Fluorine-containing copolymer, process for its production and curable composition

A fluorine-containing copolymer having fluidity at room temperature and comprising, based on entire polymer units, from 20 to 70 mol % of polymer units (1) derived from a polyfluoroolefin and from 1 to 80 mol % of polymer units (2) having a polyoxyalkylene chain having, at its terminal, a group selected from the group consisting of an active hydrogen-containing group, an epoxy group and a functional group cross-linkable by the action of moisture, the total of the polymer units (1) and the polymer units (2) being from 30 to 100 mol %.

The present invention relates to a fluorine-containing copolymer, a process 
for its production and a curable composition. 
Heretofore, in the field of sealing materials or coating materials, it has 
been desired to develop a resin which is excellent in the stretchability 
and weather resistance and which is curable at room temperature. In recent 
years, in addition to such requirements, there have been requirements for 
overcoatability and for solving a problem of formation of stain due to 
migration of a low molecular weight silicone oil or plasticizer contained 
in the resin such as a silicone resin, which may otherwise fulfill the 
above-mentioned requirements. 
For example, in the case of sealing materials, there has been a development 
from a non-stretchable oily caulking material to an elastic urethane or 
polysulfide material. Further, a weather resistant silicone material has 
been developed. However, it has a drawback that the staining due to a low 
molecular weight silicone oil is substantial. Under the circumstances, a 
modified silicone has been developed wherein the backbone structure is a 
polyalkylene oxide, and siloxane linkages are present only at the 
cross-linked sites. However, there still is a case where the weather 
resistance, etc. are inadequate, and such does not provide an adequate 
solution. 
On the other hand, as a resin curable at room temperature having high 
weather resistance, a fluoroolefin-vinylether copolymer has been known, 
and it is used for a coating composition. The coating composition made of 
such resin is excellent in the weather resistance and serves to increase 
the durability of a building structure, and its usefulness for industrial 
application is being recognized. 
However, a resin having higher flexibility is desired for application to 
sealing materials, elastomers, waterproofing material, adhesives, PCM 
coating materials or elastic coating materials which require high 
stretchability in addition to the weather resistance as in the present 
application. Further, from the viewpoint of practical application, a 
composition of one-pack type is desired. 
It is an object of the present invention to solve the above-mentioned 
problems. 
The present invention provides a fluorine-containing copolymer having 
fluidity at room temperature and comprising, based on entire polymer 
units, from 20 to 70 mol % of polymer units (1) derived from a 
polyfluoroolefin and from 1 to 80 mol % of polymer units (2) having a 
polyoxyalkylene chain having, at its terminal, a group selected from the 
group consisiting of an active hydrogen-containing group, an epoxy group 
and a functional group cross-linkable by the action of moisture, the total 
of the polymer units (1) and the polymer units (2) being from 30 to 100 
mol %. 
The present invention also provides a process for producing a 
fluorine-containing copolymer, which comprises polymerizing a fluoroolefin 
and a monomer having a polyoxyalkylene chain having, at its terminal, a 
group selected from the group consisting of an active hydrogen-containing 
group, an epoxy group and a functional group cross-linkable by the action 
of moisture and an .alpha.,.beta.-unsaturated group copolymerizable with 
the fluoroolefin. 
The present invention further provides a process for producing a 
fluorine-containing copolymer having a polyoxyalkylene chain having a 
hydroxyl group at its terminal, which comprises adding an alkylene oxide 
to a fluorine containing copolymer comprising, based on entire polymer 
units, from 20 to 70 mol % of polymer units (1) derived from a 
fluoroolefin and from 1 to 80 mol % of polymer units (3) having a 
functional group to which the alkylene oxide is to be added, the total of 
the polymer units (1) and the polymer units (3) being from 30 to 100 mol 
%. 
The present invention further provides a process for producing a 
fluorine-containing copolymer having a functional group cross-linkable by 
the action of moisture, which comprises reacting a fluorine-containing 
copolymer comprising, based on entire polymer units, from 20 to 70 mol % 
of polymer units (1) derived from a fluoroolefin and from 1 to 80 mol % of 
polymer units (4) having a polyoxyalkylene chain having a reactive group 
at its terminal, the total of the polymer units (1) and the polymer units 
(4) being from 30 to 100 mol %, and a compound having a functional group 
reactive with the reactive group of the fluorine-containing copolymer and 
a functional group cross-linkable by the action of moisture. 
Further, the present invention provides a curable composition comprising a 
curing agent and a fluorine-containing copolymer having fluidity at room 
temperature and comprising, based on entire polymer units, from 20 to 70 
mol % of polymer units (1) derived from a fluoroolefin and from 1 to 80 
mol % of polymer units (2') having a polyoxyalkylene chain having, at its 
terminal, a group selected from the group consisting of an active 
hydrogen-containing group and an epoxy group, the total of the polymer 
units (1) and the polymer units (2') being from 30 to 100 mol %. 
Still further, the present invention provides a curable composition 
containing a fluorine-containing copolymer having fluidity at room 
temperature and comprising, based on entire polymer units, from 20 to 70 
mol % of polymer units (1) derived from a fluoroolefin and from 1 to 80 
mol % of polymer units (2") having a polyoxyalkylene chain having, at its 
terminal, a functional group cross-linkable by the action of moisture, the 
total of the polymer units (1) and the polymer units (2") being from 30 to 
100 mol %. 
Now, the present invention will be described in detail with reference to 
the preferred embodiments. 
The fluorine-containing copolymer of the present invention contains from 20 
to 70 mol % of polymer units (1) derived from a fluoroolefin. The 
fluoroolefin is preferably a fluoroolefin having from 2 to 6 carbon atoms, 
more preferably from 2 to 4 carbon atoms, such as tetrafluoroethylene, 
chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl 
fluoride, hexafluoropropylene or pentafluoroethylene. Among them, a 
perfluoroolefin is most preferred wherein hydrogen is completely 
substituted by halogen. If the polymer units derived from a fluoroolefin 
are less than 20 mol %, no adequate weather resistance will be obtained, 
and staining tends to be substantial during the use for a long period of 
time, such being undesirable. If the amount of the fluoroolefin exceeds 70 
mol %, it tends to be difficult to obtain good elasticity or good adhesion 
to other materials, such being undesirable. It is particularly preferred 
that the copolymer contains from 30 to 70 mol % of the polymer units 
derived from a fluoroolefin. 
The fluorine-containing copolymer of the present invention further contains 
from 1 to 80 mol % of polymer units (2) having a polyoxyalkylene chain 
having, at its terminal, a group selected from the group consisting of an 
active hydrogen-containing group, an epoxy group and a functional group 
cross-linkable by the action of moisture. By virtue of such specific 
polymer units (2), the cured product can be an elastomer having excellent 
elasticity. Here, the active hydrogen-containing group may be a hydroxyl 
group, a carboxylic acid group, an amino group, an acid amide group or a 
thiol group. The functional group cross-linkable by the action of moisture 
may be an isocyanate group, a hydrolyzable silyl group or a thiol group. 
If the proportion of the polymer units (2) is too small, it becomes 
difficult to obtain a good elastomer. On the other hand, if the proportion 
is too large, the weather resistance or the stain resistance tends to be 
low. It is particularly preferred that the copolymer contains from 3 to 30 
mol % of the polymer units (2). 
The polymer units (2) may be those wherein the polyoxyalkylene chains as 
side chains are composed solely of ether bonds and carbon-carbon bonds, or 
those which contain other bonds such as urethane bonds, ester bonds or 
amino bonds between the main chain and the polyoxyalkylene chain. The 
polyoxyalkylene chain may be the one having at least two oxyalkylene 
units. If the number of oxyalkylene units is small, it tends to be 
difficult to obtain a desired elastomer. The larger the number of the 
oxyalkylene units, the better the elasticity of the elastomer. However, if 
it is too much, the weather resistance or stain resistance tends to be 
low. It is usually preferred that the number of oxyalkylene units is at 
most 50, more preferably at most 40. The oxyalkylene units are preferably 
oxyalkylene units having from 2 to 8 carbon atoms such as oxyethylene 
units, oxypropylene units or oxybutylene units. Such oxyalkylene chain may 
be composed of oxyalkylene units of the same type or oxyalkylene units of 
a plurality of different types. If oxyalkylene units having a small carbon 
number are used alone as the oxyalkylene units, the water resistance tends 
to be low. On the other hand, if oxyalkylene units having a large carbon 
number are used alone, the oil resistance tends to be low. It is 
particularly preferred to employ a polyoxyalkylene chain composed mainly 
of oxyalkylene units having from 3 to 6 carbon atoms. The oxyalkylene 
units may be those wherein a part of hydrogen bonded to carbon is 
substituted by halogen such as fluorine or chlorine, or by an alkyl group 
or an aryl group. Further, when the fluorine-containing copolymer of the 
present invention is used as a base for an elastic coating material, it is 
preferred to employ a polyoxyalkylene chain having at least five 
oxyalkylene units. Likewise, when the copolymer is used as a sealant base, 
it is preferred to employ a polyoxyalkylene chain having at least ten 
oxyalkylene units. 
As mentioned above, this polyoxyalkylene chain has, at its terminal, an 
active hydrogen-containing group, an epoxy group or a functional group 
cross linkable by the action of moisture. Such an active 
hydrogen-containing group, an epoxy group or a functional group 
cross-linkable by the action of moisture, may be bonded directly to the 
terminal of the polyoxyalkylene chain, or may be bonded via other bond 
such as a urethane bond or an ester bond. 
The fluorine-containing copolymer of the present invention may further 
contain other polymer units in addition to the above-described polymer 
units (1) and (2). In such a case, the total of the polymer units (1) and 
the polymer units (2) is from 30 to 100 mol % based on the entire polymer 
units. If the proportion of the polymer units (1) and (2) is too small, no 
adequate weather resistance, stain resistance and elasticity can be 
obtained. Here, other polymer units may be polymer units derived from a 
monomer copolymerizable with the fluoroolefin. The monomer copolymerizable 
with the fluoroolefin, may be an ethylenically unsaturated compound such 
as a vinyl compound, an allyl compound, an acryloyl compound or a 
methacryloyl compound. When polymer units other than the polymer units (1) 
and (2) are contained, a larger amount of polymer units will be contained 
among the polymer units (2), whereby the elasticity will be obtained more 
effectively. 
The fluorine-containing copolymer of the present invention has fluidity at 
room temperature. specifically, it preferably has fluidity at a level such 
that it is deformable by its own weight at 25.degree. C. More 
specifically, it preferably has a viscosity of at most 100,000 centipoise 
(hereinafter referred to simply as cp) at 25.degree. C. A 
fluorine-containing copolymer having a viscosity being too high is 
undesirable since the practical applicability is thereby extremely low in 
its application to e.g. a sealant. A copolymer having a viscosity of at 
most 20,000 cp at 25.degree. C. is particularly preferred, since it 
provides excellent practical applicability even when used without any 
solvent. There is no particular limitation to the lower limit of the 
viscosity. However, it is usual to employ a fluorine-containing copolymer 
having at least 300 cp at 25.degree. C. 
The fluorine-containing copolymer of the present invention can be prepared 
by e.g. the following processes. 
Firstly, there may be mentioned a process which comprises polymerizing a 
fluoroolefin and a monomer having a polyoxyalkylene chain having, at its 
terminal, a group selected from the group consisting of an active 
hydrogen-containing group, an epoxy group and a functional group 
cross-linkable by the action of moisture, and an 
.alpha.,.beta.-unsaturated group copolymerizable with the fluoroolefin. 
Secondly, there may be mentioned a process which comprises 
addition-reacting an alkylene oxide to a fluorine-containing copolymer 
(hereinafter referred to as a fluorine-containing copolymer X) comprising, 
based on entire polymer units, from 20 to 70 mol % of polymer units 
derived from a fluoroolefin and from 1 to 80 mol % of polymer units (3) 
having a functional group to which an alkylene oxide is to be added, the 
total of the polymer units (1) and the polymer units (3) being from 30 to 
100 mol %. 
Thirdly, there may be mentioned a process which comprises reacting a 
fluorine-containing copolymer (hereinafter referred to as a 
fluorine-containing copolymer Y) comprising, based on entire polymer 
units, from 20 to 70 mol % of polymer units (1) derived from a 
fluoroolefin and from 1 to 80 mol % of polymer units (4) having a 
polyoxyalkylene chain having a reactive group at its terminal, the total 
of the polymer units (1) and the polymer units (4) being from 30 to 100 
mol % with a compound having a functional group reactive with the reactive 
group of the fluorine-containing copolymer Y and a functional group 
cross-linkable by the action of moisture. 
In the first process, the monomer having a polyoxyalkylene chain having at 
its terminal, an active hydrogen-containing group, an epoxy group or a 
functional group cross-linkable by the action of moisture and an 
.alpha.,.beta.-unsaturated group copolymerizable with the fluoroolefin, 
may preferably be a monomer having an .alpha.,.beta.-unsaturated group, 
such as a vinyl group, an allyl group, an acryloyl group or a methacryloyl 
group. Such a monomer may be prepared by a method which comprises 
addition-reacting an alkylene oxide to a hydroxyl group-containing monomer 
such as a hydroxyalkylvinyl ether, a hydroxyalkylallyl ether, a reaction 
product of acrylic acid with a polyhydric alcohol, a reaction product of 
glycidylallyl ether with an alkanol amine or a phenol compound or allyl 
alcohol, or a method which comprises reacting a monomer having a reactive 
group such as a hydroxyl group, an alkoxysilyl group, an epoxy group or an 
amino group with a polyoxyalkylene compound having a group reactive with 
the above reactive group, such as an isocyanate group, an alkoxysilyl 
group or a carboxylic acid group. Further, it may be obtained by a method 
which comprises reacting to the monomer obtained by such a method, a 
compound having a functional group curable by the action of moisture, such 
as a diisocyanate compound, an isocyanate alkylsilane compound, a 
silylisocyanate compound or a mercaptoalkanoic acid. In this first 
process, if only one type of the fluoroolefin and only one type of the 
monomer having a polyoxyalkylene chain are polymerized, it is highly 
likely that they undergo alternating copolymerization. Particularly when 
the monomer having a polyoxyalkylene chain is a vinyl compound or an allyl 
compound, this possibility is extremely high. In the case of alternating 
copolymerization, other polymerization units present between polymer units 
(2) will be as little as only about one, whereby the resulting polymer 
tends to hardly have good flexibility or elasticity. It is preferred to 
employ at least two different kinds of compounds for either one or both of 
the fluoroolefin and the monomer having a polyoxyalkylene chain. 
Otherwise, in addition to the fluoroolefin and the monomer having a 
polyoxyalkylene chain, other comonomer copolymerizable therewith, may be 
copolymerized so that a number of such other polymer units will be present 
among the polymer units (2) in the resulting polymer. Usually, the latter 
method of copolymerizing a comonomer is employed. Here, the comonomer may 
be a compound having a polymerizable site such as a vinyl group, an allyl 
group, an acryloyl group or a methacryloyl group. Specifically, olefins, 
vinyl ethers, vinyl esters, allyl ethers, allyl esters, acrylic acid 
esters and methacrylic acid esters may be mentioned. Particularly 
preferred is a compound having a linear, branched or alicyclic alkyl group 
having from 1 to 15 carbon atoms. Such a comonomer may be the one wherein 
a part or all of hydrogen bonded to carbon is substituted by fluorine. In 
this first process, the proportion of the polymer units (1) is from 20 to 
70 mol %, and the proportion of the polymer units (2) is from 1 to 80 mol 
%, and the total of the polymer units (1) and the polymer units (2) is 
preferably at least 30 mol %, based on the entire polymer units. Such 
polymerization may be conducted by any one of solution polymerization, 
emulsion polymerization, suspension polymerization and bulk 
polymerization. A polymerization initiator or a polymerization initiating 
source such as ionizing radiation is applied to the predetermined amounts 
of monomers to conduct the polymerization. Various other conditions may be 
similar to those commonly employed for solution polymerization, emulsion 
polymerization, suspension polymerization or bulk polymerization. 
In the second process, the fluorine-containing copolymer X can be prepared 
by copolymerizing a fluoroolefin, a monomer having a functional group to 
which an alkylene oxide can be added or a group convertible to such a 
functional group, and if necessary, other comonomer. Here, a hydroxyl 
group or a carboxyl group is a typical example for the functional group to 
which an alkylene oxide can be added. Here, the monomer having such a 
functional group or a group convertible to such a functional group, 
includes a hydroxyalkyl vinyl ether, a hydroxyalkyl allyl ether, a 
hydroxyalkyl vinyl ester, a hydroxylalkyl allyl ester, a glycidyl vinyl 
ether, a glycidyl allyl ether, an aminoalkyl vinyl ether, an aminoalkyl 
allyl ether, an aminoalkyl vinyl ester, an aminoalkyl allyl ether, acrylic 
acid, methacrylic acid and allyl vinyl ether. As the group convertible to 
the functional group to which an alkylene oxide can be added, an ester 
group hydrolyzable after the polymerization, may be mentioned. Further, if 
necessary, it may be converted to other functional group to which an 
alkylene oxide can be added, after polymerization. For example, there may 
be mentioned a method wherein a polybasic carboxylic acid or its anhydride 
is added to a hydroxyl group to convert it to a carboxylic acid group, or 
a method wherein an alkanol amine or a phenol compound is reacted to an 
epoxy group to convert it to a hydroxyl group. In the preparation of the 
fluorine-containing copolymer X, a monomer similar to the comonomer 
described with respect to the above first process, may be copolymerized. 
In this case, it is preferred to control the polymerization so that the 
proportion of the polymer units (1) will be from 20 to 70 mol %, the 
proportion of the polymer units (3) will be from 1 to 80 mol %, and the 
total of the polymer units (1) and the polymer units (3) will be from 30 
to 100 mol %, based on the entire polymer units of the copolymer. For the 
polymerization, a method of polymerization similar to the one described 
with respect to the first process, may be employed. The addition of an 
alkylene oxide to the fluorine-containing copolymer X thus prepared, can 
be conducted in the same manner as the production of a usual polyether 
compound. 
In the third process, the fluorine-containing copolymer Y can be prepared 
by the following methods. 
Firstly, there may be mentioned a method which comprises polymerizing a 
fluoroolefin and a monomer copolymerizable with a fluoroolefin and having 
a polyoxyalkylene chain having a reactive group at the terminal. 
Secondary, there may be mentioned a method which comprises reacting a 
fluorine-containing copolymer Y' comprising from 20 to 70 mol % of polymer 
units (1) derived from a fluoroolefin and from 1 to 80 mol % of polymer 
units (5) having a reactive group, the total of the polymer units (1) and 
the polymer units (5) being at least 30 mol %, based on entire polymer 
units, and a polyoxyalkylene compound having a group reactive with the 
reactive group of the fluorine-containing copolymer Y'. 
Thirdly, there may be mentioned a method which comprises addition-reacting 
an alkylene oxide to the fluorine-containing copolymer Y" comprising from 
20 to 70 mol % of polymer units (1) derived from a fluoroolefin and from 
1 to 80 mol % of polymer units (6) having a hydroxyl group, the total of 
the polymer units (1) and the polymer units (6) being at least 30 mol %, 
based on entire polymer units. 
The first method may be conducted in the same manner as described with 
respect to the above first process. 
The fluorine copolymer Y' in the second method can be prepared in 
accordance with the method for the production of the fluorine-containing 
copolymer X in the above-mentioned second process. Further, the 
polyoxyalkylene compound capable of reacting with the fluorine-containing 
copolymer Y', can be prepared by a method which comprises reacting a 
compound such as an alkanol amine, a polyvalent isocyanate compound, an 
isocyanate alkyl acrylate, a silyl isocyanate or a polybasic carboxylic 
anhydride to a polyoxyalkylene having an alkylene oxide added in 
accordance with a usual method, or a method which comprises adding an 
alkylene oxide by a usual method to a compound such as a hydroxyalkyl 
vinyl ether. 
The third method may be conducted in the same manner as the second process 
described above. 
In the third method, the reactive group in the fluorine-containing 
copolymer Y may be a hydroxyl group, a carboxylic acid group, an amino 
group, an acid amide group, a thiol group, an active halogen-containing 
group, an epoxy group or an ethylenically unsaturated group. The compound 
having a functional group cross-linkable by the action of moisture, to be 
reacted to the fluorine-containing copolymer Y includes, for example, a 
polyvalent isocyanate compound such as hexamethylene diisocyanate or 
toluene diisocyanate, an isocyanate alkylsilane compound such as 
.gamma.-isocyanate propylmethyldimethoxysilane, a silylisocyanate compound 
such as trimethoxysilyl isocyanate, a hydrolyzable silyl group-containing 
compound such as 4-trimethoxysilyltetrahydrophthalic anhydride, or a thiol 
group-containing compound such as a mercapto alkanoic acid or a 
thiodialkanoic acid. The reaction of the fluorine-containing copolymer Y 
and the above compound, is preferably conducted by reacting an excess 
equivalent of the above-mentioned compound to the reactive group in the 
fluorine-containing copolymer Y. If the amount of the above compound to be 
reacted is small, gellation is likely to result, such being undesirable. 
It is particularly preferred to react at least one mol of the above 
identified compound per mol of the reactive group in the 
fluorine-containing copolymer Y. 
The fluorine-containing copolymer of the present invention is suitable for 
use as a base for e.g. a sealant or an elastic coating material. 
Among the fluorine-containing copolymers of the present invention, one 
having an active hydrogen-containing group or an epoxy group at the 
terminal of the polyoxyalkylene chain (hereinafter referred to as a 
fluorine-containing copolymer (a)) may be combined with a curing agent to 
obtain a curable composition (hereinafter referred to as a composition 
(a)). Likewise, among the fluorine-containing copolymers of the present 
invention, one having a functional group cross-linkable by the action of 
moisture at the terminal of the polyoxyalkylene chain (hereinafter 
referred to as a fluorine-containing copolymer (b)) makes a curable 
composition (hereinafter referred to as a composition (b)) even without 
incorporating a curing agent. Hereinafter, the composition (a) and the 
composition (b) are generally referred to simply as a composition. 
Further, the curable composition (b) may contain a curing agent. 
As the curing agent for the composition (a), a compound may be employed 
which is capable of reacting with the active hydrogen-containing group or 
the epoxy group of the fluorine-containing copolymer (a) to form a 
cross-linkage. For example, a polyvalent isocyanate compound, an 
aminoplasto compound or a polyvalent amino compound may be mentioned. 
Among them, a polyol-modified polyisocyanate compound is preferred, since 
it presents a cured product having excellent elasticity. When a polyvalent 
isocyanate compound is used as the curing agent, curing can be conducted 
with moisture, and the practical applicability is excellent. In this case, 
from the viewpoint of the reactivity with an isocyanate group, it is 
particularly preferred to employ as the fluorine-containing copolymer (a) 
a copolymer having an active hydrogen-containing group, particularly, a 
hydroxyl group. 
To the composition of the present invention, additives such as a filler, a 
curing catalyst, a solvent, a photo stabilizer, an ultraviolet absorber, a 
heat stabilizer, a leveling agent, a defoaming or a foam suppressing 
agent, may be incorporated, as the case requires. 
The filler includes reinforcing fillers such as fumed silica, precipitated 
silica, silicic anhydride, hydrous silicic acid and carbon black, fillers 
such as calcium carbonate, magnesium carbonate, diatomaceous earth, 
calcined clay, clay, talc, surface-treated aluminum hydroxide, magnesium 
hydroxide, titanium oxide, bentonite, organic bentonite, ferric oxide, 
zinc oxide, active zinc white, hydrogenated castor oil and silica 
balloons; and fibrous fillers such as asbestos, glass fibers and glass 
filaments. The filler may be incorporated in an amount of from 1 to 500 
parts by weight per 100 parts by weight of the fluorine-containing 
copolymer. 
When a curable composition having a high strength is desired to be produced 
with such a filler, a good result can be obtained by using a filler 
selected from the group consisting of fumed silica, precipitated silica, 
silicic anhydride, hydrous silicic acid, carbon black, surface-treated 
fine calcium carbonate, calcined clay, clay and active zinc white in an 
amount of from 1 to 100 parts by weight per 100 parts by weight of the 
fluorine-containing copolymer. When a curable composition having good 
elongation with low strength is desired to be produced, a good result can 
be obtained by using a filler selected from the group consisting of 
titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric 
oxide, zinc oxide and silica balloons in an amount of from 5 to 200 parts 
by weight per 100 parts by weight of the fluorine-containing copolymer. 
These fillers may, of course, be employed alone or in combination as a 
mixture of two or more different kinds. 
Now, the present invention will be described with reference to Examples. 
However, it should be understood that the present invention is by no means 
restricted to such specific Examples.

PREATION EXAMPLES 1 to 4 
Hydroxybutyl vinyl ether (HBVE) and potassium hydroxide (concentration: 
95%) were charged in the amounts as identified in Table 1 into a stainless 
steel pressure resistant reactor having an internal capacity of 5 l and 
equipped with a stirrer. Propylene oxide (PO) was gradually added thereto, 
and the reaction was conducted under a pressure of 3 kg/cm.sup.2 at 
110.degree. C. for a predetermined period of time. The liquid thereby 
obtained was purified by synthetic magnesia to obtain a vinyl ether having 
a polyoxyalkylene chain. The mol amount of added PO in each vinyl ether is 
shown in Table 1. 
TABLE 1 
______________________________________ 
Prep. Prep. Prep. Prep. 
Example 1 
Example 2 Example 3 Example 4 
______________________________________ 
HBVE (g) 1,200 580 454 312 
Potassium 
9 11 15 15 
hydroxide (g) 
PO (g) 1,800 2,900 4,540 4,690 
Reaction time 
2 4 12 18 
(hr) 
Mol amount 
3 10 20 30 
of added PO 
______________________________________ 
EXAMPLES 1 to 6 and COMATIVE EXAMPLES 1 and 2 
Into a stainless steel pressure resistant reactor having an internal 
capacity of 550 ml and equipped with a stirrer, 112 g of xylene, 112 g of 
ethanol, 1.6 g of potassium carbonate and 0.5 g of azoisobutyronitrile 
were charged, and the monomer composition as identified in Table 2 was 
thereby polymerized. The polymerization was conducted by charging monomers 
other than chlorotrifluoroethylene (CTFE) or tetrafluoroethylene (TFE), 
then dissolved air was removed under reduced pressure after liquid was 
frozen by liquid nitrogen, then introducing CTFE or TFE, gradually raising 
the temperature, maintaining the temperature at 65.degree. C., continuing 
the polymerization reaction under stirring for 10 hours, then cooling the 
reactor with water to terminate the polymerization. The reactor was cooled 
to room temperature, and then unreacted monomers were withdrawn, and the 
reactor was opened. The polymer solution was filtered, and then the 
solvent was removed by an evaporator to obtain a fluorine-containing 
copolymer. The hydroxyl value (KOH mg/g), the number average molecular 
weight, the glass transition temperature and the viscosity at 25.degree. 
C., of the fluorine-containing copolymer thus obtained, are shown in Table 
2. 
In the molecular weight measurement (by using G.P.C) of the 
fluorine-containing copolymer in each Example, no substantial peak 
corresponding to the vinyl ether obtained in Preparation Examples 1 to 4, 
was observed. This indicates that the vinyl ether having a 
polyoxypropylene chain has been copolymerized. 
TABLE 2 
__________________________________________________________________________ 
Comparative 
Examples Examples 
1 2 3 4 5 6 1 2 
__________________________________________________________________________ 
Monomers (g) 
CTFE 71 59 65 59 -- 63 58 59 
TFE -- -- -- -- 43 -- -- -- 
EVE 38 36 30 -- 30 16 33 29 
CHVE -- -- -- 63 -- -- -- -- 
HBVE -- -- -- -- -- -- 5.5 12 
Vinyl ether of Prep. 
60 5.5 -- 5.5 80 -- -- -- 
Example 2 
Vinyl ether of Prep. 
-- -- 180 -- -- -- -- -- 
Example 3 
Vinyl ether of Prep. 
-- -- -- -- -- 180 -- -- 
Example 4 
Hydroxyl value (KOH 
28.4 8.4 28 8.4 37 19 27 57 
mg/g) 
Number average mole- 
6,000 20,000 6,000 20,000 6,000 6,000 6,000 20,000 
cular weight 
Glass transition temp. 
-20 -8 -68 10 -25 -68 18 20 
(.degree.C.) 
Viscosity at 25.degree. C. (cp) 
15,000 
30,000 8,000 60,000 9,000 6,000 Non- Non- 
liquid 
liquid 
__________________________________________________________________________ 
In Table 2, CTFE denotes chlorotrifluoroethylene, TFE denotes 
tetrafluoroethylene, EVE denotes ethyl vinyl ether, CHVE denotes 
cyclohexyl vinyl ether, and HBVE denotes hydroxylbutyl vinyl ether. 
EXAMPLE 7 
Into a stainless steel pressure resistant reactor having a internal 
capacity of 550 ml and equipped with a stirrer, 145 g of xylene, 145 g of 
ethanol, 33 g of EVE (ethyl vinyl ether), 5.5 g of HBVE (hydroxylbutyl 
vinyl ether), 1 g of potassium carbonate and 0.5 g of AIBN 
(azoisobutyronitrile) were charged, and dissolved air was removed by 
solidification deaeration by means of liquid nitrogen. Then, 58 g of CTFE 
(chlorotrifluoroethylene) was introduced, and the mixture was gradually 
heated. The temperature was maintained at 65.degree. C., and the reaction 
was continued under stirring. Ten hours later, the reactor was cooled with 
water to terminate the reaction. The reactor was cooled to room 
temperature, and unreacted monomers were withdrawn. Then, the reactor was 
opened. The reaction solution was filtered, and then the solvent was 
removed by an evaporator to obtain a fluorine-containing copolymer. 
Further, into a stainless steel pressure resistant reactor having an 
internal capacity of 5 l and equipped with stirrer, 10 g of this 
fluorine-containing copolymer and 6 g of potassium hydroxide having a 
concentration of 95%, and 816 g of PO (propylene oxide) was gradually 
added. The reaction was conducted under a pressure of 3 kg/cm.sup.2 at 
110.degree. C. for 10 hours, and a transparent brown liquid thereby 
obtained was purified by synthetic magnesia to obtain the desired 
fluorine-containing copolymer having a mol amount of added PO of 20 mol. 
The obtained copolymer had a hydroxyl value of 15 (KOH mg/g), a number 
average molecular weight of 10,000 as measured by GPC, a glass transition 
temperature of -25.degree. C. and a viscosity of 12,000 cp at 25.degree. 
C. 
EXAMPLE 8 
100 g of a polyoxypropylene diol having a molecular weight of 1,000 and 15 
g of dimethylsilyl diisocyanate were mixed and reacted to obtain a 
polyoxypropylene having a terminal isocyanate group. To 100 g of the 
fluorine-containing copolymer obtained in Comparative Example 1, 30 g of 
this polyoxypropylene having a terminal isocyanate group was reacted to 
obtain a fluorine-containing copolymer having a polyoxyalkylene chain. 
This fluorine-containing copolymer had a viscosity of 16,000 cp at 
25.degree. C. 
TEST EXAMPLES 1 to 7 and COMATIVE TEST EXAMPLES 1 and 2 
To the fluorine-containing copolymers obtained in Examples 1 to 7 and 
Comparative Examples 1 and 2, a polyol-modified diisocyanate compound 
(Duranate D101, tradename, manufactured by Asahi Kasei) was added in an 
amount corresponding to NCO/OH=1, and 500 ppm of dibutyltin dilaurate was 
added as the catalyst to cure the composition. The cured product was 
tested for the breaking elongation, the breaking strength, the 50% modulus 
of elasticity, the surface adhesiveness and the weather resistance, and 
the results are shown in Table 3. 
TEST EXAMPLE 8 
The fluorine-containing copolymer obtained in Example 8 was cured with 
moisture. The cured product was tested for the breaking elongation, the 
breaking strength, the 50% modulus of elasticity, the surface adhesiveness 
and the weather resistance, and the results are shown in Table 3. 
COMATIVE TEST EXAMPLE 3 
A cured product was prepared in the same manner as in Test Example 1 except 
that instead of the fluorine-containing copolymer, a polyoxypropylene 
triol (hydroxyl value: 33.7 KOH mg/g) having a molecular weight of 5,000 
was employed. This cured product was tested for the breaking elongation, 
the breaking strength, the 50% modulus of elasticity, the surface 
adhesiveness and the weather resistance, and the results are shown in 
Table 3. 
COMATIVE TEST EXAMPLE 4 
A cured product was prepared in the same manner as in Test Example 1 except 
that instead of the fluorine-containing copolymer, a fluorine-containing 
copolymer prepared by adding 3 mols of .epsilon.-caprolactone per mol of 
the hydroxyl group of the fluorine-containing copolymer of Comparative 
Example 1, was employed. The results of various tests of this cured 
product are shown in Table 3. 
COMATIVE TEST EXAMPLE 5 
A commercially available modified silicone-type sealing material was tested 
for the breaking elongation, the breaking strength, the 50% modulus of 
elasticity, the surface adhesiveness and the weather resistance, and the 
results are shown in Table 3. 
TABLE 3 
__________________________________________________________________________ 
Test Examples Comparative Test Examples 
1 2 3 4 5 6 7 8 1 2 3 4 5 
__________________________________________________________________________ 
Fluorine-contain- 
Ex. 1 
Ex. 2 
Ex. 3 
Ex. 4 
Ex. 5 
Ex. 6 Ex. 7 
Ex. 8 
Comp. 
Comp. 
-- -- -- 
ing copolymer Ex. 1 
Ex. 2 
Breaking elonga- 
600 900 950 700 900 1,100 950 750 100 89 850 150 600 
tion (%) 
Breaking strength 
7 10 9 18 10 10 13 11 60 130 13 50 6.5 
(kg/cm.sup.2) 
50% Modulus of 
3 6 2 14 4 1.5 5 5 25 850 2 20 10 
elasticity 
(kg/cm.sup.2) 
Surface adhesive- 
0.4 0.2 0.5 0.1 0.3 0.4 0.3 0.4 0.1 0.05 
2.0 0.2 0.6 
ness (kg) 
Weather 
resistance 
Surface condition 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.circleincircle. 
.circleincircle. 
X .circleincircle. 
.largecircle. 
Elongation 
80 85 85 85 85 85 80 83 95 97 55 93 65 
retaining rate (%) 
__________________________________________________________________________ 
PREATION EXAMPLE 5 
To 100 g of the vinyl ether having a polyoxyalkylene chain obtained in 
Preparation Example 3, 16 g of .gamma.-isocyanate propylmethyl 
dimethoxysilane was reacted in the presence of 0.01 g of dibutyltin 
dilaurate at room temperature under a nitrogen atmosphere for 4 hours 
under stirring to obtain a vinyl ether having a polyoxyalkylene chain 
having a methoxysilyl terminal group. 
EXAMPLE 9 
Into a glass container having an internal capacity of 300 ml, 16.8 g of 
hexamethylene diisocyanate (hereinafter referred to simply as HDI) was 
introduced, and 200 g of the fluorine-containing copolymer of Example 3 
was gradually dropwise added thereto in a dry nitrogen gas stream under 
stirring. Then, the reaction was continued for 24 hours, and the infrared 
spectrum was measured, whereby it was confirmed that a half of the peak 
attributable to the isocyanate group of HDI was changed to a urethane 
bond. Then, the reaction was terminated by cooling to obtain 216.8 g of 
the fluorine-containing copolymer having an isocyanate group. This 
fluorine-containing copolymer had a viscosity of 9,000 cp at 25.degree. C. 
Then, 0.01 g of dibutyltin dilaurate was added to this fluorine-containing 
copolymer, and the mixture was stored in a container purged with nitrogen, 
at 50.degree. C. for 20 days. Then, the fluidity was examined, whereby no 
gellation was observed, and the fluidity was excellent. This 
fluorine-containing copolymer was coated in a thickness of 1 mm and left 
to stand still in a room under a standard condition at 20.degree. C. under 
a relative humidity of 65%, whereby the copolymer cured in 24 hours. This 
indicates that this fluorine-containing copolymer has one pack type room 
temperature curability. 
EXAMPLE 10 
Into a glass container having an internal capacity of 300 ml, 11.5 g of HDI 
was introduced, and 200 g of the fluorine-containing copolymer of Example 
6 was gradually dropwise added thereto in a dry nitrogen gas stream under 
stirring. Then, the reaction was conducted for 24 hours, and the infrared 
absorption spectrum was measured, whereby it was confirmed that a half of 
the peak attributable to the isocyanate group of HDI was changed to a 
urethane bond. Then, the reaction was terminated by cooling to obtain 
211.5 g of a fluorine-containing copolymer having an isocyanate group. 
This fluorine-containing copolymer had a viscosity of 8,000 cp at 
25.degree. C. Then, 0.01 g of dibutyltin dilaurate was added to this 
fluorine-containing copolymer, and the mixture was stored in a container 
purged with nitrogen, at 50.degree. C. for 20 days. Then, the fluidity was 
examined, whereby no gellation was observed, and the fluidity was 
excellent. This fluorine-containing copolymer was coated in a thickness of 
1 mm and left to stand still in a room under a standard condition at 
20.degree. C. under a relative humidity of 65%. The copolymer cured in 24 
hours. This indicates that this fluorine-containing copolymer has one pack 
type room temperature curability. 
COMATIVE EXAMPLE 3 
A polymer having an isocyanate group was prepared in the same manner as in 
Example 9 except that instead of the fluorine-containing copolymer, 200 g 
of a trifunctional polypropylene glycol having a molecular weight of 5,000 
and 20.2 g of HDI were used. This polymer was also found to have one pack 
type room temperature curability. 
EXAMPLE 11 
Into a glass container having an internal capacity of 300 ml, 200 g of the 
fluorine-containing copolymer of Example 3, 20.4 g of .gamma.-isocyanate 
propylmethyldimethoxysilane and 0.02 g of dibutyltin dilaurate as a curing 
catalyst were charged and stirred at room temperature under a nitrogen 
atmosphere for 4 hours. The infrared absorption spectrum of the 
fluorine-containing copolymer thus obtained was measured, whereby it was 
confirmed that the absorption attributable to the isocyanate group 
disappeared, and an absorption peak attributable to a urethane bond 
appeared, and the copolymer had an alkoxysilyl group. This 
fluorine-containing copolymer had a viscosity of 8,500 cp at 25.degree. C. 
Then, 1 g of dibutyltin dilaurate was added to this fluorine-containing 
copolymer, and the mixture was stored in a container purged with nitrogen 
gas, at 50.degree. C. for 20 days. Then, the fluidity was examined, 
whereby no gellation was observed, and the fluidity was excellent. This 
fluorine-containing copolymer was coated in a thickness of 1 mm and left 
to stand still in a room under a standard condition at 20.degree. C. under 
a relative humidity of 65%. The copolymer cured in 24 hours. This 
indicates that this fluorine-containing copolymer has one pack type room 
temperature curability. 
EXAMPLE 12 
Into a glass container having an internal capacity of 300 ml, 200 g of the 
fluorine-containing copolymer of Example 6, 14 g of .gamma.-isocyanate 
propylmethyldimethoxysilane and 0.02 g of dibutyltin dilaurate as a curing 
catalyst were charged and stirred at room temperature under a nitrogen 
atmosphere for 4 hours. The infrared absorption spectrum of the 
fluorine-containing copolymer thus obtained was measured, whereby it was 
confirmed that the absorption attributable to the isocyanate group 
disappeared, and an absorption peak attributable to a urethane bond 
appeared, and the copolymer had an alkoxysilyl group. This 
fluorine-containing copolymer had a viscosity of 8,000 cp at 25.degree. C. 
Then, 1 g of dibutyltin dilaurate was added to this fluorine-containing 
copolymer, and the mixture was stored in a container purged with nitrogen 
gas, at 50.degree. C. for 20 days. Then, the fluidity was examined, 
whereby no gellation was observed, and the fluidity was excellent. This 
fluorine-containing copolymer was coated in a thickness of 1 mm and left 
to standstill in a room under a standard condition at 20.degree. C. under 
a relative humidity of 65% The copolymer cured in 24 hours. This indicates 
that this fluorine-containing copolymer has one pack type room temperature 
curability. 
COMATIVE EXAMPLE 4 
A polymer having a methoxysilyl group was prepared in the same manner as in 
Example 11 except that instead of the fluorine-containing copolymer, 200 g 
of a trifunctional polypropylene glycol having a molecular weight of 5,000 
and 23 g of .gamma.-isocyanate propylmethyldimethoxysilane were used. This 
polymer had a viscosity of 6,000 cp at 25.degree. C. This polymer also had 
one pack type room temperature curability. 
EXAMPLE 13 
Into a glass container having an internal capacity of 300 ml, 200 g of the 
fluorine-containing copolymer having an isocyanate group of Example 9 was 
introduced, and 18 g of .gamma.-aminopropyltrimethoxysilane was gradually 
dropwise added thereto in a dry nitrogen gas stream under stirring. Then, 
the reaction was continued for 8 hours, and the infrared absorption 
spectrum was measured, whereby it was confirmed that the peak attributable 
to the isocyanate group disappeared, and it changed into a urea bond. 
Thus, a fluorine-containing copolymer having an alkoxysilyl group was 
obtained. This fluorine-containing copolymer had a viscosity of 11,000 cp 
at 25.degree. C. Then, 1 g of dibutyltin dilaurate was added to this 
fluorine-containing copolymer, and the mixture was stored in a container 
purged with nitrogen gas, at 50.degree. C. for 20 days. Then, the fluidity 
was examined, whereby no gellation was observed, and the fluidity was 
excellent. This fluorine-containing copolymer was coated in a thickness of 
1 mm and left to stand still in a room under a standard condition at 
20.degree. C. under a relative humidity of 65%. The copolymer cured in 24 
hours. This indicates that this fluorine-containing copolymer has one pack 
type room temperature curability. 
EXAMPLE 14 
Into a glass container having an internal capacity of 300 ml, 200 g of the 
fluorine-containing copolymer having an isocyanate group of Example 10 was 
introduced, and 12 g of .gamma.-aminopropyltrimethoxysilane was gradually 
dropwise added thereto in a dry nitrogen gas stream under stirring. Then, 
the reaction was continued for 8 hours, and the infrared absorption 
spectrum was measured, whereby it was confirmed that the peak attributable 
to the isocyanate group disappeared, and it changed into a urea bond. 
Thus, a fluorine-containing copolymer having an alkoxysilyl group was 
obtained. This fluorine-containing copolymer had a viscosity of 9,000 cp 
at 25.degree. C. Then, 1 g of dibutyltin dilaurate was added to this 
fluorine-containing copolymer, and the mixture was stored in a container 
purged with nitrogen gas, at 50.degree. C. for 20 days. Then, the fluidity 
was examined, whereby no gellation was observed, and the fluidity was 
excellent. This fluorine-containing copolymer was coated in a thickness of 
1 mm and left to stand still at room temperature under a standard 
condition at 20.degree. C. under a relative humidity of 65%. The copolymer 
cured in 24 hours. This indicates that this fluorine-containing copolymer 
has one pack type room temperature curability. 
COMATIVE EXAMPLE 5 
A polymer having a methoxysilyl group was prepared in the same manner as in 
Example 13 except that instead of the fluorine-containing copolymer, 200 g 
of the polymer obtained in Comparative Example 3 and 21 g of 
.gamma.-aminopropylmethyldimethoxysilane were used. This polymer also had 
on pack type room temperature curability. 
EXAMPLE 15 
Into a glass container having an internal capacity of 300 ml, 200 g of the 
fluorine-containing copolymer of Example 3 was introduced, and 0.06 g of 
triethylamine was added thereto. Then, 27.2 g of 4-trimethoxysilyl 
tetrahydrophthalic anhydride was gradually dropwise added thereto in a dry 
nitrogen gas stream at 50.degree. C. Then, the reaction was continued for 
5 hours, and the infrared absorption spectrum was measured, whereby it was 
confirmed that the absorption peak attributable to the hydroxyl group 
disappeared, and a peak attributable to a carboxylic acid appeared. Then, 
the reaction was terminated by cooling to obtain 236.8 g of a 
fluorine-containing copolymer having an alkoxysilyl group. This 
fluorine-containing copolymer had a viscosity of 9,500 cp at 25.degree. C. 
Then, 1 g of dibutyltin dilaurate was added to this fluorine-containing 
copolymer, and the mixture was stored in a container purged with nitrogen 
gas, at 50.degree. C. for 20 days. Then, the fluidity was examined, 
whereby no gellation was observed, and the fluidity was excellent. This 
fluorine-containing copolymer was coated in a thickness of 1 mm and left 
to stand still in a room under a standard condition at 20.degree. C. under 
a relative humidity of 65%. The copolymer cured in 24 hours. This 
indicates that this fluorine-containing copolymer has one pack type room 
temperature curability. 
COMATIVE EXAMPLE 6 
A polymer having an isocyanate group was prepared in the same manner as in 
Example 14 except that instead of the fluorine-containing copolymer, 200 g 
of a trifunctional polypropylene glycol having a molecular weight of 5,000 
and 32.6 g of 4-trimethoxysilyl tetrahydrophthalic anhydride were used. 
This polymer was also found to have one pack type room temperature 
curability. 
EXAMPLE 16 
Into a glass container having an internal capacity of 300 ml, 200 g of the 
fluorine-containing copolymer having an isocyanate group of Example 9 was 
introduced, and 5.8 g of allyl alcohol was gradually dropwise added in a 
dry nitrogen gas stream at 80.degree. C. under stirring. Then, the 
reaction was continued for 24 hours. The infrared absorption spectrum of 
the reaction product was measured, whereby no peak attributable to the 
isocyanate group was detected, and a peak attributable to a urethane bond 
was detected. To 100 g of the fluorine-containing copolymer thus obtained, 
8 g of .beta.,.beta.'-dimercaptodiethylether, 0.5 g of t-butyl perbenzoate 
and 0.05 g of tetramethylguanidine were added, and the mixture was slowly 
stirred and then left to stand still at 60.degree. C. for 16 hours. From 
the infrared spectrometry, it was confirmed that the product had no double 
bond. This fluorine-containing copolymer had a viscosity of 13,000 cp at 
25.degree. C. To this fluorine-containing copolymer, 0.5 g of lead dioxide 
was added, and the fluidity was examined, whereby no gellation was 
observed, and the fluidity was excellent. This fluorine-containing 
copolymer was coated in a thickness of 1 mm and left to stand still at 
room temperature under a standard condition at 20.degree. C. under a 
relative humidity of 65%. The copolymer cured in 24 hours. This indicates 
that this fluorine-containing copolymer has one pack type room temperature 
curability. 
EXAMPLE 17 
Into a stainless steel pressure resistant container having an internal 
capacity of 550 ml equipped with a stirrer, 112 g of xylene, 112 of 
ethanol, 1.6 g of potassium carbonate and 0.5 g of azoisobutyronitrile 
were charged, and 194 g of the vinyl ether obtained in Preparation Example 
5, 19 g of cyclohexyl vinyl ether and 11 g of ethyl vinyl ether were 
charged. Then, dissolved air was removed by means of liquid nitrogen. 
Then, 51 g of chlorotrifluoroethylene was introduced. The temperature was 
gradually raised and then maintained at 65.degree. C., and the 
polymerization reaction was continued under stirring for 10 hours. Then, 
the reactor was cooled with water to terminate the polymerization. The 
reactor was cooled to room temperature, unreacted monomers were withdrawn, 
and the reactor was opened. The polymer solution was filtered, and then 
the solvent was removed by an epovarator to obtain a fluorine-containing 
copolymer. The obtained fluorine-containing copolymer had a number average 
molecular weight of 6,500, a glass transition temperature of -68.degree. 
C. and a viscosity of 9,000 cp at 25.degree. C. In the molecular weight 
measurement (by means of G.P.C.) of this fluorine-containing copolymer, no 
substantial peak corresponding to the vinyl ether obtained in Preparation 
Example 5 was observed. This indicates that the vinyl ether having the 
polyoxyalkylene chain was copolymerized. 
TEST EXAMPLES 
To 100 g of each of the fluorine-containing copolymers obtained in Examples 
8 to 17 and Comparative Examples 3 to 6, the curing catalyst, titanium 
oxide and calcium carbonate were added as identified in Table 4, and the 
mixture was coated in a thickness of 2 mm on a stainless steel plate and 
left to stand at 20.degree. C. under a relative humidity of 65%. With 
respect to the films thus obtained, the breaking elongation (%), the 
breaking strength (kg/cm.sup.2), the 50% modulus of elasticity, the 
surface adhesiveness and the weather resistance were evaluated. The 
results are shown in Table 4. 
TABLE 4 
__________________________________________________________________________ 
Test Examples Comparative Test Examples 
9 10 11 12 13 14 15 16 17 3 4 5 6 
__________________________________________________________________________ 
Fluorine-containing 
Ex. 9 
Ex. 10 
Ex. 11 
Ex. 12 
Ex. 13 
Ex. 14 
Ex. 15 
Ex. 16 
Ex. 17 
Comp. 
Comp. 
Comp. 
Comp. 
copolymer Ex. 3 
Ex. 4 
Ex. 
Ex. 6 
Curing catalyst 1 (g) 
0.01 
0.01 
1.0 1.0 1.0 1.0 1.0 -- 0.01 
1.0 1.0 1.0 1.0 
Curing catalyst 2 (g) 
-- -- -- -- -- -- -- 0.5 -- -- -- -- -- 
Titanium oxide (g) 
4 4 4 4 4 4 4 4 4 4 4 4 4 
Calcium carbonate (g) 
76 76 76 76 76 76 76 76 76 76 76 76 76 
Breaking elongation 
300 500 400 700 400 600 350 450 450 350 400 400 400 
(%) 
Breaking strength 
17 15 17 16 18 17 14 15 16 14 15 16 13 
(kg/cm.sup.2) 
50% Modulus of 
5 3 4 2 5 3 4 2 3 4 3 4 3 
elasticity (kg/cm.sup.2) 
Surface adhesiveness 
0.2 0.3 0.1 0.2 0.2 0.3 0.1 0.1 0.1 1.5 1.2 1.0 1.0 
(kg) 
Weather resistance 
Surface condition 
.circleincircle. 
.largecircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.largecircle. 
.circleincircle. 
.largecircle. 
.circleincircle. 
X X X X 
Elongation 85 80 90 85 85 80 85 80 92 50 55 50 55 
retaining rate (%) 
__________________________________________________________________________ 
Curing catalyst 1 is dibutyltin dilaurate 
Curing catalyst 2 is lead dioxide 
In each Test Example, the breaking elongation, the breaking strength and 
the 50% modulus elasticity were measured in accordance with JIS K6301. The 
surface adhesiveness was measured under a load of 100 g by means of a 
Pictamac (manufactured by Toyo Seiki). The weather resistance was 
evaluated by the surface condition (.circleincircle.: no change, 
.largecircle.: no substantial problem although some decrease in gloss was 
observed, X: substantial deterioration in the surface condition) and the 
elongation retaining rate (breaking elongation after the weather resistant 
test/initial breaking elongation .times.100 (%)) after 1,000 hours of 
sunshine weather-o-meter test.