Surfactant

The surfactant of this invention is a compound of general formula (I) ##STR1## wherein R.sub.1 is an alkyl, alkenyl or aralkyl group containing 6 to 18 carbon atoms; R.sub.2 is a hydrogen atom or an alkyl, alkenyl or aralkyl group containing 6 to 18 carbon atoms; R.sub.3 is a hydrogen atom or a propenyl group; A is an alkylene group of 2 to 4 carbon atoms; n is an integer of 1 to 200.

BACKGROUND OF THE INVENTION 
The present invention relates to a surfactant. 
Surfactants are generally possessed of a diversity of activities such as 
emulsifying, dispersing, detergent, wetting, foaming and other activities 
and as such have been utilized in almost all fields of modern industry 
such as paper, rubber, plastics, metal, paints, pigments and even civil 
engineering. Recently, particularly active attempts have been made to 
utilize surfactants for improving the performance of many end products but 
several concomitant drawbacks of surfactants have also come to be 
recognized in the course of such development endeavors. 
Taking paints, printing inks, adhesives and pressure-sensitive adhesives as 
examples, surfactants are indispensable for the manufacture or 
stabilization of these products or in terms of processability. However, 
after such products have once been used for coating, printing, adhesion or 
pressure bonding, the surfactants are no longer necessary. Rather, if they 
remain in the products, surfactants tend to adversely affect the 
resistance of the film, print or adhesive layer to water and oil in many 
instances. 
Reduction of the level of addition of surfactants or increase of the 
molecular weight of surfactants have been the common approaches taken 
these days to overcome the problems but no satisfactory solutions have 
been found as yet in terms of product stability and workability. 
Meanwhile, as surfactants for use as emulsifiers for emulsion 
polymerization, anionic surfactants such as sodium dodecylbenzenesulfonate 
and nonionic surfactants such as polyoxyethylene nonylphenyl ether are 
known. However, the film of a polymer emulsion prepared using such an 
emulsifier has the drawbacks of poor resistance to water and poor bond 
strength because the emulsifier remains in free form in the polymer film. 
To obviate these problems, several reactive emulsifiers containing 
copolymerizable unsaturated groups have been proposed. 
For example, anionic reactive surfactants have been disclosed in Japanese 
Patent Publication No. 46-12472, Japanese Kokai Patent Publication No. 
54-144317, Japanese Patent Publication No. 46-34894, Japanese Patent 
Publication No. 56-29657, Japanese Kokai Patent Publication No. 51-30285, 
Japanese Patent Publication No. 49-46291, and Japanese Kokai Patent 
Publication No. 56-127697, while nonionic reactive surfactants have been 
described in Japanese Kokai Patent Publication No. 56-28208 and No. 
50-98484, among others, and emulsion polymerization of various monomers 
using these emulsifiers has been attempted. 
Generally speaking, reactive emulsifiers containing an acryl or methacryl 
group as the copolymerizable unsaturated group are well copolymerizable 
with various monomers but are unsatisfactory in terms of the stability of 
emulsion polymerization reaction, giving rise to gels in the course of 
polymerization to produce coarse emulsion grains, and/or tend to give an 
emulsion poor in storage stability. 
Reactive emulsifiers containing an allyl group as said copolymerizable 
unsaturated group have also been described in Japanese Kokai Patent 
Publication No. 62-100502, No. 62-221431 and No. 63-23725, among others, 
but these emulsifiers are often poor in copolymerizability with monomers 
and the polymer films molded from emulsions obtainable with such 
emulsifiers are not fully satisfactory in water resistance and in bond 
strength. 
SUMMARY OF THE INVENTION 
It is an object of the present invention to provide a surfactant which acts 
as a surfactant in the course of manufacture, storage or processing of 
products such as paints, printing inks, adhesives, pressure-sensitive 
adhesives or the like but terminates its function as a surfactant in due 
course thereafter. 
It is a further object of the present invention to provide a surfactant 
which, when used as an emulsifier for emulsion polymerization, insures 
good stability of emulsion polymerization and marked improvements in the 
water resistance and bonding characteristic of the polymer film obtainable 
from the resulting polymer emulsion. 
The surfactant of the present invention is a compound of the following 
general formula (I) 
##STR2## 
wherein R.sub.1 is an alkyl, alkenyl or aralkyl group containing 6 to 18 
carbon atoms; R.sub.2 is a hydrogen atom or an alkyl, alkenyl or aralkyl 
group containing 6 to 18 carbon atoms; R.sub.3 is a hydrogen atom or a 
propenyl group; A is an unsubstituted or substituted alkylene group of 2 
to 4 carbon atoms; n is an integer of 1 to 200.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
In the compound of general formula (I) which constitutes the surfactant of 
the present invention, the substituent group R.sub.1 is an alkyl, alkenyl 
or aralkyl group containing 6 to 18 carbon atoms. The alkyl group 
includes, among others, hexyl, heptyl, octyl, nonyl, decyl, undecyl, 
dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and 
octadecyl. 
The alkenyl group includes, among others, hexenyl, heptenyl, octenyl, 
nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, 
pentadecenyl, hexadecenyl, heptadecenyl and octadecenyl. 
The aralkyl group includes, among others, styryl, benzyl and cumyl. 
The above alkyl, alkenyl and aralkyl groups may be mixedly present in the 
compound of general formula (I). 
The substituent group R.sub.2 is a hydrogen atom or an alkyl, alkenyl or 
aralkyl group containing 6 to 18 carbon atoms. This alkyl group includes, 
among others, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. 
These groups may be mixedly present. 
The alkenyl group includes, among others, hexenyl, heptenyl, octenyl, 
nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, 
pentadecenyl, hexadecenyl, heptadecenyl and octadecenyl. 
The aralkyl group includes, among others, styryl, benzyl and cumyl. 
The above alkyl, alkenyl and aralkyl groups may occur mixedly in the 
compound of general formula (I). 
The propenyl group may occur as trans-and-cis-isomers. For the purpose of 
the present invention, these isomers may be used independently or as a 
mixture, although the trans-configuration is preferred. 
The symbol A means an alkylene group of 2 to 4 carbon atoms. Thus, it may 
for example be ethylene, propylene, butylene or isobutylene as such, and 
(AO).sub.n may for example be a homopolymer or a block or random copolymer 
of ethylene oxide, propylene oxide, butylene oxide or isobutylene oxide. 
The degree of polymerization, n, is an integer of 1 to 200 and preferably 
of 2 to 100. 
The conditions of the reaction for producing the surfactant of the present 
invention are not critical. For example, this surfactant can be produced 
by addition reaction of an alkylene oxide such as ethylene oxide (EO) or 
propylene oxide (PO) to an alkylated propenyl phenol in the conventional 
manner. 
The surfactant of the invention, when used in a paint, printing ink, 
adhesive or pressure-sensitive adhesive, acts as a surfactant in the 
course of manufacture, storage or even processing thereof and, then, cease 
to function as a surfactant in due course thereafter. 
Furthermore, the surfactant of the invention can be used as an emulsifier 
for emulsion polymerization, a dispersing agent for suspension 
polymerization, a dispersing agent for dyes and pigments, an emulsifier 
for waxes, a finishing agent for fibers, an emulsifier-dispersant for 
agrochemicals, an antistatic agent for synthetic resin and so on. In these 
and other applications, the aforesaid adverse effect of a residual 
surfactant can be drastically reduced. 
As monomers which can be emulsion-polymerized using the surfactant of the 
invention as an emulsifier, there may be reckoned acrylic monomers such as 
acrylic acid, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 
methyl methacrylate, acrylonitrile, acrylamide, hydroxyethyl acrylate, 
etc., aromatic monomers such as styrene, divinylbenzene, etc., vinyl ester 
monomers such as vinyl acetate, halogenated olefinic monomers such as 
vinyl chloride, vinylidene chloride, etc.; conjugated diolefin monomers 
such as butadiene, isoprene, chloroprene, etc., as well as ethylene, 
maleic anhydride, methyl maleate, and so on. 
The surfactant of the invention can be used in the emulsion polymerization 
of one or more of said monomers. 
Any of the common polymerization initiators can be used in emulsion 
polymerization reactions employing the surfactant of the invention. Thus, 
for example, hydrogen peroxide, potassium persulfate, 
azobisisobutyronitrile, benzoyl peroxide, etc. can be utilized. 
The polymerization accelerator may for example be sodium hydrosulfite or 
ferrous ammonium sulfate. 
The proportion of the surfactant of the present invention is generally 0.1 
to 20 weight percent, preferably 0.2 to 5.0 weight percent, based on the 
total monomer. If desired, other emulsifiers or protective colloids may be 
used in conjunction. 
Since the surfactant of the present invention contains a propenyl group in 
the hydrophobic moiety of its molecule, it is highly copolymerizable with 
polymerizable monomers, particularly vinyl monomers, and as such is 
readily incorporated in the polymer structure. Therefore, it acts 
effectively as a reactive emulsifier of the copolymerization type, 
featuring a marked decrease in the residual amount of free emulsifier in 
the polymer film formed from the emulsion, thus contributing greatly to 
the water resistance and bonding performance of the film. In addition, the 
surfactant of the invention brings forth marked improvements in the 
stability of emulsion polymerization and the foaming potential and 
mechanical stability of the polymer emulsion. 
The polymer emulsion made available by addition of the surfactant of the 
present invention can be applied, as an adhesive, coating agent, 
impregnation assisting agent or the like, to wood, metal, paper, cloth, 
concrete and other substrate materials. 
The following examples and comparative examples are intended to illustrate 
the invention in further detail and should by no means be construed as 
defining the metes and bounds of the invention. It should also be 
understood that, in the following description, all percents (%) and parts 
are by weight. 
EXAMPLE 1 
In an autoclave, 260 g (1 mole) of nonylpropenylphenol was reacted with 880 
g (20 moles) of ethylene oxide in the presence of potassium hydroxide as 
the catalyst at a pressure of 1.5 kg/cm.sup.2 and a temperature of 
130.degree. C. to prepare a nonylpropenylphenol-ethylene oxide (20 moles) 
adduct which was designated as surfactant (A). The structure of this 
surfactant (A) was confirmed by nuclear magnetic resonance spectrometry 
(FIG. 1). The NMR parameter settings were as follows. 
Nucleus: .sup.1 H. 
Resonance frequency: 270 MHz. 
Solvent: deuteriochloroform. 
Temperature: room temperature. 
Reference standard: TMS. 
Pulse: 45.degree. pulse. 
An octylpropenylphenol-ethylene oxide (50 moles) adduct was similarly 
prepared using 2,200 g (50 moles) of ethylene oxide and this adduct was 
designated as surfactant (B). 
EXAMPLE 2 
In an autoclave, 342 g (1 mole) of distyrylpropenylphenol was reacted first 
with 580 g (10 moles) of propylene oxide and then with 1,320 g (30 moles) 
of ethylene oxide in the presence of potassium hydroxide as the catalyst 
at a pressure of 1.5 kg/cm.sup.2 and a temperature of 130.degree. C. and 
the resulting distyrylpropenylphenol-propylene oxide (10 moles)/ethylene 
oxide (30 moles) adduct was designated as surfactant (C). 
EXAMPLE 3 
Surfactants (D) through (G), shown in Table 1, were prepared as in Examples 
1 and 2. 
TABLE 1 
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Surfactant 
______________________________________ 
(D) Octyldipropenylphenol-ethylene oxide (10 moles) 
adduct 
(E) Octyldipropenylphenol-ethylene oxide (100 moles) 
adduct 
(F) Dodecylpropenylphenol-ethylene oxide (20 moles)/ 
propylene oxide (10 moles) random adduct 
(G) Dodecylpropenylphenol-butylene oxide (4 moles)/ 
ethylene oxide (30 moles) block adduct 
______________________________________ 
EXAMPLE 4 
Each of the surfactants (A) through (G) of the invention as prepared in 
Examples 1, 2 and 3 was dissolved in water at a final concentration of 
0.1% and the surface tension of the solution was measured by the Traube 
method. As controls, the surface tensions of similar solutions of the 
conventional surfactants were also measured. The results are shown in 
Table 2. 
TABLE 2 
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Surface tension 
Surfactant 0.1%, 25.degree. C. (dyne/cm) 
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The invention 
Surfactant (A) 37 
Surfactant (B) 48 
Surfactant (C) 44 
Surfactant (D) 28 
Surfactant (E) 54 
Surfactant (F) 36 
Surfactant (G) 39 
Control 
Sodium dodecylbenzenesulfonate 
36 
Nonylphenol-EO (10 moles) adduct 
31 
Nonylallylphenol-EO (20 moles) adduct 
38 
______________________________________ 
EXAMPLE 5 
Using each of the surfactants (A), (D) and (F) of the invention as prepared 
in Examples 1 and 3, the carbon black dispersing power and kerosene 
emulsifying power were determined. As controls, the corresponding powers 
of the conventional surfactants were also determined. The results are 
shown in Table 3. 
The methods for determination are as follows. Dispersing power: A 
common-stoppered 100 ml measuring cylinder was charged with 1 g of the 
test surfactant, 10 g of carbon black and a sufficient quantity of water 
to make 100 ml. The measuring cylinder was shaken 100 times in a minute 
and, then, allowed to stand at 25.degree. C. for 1 hour. Thereafter, 30 ml 
of the top layer of the suspension was withdrawn and filtered through a 
glass filter. The residue was dried at 105.degree. C. and weighed. The % 
dispersing power was calculated by means of the following equation. 
##EQU1## 
Emulsifying power: A graduated common-stopped test tube of 20 ml capacity 
was charged with 5 ml of a 0.5% aqueous solution of the test surfactant 
and 5 ml of kerosene. After the tube was shaken 100 times in a minute, it 
was allowed to stand at 25.degree. C. for one hour. Thereafter, the volume 
(ml) of the emulsion layer was measured and the % emulsifying power was 
calculated by means of the following equation. 
TABLE 3 
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##STR3## 
Dispersing Emulsifying 
Surfactant power (%) power (%) 
______________________________________ 
The Surfactant (A) 80 75 
inven- Surfactant (D) 85 95 
tion Surfactant (F) 90 80 
Con- Sodium dodecyl- 70 55 
trol benzenesulfonate 
Nonylallyl- 65 70 
phenol-EO (20 moles) 
adduct 
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EXAMPLE 6 
A polypropylene nonwoven fabric (2.5 cm.times.10 cm) was immersed in a 1% 
aqueous solution of each test surfactant (Table 4) for one minute and, 
then, taken out and dried in a hot air current at 120.degree. C. for 30 
minutes. 
The nonwoven fabric treated as above was suspended over a 100 ml beaker 
containing 50 ml of water, with a lower 1 cm portion of the fabric being 
immersed in the water. After 5 minutes, the height of water penetration 
(height from the water level) was measured (the baseline value before 
laundering). 
For testing the laundering resistance, the surfactant-treated and dried 
nonwoven fabric was washed in running water for one minute and, after 
drying, subjected to the same water penetration test as above (the value 
after laundering). 
The values before and after laundering are shown in Table 4. 
TABLE 4 
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Before laun- 
After laun- 
Surfactant dering (mm) 
dering (mm) 
______________________________________ 
The invention 
Surfactant (A) 17 14 
Surfactant (B) 14 11 
Surfactant (D) 21 17 
Control 
Sodium dodecyl- 
18 1 
benzenesulfonate 
Nonylphenol-EO 16 2 
(10 moles) adduct 
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EXAMPLE 7 
To 300 g of water were added 30 g of polyvinyl alcohol with a 
saponification degree of 88 mole % and a viscosity average polymerization 
degree of 1,700 and 5 g of the surfactant shown in Table 5, followed by 
stirring while warming. To the resulting solution was added 240 g of vinyl 
acetate monomer dropwise, and using 1 g of ammonium persulfate as an 
initiator, the emulsion polymerization reaction was carried out under the 
usual conditions to give a polymer emulsion. 
As a film-forming aid, 30 g of dioctyl phthalate was added to the emulsion 
and the adhesive power of the composition was measured. The results are 
shown in Table 5. 
TABLE 5 
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Water- *2 
Dry adhe- *1 
resistant 
sive power adhesive power 
Surfactant (kg/cm.sup.2) 
(kg/cm.sup.2) 
______________________________________ 
The invention 
Surfactant (B) 195 160 
Surfactant (E) 210 185 
Surfactant (G) 200 160 
Control 
Sodium dodecyl- 
92 10 
benzenesulfonate 
Nonylallyl- 180 90 
phenol-EO 
(20 moles) 
adduct 
Lauryl alcohol- 
120 35 
EO (20 moles) 
adduct 
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*1: The compressive shear adhesive strength of birch/birch testpieces was 
measured in accordance with JISK 6804. 
*2: The above testpieces were immersed in water at 30.degree. C. for 3 
hours and the compressive shear adhesive strength was then measured in th 
same manner as above. 
EXAMPLE 8 
A reactor equipped with a stirrer, reflux condenser, thermometer and drip 
funnel was charged with 294 g of deionized water and 6 g of the test 
surfactant (Table 6) and the internal temperature of the reactor was 
increased to 80.degree. C. 
After the dissolved oxygen was removed by nitrogen gas purging, 20 g of 
ethyl acrylate and 0.5 g of ammonium persulfate were added for preliminary 
polymerization and starting 10 minutes after the beginning of 
polymerization, ethyl acrylate was added dropwise over a period of 3 hours 
for further polymerization to prepare a polymer emulsion. 
The stability of the emulsion polymerization reaction, the mechanical 
stability of the product emulsion, foaming power and the water resistance 
test data on the polymer film obtained from the emulsion are shown in 
Table 6. 
As controls, the conventional emulsions were also tested for the same 
parameters. 
TABLE 6 
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Stability Mechan- Foam- 
of *3 ical *4 ing *5 Water- *6 
polymer- stability 
power resistance 
Surfactant ization (%) 
(%) (ml) (hrs) 
______________________________________ 
The invention 
Surfactant (A) 
0.1 0.06 0 .gtoreq.300 
Surfactant (B) 
0.2 0.03 0 .gtoreq.300 
Surfactant (C) 
0.08 0.10 1 .gtoreq.300 
Surfactant (D) 
0.1 0.09 1 .gtoreq.300 
Surfactant (E) 
0.3 0.11 0 250 
Surfactant (F) 
0.2 0.07 0 .gtoreq.300 
Surfactant (G) 
0.2 0.08 0 .gtoreq.300 
Control 
Nonylphenol- 
5.5 3.2 40 4 
EO (40 moles) 
adduct 
Sodium dodecyl- 
2.8 2.6 70 2 
benzenesul- 
fonate 
______________________________________ 
*3: The test emulsion was filtered through a #150 wiremesh sieve and the 
residue was rinsed with water and dried. The weight of the dried solid 
residue was expressed in percentage based on the weight of monomer charge 
*4: Using a Marlon tester, 50 g of the test emulsion was stirred at 1000 
rpm under a load of 10 kg for 5 minutes and, then, filtered through a #15 
wiremesh sieve. The residue was rinsed with water and dried and the weigh 
of the dried residue was expressed in percentage based on the solid 
content of the emulsion. 
*5: The test emulsion was diluted twofold with water and 30 ml of the 
dilution was put in a 100 ml Nessler tube. The tube was turned upside dow 
30 times and, then, allowed to stand upright for 5 minutes. The volume of 
the resulting foam was then measured. 
*6: The test emulsion was cast on a glass plate to prepare a 0.5 mm thick 
film. This film was immersed in water and the duration of time till 4.5 
point characters became no longer legible through the film was measured. 
EXAMPLE 9 
A mixed monomer emulsion was prepared by admixing 100 g of butyl acrylate, 
100 g of styrene, 290 g of deionized water, 0.5 g of potassium persulfate 
and 10 g of the test surfactant (Table 7) and the dissolved oxygen was 
removed by nitrogen gas purging. 
A reactor equipped with a stirrer, reflux condenser, thermometer and drip 
funnel was charged with 100 g of the above monomer emulsion and the 
polymerization reaction was conducted at a temperature of 80.degree. C. 
Then, the balance, 400.5 g, of the monomer emulsion was added dropwise over 
a period of 3 hours for further polymerization to prepare a polymer 
product emulsion. 
The stability of the emulsion polymerization, the mechanical stability and 
foamability of the product emulsion and the water resistance and contact 
angle test data on the polymer film obtained from the emulsion are shown 
in Table 7. The conventional emulsifiers were also tested for the same 
parameters. 
TABLE 7 
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Stability of 
Mechan- Foam- Water Con- 
polymeriza- 
ical ing resis- 
tact 
tion stability 
power tance angle 
Surfactant 
(%) (%) (ml) (hrs) (.degree.) 
______________________________________ 
The invention 
Surfactant (A) 
0.2 0.03 0 .gtoreq.300 
140 
Surfactant (C) 
0.1 0.07 0 .gtoreq.300 
130 
Control 
Oleyl alcohol- 
8.3 4.5 32 10 .ltoreq.5 
EO (15 moles) 
adduct 
Sodium 1.2 3.6 60 6 .ltoreq.5 
laurylsulfate 
______________________________________ 
EXAMPLE 10 
A reactor equipped with a stirrer, reflux condenser, thermometer and drip 
funnel was charged with 250 g of deionized water and 5 g of the surfactant 
shown in Table 8 and the internal temperature of the reactor was increased 
to 80.degree. C. 
After the dissolved oxygen was removed by nitrogen gas purging, a 20 g 
portion of a monomer mixture consisting of 125 g of butyl acrylate and 125 
g of methyl methacrylate and 0.5 g of ammonium persulfate was added for 
preliminary polymerization. Starting 10 minutes after the beginning of 
polymerization, the balance of the monomer mixture was added dropwise over 
a period of 3 hours for additional polymerization to give a polymer 
emulsion. 
As controls, polymer emulsions were prepared using the reactive emulsifiers 
shown in Table 8 in the same manner. 
The stability of the emulsion polymerization reaction, the unreacted 
emulsifier content of the resulting emulsion and the contact angle and 
adhesion test data on the polymer film obtained from the emulsion are 
shown in Table 8. 
TABLE 8 
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Stability of 
Un- *10 Adhe- 
polymeriza- 
reacted Contact sive *11 
tion emulsifier angle power 
(%) (%) (.degree.) 
(g/cm) 
______________________________________ 
The invention 
Surfactant (A) 
0.1 2 150 800 
Surfactant (D) 
0.3 5 120 780 
Control 
Reactive *7 
0.4 15 80 400 
emulsifier (1) 
Reactive *8 
58.6 10 -- *12 -- *12 
emulsifier (2) 
Reactive *9 
4.3 47 .ltoreq.5 
280 
emulsifier (3) 
______________________________________ 
*7: Octylallylphenolethylene oxide (30 moles) adduct 
*8: Lauryl alcoholethylene oxide (15 moles) adduct acrylate ester 
*9: 1Nonylphenoxypolyoxyethylene (EO 20 moles 
adduct)2-hydroxy-3-allyloxypropane 
*10: The polymer emulsion was treated with methanol for gelation and 
filtered to separate the filtrate. The polymer gel was washed with 3 
portions of 50% methanol and the washes and the filtrate were combined an 
concentrated to dryness. The dried residue was washed with a few portions 
of 50% methanol and the amount of the emulsifier in the washes was 
measured by gel permeation chromatography (GPC). 
*11: A polymer film reinforced with a 0.5 mm thick fabric was prepared on 
a glass sheet and a 180.degree. peeling strength was measured at 
25.degree. C. 
*12: No polymer emulsion was obtained. Therefore, no measurement could be 
made.