.2 
EQU (n--C.sub.4 H.sub.9).sub.2 Sn(OCOCH.dbd.CHCOOCH.sub.3).sub.2 
EQU (n--C.sub.4 H.sub.9).sub.2 Sn(OCOCH.dbd.CHCOOC.sub.4 H.sub.9 --n).sub.2 
EQU (n--C.sub.8 H.sub.17).sub.2 Sn(OCOC.sub.11 H.sub.23 --n).sub.2 
EQU (n--C.sub.8 H.sub.17).sub.2 Sn(OCOCH.dbd.CHCOOCH.sub.3).sub.2 
EQU (n--C.sub.8 H.sub.17).sub.2 Sn(OCOCH.dbd.CHCOOC.sub.4 H--n).sub.2 
EQU (n--C.sub.8 H.sub.17).sub.2 Sn(OCOCH.dbd.CHCOOC.sub.8 H.sub.17 --iso).sub.2 
EQU Sn(OCOC.sub.8 H.sub.17 --n).sub.2, etc; 
mercaptide type organic tin compounds, such as, 
EQU (n--C.sub.4 H.sub.9).sub.2 Sn(SCH.sub.2 COO) 
EQU (n--C.sub.4 H.sub.9).sub.2 Sn(SCH.sub.2 COOC.sub.8 H.sub.17 --iso).sub.2 
EQU (n--C.sub.8 H.sub.17).sub.2 Sn(SCH.sub.2 COO) 
EQU (n--C.sub.8 H.sub.17).sub.2 Sn(SCH.sub.2 CH.sub.2 COO) 
EQU (n--C.sub.8 H.sub.17).sub.2 Sn(SCH.sub.2 COOCH.sub.2 CH.sub.2 OCOH.sub.2 S) 
EQU (n--C.sub.8 H.sub.17).sub.2 Sn(SCH.sub.2 COOCH.sub.2 CH.sub.2 CH.sub.2 
CH.sub.2 OCOH.sub.2 S) 
EQU (n--C.sub.8 H.sub.17).sub.2 Sn(SCH.sub.2 COOC.sub.8 H.sub.17 --iso).sub.2 
EQU (n--C.sub.8 H.sub.17).sub.2 Sn(SCH.sub.2 COOC.sub.12 H.sub.25 --n).sub.2 
##STR5## 
sulfide type organic tin compounds, such as, 
##STR6## 
organic tin oxides, such as, (n--C.sub.4 H.sub.9).sub.2 SnO, (n--C.sub.8 
H.sub.17)SnO, etc; reaction products of organic tin oxides, such as, 
(n--C.sub.4 H.sub.9)SnO, (n--C.sub.8 H.sub.17)SnO, etc, with ester 
compounds, su such as, ethyl silicate, ethyl silicate 40, dimethyl 
maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl 
phthalate, dioctyl phthalate, etc; and the like. 
The curing catalyst may be used in an amount of preferably 0.01 to 10 parts 
by weight, and more preferably 0.1 to 8 parts by weight, per 100 parts by 
weight of the silyl group containing vinyl type resin. 
The solvent used in this invention may be a solvent which can dissolve both 
the silyl group containing vinyl type resin, and the curing catalyst; or a 
solvent, which, although not dissolving both, can be mixed with one or 
more other solvents, and does not cause any precipitate when bringing the 
two liquids into association. For example, there may be used, those 
solvents used in conventional paints, coatings, etc, such as aliphatic 
hydrocarbons, aromatic hydrocarbons, alcohols, ketones, esters, ethers, 
alcohol esters, ketone alcohols, ether alcohols, ketone ethers, ketone 
esters, ester ethers, and the like. Furthermore, when these solvents 
contain an alkyl alcohol and/or a hydrolyzable ester, the storage 
stability of the one composition of this invention will be especially 
enhanced. 
As the alkyl alcohol usable in the invention in the solvent, an alcohol 
having 1 to 10 carbon atoms in the alkyl, is preferred. Also, there may be 
used, one or more of the following: methyl alcohol, ethyl alcohol, 
n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 
sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, 
hexyl alcohol, octyl alcohol, cellosolve, and the like. 
As the hydrolyzable ester usable in the invention in the solvent, one or 
more of the following may be used: trialkyl orthoformates, such as 
trimethyl orthoformate, triethyl orthoformate, triporopyl orthoformate, 
tributyl orthoformate, etc; tetraalkyl orthosilicates, such as, 
tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl 
orthosilicate, tetrabutyl orthosilicate, etc; and hydrolyzable organic 
silicon compounds having the formula: 
EQU R.sub.4-n SiX.sub.n 
wherein X is a hydrolyzable group, R is a monovalent organic group 
optionally containing a functional group, and n is an integer of 1,2,3, or 
4, preferably 3 or 4, such as, ethyl silicate 40, methyltrimethoxysilane, 
methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, 
phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, 
vinyltriethoxysilane, .gamma.-methacryloxyproppyltrimethoxysilane, 
.gamma.-mercaptopropyltrimethoxysilane, etc; and partial hydrolyzates 
thereof. 
The amount of solvent may vary, depending on the molecular weight or on the 
composition of the silyl group containing vinyl type resin. The amount of 
solvent is employed according to the solids concentration or viscosity 
required in actual use. The solvents above listed and the like may be used 
singly or in a mixture of two or more. Similarly, with the curing 
catalysts, they may be used singly or in a mixture of two or more. 
In addition, it is also possible to enhance the adhesion of the composition 
to for example, an inorganic surface upon curing, by adding a compound to 
the inventive composition blend, a compound having at least one silicon 
atom attached to a hydrolyzable group in the molecule, such as a silane 
coupling agent or a reaction product thereof. 
Since one pack compositions of this invention can cure at ambient 
temperatures, or lower temperatures, and the cured products have excellent 
properties, such as excellent adhesion, weather resistance, hardness, etc, 
they are useful as paints, coatings, coating agents, primers, adhesives, 
sealants, etc, for various surfaces, such as inorganic surfaces (e.g. iron 
plates, tin plates, galvanized plates, aluminum plates, zinc steel 
platess, tiles, slates, etc) and organic surfaces (e.g. wood, paper, 
cellophane, plastic, organic paint coatings, etc). Since the inventive 
composition is capable of being cured at low temperatures, it may be used 
as paints for protecting against corrosion, such as on bridges, face 
coatings, as paints for repairing automobiles, as paints for organic 
substance surfaces, and the like. 
Furthermore, the invention maybe further blended with various resins 
currently employed as paints, coating agents, primers, adhesives, etc. For 
example, the inventive compositions may be mixed in appropriate 
proportions with lacquer type paints, acryl lacquer type paints, 
thermosetting acrylic paints, alkyd paints, melamine paints, epoxy type 
paints, etc, and can improve physical properties, such as adhesion, 
weather resistance, etc, of these other paints, coatings, etc.

The invention will now be more particularly described with reference to 
actual examples, which examples are illustrative of the principles of the 
invention and are not to be construed to be limiting of the invention. 
Preparation of the Silyl Group Containing Vinyl Resin 
EXAMPLE 1 
A solution of 2 g of azobisisobutylonitrile in 30 g of styrene, 16 g of 
allyl methacrylate, 20 g of methyl methacrylate, 19 g of n-butyl 
methacrylate, 14 g of butyl acrylate, 4 g of maleic anhydride and 2 g of 
n-dodecylmercaptan was added dropwise to 90 g of a xylene solvent, heated 
to 90.degree. C., and the mixture was reacted for 10 hours to obtain a 
vinyl type copolymer containing allyl type unsaturated groups and having a 
molecular weight of 8,000. The molecular weight was measured by ordinary 
method, such as the GPC method (gel permeation column method), as in the 
other examples. The infrared spectrum of this product showed an absorption 
of the carbon-carbon double bond at 1648 cm.sup.-1 and an absorption of 
the acid anhydride at 1780 cm.sup.-1. The resultant polymer solution was 
distilled under reduced pressure to remove 40 g of the solvent. 
To 16 g of the obtained solution of the vinyl copolymer containing allyl 
type unsaturated groups, was added a solution of 1.5 g of 
methyldimethoxysilane and 0.0005 g of chloroplatinic acid, in isopropanol. 
Reaction of the mixture was effected, under sealed conditions, at 
90.degree. C. for 6 hours. In the infrared spectrum of this product, 
absorption at 1648 cm.sup.-1 was found not to exist. Thus, a silyl group 
containing vinyl type resin was obtained. 
EXAMPLE 2 
A solution of 2 g of azobisisobutylonitrile in 30 g of styrene, 22 g of 
65-methacryloxypropyltrimethoxysilane, 22 g of methyl methacrylate, 15 g 
of n-butyl methacrylate, 18 g of butylacrylate, was added dropwise to 70 g 
of xylene heated to 120.degree. C., and the resulting mixture was reacted 
for 10 hours to obtain a silyl group containing vinyl type resin having a 
molecular weight of 12,000. 
EXAMPLE 3 
A solution of 2 g of azobisisobutylonitrile in 30 g of styrene, 22 g of 
.gamma.-methacryloxypropyltrimethoxysilane, 22 g of methyl methacrylate, 
15 g of n-butyl methacrylate, 18 g of butyl acrylate, 4 g of acrylamide, 
10 g of n-butanol and 2 g of n-dodecylmercaptan, was added dropwise to 70 
g of xylene, heated to 90.degree. C., and the resulting mixture was 
reacted for 10 hours to obtain a silyl group containing vinyl type resin 
having a molecular weight of 8,000. 
EXAMPLE 4 
A solution of 2 g of azobisisobutylonitrile in 30 g of styrene, 22 g of 
.gamma.-methacryloxypropyltrimethoxysilane, 22 g of methyl methacrylate, 
13 g of n-butyl methacrylate, 18 g of butyl acrylate, 2 g of 
2-hydroxypropylmethacrylate, 10 g of n-butanol and 4 g of 
n-dodecylmercaptan was added dropwise to 70 g of xylene heated to 
90.degree. C., and the mixture was reacted for 10 hours to obtain a silyl 
group containing vinyl type resin, and having a molecular weight of 6,000. 
Preparation of Blend of Resin, Catalyst and Solvent 
To each of resin solutions obtained in Examples, 1,2,3,4 described above, 
there were added, respectively, curing catalyst(s) and solvent(s) and 
other additives where indicated, as set forth in the following Table 1. 
Each mixture was then diluted with n-butyl acetate to the solid 
concentratio (% by weight) indicated in Table 1. 
TABLE 1 
__________________________________________________________________________ 
Solids 
Solution Viscosity 
Solvent and/or 
Concen- after 20 
Pencil 
Ex. 
Curing Catalyst*.sup.4 
Additive*.sup.5 
tration 
Initial 
days (50.degree. C.) 
Hardness 
__________________________________________________________________________ 
1 Q631*.sup.1 (3) 
methanol (10) 
45 180 195 F 
2 Stann JF-98*.sup.2 (3) 
methanol (10), Ethyl 
42 100 200 2H 
silicate (5), methyl 
orthoformate (5) 
3 Tetraethylene- 
methanol (5), methyl 
50 180 290 F 
pentamine (3) 
orthoformate (3) 
3 Stann OM*.sup.3 (2) 50 185 400 H 
Stann OM (2) 
methanol (10) 
50 100 270 H 
Stann OM (2) 
ethyl silicate (5) 
50 200 350 H 
Stann OM (2) 
methanol (10), methyl 
50 110 200 H 
orthoformate (2) 
4 p-toluenesulfo- 
methyl orthoformate (2) 
55 120 140 2H 
nic acid (1) 
Dibutyltin di- 55 200 300 2H 
laurate (3) 
Dibutyltin di- 
methyltrimethoxysilane (5) 
55 200 250 2H 
laurate (2) 
__________________________________________________________________________ 
NOTES 
*.sup.1 = epoxy resin curing catalyst produced by Mitsui Petrochemical 
Epoxy Co, Ltd.? 
*.sup. 2 = stabilizer for vinyl chloride polymers (mercaptide type tin 
compound) produced by Sankyo Organic Chemical Co, Ltd. 
*.sup.3 = trade name for a stabilizer for vinyl chloride polymers 
(carboxylic acid type tin compound) produced by Sankyo Organic Chemical 
Co, Ltd. 
*.sup.4,*.sup.5 = Units parts by weight per 100 parts by weight of the 
resin solids in the example. 
Then the resulting mixture was blended using an ordinary blender until 
substantially homogeneous, and then sealed in a tin paint can, and stored 
at 50.degree. C. for 20 days. After storage, changes in solution viscosity 
of the blends were examined. The results of such changes are shown in 
Table 1. Each of the above one-pack blends was coated on a soft steel 
plate, and cured by heating at 60.degree. C. for 30 minutes, to produce a 
coating on the surfaces of soft steel plate. After 5 days, the pencil 
hardness of the coatings were measured, and the results thereof are shown 
in the Table 1. 
As described, it can be seen that the one-pack compositions of this 
invention, have excellent storage stability, and at the same time, the 
coatings produced after curing at low temperatures, produce excellent 
hardness of coating. 
The foregoing description is illustrative of the principles of the 
invention. Numerous modifications and extensions thereof would be apparent 
to the worker skilled in the art. All such modifications and extensions 
are to be considered to be within the spirit and scope of the invention.