A one-part curing composition comprising a compound (a) having two or more structural groups, per molecule, expressed by the general formula: ##STR1## wherein R.sup.1, R.sup.2, and R.sup.3 are groups selected from an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a chloromethyl group, and a polymer (b) having two or more isocyanate groups per molecule, has a good stability in storage under conditions which exclude moisture and humidity, and which further cures in the presence of humidity. This composition does not foam under high temperatures and humidities and has a good heat resistance.

TECHNICAL FIELD 
The present invention relates to a one-part curing composition which cures 
in the humidity in the air, more particularly it relates to a one-part 
curing composition which comprises as essential constituents a compound 
having two or more silylthio ether bonds per molecule and a polymer having 
two or more isocyanate groups per molecule, which cures naturally in the 
humidity in the air, and which can be used as a sealing material. 
BACKGROUND ART 
Polymers having two or more isocyanate groups per molecule can readily 
polymerize by a reaction with an active hydrogen containing compound or 
water, and are widely used in fields such as sealing materials, caulking 
materials, adhesives, and paints. These isocyanate group-containing 
polymers are mixed with diamines, amino alcohols, glycols, polyols, etc. 
and are used as one-part or two-part curing compositions. 
Of these, some one-part curing compositions cure in the humidity in the air 
by the curing mechanism of formula (1): 
##STR2## 
(where R is a divalent organic group). 
The carbon dioxide gas produced during the curing gives rise to swelling, 
foaming, and gas pockets. In particular, in a one-part curing composition 
with a fast curing speed, gas pockets easily occur inside the cured 
substance or near the interface between the cured substance and the object 
to which it adheres, having a detrimental effect on the sealing effect and 
strength and the adhesion to the object. Further, there is the problem 
that when the cured substance is heated, foaming, and softening or 
embrittlement of the cured substance occurs. 
To resolve these problems, various proposals have been made in the past. 
For example, Japanese Examined Pat. Publication (Kokoku) No. 44-2114 
discloses the addition of calcium oxide to the composition so as to absorb 
the carbon dioxide gas produced during curing. Further, Japanese 
Unexamined Pat. Publication (Kokai) No. 52-17560 discloses the use of a 
reaction of polyalkylene ether diol and polyalkylene triol with an excess 
of diisocyanate polymer having equivalent isocyanate groups and the use of 
a polymer which blocks the remaining isocyanate groups to suppress the 
foaming due to carbon dioxide gas so as to provide a one-part curing 
composition with a fast curing no speed. Further, German Pat. No. 
2,116,882, No. 2,521,841, No. 2,651,479, and No. 2,718,393 disclose 
methods for curing without generation of carbon dioxide gas by the 
addition of enamine or compounds containing an enamine group, an alidimine 
group, or a ketimine group. 
However, the method disclosed in Japanese Examined Pat. Publication 
(Kokoku) No. 44-2114 suffers from the problem that the generation of 
carbon dioxide gas under high temperature and humidity conditions exceeds 
the absorption by the calcium oxide and thus it is difficult to completely 
prevent foaming due to the carbon dioxide gas. Further, the method 
disclosed in Japanese Unexamined Pat. Publication (kokai) No. 52-17560 has 
the defect that foaming occurs under high temperature and humidity 
conditions and further that the usable isocyanate containing polymers are 
limited. Further, in the methods disclosed in German Pat. No. 2,116,882, 
No. 2,521,841, No. 2,651,479, No. 2,718,393, the active 
hydrogen-containing compounds used are limited to amines and the curing 
speed is slow. Further, the softening or embrittlement of the cured 
substance upon high temperature heating is considered to derive from the 
urethane bonds or urea bonds in the cured substance and, in the case of 
the use of polyamines or polyols as curing agents, improvement is 
difficult. 
DISCLOSURE OF THE INVENTION 
An object of the present invention is to provide a one-part curing 
composition which avoids foaming due to carbon dioxide gas, and the 
problems in conventional one-part curing compositions using 
isocyanate-containing polymers as basic components, and enables curing by 
a curing mechanism free from generation of carbon dioxide gas. 
Another object of the present invention is to provide a one-part curing 
composition free from foaming under high temperature and humidity 
conditions, with a fast curing speed even at low temperature, and with 
superior heat resistance. 
The present invention provides a one-part curing composition comprising (a) 
a compound having two or more structural groups, per molecule, expressed 
by the general formula: 
##STR3## 
wherein, R.sup.1, R.sup.2, and R.sup.3 are groups selected from an alkyl 
group having 1 to 6 carbon atoms, phenyl group, and chloromethyl group, 
and (b) a polymer having two or more isocyanate groups per molecule.

DESCRIPTION OF THE PREFERRED EMBODIMENTS 
When R.sup.1, R.sup.2, and R.sup.3 in the general formula (I) are alkyl 
groups, each alkyl group preferably has one to two carbon atoms. Further, 
the structural group of the general formula: 
##STR4## 
is more preferable because the materials are readily available and the 
rate of reaction with water is fast. In particular, in the above formula, 
it is preferable that R.sup.1 is a methyl group. 
The structural group of general formula (I) hydrolyzes due to the moisture 
in the air to be thereby converted to a thiol group containing active 
hydrogen. 
Compound (a) having the structural group of general formula (I) preferably 
has a molecular weight of 200 to 10,000, particularly 300 to 3,000. If the 
molecular weight is less than 200, the hydrolysis speed is strikingly 
fast, so handling of the compound becomes difficult and, further, the 
storage stability of the composition declines. Further, when the molecular 
weight is over 10,000, the hydrolysis speed becomes slower and the curing 
speed of the composition becomes slower. Compound (a) preferably is in a 
liquid state at 20.degree. C. 
As the compound (a) with two or more structural groups expressed by general 
formula (I) per molecule, there is, for example, the following: 
##STR5## 
where q' is an integer from 0 to 25, and z is an integer from 1 to 4, the 
mean value of which is about 2. 
A polymer with a q' of over 25 is not preferable since it has poor 
compatibility with isocyanate group-containing polymers, in particular 
urethane prepolymers having skeletons of polyether or polyester. 
Among the compounds, particularly preferable is 
##STR6## 
where r is an integer of from 0 to 10. 
##STR7## 
where R.sup.5 and R.sup.6 are alkylene groups with two or three carbon 
atoms and s is an integer from 0 to 50; 
This is preferable since it has good compatibility with urethane 
prepolymers. 
In addition, the following compounds are suitable as the compound (a): 
##STR8## 
where m is an integer from 0 to 25 and R.sup.4 is hydrogen or a methyl 
group, 
##STR9## 
Of course, the compound (a) mixed in the one-part curing composition of the 
present invention may be one or two types or more. 
The compound having two or more structural groups of the general formula 
(I) in a molecule may be synthesized by causing a reaction of a 
commercially available silylation reagent etc. with a known compound 
having two or more thiol groups in a molecule to convert the thiol groups 
to trialkylsilylthio groups. 
Here, as the known compound having thiol groups used as the raw material, 
mention may be made of the liquid polysulfide polymer disclosed in the 
specification of U.S. Pat. No. 2,466,963, but a compound with the 
structure expressed by the general formula: 
##STR10## 
where, in the formula, q is an integer from 1 to 25, preferably 1 to 10, 
and z is an integer from 1 to 4, with a mean value of about 2, or 
EQU HS.multidot.CH.sub.2 CH.sub.2 OCH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2 SH(II') 
is preferable. 
Further, the polysulfide compound expressed by general formula (II) 
sometimes has introduced therein a small amount of a crosslinking agent in 
its synthesis stage and a unique structure derived from the crosslinking 
agent may be present in the skeleton. Further, in addition to the 
disulfide bonds shown in general formula (II), it is possible for a small 
amount of monosulfide bonds, trisulfide bonds and tetrasulfide bonds to be 
present, but the mean value of the number of sulfur atoms is two so they 
are shown by disulfide bonds. 
Further, as other known compounds, mention may be made, for example, of 
polyoxyalkylenepolyol disclosed in Japanese Examined Pat. Publication 
(Kokoku) No. 47-48,279 and having the structure shown by general formula 
(III), polymercaptan disclosed in the specification of U.S. Pat. No. 
4,092,293 and having the structure shown by general formula (IV), 
mercaptanterminated liquid polymers having 
##STR11## 
at least in part of the skeleton, for example a mercaptan terminated 
liquid polymer disclosed in the specification of U.S. Pat. No. 3,923,748 
and having a urethane group-containing structure expressed by general 
formula (V), a liquid polythioether disclosed in the specification of U.S. 
Pat. No. 4,366,307 and having the structure expressed by general formula 
(VI), which has mercaptan terminals, a poly(oxyalkylene)-polyester-poly 
(monosulfide)-polythiol disclosed in Japanese Examined Pat. Publication 
(Kokoku) No. 52-34,677, the butadiene mercaptan polymer disclosed in the 
specification of U.S. Pat. No. 3,282,901, the mercaptancontaining polymers 
disclosed in the specification of U.S. Pat. No. 3,523,985, and the 
mercapto-organopolysiloxane disclosed in Japanese Examined Pat. 
Publication (Kokoku) No. 55-39,261, Japanese Examined Pat. Publication 
(Kokoku) No. 60-3,421, etc. It is possible to use these as a materials. 
##STR12## 
wherein, u, v, w, x, and y are integers from 2 to 100 and R.sup.4 is 
hydrogen or a methyl group. 
Further, as other thiol group-containing compounds, there are known 
polymers such as 
EQU HS(CH.sub.2 CH.sub.2 O)SCH.sub.2 CH.sub.2 SH 
wherein s is an integer of from 0 to 50, and monomers such as 
##STR13## 
As a method for converting the thiol groups included in these known thiol 
group-containing compounds into trialkylsilyl groups, it is possible to 
cause a reaction between halogenosilanes, expressed by the general 
formula: 
EQU R.sup.1 R.sup.2 R.sup.3 SiX (VII) 
of an equal molar amount or more of the thiol groups included in the raw 
material compound and triethylamine. 
R.sup.1, R.sup.2, and R.sup.3 in general formula (VII) are as explained 
previously and X expresses a halogen atom. As specific examples of these 
halogenosilanes, there are trimethylchlorosilane, trimethylbromosilane, 
trimethyliodosilane, dimethylphenylchlorosilane, 
chloromethyldimethylchlorosilane, etc., but from the reactivity with thiol 
groups, the ease of removal of by-products, and economy, 
trimethylchlorosilane is particularly preferable. Further, as the method 
for converting the thiol groups included in the known thiol 
group-containing polymers, mentioned above, into trimethylsilylthio 
groups, it is possible to cause a reaction of 
N,O-bis(trimethylsilyl)acetoamide or N,N'-bis(trimethylsilyl)urea, in an 
amount one-half a mole or more, with respect to the thiol groups included 
in the raw material compound. 
Further, as the method for converting the thiol groups in the known 
compound to trimethylsilylthio groups, it is possible to cause a reaction, 
under the presence of a suitable reaction catalyst, of one-half a mole or 
more, preferably an equimolar amount to three mole amount, of 
hexamethyldisilazane, with respect to the thiol groups included in the 
compound. As the reaction catalyst, use may be made of substances 
described in J. Org. Chem., 47, 3966 (1982), but of these it is 
particularly preferably to use 0.001 to 0.1 equivalent of imidazole or 
saccharin with respect to the raw material compound. 
Even when using one of the above-mentioned methods for converting thiol 
groups to trialkylsilylthio groups, a large excess of a silylating agent 
is needed when the known raw material compound includes, in addition to 
thiol groups, hydroxyl groups, amino groups, and other functional groups, 
which are reactable with silylating agents, and when, for the raw 
material, use is made of a compound having the structure of general 
formula (III) and (V). This is not preferable procedure-wise or 
economically. 
Next, as the isocyanate group-containing polymer of the component (b) of 
the present invention, use may be made of commercially available polyester 
type urethane prepolymers, polyether type urethane prepolymers, etc., but 
of these, particularly preferable is a polymer with a molecular weight of 
500 to 20,000 including two or more isocyanate groups at the terminals. 
More preferable is one of 2000 to 8000. With a molecular weight under 500, 
the reactivity of the isocyanate groups rises and the storage stability 
deteriorates. Further, foaming easily occurs. Further, when over 20,000, 
the reactivity of the isocyanate is low and the curing ability declines. 
These isocyanate group-containing polymers may be obtained as reaction 
products of organic polyisocyanates with active hydrogen-containing 
compounds. 
As examples of active hydrogen-containing compounds, there are 
hydroxyl-terminated polyester, polyhydroxypolyalkyleneether, 
hydroxyl-terminated polyurethane polymers, polyvalent polythioether, 
polyacetal, aliphatic polyol; alkane, alkene, alkin, and other aliphatic 
thiols with two or more SH groups; diamines including aromatic, aliphatic, 
heterocyclic diamines, etc.; and mixtures of the same. 
Further, as examples of organic polyisocyanates, there are diisocyanates 
such as m-phenylenediisocyanate, toluene-2,4-diisocyanate, 
hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate, 
cyclohexane-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 
1-methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4-diisocyanate, and 
4,4'-biphenylenediisocyanate; triisocyanates such as 
4,4,'"-triphenylmethanetriisocyanate, and toluene-2,4,6-triisocyanate; and 
tetraisocyanate such as 4,4'-dimethyldiphenylmethane-2,2', 
5,5,-tetraisocyanate. These may be used alone or in the form of a mixture. 
Further, in the present invention, regarding the mixing ratio of the 
compound (a) and the polymer (b), the molar ratio of the structural groups 
of general formula (I) to the isocyanate groups is 0.3 to 2.0, preferably 
0.8 to 1.2. 
When the molar ratio of the structural groups of general formula (I) to the 
isocyanate groups is less than 0.3, the crosslinking points increase, the 
cured product becomes harder, and the elongation declines. Further, the 
residual isocyanate groups in the cured product become a cause of foaming. 
When the molar ratio of the structural groups of general formula (I) to the 
isocyanate groups is over 2.0, the compound with the structural groups of 
general formula (I) behaves as a terminal short-stopping agent and 
strikingly interferes with the polymerization of the composition, so this 
is not desirable. 
To reduce the cost and improve the handling property of the composition and 
the physical properties of the cured product, the composition of the 
present invention may have added thereto, in addition to the 
above-mentioned two essential components, fillers such as calcium 
carbonate, carbon black, and titanium oxide, and plasticizers such as 
butylbenzyl phthalate, and dioctyl phthalate. 
However, to obtain a one-part curing composition with a superior storage 
stability, it is preferable to use, fully dehydrated fillers and 
plasticizers, which are free from hydroxyl groups, amino groups, thiol 
groups, and other functional groups and do not have striking acidity or 
alkalinity. 
Further, the composition of the present invention may have added thereto a 
powdered molecular sieve with the aim of enhancing the storage stability. 
Further, the composition of the present invention preferably has added 
thereto a catalyst for ensuring rapid and reliable curing after 
application. As the catalyst, there are reaction catalysts between the 
thiol groups which are formed by hydrolysis of the structural groups of 
general formula (I) due to the humidity in the air, and the isocyanate 
groups, and catalysts capable of hydrolyzing the structural groups of 
general formula (I). 
As the former reaction catalysts, use may be made of tertiary amine 
catalysts such as triethylenediamine, triethylamine, 
pentamethylenediethylenetriamine, N,N-dimethylcyclohexylamine, and 
N,N-dicyclohexylmethylamine; and metal catalysts, primarily 
organomethallic catalysts such as dibutyltin diacetate, dibutyltin 
dilaurate, dibutyltin dimalate, and lead octenate. 
The amount of these catalysts used differs according to the molecular 
weight and structure of the compound (a) and polymer (b), but preferably 
addition is made of 0.01 to 1.0 part by weight, particularly preferably 
0.1 to 0.3 part by weight, per 100 parts by weight of the compound (a) and 
polymer (b). With less than 0.01 part by weight, the curing speed of the 
composition declines, so this is not preferable. Further, over 1.0 part by 
weight, there is an adverse effect on the storage stability of the 
composition, so this too is not preferable. 
Further, as the latter hydrolysis catalyst for the structural groups of 
general formula (I), use may be made in general of amines. As these 
amines, tertiary amines are particularly preferable. For example, 
triethylamine, tripropylamine, tributylamine, pyridine, 
N-methyl-2-pyrrolidone, dimethylaniline, benzyldimethylamine, 
hexamethylenetetramine, 2,4,6-trisdimethylaminomethylphenol, and 
diphenylguanidine, among which hexamethylenetetramine and 
2,4,6-trisdimethylam.noi methylphenol, and diphenylguanidine are 
preferable as they lack volatility. 
The amount of amines used is preferably 0.01 to 3.0 parts by weight per 100 
parts by weight of the compound of component (a). When over 3.0 parts by 
weight, the storage stability deteriorates and when under 0.01 part by 
weight, the hydrolysis does not progress, so these are not preferable. 
The composition of the present invention contains a compound having two or 
more structural groups per molecule, inert to an isocyanate group, 
expressed by general formula (I) and a polymer having two or more 
isocyanate groups per molecule, so in a state shut out from moisture and 
humidity, storage stability as a one-part curing composition is imparted. 
Further, in the present composition, the structural groups of general 
formula (I) of the composition easily hydrolyze due to the humidity in the 
air, as shown in formula (2), thereby to be converted to thiol groups. The 
produced thiol groups react with the polymer with the isocyanate groups as 
shown by formula (3) and polymerize to cure. That is, the composition of 
the present invention can be used as a one-part curing composition. 
##STR14## 
(R', R" are organic groups) 
Below, an explanation will be given of synthesis examples of the compound 
(a) having structural groups shown by general formula (I) and examples of 
the one-part curing composition of the present invention. 
SYNTHESIS EXAMPLE 1 
A 500 g amount (0.5 mole) of a liquid polysulfide expressed by 
EQU HS(CH.sub.2 CH.sub.2 OCH.sub.2 OCH.sub.2 CH.sub.2 SS).sub.5 CH.sub.2 
CH.sub.2 O CH.sub.2 OCH.sub.2 CH.sub.2 SH 
(made by Toray Thiokol Co., Thiokol LP-3), 161 g (1.0 mole) of 
hexamethyldisilazane, 0.5 g (0.0024 mole) of saccharin, and 50 g of 
dichloroethane were charged into a 1 liter capacity reactor provided with 
a condenser and a stirrer, heated to 120.degree. C., and stirred for 5 
hours. Vacuum distillation was carried out to remove the dichloroethane, 
and excess hexamethyldisilazane and by-products and obtain the polymer 
shown by the following structural formula: 
##STR15## 
SYNTHESIS EXAMPLE 2 
A charge composed of 182 g (1.0 mole) of triethylene glycol dimercaptan 
expressed by the formula: 
EQU HS(CH.sub.2 CH.sub.2 O).sub.2 CH.sub.2 CH.sub.2 SH, 
322 g (2.0 mole) of hexamethyldisilazane, 1.0 g (0.005 mole) of saccharin, 
and 50 g of dichloroethane was treated in the same way as Synthesis 
Example 1 to obtain the compound shown by the following structural 
formula: 
EQU (CH.sub.3).sub.3 SiS(CH.sub.2 CH.sub.2 O).sub.2 CH.sub.2 CH.sub.2 
SSi(CH.sub.3).sub.3. 
SYNTHESIS EXAMPLE 3 
A charge composed of 216 g (0.5 mole) of pentaerythritol tetrathioglycolate 
expressed by the formula: 
EQU HSCH.sub.2 COOCH.sub.2 C(CHOCOCH.sub.2 SH).sub.3, 
322 g (2.0 mole) of hexamethyldisilazane, 1.0 g (0.005 mole) of saccharin, 
and 50 g of dichloroethane was treated in the same way as Synthesis 
Example 1 to obtain the compound shown by the following structural 
formula: 
EQU (CH.sub.3).sub.3 SiSCH.sub.2 COOCH.sub.2 C(CH.sub.2 OCOCH.sub.2 
SSi(CH.sub.3).sub.3 }.sub.3 
A catalyst, a filler, a plasticizer, and a molecular sieve were 
incorporated with each of the compounds containing two or more structural 
groups of the general formula (I) obtained in the synthesis examples and a 
commercially available isocyanate group-containing polymer to obtain the 
composition of the present invention, and its performance was evaluated. 
As the commercially available isocyanate group-containing polymer, use was 
made of three types of polymers (Sanprene SEL-No. 3, No. 23, and No. 25) 
of Sanyo Chem. Ind. Ltd., with a PPG skeleton terminated with tolylene 
diisocyanate (TDI), alone or in mixture. 
______________________________________ 
Product name Viscosity (CSP/30.degree. C.) 
NCO (%) 
______________________________________ 
Sanprene SEL No. 3 
7000 3.6 
Sanprene SEL No. 23 
5000 3.2 
Sanprene SEL No. 25 
9000 2.2 
______________________________________ 
EXAAMPLE 1 
A paste of the composition shown in Table 1 (PM-1) was prepared by heating, 
drying, and mixing under reduced pressure. A 45 parts by weight of the 
polymer obtained in Synthesis Example 1 and 100 parts by weight of 
Sanprene SEL No. 3 were heated at 60.degree. C. for 20 minutes and then 
stirred to obtain a polymer composition (1). The polymer composition was 
mixed together in a nitrogen stream so as to prevent the moisture into the 
system. 
TABLE 1 
______________________________________ 
Formulation of PM-1 
Ingredients Parts by weight 
______________________________________ 
CaCO.sub.3 140 
Butylbenzyl phthalate 
85 
Powdered molecular sieve 
4 
______________________________________ 
The following evaluation was carried out using the composition obtained by 
mixing under reduced pressure at room temperature 300 parts by weight of 
PM-1 with 100 parts by weight of the polymer composition (1) obtained 
above. 
The degree of the storage stability of the composition was considered in 
terms of the time after sealing air tightly the mixture in a tube until 
the mixture became viscous or solidified, at various temperatures, making 
extrusion impossible. 
Using this composition a one-sided bead of a width of 12 mm and a depth of 
15 mm was prepared. This was exposed to various temperatures and 
humidities and cut after fixed intervals. The thickness of the cured 
portion from the surface (in units of mm) was measured and used as the 
degree of curability. 
Further, the composition was allowed to stand at 20.degree. C. under a 
relative humidity of 55 percent and the tack-free time measured. The 
tack-free time (TF) means the time until the composition formed a film on 
its surface and the tackiness of the film was lost. The results are shown 
in Table 3. 
EXAMPLE 2 
A charge composed of 36 parts by weight of the polymer obtained in 
Synthesis Example 1 and 100 parts by weight of Sanprene SEL No. 3 was 
heated at 60.degree. C. for 20 minutes with stirring, then added with 0.1 
part by weight of triethylamine, then further heated at 60.degree. C. for 
20 minutes with stirring to obtain a polymer composition (2). The polymer 
composition (2) was mixed together in a nitrogen stream so as to prevent 
the moisture into the system. 
A 100 parts by weight amount of the polymer composition (2) and 300 parts 
by weight of the PM-1 of Table 1 were mixed to obtain a composition which 
was used for measurement of the storage stability, curability, and TF in 
the same way as Example 1. The results are shown in Table 3. 
EXAMPLE 3 
A charge composed of 45 parts by weight of the polymer obtained in 
Synthesis Example 1 and 100 parts by weight of Sanprene SEL No. 3 was 
heated at 60.degree. C. for 20 minutes with stirring, then added with 0.1 
part by weight of N,N-dimethylcyclohexylamine, then further heated at 
60.degree. C. for 20 minutes with stirring to obtain a polymer composition 
(3). The polymer composition (3) was mixed together in a nitrogen stream 
so as to prevent the moisture into the system. 
A 100 parts by weight amount of the polymer composition (3) and 300 parts 
by weight of the PM-1 shown in Table 1 were mixed to obtain a composition 
which was used for measurement of the storage stability, curability, and 
TF in the same way as Example 1. The results are shown in Table 3. 
EXAMPLE 4 
A charge composed of 45 parts by weight of the polymer obtained in 
Synthesis Example 1 and 100 parts by weight of Sanprene SEL No. 3 were 
heated at 60.degree. C. for 20 minutes with stirring, then added with 0.1 
part by weight of triethylamine and 0.1 part by weight of 
diphenylguanidine, then further heated at 60.degree. C. for 20 minutes and 
stirred to obtain a polymer composition (4). The polymer composition (4) 
was mixed together in a nitrogen stream so as to prevent entry of moisture 
into the system. 
A 100 parts by weight amount of the polymer composition (4) and 300 parts 
by weight of the PM-1 shown in Table 1 were mixed to obtain a composition 
which was used for measurement of the storage stability, curability, and 
TF in the same way as Example 1. The results are shown in Table 3. 
EXAMPLE 5 
A charge composed of 32 parts by weight amount of the polymer obtained in 
Synthesis Example 1 and 100 parts by weight of Sanprene SEL No. 23 were 
heated at 60.degree. C. for 20 minutes with stirring, then added with 0.1 
part by weight of triethylamine, then further heated at 60.degree. C. for 
20 minutes and stirred to obtain a polymer composition (5). The polymer 
composition (5) was mixed together in a nitrogen stream so as to prevent 
entry of moisture into the system. 
A 100 parts by weight amount of the mixed polymer (5) and 300 parts by 
weight of the PM-1 shown in Table 1 were mixed to obtain a composition 
which was used for measurement of the storage stability, curability, and 
TF in the same way as Example 1. The results are shown in Table 3. 
EXAMPLE 6 
A charge composed of 48 parts by weight of the polymer obtained in 
Synthesis Example 1, 100 parts by weight of Sanprene SEL No. 23, 25 parts 
by weight of Sanprene No. 25, plus 0.16 part by weight of triethylamine 
was treated by the same procedure as in Example 2 to obtain a polymer 
composition (6). A 100 parts by weight amount of the mixed polymer 
composition (6) and 300 parts by weight of the PM-1 shown in Table 1 were 
mixed to obtain a composition which was used for measurement of the 
storage stability, curability, and TF in the same way as Example 1. The 
results are shown in Table 3. 
EXAMPLE 7 
A paste of the composition shown in Table 2 (PM-2) was prepared by heating 
and drying under reduced pressure. 
A charge composed of 38 parts by weight of the polymer obtained in 
Synthesis Example 1, 100 parts by weight of Sanprene SEL No. 23, 25 parts 
by weight of Sanprene No. 25, plus 0.16 part by weight of triethylamine 
was treated by the same procedure as in Example 2 to obtain a polymer 
composition (7). A 100 parts by weight amount of the polymer composition 
(7) and 300 parts by weight of the PM-2 shown in Table 2 were mixed to 
obtain a composition which was used for measurement of the storage 
stability, curability and TF in the same way as Example 1. The results are 
shown in Table 3. 
TABLE 2 
______________________________________ 
Formulation of PM-2 
Mixture Parts by weight 
______________________________________ 
CaCO.sub.3 145 
Dioctyl phthalate 80 
Powdered molecular sieve 
4 
______________________________________ 
Further, the composition was used for measurement of the tensile properties 
according to JIS A-5758 (physical property measurement method A). The 
results are shown in Table 4. 
Further, the composition was used for measurement of the tensile properties 
at a pulling speed of 500 mm/min according to ASTM 638-84 TYPE IV 
(physical property measurement method B). The results are shown in Table 
5. 
EXAMPLE 8 
A charge composed of 39 parts by weight of the polymer obtained in 
Synthesis Example 1, 100 parts by weight of Sanprene SEL No. 3, and 0.1 
parts by weight of triethylamine was treated by the same procedure as in 
Example 2 to obtain a polymer composition (8). A 100 parts by weight 
amount of the polymer composition (8) and 300 parts by weight of the PM-1 
shown in Table 1 were mixed to obtain a composition which was used to 
prepare samples for measurement of physical properties in the same way as 
Example 7. Then, after aging, the tensile properties were measured 
according to the physical property measurement method A. The results are 
shown in Table 4. 
EXAMPLE 9 
A charge composed of 39 parts by weight of the polymer obtained in 
Synthesis Example 1, 100 parts by weight of Sanprene SEL No. 3, and 0.1 
part by weight of triethylamine was treated by the same procedure as in 
Example 2 to obtain a polymer composition (9). A 100 parts by weight 
amount of the polymer composition (9) and 300 parts by weight of the PM-1 
shown in Table 1 were mixed to obtain a composition which was used for 
measurement of tensile properties in the same way as Example 8. The 
results are shown in Table 4. 
EXAMPLE 10 
A charge composed of 49 parts by weight of the polymer obtained in 
Synthesis Example 1, 100 parts by weight of Sanprene SEL No. 3, and 0.1 
part by weight of triethylamine was treated by the same procedure as in 
Example 2 to obtain a polymer composition (10). 
A 100 parts by weight amount of the mixed polymer composition (10) and 300 
parts by weight of the PM-1 shown in Table 1 were mixed to obtain a 
composition which was used for measurement of tensile properties in the 
same way as Example 8. The results are shown in Table 4. 
EXAMPLE 11 
A charge composed of 59 parts by weight of the polymer obtained in 
Synthesis Example 1, 100 parts by weight of Sanprene SEL No. 3, and 0.1 
part by weight of triethylamine was treated by the same procedure as in 
Example 2 to obtain a polymer composition (11). 
A 100 parts by weight amount of the polymer composition (11) and 300 parts 
by weight of the PM-1 shown in Table 1 were mixed to obtain a composition 
which was used for measurement of tensile properties in the same way as 
Example 8. The results are shown in Table 4. 
EXAMPLE 12 
A charge composed of 15 parts by weight of the polymer obtained in 
Synthesis Example 1, 100 parts by weight of Sanprene SEL No. 23, 25 parts 
by weight of Sanprene No. 25, plus 0.16 part by weight of triethylamine 
was treated by the same procedure as in Example 2 to obtain a polymer 
composition (12). A 100 parts by weight amount of the polymer composition 
(12) and 300 parts by weight of the PM-1 shown in Table 1 were mixed to 
obtain a composition which was used for measurement of the storage 
stability, curability, and TF in the same way as Example 1. The results 
are shown in Table 3. 
EXAMPLE 13 
A charge composed of 15 parts by weight of the polymer obtained in 
Synthesis Example 3, 100 parts by weight of Sanprene SEL No. 23, 25 parts 
by weight of Sanprene No. 25, plus 0.16 part by weight of triethylamine 
was treated by the same procedure as in Example 2 to obtain a polymer 
composition (13). A 100 parts by weight amount of the polymer composition 
(13) and 300 parts by weight of the PM-1 shown in Table 1 were mixed to 
obtain a composition which was used for measurement of the storage 
stability, curability, and TF in the same way was Example 1. The results 
are shown in Table 3. 
COMATIVE EXAMPLE 1 
To 100 parts by weight of Sanprene SEL No. 3 was added 0.1 part by weight 
of triethylamine and the mixture treated by the same procedure as in 
Example 2 to obtain a polymer composition (14). A 100 part by weight 
amount of the polymer composition (14) and 300 parts by weight of the PM-1 
shown in Table 1 were mixed to obtain a composition which was used for 
measurement of the storage stability and curability in the same way as 
Example 1. The results are shown in Table 3. 
COMATIVE EXAMPLE 2 
To 100 parts of weight of Sanprene SEL No. 23 was added 0.1 parts by weight 
of triethylamine and the mixture treated by the same procedure as in 
Comparative Example 1 to obtain a composition which was used for 
measurement of the storage stability and curability in the same way as 
Example 1. The results are shown in Table 3. 
COMATIVE EXAMPLE 3 
To 100 parts by weight of Sanprene SEL No. 25 was added 0.1 part by weight 
of triethylamine and the mixture treated by the same procedure as in 
Comparative Example 1 to obtain a composition which was used for 
measurement of the storage stability and curability in the same way as 
Example 1. The results are shown in Table 3. 
COMATIVE EXAMPLE 4 
A commercially available one-part urethane sealant (made by Auto Chem. Ind. 
CO., Auton Sealer 101A) was used for measurement of the storage stability, 
curability, and TF in the same way as Example 1. Further, the physical 
properties of the cured substance and the physical properties after 
heating were measured in the same way as Example 8, the results of which 
are shown in Table 3 and Table 5. There were no problems in the physical 
properties of the cured substance and the physical properties after 
heating, but the curing speed was slow and thus inferior. 
TABLE 3 
__________________________________________________________________________ 
Ex. 1 
Ex. 2 
Ex. 3 
Ex. 4 
Ex. 5 
Ex. 6 
Ex. 7 
Ex. 12 
Ex. 13 
C. Ex. 1 
C. Ex. 2 
C. Ex. 
C. Ex. 
__________________________________________________________________________ 
4 
Storage stability 
50.degree. C. (days) 
-- 3 4 -- 4 15 4 3 -- -- -- -- 
35.degree. C. 
60 4 10 60 20 60 More 
10 -- -- -- -- 
than 
30 
20.degree. C. 
More More 
More 
More -- -- -- -- 
than than 
than 
than 
200 200 100 200 
Curability 
20.degree. C., 55% RH 
1 day* -- -- -- -- -- -- -- 1.4 3.0 Foamed 
Foamed 
Foamed 
1.0 
2 days -- -- -- -- -- 3.3 2.3 3.1 4.5 2.0 
3 days 3.0 
4.1 6.0 
8.0 
3.4 3.7 2.9 4.2 5.6 2.8 
10.degree. C., 40% RH 
3 days 1.0 
-- -- -- -- 2.1 1.7 2.6 3.6 Foamed 
Foamed 
Foamed 
1.0 
5 days 1.8 
2.8 4.5 
4.2 
2.6 -- -- -- -- 1.2 
7 days 3.0 
3.8 5.3 
5.1 
3.4 3.9 2.9 4.7 5.2 1.8 
TF (tackfree, 
1.2 
1.0 0.5 
1.0 
1.5 2.0 2.5 0.5 0.5 -- -- -- 5.0 
hour) 
__________________________________________________________________________ 
*Days of exposure. 
TABLE 4 
______________________________________ 
Aging conditions and 
measurement items 
Ex. 8 Ex. 9 Ex. 10 
Ex. 11 
Ex. 7 
______________________________________ 
35.degree. C., 55% RH .times. 5 days 
50% Modulus (kg/cm.sup.2) 
5.9 5.3 1.5 0.6 3.0 
100% Modulus (kg/cm.sup.2) 
-- -- 2.0 0.8 3.8 
150% Modulus (kg/cm.sup.2) 
-- -- 2.3 1.0 4.0 
Breaking strength (kg/cm.sup.2) 
6.1 5.5 2.8 1.8 5.6 
Elongation (%) 56 60 340 470 380 
______________________________________ 
Measurement temperature 20.degree. C. 
TABLE 5 
______________________________________ 
Aging conditions and measurement items 
Ex. 7 Comp. Ex. 4 
______________________________________ 
20.degree. C., 55% RH .times. 3 days 
100% Modulus (kg/cm.sup.2) 
4.6 2.4 
200% Modulus (kg/cm.sup.2) 
5.4 4.4 
300% Modulus (kg/cm.sup.2) 
6.1 6.5 
Breaking strength (kg/cm.sup.2) 
10.4 14.8 
Elongation (%) 550 850 
20.degree. C., 55% RH .times. 3 days + heating 
(90.degree. C.) .times. 7 days 
100% Modulus (kg/cm.sup.2) 
4.4 4.3 
200% Modulus (kg/cm.sup.2) 
6.5 7.2 
300% Modulus (kg/cm.sup.2) 
7.8 10.3 
Breaking strength (kg/cm.sup.2) 
14.7 19.8 
Elongation (%) 730 930 
20.degree. C., 55% RH .times. 3 days + heating 
(90.degree. C.) .times. 14 days 
100% Modulus (kg/cm.sup.2) 
4.2 4.2 
200% Modulus (kg/cm.sup.2) 
6.8 6.4 
300% Modulus (kg/cm.sup.2) 
7.9 9.0 
Breaking strength (kg/cm.sup.2) 
16.0 16.1 
Elongation (%) 800 950 
______________________________________ 
Measurement temperature 20.degree. C. 
CAPABILITY OF EXPLOITATION IN INDUSTRY 
The composition of the present invention comprises a compound (a) having 
two or more structural groups expressed by general formula (I) per 
molecule and a polymer (b) having two or more isocyanate groups per 
molecule, so is provided with both stability in storage and curing ability 
after application and is superior as a one-part curing composition. 
Further, the composition of the present invention can make use of all 
sorts of urethane polymers. Further, the composition of the present 
invention does not foam even under high temperature and humidity 
conditions where the curing speed is fast and, further, resolves the 
problems of post-heating foaming, changes in physical properties, etc. 
which plagued the conventional one-part and two-part urethane cured 
substances thus enabling acquisition of a cured substance superior in heat 
resistance. Further, the addition of a suitable catalyst gives it a 
superior curability even under low temperature conditions. 
The composition of the present invention is useful as a sealing material, 
caulking material, paint, adhesive, etc.