United States Patent (19) 11) 4,199,490

Kamiya et al. 45 Apr. 22, 1980

54 BLOCK COPOLYMER LATEX 56 References Cited
COMPOSITION U.S. PATENT DOCUMENTS
3,265,765 8/1966 Holden et al. ....................... 260/876
75 Inventors: Shunji Kamiya; Kunio Satake; 3,293,197 12/1966 Vincent et al. ............ 260/29.7 DX
Tomiho Sone, all of Yokohama; 3,304,281 2/1967 Tucker ....................... 260/29.7 DX
Tsutomu Teraoka, Kanagawa, all of 3,458,602 12/1962 Pollock ................................ 260/880
Japan 3,539,475 11/1970 Yoshioka et al........... 260/29.7 DX
3,700,757 10/1972 LaHeijet al. .............. 260/29.7 DX
73 Assignee: Asahi Kasei Kogyo Kabushiki Kaisha, 3,878,153 4/1975 Driscoll .......................... 260/29.7 D
Tokyo, Japan FOREIGN PATENT DOCUMENTS
644022 10/1950 United Kingdom ............... 260/29.7 D .
(21) Appl. No.: 769,102 OTHER PUBLICATIONS
(22 Filed: Feb. 16, 1977 Blackley, High Polymer Latices, I, (Applied Science
1966), pp. 265-266.
Related U.S. Application Data Primary Examiner-Paul Lieberman
Attorney, Agent, or Firm-Armstrong, Nakaido,
63 Continuation of Ser. No. 574,968, May 6, 1975, aban Marmelstein & Kubovcik
doned.
57 ABSTRACT
30 Foreign Application Priority Data A block copolymer latex composition comprising (A)
an aqueous latex containing at least one of block copoly
May 7, 1974 JP Japan .................................. 49-50416 mers consisting of conjugated diolefin blocks and
Jul. 3, 1974 JP Japan ...... ... 49.76028 monovinyl-substituted aromatic compound blocks pre
Dec. 2, 1974 JP Japan ................................ 49.138197 pared by solution-polymerization, and having a molecu
Dec. 2, 1974 JP Japan ................................ 49.138198 lar weight of 5,000 to 500,000 and a content of monovi
Dec. 4, 1974 JP Japan ................................ 49-138529 nyl-substituted aromatic compound of 10 to 70% by
weight, and (B) a latex of rubber system, latex of syn
51) int. C.’.............................................. CO8ELS3/OO thetic resin system or a mixture thereof, the composi
52 U.S.C. ...................... 260/29.7 D; 260/29.7 NR; tion containing 5 to 87% by weight of (A) and 95 to
260/29.7 W; 260/29.7 H; 260/29.7 T; 260/29.7 13% by weight of (B) in terms of solid matters, has very
EM; 260/29.7 PT; 260/5; 525/95; 525/96; superior film-forming properties and provides films
525/98; 525/99 having improved strength.
58) Field of Search ................. 260/29.7 D, 29.7 WR,
260/29.7 W 7 Claims, No Drawings
 4,199,490
1. 2
copolymer has a high minimum film-forming tempera
BLOCK COPOLYMER LATEX COMPOSITON ture, which will be hereinafter referred to as MFT, and
thus has such a disadvantage that a film cannot be
This is a continuation, of application Ser. No. formed under the natural conditions. MFT used herein
574,968, filed May 6, 1975 now abandoned. 5 is a film-forming temperature measured according to
DESCRIPTION OF THE INVENTION the temperature gradient plate method proposed by
Thomas F. Protzman (Journal of Applied Polymer
This invention relates to an improvement in a film
forming property of block copolymer latex consisting Science, For the
Vol. 4, pages 81-85).
improvement offilm-forming property, there
of conjugated diolefin and monovinyl-substituted aro 10 have been so far utilized an internal plasticization
matic compound, and also relates to an improvement in
a film strength of latex of rubber system, latex of syn method, an external plasticization method, a tentative
plasticization method, etc. The internal plasticization
thetic resin system or their mixture.
As the latex of synthetic rubber system such as latex component monomer for
method is a method
(the
copolymerization with a soft
monomer capable of forming
of styrene-butadiene copolymers, the latex prepared by 15 homopolymers having a low
emulsion polymerization is usually used for practical ture, but it is not appropriate asglass transition tempera
purposes, but as a result of recent rapid development in the film-forming property of latex obtainedforbyimproving
a method
emulsify
polymerization technique, many kinds of synthetic rub ing the block copolymer prepared by solution-polymer
ber of solution-polymerization type having various fea ization. The external plasticization method is the one
tures have been prepared and have been tried to be used 20 based on the use of a plasticizer, which is added at or
as latex.
According to an ordinary process for preparing a after the preparation of latex. When the plasticizer is
added at the preparation of latex, the block copolymer
latex from such synthetic rubber of solution-polymeri shows
zation type, an emulsifying agent and water are added effect ina softening phenomenon due to the plasticization
the step of preparing the latex, and emulsifica
to a polymerization solution of rubber or a solution of 25 tion
solid rubber dissolved in an appropriate solvent to emul sion isofattained insufficiently. As a result, only an emul
relatively large particle sized is obtained, and the
sify the solution, and then the solvent is removed from emulsified particles are liable to undergo recoagulation.
the resulting emulsion by stripping or flashing or the
like. The resulting latex is the so-called diluted latex, Thus, there are problems in the stabilization of latex.
and can be utilized as such, but it can be concentrated, 30 When a plasticizer is added after the preparation of
if necessary, by creaming, centrifugal separation or latex, the plasticizer must be emulsified and dispersed in
other operation. water, and then must be absorbed into the particles of
As one of synthetic rubbers having the features, ob block copolymer while dispersing the plasticizer
tained by solution-polymerization, there are available through water. A sufficient plasticization is necessary
alternating block copolymers consisting of (A) monovi 35 for forming a homogeneous latex film at a low tempera
nyl-substituted aromatic compound blocks and (B) con ture. That is, a long period of time and a large amount
jugated diolefin polymer blocks, represented by the of the plasticizer are necessarily required. Especially,
following general formulae: use of a large amount of plasticizer considerably lowers
A - B - A, or the mechanical properties of latex film, and thus is not
40 preferable. The tentative plasticization method is the
(A - B), or one based on the use of a tentative plasticizer which
B-A - B)n, Or
plays a role of plasticizer only in the formation offilm to
promote the film formation, and evaporates off as rapid
(A - B-9A, or as possible after the formation of the film to improve the
45 mechanical properties of the film. However, the tenta
(A - B)nX tive plasticizer is expensive, and at the same time a large
amount of an organic solvent must be used. Thus, there
wherein A represents a block consisting substantially of are pending problems in safety and sanitation of work
monovinyl-substituted aromatic compound polymers, B ers, fire, air pollution, etc.
blocks consisting substantially of conjugated diolefin 50 Latex of rubber system or synthetic resin system is
polymers, n an integer of 2 to 10, man integer of 3 to 7, used in a wide range of applications such as an immer
and Xan residue derived from a multi-functional com sion molding product, cast molding product, foam rub
pound in which m polymer chains A-B are combined ber, rubber threads, paper processing agent, carpet siz
with each other. These alternating block copolymers ing agent, fiber processing agent, surface coating agent,
are called "thermoplastic elastomer", and show a high 55 adhesive, pressure-sensitive adhesive, paint binder, non
strength, high degree of elongation and a low residual woven fabric binder, latex-added asphalt, cement addi
strain characteristic, which are equivalent to those of tive, etc. However, in order to obtain latex of rubber
the ordinary vulcanized rubber, in such a state that the system having a good strength characteristic, there is
cross-linking treatment, which is usually carried out such a disadvantage that the latex must be subjected to
with a sulfur compound, etc., is not conducted. An 60 cross-linking treatment with a sulfur compound, metal
aqueous latex of such block copolymer is useful as an oxide, peroxide, or the like. In order to obtain latex of
immersion molding product, cast molding product, synthetic resin system having a good strength charac
foam rubber, rubber threads, paper processing agent, teristic, the latex must be copolymerized with a special
carpet sizing agent, fiber processing agent, surface coat monomer of self-cross-linking type or must be cross
ing agent, adhesive, pressure-sensitive adhesive, paint 65 linked by means of a cross-linking agent. A film ob
binder, non-woven fabric binder, latex-added asphalt, tained from the cross-linked latex of synthetic resin
cement additive, etc. when its peculiar characteristics system usually has a high tensile strength, but has such
are utilized. However, the aqueous latex of such block a disadvantage as a low elongation.
 4,199,490
3 4.
As a result of various studies on an improvement of
film-forming property of latex of block copolymer con
sisting of conjugated diolefin and monovinyl-sub
stituted aromatic compound, and also on an improve
ment of a strength characteristic of latex of rubber sys
tem, latex of synthetic resin system or a mixture thereof,
the present inventors have found that the film-forming
property and strength characteristics, which have been
so far disadvantages of these respective latexes, can be
remarkably improved by mixing the latex of block co
polymer with the latex of rubber system, or latex of
synthetic resin system or a mixture thereof, and have
established the present invention.
The present invention resides in a block copolymer
latex composition comprising (A) an aqueous latex con 15
taining at least one of block copolymers consisting of
conjugated diolefin blocks and monovinyl-substituted
aromatic compound blocks prepared by solution
polymerization, and having a molecular weight of 5,000
to 500,000 and a content of monovinyl-substituted aro 20
matic compound of 10 to 70% by weight, and (B) a latex
of rubber system, latex of synthetic resin system or a
mixture thereof, the composition containing 5 to 87%
by weight of (A) and 95 to 13% by weight of (B) in
terms of solid matters.
The block copolymers used in the present invention
are represented by the general formulae: A - B - A, (A
- B), B-(A - B), (A - B)nA or (A - B).m.X, where A, B,
X, in and m have the same meanings as defined above,
and can be polymerized by living anion polymerization
with an initiator on the basis of an alkali metal. The
monovinyl-substituted aromatic compound includes
styrene, o- or p-vinyltoluene, vinylxylene, ethylstyrene,
isopropylstyrene, ethylvinyltoluene, tert-butylstyrene,
diethylstyrene, vinylnaphthalene, etc., and can be used
in a combination of these two or more. The conjugated
diolefin includes 1,3-butadiene, 1,3-pentadiene, iso
prene, 2,3-dimethylbutadiene, etc. and can be used in a
combination of these two or more. Preferable combina
tions are that of 1,3-butadiene with styrene and that of 40
isoprene with styrene. Such block copolymers can be
obtained by successive polymerizations of monomers
into the individual blocks in the presence of said initia
tor, or by simultaneous introduction and polymerization
of at least two kinds of monomers having different co 45
polymerization reactivity ratios, or by coupling living
block copolymers by said initiator. The block copoly
mer represented by said (A - B).X can be obtained by
coupling living block copolymers of A - Beby a multi
functional coupling agent. For example, such a tetra SO
functional coupling agent as silicon tetrachloride can be
used. Molecular weight of the block copolymer is 5,000
to 500,000. If the molecular weight is less than 5,000, the
film obtained from the latex has a poor mechanical
strength. If the molecular weight exceeds 500,000, a 55
viscosity of solution will be higher at the emulsification,
and consequently the emulsification becomes incon
plete or difficult. The properties of the resulting latex
are given unfavorable influences. It is necessary to se
lect the content of monovinyl-substituted aromatic 50
compound polymer block in the block copolymer in a
range of 10 to 70% by weight on the basis of the total
polymers. If the content is outside said range, a feature
as a thermoplastic elastomer cannot be fully established.
One embodiment of a process for producing a latex of 65
block copolymers is given below.
A polymerization product solution can be used as it
is, as a polymer solution for producing the latex of block
copolymer, or solid state rubber of the block copolymer
may be dissolved in a solvent such as benzene, toluene,
xylene, cyclohexane, cyclooctane, chloroform, carbon
tetrachloride, trichlene, methane dichloride, etc. It is
preferable to use the polymer solution usually at a con
centration of 5 to 50% by weight.
Non-ionic, anionic or cationic emulsifying agents are
used for producing the latex of block copolymers, and
their amount to be used is not restricted, but it is prefer
O able to use 0.1 to 15 parts by weight of the emulsifying
agent per 100 parts by weight of the block copolymer.
As the anionic emulsifying agent, at least one of higher
fatty acid salts, rosin acid salts, disproportionated rosin
acid salts, sulfuric acid ester salts of higher alcohol,
sulfuric acid ester salts of polyethylene glycol ether,
amide-bonded (or ester-bonded) sulfuric acid ester salts,
amide-bonded (or ether-bonded) sulfonates, alkylary
sulfonates, ether-bonded (or ester-bonded or amide
bonded) alkylaryl sulfonates, and formalin-condensed
naphthalene sulfonates, but the anionic emulsifying
agents are not restricted thereto. Examples of the ani
onic emulsifying agents include potassium oleate, so
dium laurate, sodium rosinate, disproportionated potas
sium rosinate, sodium dodecylbenzene sulfonate, trie
25 thanolaminedodecylbenzene sulfonic acid salt, sodium
salt of sulfuric acid ester of laury alcohol, anmonium
mononaphthalene sulfonate, sodium oleoylmethyltau
rate, sodium dioctylsulfosuccinate, sodium dodecyldi
phenylether disulfonate, etc. When said emulsifying
30 agent is used, it can be directly dissolved in water. Al
ternatively a higher fatty acid, rosin acid, dispropor
tionated rosin acid, dodecylbenzene sulfonic acid or the
like is dissolved in the solution of the block copolymer
and an aqueous alkali solution (for example, an aqueous
35 solution of sodium hydroxide, etc.) is used as a dispers
ing medium to form salts of higher fatty acid, salts of
rosin acid, salts of disproportionated rosin acid, salts of
dodecylbenzenesulfonic acid or the like, when the aque
ous solution is mixed with the solution of the block
copolymer.
As the non-ionic emulsifying agent, at least one of the
compounds represented by the following general for
mulae:
RO - R2, OH or
O
Af
reo-R:9-o-ro
OH
wherein R1 is an alkyl group having 8 to 18 carbon
atoms or alkylphenyl group having an alkyl group of 8
to 12 carbon atoms; R2 an alkylene group having 2 to 5
carbon atoms; n' an integer of 3 to 50, is used.
Examples of the non-ionic emulsifying agent include
polyoxyethylene nonylphenyl ether, polyoxyethylene
lauryl ether, polyoxyethylene nonylphenyl ether phos
phoric acid ester, polyoxyethylenepropylene nonyl
phenyl ether phosphoric acid ester, etc. Furthermore,
other non-ionic emulsifying agents than those repre
sented by said general formula, for example, sorbitan
ester type (sorbitan monopalmitate, Sorbitan monostea
rate, etc.), sorbitan ester ether type (polyoxyethylene
sorbitan monostearate, etc.), oxyethylene oxypropylene
block copolymer, etc. can be used, but the non-ionic
emulsifying agent is not restricted thereto. These non
 4,199,490
5 6
ionic emulsifying agent can be used together with said
anionic emulsifying agent to prevent deposition, and
coagulation of latex particles at the emulsification, sol
vent removal or concentration when the latex is pro
duced by means of said anionic emulsifying agent, or
further improve the mechanical stability of the latex
thus produced.
As the cationic emulsifying agent, at least one of
aliphatic amine salts, quaternary ammonium salts, alkyl
pyridinium salts, or the like is used, but the cationic 10
emulsifying agent is not restricted thereto.
Examples of the cationic emulsifying agents include
octadecyltrimethylammonium chloride, alkyldimethyl
benzylammonium chloride, polyoxyethylene alkyla
mine, octadecylamine acetate, alkylisoquinolium bro 15
mide, etc. These cationic emulsifying agents can be used
together with the non-ionic emulsifying agent without
any trouble. Particularly preferable emulsifying agent is
a combination of the higher fatty acid salt, a rosin acid
salt or disproportionated rosin acid with the non-ionic
emulsifying agent represented by said general formula.
In the present invention, any well known emulsifier
can be used, so long as it has a sufficiently powerful
emulsifying ability. For example, a homomixer, homog
enizer, dispermill, colloid mill, etc. are available. Two 25
kinds of the emulsifiers can be used in combination, if
required.
Then, the solvent is removed from the emulsified
solution to obtain a dilute latex by the well known art of
removing the solvent, for example, by distillation based 30
on a jacket heating, or by steam distillation based on
direct injection of steam into the emulsified solution.
The dilute latex thus obtained usually has a concen
tration of solid matters of 5 to 50% by weight. The
dilute latex can be further concentrated to a higher 35
concentration of solid matters by creaming, centrifugal
separation or water evaporation. Particularly, the con
centration by centrifuge is effective, and preferable
because of its good reproducibility.
Examples of latex of rubber system used in the pres
ent invention include natural rubber latex, styrene
butadiene copolymer latex, methyl methacrylate
butadiene copolymer latex, acrylonitrile-butadiene co
polymer latex, isoprene-isobutylene copolymer latex,
styrene-butadiene-vinylpyridine copolymer latex, ethy 45
lene-propylene copolymer latex, ethylene-propylene
diene copolymer latex, chloroprene polymer latex, bu
tadiene polymer latex, isoprene polymer latex, etc.
These latices can be modified with carboxyl group,
hydroxyl group, etc. 50
Examples of latex of synthetic resin system used in
the present invention include latices of acrylic acid ester
system, for example, acrylic acid ester polymer latices
such as methyl acrylate polymer latex, ethyl acrylate
polymer latex, butyl acrylate polymer latex, 2-ethyl 55
hexyl acrylate polymer latex, etc., or copolymer latices
of mutual acrylic acid esters such as ethyl acrylate-butyl
acrylate copolymer latex, butyl acrylate-2-ethylhexyl
acrylate copolymer latex, etc. or copolymer latices of
acrylic acid ester with at least one of copolymerizable 60
monomers, such as acrylic acid ester-vinyl acetate co
polymer latex, acrylic acid ester-styrene copolymer
latex, acrylic acid ester-methyl methacrylate copolymer
latex, etc.; latices of vinyl acetate system, for example,
vinyl acetate polymer latex, and copolymer latices of 65
vinyl acetate with at least one of copolymerizable mon
omers such as vinyl acetate-ethylene copolymer latex,
vinyl acetate-ethylene-acrylic acid copolymer latex,
vinyl acetate-acrylic acid copolymer latex, vinyl ace
tate-maleic anhydride copolymer latex, vinyl acetate
maleic anhydride copolymer latex, vinyl acetate-maleic
acid ester copolymer latex, vinyl acetate-veova copoly
mer latex, vinyl acetate-vinyl chloride copolymer latex,
vinyl acetate-vinyl chloride-acrylic acid copolymer
latex, etc.; vinyl chloride polymer latex; vinylidene
chloride polymer latex; vinyl chloride-vinylidene chlo
ride copolymer latex; urethane polymer latex; polyam
ide latex; polyester latex, etc.
A mixing ratio of (A) latex of block copolymer to (B)
latex of rubber system, or latex of synthetic resin system
or a mixture thereof is selected from a range of (A):(B)
being 5-87% by weight: 95-13% by weight in terms of
solid matters.
When an improvement of the film-forming property
of the latex of block copolymer is desired, a preferable
range for the mixing ratio of (A) latex of block copoly
mer to (B) latex of rubber system or latex of synthetic
resin system or a mixture thereof is (A):(B) being
63-83% by weight: 37-17% by weight in terms of solid
matters. When an improvement of the strength charac
teristics of latex of rubber system, or latex of synthetic
resin system, or a mixture thereof is desired, a preferable
range for the mixing ratio of (A) latex of block copoly
mer to (B) latex of rubber system, later of synthetic
resin system or a mixture thereof is (A):(B) being
10-65% by weight:90-35% by weight, more preferably
10-50% by weight: 90-50% by weight, in the terms of
solid matters. The reasons for the restriction to said
range are that, when the amount of the latex of block
copolymer is less than 5% by weight, the effect upon
the improvement of strength characteristics of the latex
of rubber system, or latex of synthetic resin system or a
mixture thereof is poor, and when it exceeds 87% by
weight, the effect upon the improvement of film-form
ing properties of the latex of block copolymer by the
addition of the latex of rubber system, latex of synthetic
resin system or a mixture thereof is poor.
In the block copolymer latex composition of the pres
ent invention, the latex of block copolymer having the
improved film-forming properties is applicable to the
uses where the latex of rubber system, latex of synthetic
resin system or a mixture thereof is employed, and is
useful particularly as an adhesive, fiber-processing
agent, non-woven fabric, or carpet sizing agent. Fur
thermore, the latex of rubber system, latex of synthetic
resin system or a mixture thereof having the improved
strength characteristics can be used in the applications
where various latices are employed so far, with a better
effect, and is useful particularly as a carpet sizing agent
and fiber-processing agent, capable of providing an
improved tensile strength and elongation, an adhesive
having an improved bonding strength, and an adhesive
for adhesive tape having an improved peeling strength
and anti-creep property.
The block copolymer latex composition of the pres
ent invention can contain an ordinarily applicable
amount of antiseptics, plasticizer, defoaming agent,
thickener, anti-freeze agent, tackifier, filler, foaming
agent or other materials, depending upon their uses.
Now, the present invention will be described in de
tail, referring to Examples, but Examples will not be
limitative of the scope of the present invention.
EXAMPLE 1
To a 15 wt.% n-hexane solution containing 41 g of a
monomer mixture of 1,3-butadiene and styrene in a ratio
 7
4,199,490
8
of 50:50 by weight was added 1 millimole of n-butyl presence of 3 parts by weight of polyoxyethylene non
lithium as an active lithium in a nitrogen atmosphere, ylphenyl ether (mean degree of polymerization of oxy
and polymerization was conducted at 60° C. for 4 hours. ethylene of 15) per 100 parts by weight of the block
After aimost all the monomers were copolymerized, a copolymer in addition to sodium rosinate as the emulsi
15 wt.% n-hexane solution containing 59 g of a mono- 5 fying agent of Example 1. To 100 parts by weight of
mer mixture of 1,3-butadiene and styrene in a ratio of total solid matters of the concentrated latex were added
65:35 by weight was added to the resulting solution of various amounts of carboxylated styrene-butadiene co
active copolymers, and polymerization was conducted polymer latex (made by Asahi Dow K.K., Japan, Dowl
at 70° C. for 2 hours, and further at 85 C. for one hour.
After almost all the additional monomers were copoly O atex ing
DL 620, total solid matters: 50% by weight), rang
from 20 to 80 parts by weight in terms of the solid
merized, 1 g of 2,6-di-tert-butyl-p-cresol was added matters, and homogeneous dispersions were prepared
thereto as a stabilizer, and the n-hexane solvent was therefrom by simple stirring, and subjected to the same
removed therefrom by drying, whereby 100 g of ulti determinations as in Example 1. The results are shown
mate block copolymer was obtained. The copolymer in Table 2.
thus obtained was thermoplastic elastomer consisting of 15
1,3-butadiene and styrene containing 40% by weight of Table 2
styrene and had a molecular weight of about 100,000. Amounts of carboxylated
To 100 parts by weight of a toluene solution of said styrene-butadiene copolymer
block copolymer (polymer concentration: 10% by latex added, in terms of solid
matters, parts by weight
weight) was added 100 parts by weight of an aqueous 20 Item 0 20 40 60 80
sodium rosinate solution containing 5 parts by weight of .
sodium rosinate per 100 parts by weight of the block Tensile MFT (°C)
300% modulus
68.6 5.3 15.2 14.6 14.6
copolymer, and the resulting mixture was emulsified in character- (kg/cm) 30 33 38 47 53
a dispermill. The resulting emulsified solution was im istics Tensile
mediately charged into a toluene-removing vessel pro 25 strength 23S 230 228 203 198
vided with a heating jacket, and toluene was evaporated (kg/cm)
off by heating. At that time, a portion of water was Elongation
(%) 900 860 80 780 720
evaporated together with toluene, and a dilute latex
having a concentration of solid matters of 13.5% by
weight was obtained. The dilute latex was continuously 30 EXAMPLE 3
charged into a cylindrical centrifugal separator, and a
concentrated latex having a concentration of total solid Rosin acid was added to the toluene solution of the
matters of 55% by weight was obtained at about 12,000 block copolymer of Example 1 so that 5 parts by weight
rpm. To 100 parts by weight of total solid matters of of rosin acid might be dissolved per 100 parts by weight
said concentrated latex (this means and also will means of
hereinafter that to the concentrated latex thus obtained
the block copolymer, and the resulting solution was
mixed with an aqueous solution containing an equimo
was added another latex in a ratio of amounts based lar amount of sodium hydroxide to that of rosin acid in
upon 100 parts by weight of total solid matters in the a ratio of 1:1 by weight. A concentrated latex having a
concentrated latex) were added various amounts of concentration of total solid matters of 54% by weight
natural rubber latex (total solid matters: 59% by weight) 40 was obtained by emulsification in the same manner as in
ranging from 20 to 80 parts by weight in terms of solid Example 1. To 100 parts by weight of total solid matters
matters, and homogeneous dispersions were prepared of the concentrated latex were added various amounts
by simple stirring with a stirrer rod. The latex composi of styrene-butadiene copolymer latex (made by Asahi
tions thus obtained were subjected to determination of Dow K.K., Japan, Dowlatex DL 612, total solid mat
MFT by a temperature gradient plate method proposed as ters: 48% by weight), ranging from 20 to 80 parts by
by Protzman, and further to the determination of tensile weight in terms of solid matters, and homogeneous
characteristics of film by preparing films from the latex dispersions were prepared by simple stirring, and sub
compositions at 80°C. The results are shown in Table 1 jected to the same determinations as in Example 1. The
in comparison with the case of concentrated latex of results are shown in Table 3.
block copolymer, alone. 50 Table 3
Table 1 Amounts of styrene-butadiene
Amount of natural rubber latex copolymer latex added, in terms
added in terns of solid matters, of solid matters, parts by weight
parts by weight tem O 20 40 60 80
Etern O 20 40 60 80 55 MFT (°C) 68.4 5.3 5.2 4.8 14.8
MFT (C.) 68.0 S.0 14.8 14.8 14.6 Tensile 300% modulus
Tensile 300% modulus character- (kg/cm) 30 29 28 26 26
character- (kg/cm) 3. 29 26 23 19 istics Tensile
istics Tensile strength 230 221 208 196 189
strength (kg/cm
(kg/cm) 238 210 195 18O 162 60 Elongation
Elongation (%) 890 880 840 820 80
(%) 890 880 850 840 790

EXAMPLE 2
A concentrated latex (total solid matters: 57% by
weight) was prepared in the same manner as in Example
l, except that the emulsification was carried out in the
EXAMPLE 4
65
A concentrated latex (total solid matters: 55% by
weight) was prepared by emulsification in the same
manner as in Example 1, except that the same amount of
disproportionated potassium rosinate was used in place
 9
4,199,490
10
of sodium rosinate of Example 1. To 100 parts by and subjected to the same determinations as in Example
weight of total solid matters of the concentrated latex 1. The results are given in Table 6.
were added various amounts of carboxylated methyl Table 6
methacrylate-butadiene copolymer latex (made by
Takeda Yakuhin Kogyo K.K., Japan, Croslene 2M-34, 5 Amounts of chloroprene polymer
latex added, in terms of solid
total solid matters: 48% by weight), ranging from 20 to matters, parts by weight
80 parts by weight in terms of solid matters. Homogene Item O 20 40 60 80
ous dispersions were prepared therefrom by simple
stirring, and subjected to the same determinations as in Tensile MFT (c.)
300% modulus
69.0 160 15.6 15.2 15.0
Example 1. The results are shown in Table 4. 10 character- (kg/cm) 3. 30 29 29 30
Table 4 istics Tensile
strength 240 220 2.08 99 196
Amounts of carboxylated methyl (kg/cm)
methacrylate-butadiene copolymer Elongation
added, in terms of solid matters, (%) 890 - 900 900 890 880
parts by weight 15
Item 0. 20 40 60 80
MFT (c.) 68.0 14.8 14.8 14.6 14.4 EXAMPLE 7
Tensile 300% modulus
character- (kg/cm) 31. 32 31 32 34 A concentrated latex (total solid matters: 58% by
istics Tensile
strength 239 232 235 230 229
20 weight) was prepared in the same manner as in Example
(kg/cm) 1, except that the emulsification was carried out in the
Elongation presence of 3 parts by weight of polyoxypropylene
(%) 900 890 870 850 810 palmityl ether (mean degree of polymerization of poly
oxypropylene: 10) per 100 parts by weight of the block
25 copolymer in addition to the disproportionated potas
EXAMPLE 5 sium rosinate as the emulsifying agent of Example 4. To
A concentrated latex (solid matters: 53% by weiht) 100 parts by weight of total solid matters of the concen
was prepared in the same manner as in Example 1, ex trated latex were added various amounts of isoprene
cept that cyclohexane was used in place of toluene for 30 isobutylene copolymer latex (made by Esso Chemical
dissolving the block copolymer of Example 1. To 100 K.K., Japan, Butyl latex 100, total solid matters: 61% by
parts by weight of total solid matters of the concen weight), ranging from 20 to 80 parts by weight in terms
trated latex were added various amounts of styrene of solid matters. Homogeneous dispersions were pre
butadiene-vinylpyridine copolymer latex (made by pared therefrom by simple stirring, and subjected to the
Japan Synthetic Rubber Co., Ltd., Japan, JSR 0650, same determinations as in Example 1. The results are
total solid matters: 40% by weight), ranging from 20 to 35 given in Table 7.
80 parts by weight in terms of solid matters. Homogene Table 7
ous dispersions were prepared by simple stirring, and Amounts of isoprene-isobutylene
subjected to the same determinations as in Example 1. copolymer latex added, in terms
The results are shown in Table 5. of solid matters, parts by weight
40 Item O 20 40 60 80
Table 5 MFT (C) 68.4 21.4 16.4 16.0 15.2
Amounts of styrene-butadiene Tensile 300% modulus
vinylpyridine copolymer latex character- (kg/cm) 30 28 26 22 21
added, in terms of solid matters, istics Tensile

Item
-
O
parts by40 weight60 -
20 80
45 strength
(kg/cm)
240 200 188 150 134
Elongation
MFT (c.) 68.0 15.8 5.6 14.6 4.2 (%) 900 920 940 960 1,000
Tensile 300% modulus
character- (kg/cm) 30 28 27 25 22
istics Tensile
strength 230 209 199 196 188 50 EXAMPLE 8
(kg/cm)
Elongation To 100 parts by weight of total solid matters of the
(%) 910 900 880 block copolymer latex (total solid matters: 55% by
890 860
weight) obtained in Example 1 were added various
55 amounts of acrylic acid ester polymer latex (made by
EXAMPLE 6 Sumitomo Chemical Co., Ltd., Japan, Sumitex Resin
A concentrated latex (total solid matters: 57% by ing from 20 tototal
AMH-1000, solid matters: 40% by weight), rang
80 parts by weight in terms of solid mat
weight) was prepared in the same manner as in Example ters. Homogeneous dispersions were prepared there
l, except that a benzene solution containing 20% by from by
weight of the block copolymer was used in place of the 60 minationssimple
as in
stirring, and subjected to the same deter
Example 1. The results are given in
toluene solution containing 10% by weight of the block Table 8.
copolymer of Example 1. To 100 parts by weight of
total solid matters of the concentrated latex were added Table 8
various amounts of chloroprene polymer latex (made by Amounts of acrylic acid ester
Showa Neoprene K.K., Japan, Neprene latex 571, total 65 polymer latex added, in terms of
solid matters: 50% by weight), ranging from 20 to 80 solid matters, parts by weight
parts by weight in terms of solid matters. Homogeneous Item O 20 40 60 80
dispersions were prepared therefrom by simple stirring, MFT (°C) 66.8 51.2 4.8 14.6 14.6
 4,199,490 12
11
Table 8-continued EXAMPLE 11
Amounts of acrylic acid ester To a 15 wt.% toluene solution containing 30 g of
polymer latex added, in terms of styrene was added 0.126 moles of n-butyl-lithium as an
solid matters, parts by weight 5 active lithium compound in a nitrogen atmosphere, and
Item 0. 20 40 60 80
polymerization was conducted at 50 C. for 5 hours.
Tensile 300% modulus After more than 99% of the added styrene was poly
character- (kg/cm) 28 36 48 53 68 merized, a 10 wt.% toluene solution containing 70 g of
istics Tensile
strength 243 222 190 173 162 1,3-butadiene was added thereto, and polymerization
(kg/cm) 10 was conducted at 50 C. for 7 hours. After more than
Elongation 99% of the added 1,3-butadiene was polymerized, cou
(%) 900 820 750 640 580 pling reaction was carried out by adding 0.032 moles of
silicon tetrachloride without losing the activity. The
resulting polymer was block copolymer of type (A -
EXAMPLE 9 15 B)4Si having branched chains, and after 1 g of 2,6-di
To 100 parts by weight of total solid matters of the tert-butyl-p-cresol was added to the resulting solution
block copolymer latex (total solid matters: 55% by of block copolymer as a stabilizer, the copolymer was
weight) obtained in Example 4 were added various deposited in methanol. The copolymer was thermoplas
amounts of acrylic acid ester polymer latex (made by 0 containing tic elastoner consisting of 1,3-butadiene and styrene
Dainippon Ink Kagakukogyo K.K., Japan, voncoat ular weight30% by weight of styrene, and had a molec
R-3350, total solid matters: 45% by weight), ranging acid was dissolved in140,000.
of about Disproportionated rosin
a toluene solution of the block
from 20 to 80 parts by weight in terms of solid matters. copolymer
Homogeneous dispersions were prepared therefrom by tration: 25%having branched chains (polymer concen
by weight) so that 5 parts by weight of the
simple stirring, and subjected to the same determina 25 disproportionated
tions as in Example 1. The results are shown in Table 9. parts by weight ofrosin acid might be dissolved per 100
the block copolymer with branched
chains, and the resulting solution was mixed with an
Table 9 aqueous solution containing an equimolar amount of
Amounts of acrylic acid ester 30 sodium hydroxide to that of the disproportionated rosin
polymer latex, in terms of solid acid in a mixing ratio of 1:1 by weight. Emulsification
matters, parts by weight was carried out in the same manner as in Example 1,
Item 0 20 40 60 80 whereby a concentrated latex containing 54% by
MFT (C) 66.8 14.0 14.0 13.8 13.6 weight of total solid matters was prepared. To 100 parts
Tensile 300% modulus
35
by weight of total solid matters of the concentrated
character- (kg/cm) 30 27 25 22 20 latex were added various amounts of acrylic acid ester
istics Tensile
strength 243 212 190 172 156
polymer latex (made by Dainippon Ink Kagakukogyo
(kg/cm) K.K., Japan, Voncoat R-3350, total solid matters: 45%
Elongation by weight), ranging from 20 to 80 parts by weight in
(%) 900 900 890 890 900
40
terms of solid matters. Homogeneous dispersions were
prepared therefrom by simple stirring, and subjected to
the same determinations as in Example 1. The results
EXAMPLE 10 are shown in Table 11.
To 100 parts by weight of total solid matters of the Table
block copolymer latex (total solid matters: 53% by 45 Amounts of acrylic acid ester
weight) obtained in Example 5 were added various polymer added, in terms of solid
amounts of styrene-acrylic acid ester copolymer latex matters, parts by weight
tem 0. 20 40 60 80
(made by Asahi Kasei Kogyo K.K., Polytron A-45, MFT (c.) 67.4 15.2 14.8 14.4 4.0
total solid matters: 55% by weight), ranging from 20 to
80 parts by weight in terms of solid matters. Homogene 50 Tensile 300% modulus
character- (kg/cm) 27 25 22 20 18
ous dispersions were prepared therefrom by simple istics Tensile
stirring, and subjected to the same determinations as in strength
(kg/cm)
290 268 244 222 198
Example 1. The results are shown in Table 10. Elongation
Table 10 (%) 890 900 900 890 900
55
Amounts of styrene-acrylic acid
ester copolymer latex added, in
terms of solid matters, EXAMPLE 12
parts by weight
tern O 20 40 60 80
A concentratid latex (total solid matters: 56% by
60 weight) was prepared in the same manner as in Example
Tensile
MFT (C.)
300% modulus
66.6 21.0 15.8 15.2 14.6 l, except that block copolymer of type A-B-A consist
character- (kg/cm) 30 30 34 37 40 ing of styrene and 1,3-butadiene (made by Shell Chemi
istics Tensile cal Company, U.S.A., Kraton 101, amount of bonded
strength 240 222 199 180 175 styrene: 28%, molecular weight: 76,000) was used in
(kg/cm) 65 place of the block copolymer consisting of styrene and
Elongation 1,3-butadiene prepared in Example 1. To 100 parts by
(%) 880 870 850 820 800
weight of total solid matters of the concentrated latex
were added various amounts of acrylic acid ester poly
 4,199,490
13 i4
mer latex (made by Dainippon Ink Kagakukogyo K.K., Table 14-continued
Japan, Voncoat R-3350, total solid matters; 45% by Amounts of vinyl acetate-ethylene
weight), ranging from 20 to 80 parts by weight in terms copolymer latex added, in terms
of solid matters. Homogeneous dispersions were pre of solid matters,
pared therefrom by simple stirring, and subjected to the 5 parts by weight
same determinations as in Example 1. The results are tem O 20 40 60 80
shown in Table 12. strength 243 228 202 190 85
Table 12 (kg/cm)
Elongation
Amounts of acrylic acid ester O (%) 900 87O 860 830 800
polymer latex added, in terms
of solid matters, parts by weight
Item 0 20 40 60 80
MFT (C) 68.2 5.4 5.0 4.4 14.2
EXAMPLE 1.5
Tensile 300% modulus
character- (kg/cm) 31 28 28 24 To 100 parts by weight of total solid matters of the
22 15 block
istics Tensile copolymer latex (total solid matters: 53% by
strength 292 2.76 250 2.38 200 weight) obtained in Example 5 were added various
(kg/cm) amounts of vinyl acetate-maleic acid ester copolymer
Elongation latex (made by Hoechst Gosei K.K., Japan, Movinyl
(%) 920 900 900 90 900
2O DM2H, total solid matters: 51% by weight) ranging
from 20 to 80 parts by weight in terms of solid matters.
EXAMPLE 13 Homogeneous dispersions were prepared therefrom by
simple stirring, and subjected to the same determina
To 100 parts by weight of total solid matters of the tions as in Example 1. The results are given in Table 15.
block copolymer latex (total solid matters: 55% by 25
weight) obtained in Example 1 were added various Table 15
amounts of vinyl acetate polymer latex (made by Ho
echst Gosei K.K., Japan, Movinyl 50M, total solid mat Amounts of vinyl acetate-maleic
ters: 50% by weight), ranging from 20 to 80 parts by acid ester copolymer latex added,
in terms of solid matters,
weight in terms of solid matters. Homogeneous disper- 30 parts by weight
sions were prepared therefrom by simple stirring, and tem 0 20 40 60 80
subjected to the same determinations as in Example 1. MFT (C) 66.6 14.8 4.3 40 40
The results are given in Table 13. Tensile 300% modulus
Table 13 character- (kg/cm) 30 32 34 35 37
Amounts of vinyl acetate polymer 35 istics Tensile
strength 240 232. 210 2.02 190
latex added, in terms of solid (kg/cm)
matters, parts by weight Elongation
tem O 20 40 60 80
(%) 880 860 830 800 780
MFT (C) 66.8 20 2.0.2, 19.6 9.4
Tensile 300% modulus 40
character- (kg/cm) 30 38 4. 56 67
istics Tensile EXAMPLE 16
strength 243 220 196 170 1S6
(kg/cm) To 100 parts by weight of total solid matters of the
Elongation block copolymer latex having branched chains (total
(%) 900 820 TO 660 600 45 solid matters: 54% by weight) obtained in Example 11
were added various amounts of vinyl acetate-ethylene
copolymer latex (made by Sumitomo Chemical Co.,
EXAMPLE 4 Ltd., Japan, Sumikaflex 751, total solid matters: 50% by
To 100 parts by weight of total solid matters of the weight) ranging from 20 to 80 parts by weight in terms
block copolymer latex (total solid matters: 55% by 50 of solid matters. Homogeneous dispersions were pre
weight) obtained in Example 4 were added various pared therefrom by simple stirring, and subjected to the
amounts of vinyl acetate-ethylene copolymer latex same determinations as in Example 1. The results are
(made by Dainippon Ink Kagakukogyo K.K., Japan, given in Table 16.
Evadic EP-11, total solid matters: 54% by weight) rang 55 Table 16
ing from 20 to 80 parts by weight in terms of solid mat Amounts of vinyl acetate-ethylene
ters. Homogeneous dispersions were prepared by sim copolymer latex added,
ple stirring, and subjected to the same determinations as in terms of solid matters,
in Example 1. The results are given in Table 14. parts by weight
Table 14 Item O 20 40 60 80
60
Amounts of vinyl acetate-ethylene MFT (C) 67.4 5.8 15.4 4.8 4.2
copolymer latex added, in terms Tensile 300% modulus
of solid matters, character- (kg/cm) 27 26 22 20 20
- parts by weight istics Tensile
strength 288 258 230 199 68
item 0 20 40 60 80 65 (kg/cm)
MFT (°C) 66.8 220 15.8 15.0 4.6 Elongation
Tensile 300% modulus (%) 890 900 900 900 920
character- (kg/cm) 30 31 30 3. 33
istics Tensile
 4,199,490
5 16
EXAMPLE 7 amount of polyoxyethylene nonylphenyl ether (mean
degree of polymerization of oxyethylene: 15) was used
A concentrated latex (total solid matters: 55% by in place of sodium rosinate of Example 1. To 100 parts
weight) was prepared by emulsification in the same by weight of total solid matters of the concentrated
manner as in Example 1, except that the same amount of 5 latex were added various amounts of carboxylated
sodium dodecylbenzene sulfonate was used in place of methyl methacrylate-butadiene copolymer latex (made
sodium rosinate of Example 1. To 100 parts by weight by Takeda Yakuhin Kogyo K.K., Japan, Croslene 2M
of total solid matters of the concentrated latex were 34, total solid matters of 48% by weight) ranging from
added various amounts of carboxylated styrene-butadi 20 to 80 parts by weight in terms of solid matters. Ho
ene copolymer latex (made by Asahi Dow K.K., Japan, O mogeneous dispersions were prepared therefrom by
Dowlatex DL 620, total solid matters of 50% by simple stirring, and subjected to the same determina
weight) ranging from 20 to 80 parts by weight in terms tions as in Example 1. The results are given in Table 19.
of solid matters. Honogeneous dispersions were pre
pared therefrom by simple stirring and subjected to the
same determinations as in Example 1. The results are 15 Table 19
given in Table i7. Amounts of carboxylated methyl
methacrylate-butadiene copolymer
Table 17 latex added,
Amounts of carboxylated styrene in terns of solid matters,
butadiene copolymer latex added, parts by weight
in terms of solid matters, 20 Item O 20 40 60 80
parts by weight
ten 2O 40 60 80 MFT (c.) 68.2 4.8 14.8 4.7 14.5
Tensile 300% nodulus
MFT (C.) 67.9 5. S.O 4.7 4.4 character- (kg/cm) 3. 32 32 33 34
Tensile 300% nodus istics Tensile
character- (kg/cm) 30 33 37 44 50 25 strength 240 233 235 228 225
istics Tensie (kg/cm)
strength 240 233 230 221 22 Elongation
(kg/cm) (%) 900 890 870 850 820
Eiongation.
(%) 910 880 800 780 740
30 EXAMPLE 2.0
EXAMPLE 8 A concentrated latex (total solid matters: 58% by
A concentrated latex (total solid matters: 56% by weight) was likewise prepared by emulsification in the
weight) was likewise prepared in the same manner as in same manner as in Example 1, except that the same
Example , except that the emulsification was carried 35 amount of polyoxypropylene decylphenyl ether (mean
out in the presence of 2 parts by weight of polyoxyeth degree of polymerization of oxypropylene: 15) was used
ylene nonylphenyl ether (nean degree of polymeriza in place of sodium rosinate of Example 1. To 100 parts
tion of oxyethylene: 15) per 100 parts by weight of the by weight of total solid matters of the concentrated
block copolymer in addition to sodium dodecylbenzene latex were added various amounts of isoprene-isobuty
sulfonate as the emulsifying agent of Example i7. To lene copolymer latex (made by Esso Kagaku K.K.,
100 parts by weight of total solid matters of the concen Japan, Butyl latex 100, total solid matters of 61% by
trated latex were added various amounts of styrene weight) ranging from 20 to 80 parts by weight in terms
butadiene copolymer latex (made by Asahi Dow K.K., of solid matters. Homogeneous dispersions were pre
Japan, Dowlatex DL 612, total solid matters of 48% by pared by simple stirring, and subjected to the same
weight), ranging from 20 to 80 parts by weight in terms 45 determinations as in Example 1. The results are given in
of solid matters. Homogeneous dispersions were pre Table 20.
pared therefrom by simple stirring, and subjected to the Table 20
same determinations as in Example 1. The results are Amounts of isoprene-isobutylene
given in Table 18. copolymer latex added,
50 in terms of solid matters,
- Parts by weight
Amounts of styrene-butadiene Item O 20 40 60 EO
copolymer latex added,
in terms of solid matters, MFT (C.) 68.6 2.2 6.8 15.6 15.0
parts by weight Tensile 300% modulus
ten O 2O 40 60 80 55 character-
istics
(kg/cm)
Tehsile
3O 28 26 23 22
MFT (°C) 68.0 15.3 SO 148 14.7 strength 244 200 186 54 30
Tensile 300% sodius (kg/cm)
character- (kg/cm) 30 29 28 27 25 Elongation
istics Tensile (%) 92O 920 930 960 990
strength 238 229 22O 2O2 195
(kg/cm) 60
Elongation
(%) 900 890 860 840 830 EAMPLE 2.
A concentrated latex (total solid content: 54% by
EXAMPLE 9 65
weight) was likewise prepared in the same manner as in
Example 17, except that cyclohexane was used in place
A concentrated latex (total solid matters: 53% by of toluene as the solvent of Example 17. To 100 parts by
weight) was likewise prepared by emulsification in the weight of total solid matters of the concentrated latex
same manner as in Example 1, except that the same were added various amounts of acrylic acid ester poly
 4,199,490
17 18
mer latex (made by Dainippon Ink Kagakukogyo K.K., Table 23
Japan, Voncoat R-3350, total solid matters of 45% by Amounts of vinyl acetate.
weight) ranging from 20 to 80 parts by weight in terms polymer latex added,
of solid matters. Homogeneous dispersions were pre in terms of solid matters,
pared therefrom by simple stirring, and subjected to the parts by weight
same determinations as in Example 1. The results are Item O 20 40 60 80
given in Table 21. MFT (c.) 67.9 220 2.6 204 19.8
Table 21 Tensile 300% modulus
character- (kg/cm) 30 37 46 53 66
Amounts of acrylic acid ester istics Tensile
polymer latex added, strength 240 220 201 178 160
in terms of solid matters, (kg/cm)
parts by weight Elongation
ten O 20 40 60 80 (%) 90 830 790 00 620
MFT (C) 68.0 14.8 4.7 14.3 14.0
Tensile 300% modulus
character- (kg/cm) 30 28 25 23 2. EXAMPLE 24
istics Tensile
strength
Elongation
242 220 200 182 163 A concentrated latex (total solid matters: 55% by
(%) 910 900 900 90 900
weight) was likewise prepared in the same manner as in
Example 1, except that block copolymers of type
A-B-A consisting of styrene and 1,3-butadiene (made by
EXAMPLE 22 Shell Chemical Company, U.S.A., Kraton 101, amount
of bonded styrene of 28%, molecular weight of 76,000)
A concentrated latex (total solid matters: 57% by were used in place of the block copolymer consisting of
weight) was likewise prepared in the same manner as in as styrene and 1,3-butadiene prepared in Example 1, and
Example 1, except that the block copolymer with further the same amount of polyoxyethylene nonylphe
branched chains consisting of styrene and 1,3-butadiene nol phosphite (mean degree of polymerization of oxy
prepared in Example 11 was used in place of the block ethylene: 15) was used in place of sodium rosinate as the
copolymer consisting of styrene and 1,3-butadiene pre emulsifying agent. To 100 parts by weight of total solid
pared in Example 1, and further the same amount of 30 matters of the concentrated latex were added various
polyoxypropylene palmityl ether (mean degree of poly amounts of vinyl acetate-ethylene copolymer latex
oxypropylene of 10) was used in place of sodium rosin (made by Sumitomo Chemical Co., Ltd., Japan,
ate as the emulsifying agent. To 100 parts by weight of Sumikaflex 751, total solid matters: 50% by weight)
total solid matters of the concentrated latex were added ranging from 20 to 80 parts by weight in terms of solid
various amounts of styrene-acrylic acid ester copolymer 35 matters. Homogeneous dispersions were prepared by
latex (made by Asahi Kasei Kogyo K.K., Japan, Poly simple stirring, and subjected to the same determina
tron A-45, total solid matters of 55% by weight), rang tions as in Example 1. The results are given in Table 24.
ing from 20 to 80 parts by weight in terms of solid mat
ters. Homogeneous dispersions were prepared there Table 24
from by simple stirring, and subjected to the same deter Amounts of vinyl acetate-ethylene
minations as in Example 1. The results are given in copolymer latex added,
Table 22. in terms of solid matters,
Table 22 parts by weight
tem O 20 40 60 80
Amounts of styrene-acrylic acid
ester copolymer latex added, MFT (c.) 68.2 4.8 14.4 3.8 13.6
in terms of solid matters, Tensile 300% modulus
parts by weight
Item O 20 40 60 80 character- (kg/cm) 30 30 27 26 24
istics Tensile
MFT (C) 68.2 24 6.4 15.8 5.2 strength 288 260 252 228 210
Tensile 300% modulus (kg/cm)
character- kg/cm) 28 30 30 36 37 Elongation
istics Tensile (%) 930 960 980 990 1,020
strength 296 272 249 222 213
(kg/cm)
Elongation
(%) 900 880 840 840 820 COMPARATIVE EXAMPLE 1.
A concentrated latex (total solid matters: 53% by
EXAMPLE 23
weight) was likewise prepared in the same manner as in
Example 1, except that styrene polymer (made by Asahi
To 100 parts by weight of total solid matters of the Dow K.K., Japan, Styron 683) was used in place of the
concentrated latex (total solid matters: 55% by weight) 60 block copolymer consisting of styrene and 1,3-butadi
prepared in Example 17 were added various amounts of ene of Example 1. To 100 parts by weight of total solid
vinyl acetate polymer latex (made by Hoechst Gosei matters of the concentrated latex were added various
K.K., Japan, Movinyl 50M, total solid matters: 50% by amounts of natural rubber latex (total solid matters of
weight) ranging from 20 to 80 parts by weight in terms 59% by weight), carboxylated styrene-butadiene co
of solid matters. Homogeneous dispersions were pre- 65 polymer latex (made by Asahi Dow K.K., Japan, Dowl
pared therefrom, and subjected to the same determina atex DL 620, total solid matters of 50% by weight),
tions as in Example 1. The results are given in Table 23. acrylic acid ester polymer latex (made by Dainippon
Ink Kagakukogyo K.K., Japan, Voncoat R-3350, total
 4,199,490 2O
19
solid matters: 45% by weight), and vinyl acetate poly Table 29
mer latex (made by Hoechst Gosei K.K., Japan, Movi Amounts of carboxylated styrene
nyl 50 M, total solid matters: 50% by weight), each butadiene copolymer latex added,
ranging from 20 to 80 parts by weight in terms of solid in terms of solid matters, parts by weight
matters. Homogeneous dispersions were prepared by Item O 20 40 60 80
simple stirring, and subjected to determination of MFT MFT (C) 100 or 100 or 100 or 100 or 100 or
in the same manner as in Example 1. No lowering in Oe note 1OC Oc Ote

MFT was observed. The results are given in Tables 25

to 28. O Table 30
Table 25 Amounts of
Amounts of natural rubber added, acrylic acid ester polymer latex added,
in terms of solid matters, parts by weight in terms of solid matters, parts by weight
Item 0. 20 40 60 80 Item O 20 40 60 80
MFT (c.) 100 or 100 or 100 or 100 or 100 or 15 MFT (C) 100 or 100 or 100 or 100 or 100 or
Ore Oe more Ofe Oe Oe Ote Oc Ote fore

Table 26 Table 31
Amounts of carboxylated styrene 20 Amounts of vinyl acetate
butadiene copolymer latex added, ethylene copolymer latex added,
in terms of solid matters, parts by weight in terms of solid matters, parts by weight
Item 0 20 40 60 80
Item O 20 40 60 80
MFT (C) 100 or 100 or 100 or 100 or 100 or
MFT (C.) 100 or 100 or 100 or 100 or 100 or re ore Oe Obre O
de fore C Oe Oc 25

Table 27 EXAMPLE 25
Amounts of To a 15 wt.% hexane solution containing 33 g of a
acrylic acid ester polymer latex added, 30 monomer mixture of 1,3-butadiene and styrene in a ratio
in terms of solid matters, parts by weight of 40:60 by weight was added 1 millimole of n-butyl
Item 0 20 40 60 80 lithium as an active lithium, and polymerization was
MFT (c.) 100 or 100 or 100 or 100 or 100 or conducted at 60° C. for 4 hours. After almost all the
Ore OE more Ore Oe monomers were copolymerized, a 15 wt.% n-hexane
solution containing 67 g of a monomer mixture of 1,3-
35
butadiene and styrene in a ratio of 70:30 by weight was
Table 28 added to the resulting active copolymer solution, and
Amounts of polymerization was conducted at 70 C. for 2 hours, and
vinyl acetate polymer latex added, further at 85°C. for one hour. Then, 1 g of 2,6-di-tert
in terms of solid matters, parts by weight 40 butyl-p-cresol was added thereto as a stabilizer, and the
Itern 0 20 40 60 80 n-hexane solvent was removed therefrom by drying,
MFT (c.) 100 or 100 or 100 or 100 or 100 or whereby 100 g of ultimate block copolymer was ob
Inore more Oe Ore Oe tained. The resulting copolymer was a thermoplastic
elastomer consisting of 1,3-butadiene and styrene, and
45 had a molecular weight of about 100,000. To 100 parts
COMPARATIVE EXAMPLE 2 by weight of a toluene solution of the block copolymer
A concentrated latex polymer (total solid matters: (polymer concentration: 10% by weight) was added 100
55% by weight) was likewise prepared in the same parts by weight of an aqueous solution containing 5
parts by weight of sodium rosinate per 100 parts by
manner as in Example 18, except that styrene polymer 50 weight of the block copolymer and 3 parts by weight of
(made by Asahi Dow K.K., Japan, Styron 683) was polyoxyethylene
used in place of the block copolymer consisting of sty polymerization ofnonylphenyl oxyethylene:
ether (mean degree of
15) per 100 parts by
rene and 1,3-butadiene of Example 18. To 100 parts by weight of the block copolymer, and the resulting mix
weight of total solid matters of the concentrated latex ture was emulsified by a dispermill. The
were added various amounts of carboxylated styrene 55 sified solution was immediately charged resulting into a
emul
toluene
butadiene copolymer latex (made by Asahi Dow K.K., removing vessel provided with a heating jacket, and
Japan, Dowlatex DL 620, total solid matters of 50% by toluene was evaporated off by heating. At that time, a
weight), acrylic acid ester polymer latex (made by Dai portion of water was evaporated together with toluene,
nippon Ink Kagakukogyo K.K., Japan, Voncoat R whereby a dilute latex having a concentration of solid
3350, total solid matters of 45% by weight) and vinyl 60 matters of 13.5% by weight was obtained. Then, the
acetate-ethylene copolymer latex (made by Sumitomo latex was continuously charged in a cylindrical centrifu
Chemical Co., Ltd., Japan, Sumikaflex 751, total solid gal separator, and a concentrated latex containing 55%
matters of 50% by weight), each ranging from 20 to 80 by weight of total solid matters was obtained at about
parts by weight in terms of solid matters. Homogeneous 12,000 rpm. The resulting block copolymer latex was
dispersions were prepared therefrom by simple stirring, 65 mixed with styrene-butadiene copolymer latex (made
and subjected to determination of MFT in the same by Asahi Dow K.K., Japan, Dowlatex DL 612, total
manner as in Example 1. No lowering in MFT was solid matters of 48% by weight) in various mixing ra
observed. The results are shown in Table 29 to 31. tios, and homogeneous dispersions were prepared there
 21 4,199.490 22
from by simple stirring. Films were made from the The resulting block copolymer latex was mixed with
dispersions at 80 C., and their tensile characteristics styrene-acrylic acid ester copolymer latex (made by
were measured. The results are given in Table 32 in Asahi Kasei Kogyo K.K., Japan, Polytron A-45, total
comparison with the case of styrene-butadiene copoly solid matters: 55% by weight) in various mixing ratios.
mer latex, alone. Homogeneous dispersions were prepared therefrom by
Table 32 simple stirring, and subjected to the same determina
Amounts of tions as in Example 25. The results are given in Table
block copolymer latex added, 35.
in terms of solid matters, Table 35
- by Welsht 10
Amounts of
Item O 10 30 50 70
Tensile strength (kg/cm) 37 80 35 18O 205
block copolymer latex added,
in terms of solid matters,
Elongation (%) 530 620 30 810 840 % by weight
tem O 10 30 50 70
15 Tensile strength (kg/cm). 135 50 172 190 202
EXAMPLE 26 Elongation (%) 380 460 60 740 830
A concentrated latex (total solid matters: 56% by
weight) was prepared in the same manner as in Example
25, except that cyclohexane was used in place of toluene 20 EXAMPLE 29
as the solvent of Example 25. The resulting block co The block copolymer latex having branched chains
polymer latex was mixed with carboxylated styrene prepared in Example 11 was mixed with vinyl acetate
butadiene copolymer latex (made by Takeda Yakuhin ethylene copolymer latex (made by Dainippon
Kogyo K.K., Japan, Croslene SA-22, total solid mat Kagakukogyo K.K., Japan, Evadic EP-11, total solid
ters: 47% by weight) in various mixing ratio. Homoge 25 matters: 54% by weight) in various mixing ratios. Ho
neous dispersions were prepared therefrom by simple mogeneous dispersions were prepared therefrom by
stirring and subjected to the same determinations as in simple stirring, and subjected to the same determina
Example 25. The results are shown in Table 33. tions as in Example 25. The results are given in Table
Table 33 36.
Amounts of 30 Table 36
block copolymer latex added,
in terms of solid matters, Amounts of
- by weight block copolymer latex having
tem O O 30 50 70 branched chains added,
in terms of solid matters,
Tensile strength (kg/cm) 43 94 152 188 22 % by weight
Elongation (%) 900 910 900 900 90 35
Item 0 O 30 50 70
Tensile strength (kg/cm) 70 32 166 200 240
Elongation (%) 400 520 60 730 820
EXAMPLE 27
A concentrated latex total solid matters of 54% by 40 As shown in Examples 1 to 24, the latex composition
weight) was likewise prepared in the same manner as in consisting of block copolymer latex consisting of conju
Example 25, except that 5 parts by weight of sodium gated diolefinand monovinyl-substituted aromatic com
dodecylbenzene sulfonate was used per 100 parts by pound, and a latex of rubber system, latex of synthetic
weight of the block copolymer in place of the emulsify resin system or a mixture thereof has a very effectively
ing agent of Example 25. The resulting block copoly 45 improved film-forming property of the block copoly
mer latex was mixed with acrylic acid ester polymer mer latex without impairing the features of the block
latex (made by Dainippon Ink Kagakukogyo K.K., copolymer latex. Furthermore, as shown in Examples
Japan, Voncoat R-3350, total solid matters of 45% by 25 to 29, the latex composition has a very effectively
weight) in various mixing ratio. Homogeneous disper improved tensile characteristics of films of the latex of
sions were prepared therefrom by simple stirring and 50 rubber system, latex of synthetic resin system or a mix
subjected to the same determinations as in Example 25. ture thereof.
The results are shown in Table 34. What is claimed is:
Table 34 1. A latex composition comprising 63-83% by weight
Amounts of (per solid matter) of (A) an aqueous latex of at least one
block copolymer latex added, 55 block copolymer consisting of conjugated diolefin
in terms of solid matters, blocks and 10-70% by weight of monovinyl-substituted
Item O O 30 50 70
aromatic compound blocks and having a molecular
weight of 5,000-500,000 prepared by solution polymeri
Tensile strength (kg/cm) 10 62 116 56 190 zation, and 37-17% by weight (per solid matter) of (B)
Elongation (%) 990 970 940 900 890 60 a rubber latex, a synthetic resin latex, a mixture of these
latices or a latex in which the constitutional elements of
EXAMPLE 28
the rubber or synthetic resin are modified with carboxyl
or hydroxyl groups.
A concentrated latex (total solid matters: 58% by 2. A latex composition of block copolymer according
weight) was likewise prepared in the same manner as in 65 to claim 1 wherein said monovinyl-substituted aromatic
Example 25, except that a 20 wt.% block copolymer compound is at least one member selected from the
solution in benzene was used in place of a 10 wt.% group consisting of styrene, o- or p- vinyltoluene, vi
block copolymer solution in toluene of Example 25. nylxylene, ethylstyrene, isopropylstyrene, ethylvinyl
 4,199,490 24
23
toluene, tertiary-butylstyrene, diethylstyrene and vinyl polymer latex, butadiene polymer latex and isoprene
naphthalene. polymer latex.
3. A latex composition of block copolymer according 7. A latex composition of block copolymer according
to claim 1 wherein said conjugated diolefin is at least to claim 1 wherein said synthetic resin type latex is at
one member selected from the group consisting of 1,3-
least one member selected from the group consisting of
methyl acrylate polymer latex, ethyl acrylate polymer
butadiene, 1,3-pentadiene, isoprene and 2,3-dimethyl latex, butyl acrylate polymer latex, 2-ethylhexyl acry
butadiene. late polymer latex, ethyl acrylate-butyl acrylate copoly
4. A latex composition of block copolymer according mer latex, butyl acrylate-2-ethylhexyl acrylate copoly
to claim 1 wherein said block copolymer consists of 10 mer latex, acrylic acid ester-vinyl acetate copolymer
1,3-butadiene blocks and styrene blocks. latex, acrylic acid ester-styrene copolymer latex, acrylic
5. A latex composition of block copolymer according acid ester-methyl methacrylate copolymer latex, vinyl
to claim 1 wherein said block copolymer consists of mer acetate polymer latex, vinyl acetate-ethylene copoly
isoprene blocks and styrene blocks. latex, vinyl acetate-ethylene-acrylic acid copoly
5 mer latex, vinyl acetate-acrylic acid copolymer latex,
6. A latex composition of block copolymer according vinyl acetate-maleic anhydride copolymer latex, vinyl
to claim 1 wherein said rubber latex is at least one mem acetate-maleic acid ester copolymer latex, vinyl acetate
ber selected from the group consisting of natural rubber veova copolymer latex, vinyl acetate-vinyl chloride
latex, styrene-butadiene copolymer latex, methyl me copolymer latex, vinyl acetate-vinyl chloride-acrylic
thacrylate-butadiene copolymer latex, acrylonitrile 20 acid copolymer latex, vinyl chloride polymer latex,
butadiene copolymer latex, isoprene-isobutylene co vinylidene chloride polymer latex, vinyl chloride
polymer latex, styrene-butadiene-vinylpyridine copoly vinylidene chloride copolymer latex, urethane polymer
mer latex, ethylene-propylene copolymer latex, ethy latex, polyamide latex and polyesters
latex.
lene-propylene-diene copolymer latex, chloroprene
25

30

35

45

50

55

60

L - m