Note: Descriptions are shown in the official language in which they were submitted.
` 214513~
Thermoplastic-molding materials comprising a graft copolymer and
an olefin copolymer
5 The prèsent invention relates to thermoplastic molding materials
containing essentially
(A) from 20 to 99 % by weight of at least one graft copolymer,
obtainable essentially from
~al) from 30 to 90 % by weight of a core obtainable by poly-
merization of a monomer mixture consisting essentially of
(all) from 80 to 99.99 % by weight of at least one C1-C10-alkyl
ester of acrylic acid,
(al2) from 20 to 0.01 % by weight of a copolymerizable,
polyfunctional crosslinking monomer and
20 ~al3) from 0 to 40 % by weight of a further copolymerizable,
monoethylenically unsaturated monomer, and
(a2) from 70 to 10 % by weight of a graft shell obtainable by
polymerization of a monomer mixture in the presence of the
core (al), consisting essentially of
(a21) from 50 to 100 % by weight of a styrene compound of the
general formula (I)
R1C=CH2
~ (I)
R2
where R1 and R2, independently of one another, are each hydrogen
or Cl-C8-alkyl and/or of a C1-C8-alkyl ester of methacrylic or
acrylic acid,
40 (a22) from 50 to 0 % by weight of a monofunctional comonomer, and
(B) from 80 to 1 % by weight of a copolymer obtainable from at
least one alpha-olefin and at least one polar comonomer,
with the proviso that vinyl acetate or a vinylaromatic
monomer are not used as monomers, and
214~13~
.
tc) from~0 to 50 ~ by weight, based on the total weight of
components (A), (B) and (C), of a thermoplastic polymer
obtainable by polymerization of a monomer mixture
consisting essentially of
cl) from 50 to 100 % by weight of a vinylaromatic monomer
and/or of a Cl-C8-alkyl ester of methacrylic or acrylic
acid and
10 ~c2) from 50 to 0 % by weight of a monofunctional comonomer.
The present invention furthermore relates to a process for the
preparation of the novel thermoplastic molding materials, their
use and moldings and films produced therefrom.
EP-A 526 813 describes polymer alloys comprising a graft polymer
having a core based on a crosslinked alkyl acrylate and, if re-
quired, comonomers and a shell obtainable by polymerization of a
vinylaromatic monomer, an ethylenically unsaturated nitrile and/
20 or an alkyl (meth)acrylate, an ethylene~vinyl acetate copolymer
and an elastomeric copolymer, and the use of these polymer alloys
for the production of deep-drawable flexible films.
The disadvantage of films produced by the process described in
25 EP-A 526 813 is that the mixtures described tend to become dis-
colored during processing and have a disadvantageous ratio of
tensile strength to elongation at break. Furthermore, such films
exhibit severe fogging when processed under conditions similar to
those used in practice. In addition, four components are required
30 for producing the molding materials according to EP-A 526 813.
DE-A 3,149,358 describes thermoplastic molding materials obtain-
able from a graft copolymer having a core of a crosslinked alkyl
acrylate and, if required, comonomers and a shell obtainable by
35 polymerization of a vinylaromatic monomer and an ethylenically
unsaturated monomer, and a copolymer obtainable by polymerization
of a vinylaromatic monomer and an ethylenically unsaturated mono-
mer. Films produced from these thermoplastic molding materials
have the disadvantage that their elongation at break is too small
40 and at the same time their hardness is too high.
Plastics films having a leather-like appearance are also used,
for example for lining the interior of motor vehicles. The plas-
tic currently used is usually PVC, as a mixture with various
45 vinyl polymers and plasticizers. These films are not completely
`; ` 21~Sl~
-
stable to~aging and high temperatures, contain volatile compo-
nents and are naturally halogen-cont~;n;ng (cf. DE-A 42 11 415).
It is an object of the present invention to provide further ther-
5 moplastic molding materials which can be procesQed to give filmswhich have a balanced ratio of tensile strength, elongation at
break, tear propagation strength, hardness and color stability
during processing. In particular, film tear propagation strengths
of at least 35 N/mm according to DIN 53515 should be achieved and
lO halogen-free films which are stable to aging, have a leather-like
appearance and contain less volatile components than correspond-
ing prior art films should be obtained.
We have found that this object is achieved by the thermoplastic
15 molding materials defined at the outset.
We have also found a process for their preparation, their use for
the production of moldings and films, and molding and films pro-
duced from the novel thermoplastic molding materials.
The novel thermoplastic molding materials contain essentially
(A) from 20 to 99, preferably from 30 to 98, particularly
preferably from 60 to 95, % by weight of at least one graft
copolymer, obtainable essentially from
(al) from 30 to 90, preferably from 40 to 80, particularly
preferably from 50 to 70, % by weight of a core obtainable
by polymerization of a monomer mixture consisting
essentially of
(all) from 80 to 99.99, preferably from 90 to 99.8, particularly
preferably from 97 to 99, % by weight of at least one
C1-C10-alkyl ester of acrylic acid,
(al2) from 20 to 0.01, preferably from 10 to 0.2, particularly
preferably from 3 to 1, % by weight of a copolymerizable,
polyfunctional crosslinking monomer and
90 (al3) from 0 to 40, preferably from 0 to 10, % by weight of a
further copolymerizable, monoethylenically unsaturated
monomer, and
` 21451~
(a2) from~70 to 10, preferably from 60 to 20, particularly
preferably from 50 to 30, % by weight of a graft shell
obtainable by polymerization of a monomer mixture in the
presence of the core (al), consisting essentially of
(a21) from 50 to 100, preferably from 55 to 95, particularly
preferably from 60 to 90, % by weight of a styrene compound
of the general formula (I)
R1C=CH2
~ (I)
R2
where R1 and R2, independently of one another, are each hydrogen
or Cl-CB-alkyl and/or of a C1-C8-alkyl ester of methacrylic or
acrylic acid, and
20 (a22) from 50 to 0, preferably from 45 to 5, particularly
preferably from 40 to 10, % by weight of a monofunctional
comonomer, and
(B) from 80 to 1, preferably from 60 to 3, particularly
preferably from 50 to 4, % by weight of a copolymer
obtainable from at least one alpha-olefin and at least one
polar comonomer, with the proviso that vinyl acetate or a
vinylaromatic monomer are not used as monomers, and
30 (C) from 0 to 50, preferably from 0 to 45, particularly
preferably from 0 to 40, % by weight, based on the total
weight of components (A), (~) and (C), of a thermoplastic
polymer obtainable by polymerization of a monomer mixture
consisting essentially of
(cl) from 50 to 100, preferably from 55 to 90, particularly
preferably from 60 to 85, % by weight of a vinylaromatic
monomer and/or of a C1-C8-alkyl ester of methacrylic or
acrylic acid and
gO
(c2) from 50 to 0, preferably from 45 to 10, particularly
preferably from 40 to 15, % by weight of a monofunctional
comonomer.
45 Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acry-
late, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate,
n-octyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate and
214513~
n-decyl acrylate and mixtures thereof, preferably n-butyl acry-
late, 2-ethylhexyl acrylate or mixtures thereof, particularly
preferably n-butyl acrylate, may be used as Cl-C10-alkyl esters of
acrylic acid (c~ ponent (all)).
Monomers which contain two, three or four, preferably two, double
bonds which are capable of undergoing copolymerization and are
not conjugated in the 1,3 position are used a~ copolymerizable,
polyfunctional crosslinking monomers. Such monomers suitable for
10 crosslinking are, for example, vinylbenzenes, such as divinylben-
zene and trivinylbenzene, diallyl maleate, diallyl fumarate,
diallyl phthalate, triallyl cyanurate and triallyl isocyanurate.
The tricyclodecenyl acrylates Ia and Ib
~\ ~ 0-C-CH=CHz ~ ~ 0-C-CH=CHz
Ia Ib
have proven particularly suitable monomers for component (al2)
(cf. DE-A 1,260,135) and can also be used in the form of their
mixtures.
Examples of further copolymerizable, monoethylenically unsatu-
rated monomers (component (al3)) are
butadiene, isoprene
30 vinylaromatic monomers, such as styrene, substituted styrene of
the general formula I;
methacrylonitrile, acrylonitrile;
35 acrylic acid, methacrylic acid;
Cl-C4-alkyl esters of methacrylic acid, such as methyl meth-
acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl
methacrylate, n-butyl methacrylate, isobutyl methacrylate,
40 sec-butyl methacrylate, tert-butyl methacrylate;
C1-C4-alkyl esters of methacrylic or acrylic acid, the alkyl
radical~ being monosubstituted by phenyl or naphthyl, the
naphthol and phenol which is unsubstituted or substituted by up
45 to two C1-C4-alkyl groups, such as phenyl acrylate, phenylethyl
methacrylate, phenylethyl acrylate, benzyl methacrylate, benzyl
acrylate, phenylpropyl methacrylate, phenylpropyl acrylate,
21~131
phenylbutyl methacrylate, phenylbutyl acrylate, 4-methylphenyl
acrylate and naphthyl acrylate, and phenoxyethyl methacrylate and
phenoxyethyl acrylate;
5 vinyl methyl ether and compatible mixtures thereof.
Styrene, a-methylstyrene and styrenes alkylated in the nucleus
with C1-C8-alkyl, such as p-methylstyrene or tert-butylstyrene are
preferably used as the styrene c~ ,oulld of the general formula
10 (I) (component (a21)), particularly preferably styrene and a-me-
thylstyrene.
According to the invention, methyl methacrylate (MMA), ethyl
methacrylate, n-propyl methacrylate, isopropyl methacrylate,
15 n-butyl methacrylate, isobutyl methacrylate, sec-butyl meth-
acrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl
methacrylate, heptyl methacrylate, octyl methylacrylate or
2-ethylhexyl methacrylate, particularly preferably methyl
methacrylate, are used as C1-C8-alkyl esters of methacrylic or
20 acrylic acid, as well as mixtures of these monomers, methyl
acrylate (MA), ethyl acrylate, propyl acrylate, n-butyl acrylate,
isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate,
pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate
or 2-ethylhexyl acrylate, particularly preferably n-butyl
25 acrylate, and mixtures of these monomers with one another and
with the methacrylates and/or styrene compounds of the general
formula I.
According to the invention, monomers selected from the group con-
30 sisting of methacrylonitrile, acrylonitrile, N-C1-C8-alkyl-,
N-Cs-C8-cycloalkyl- and N-C6-C10-aryl-substituted maleimides, such
as N-methyl-, N-phenyl-, N-dimethylphenyl- and N-cyclohexyl-
maleimide and maleic anhydride, preferably acrylonitrile, are, if
desired, used as monofunctional comonomers (component (a22)).
~5
In a preferred embodiment, a mixture of styrene (S) and acrylo-
nitrile (AN) in a molar S/AN ratio of, usually, from 4.5:1 to
0.5:1, preferably from 2.2:1 to 0.65:1, styrene alone, a mixture
of acrylonitrile and methyl methacrylate (MMA) or MMA alone is
40 used for producing the graft shell (a2).
Component (A) is prepared by conventional methods, for example by
those described in DE-A 3,149,358.
45 For this purpose, the core (al) is first prepared by polymerizihg
the aarylate or acrylates (all) and the polyfunctional monomers
(al2) which effect crosslinking, with or without the further
214513~
comonomers~(al3), in the conventional aqueous emulsion in a man-
ner known per se, at from 20 to 100 C, preferably from 50 to 80 C.
The conventional emulsifiers, such as alkali metal salts of al-
kyl- or alkylarylsulfonic acids, alkylsulfate, fatty alcohol sul-
5 fonates, salts of higher fatty acids of 10 to 30 carbon atoms,sulfosuccinates, such as Aerosol~ OT (Cyanamid), ether sulfonates
such as Disponil~ FES61 (Henkel), or resin soaps, may be used.
Sodium salts of alkanesulfonates or fatty acids of 10 to 18
carbon atoms are preferably taken. It is advantageous to use the
10 emulsifiers in amounts of from 0.3 to 5, in particular from 1 to
2, % by weight, based on the monomers used in the preparation of
the core (al). In general, the water/monomer ratio of from 2:1 to
0.7:1 is employed.
15 The polymerization initiators used are in particular the conven-
tional persulfates, but redox systems are also suitable. The
a~ount of initiators depends as a rule on the desired molecular
weight and is usually from 0.1 to 1 % by weight, based on the
monomers used in the preparation of the core (al).
The polymerization asgistants which may be used in the polymer-
ization are the conventional buffer substances by means of which
a pH of, preferably, from 6 to 9 is obtained, for example sodium
bicarbonate and sodium pyrophosphate, and from 0 to 3 % by weight
25 of a molecular weight regulator, such as a mercaptan, a terpinol
or dimeric alpha-methylstyrene.
The exact polymerization conditions, in particular the type,
metering and amount of the emulsifier, are as a rule determined
30 specifically within the abov -ntioned ranges so that the result-
ing latex of the crosslinked acrylate polymer (al) has a d50 value
of from 60 to 1000 nm, preferably from 80 to 800 nm, particularly
preferably from 100 to 600 nm. The particle size distribution of
the latex should preferably be narrow.
In principle, it is also possible to prepare the grafting base by
a method other than that of emulsion polymerization, for example
by mass or solution polymerization, and subsequently to emulsify
the polymers obtained. The processes for this purpose are known.
The graft rubber particles (A) usually have a particle size (d50)
of from 60 to 1500 nm, preferably from 100 to 1200 nm.
In order to obtain a very tough molding material, graft rubber
45 particles (A) having a particle size (d50) of from 200 to 1000 nm
are used in a preferred embodiment.
21gS13~
-
In a further preferred embodiment, a mixture of graft rubber par-
ticles (A) of different sizes and having a bimodal particle size
distribution is used. Particularly preferably, from 0.5 to 99.5 %
by weight of this mixture have a particle size (d50) with a mean
5 diameter of from 200 to 1000 nm, and from 99.5 to 0.5 % by weight
of the mixture have a particle size (dsO) with a mean diameter of
from 60 to 190 nm.
The chemical composition of the two graft copolymers is prefer-
10 ably the same, although the shell of the coarse-particled graft
copolymers may in particular have a two-stage composition.
The graft shell (component (a2)) is also prepared, as a rule, by
known polymerization methods, such as emulsion, mass, solution or
15 suspension polymerization, preferably an aqueous emulsion in the
presence of an aqueous emulsion of the core (al) (cf. DE-A
1,260,135, DE-A 3,149,358 and German Patent 1,164,080). In a
preferred embodiment, the graft copolymerization is carried out
in the same system as the polymerization of the core (al), and,
20 if required, further emulsifier and initiator may be added. These
need not be identical to the emulsifiers or initiators used for
the preparation of the core (al). Emulsifier, initiator and
polymerization assistants may each be initially taken alone or as
a mixture for the emulsion of the core (al). Any possible com-
25 bination or initially taken mixture and feed on the one hand andinitiator, emulsifier and polymerization assistants on the other
hand is suitable. The preferred embodiments are known to a person
skilled in the art. The monomer or monomer mixture to be grafted
on may be added to the reaction mixture all at once, batchwise in
30 a plurality of stages or continuously during the polymerization.
C2-C8-Alpha-olefins, such as ethene, propene, but-l-ene, pent-
1-ene, hex-1-ene, hept-1-ene and oct-l-ene, or mixtures thereof
may be used as alpha-olefins for the preparation of component
35 (~), preferably ethene and propene.
Examples of polar comonomers which, according to the invention,
should not include vinyl acetate and vinylaromatic monomers are
alpha-beta-unsaturated C3-C8-carboxylic acids and available
40 anhydrides thereof, such as acrylic acid, methacrylic acid,
maleic acid, maleic anhydride, fumaric acid, itaconic acid and
glycidyl esters thereof and esters with C1-C8-alkyl alcohols whose
alkyl radicals may be monosubstituted by phenyl or naphthyl,
naphthol and phenol which is unsubstituted or substituted by up
45 to two Cl-C4-alkyl groups, such as methyl methacrylate, methyl
acrylate, ethyl methacrylate, ethyl acrylate, n-butyl acrylate,
isobutyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl
214513~
acrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate,
phenyl acrylate, phenylethyl methacrylate, phenylethyl acrylate,
benzyl methacrylate, benzyl acrylate, phenylpropyl methacrylate,
phenylpropyl acrylate, phenylbutyl methacrylate, phenylbutyl
5 acrylate, 4-methylphenyl acrylate and naphthyl acrylate, and
phenoxyethyl methacrylate and phenoxyethyl acrylate;
methacrylonitrile, acrylonitrile;
10 carbon monoxide.
In a preferred embodiment, copolymers which can be prepared from
(I) 40-75 % by weight of ethylene, 5-20 % by weight of carbon
monoxide and 20-40 % by weight of n-butyl acrylate, for example
15 commercially available as ELVALOY~ HP-4051 (DuPont), or (II)
50-98,9 % by weight of ethylene, 1-45 % by weight of n-butyl
acrylate, 0,1-20 % by weight of methacrylic and/or acrylic acid
and~or maleic anhydride are used as component (B).
20 The copolymers (B) are prepared in a manner known per se (cf.
US 2,897,183 and US 5,057,593). The preparation is usually car-
ried out by free radical polymerization. The initiators used are,
as a rule, peroxides, such as lauryl peroxide, tert-butyl perace-
tate, tert-butyl peroxypivalate, di-tert-butyl peroxide, di-(sec-
25 butyl) peroxydicarbonate, tert-butyl peroctoate and tert-butyl
perisononanoate, preferably tert-butyl peroxypivalate and tert-
butyl perisononanoate. In general, azo-containing initiators,
such as azobisisobutyronitrile, are also suitable.
30 The choice of the suitable initiator is usually made dependent on
the polymerization temperature to be chosen, which as a rule is
from 100 to 300 C, preferably from 130 to 280 C. The pressure dur-
ing the polymerization is chosen as a rule in the range from 100
to 400, preferably from 150 to 250, MPa. The amount of initiator
35 is chosen in general to be from 1 to 50, preferably from 2 to
20 mol per 106 mol of the amount of polar copolymer used.
The polymerization is usually carried out in a continuous stirred
reactor. Such a reactor is described in, for example,
40 US 2,897,183. The reaction time is as a rule from 30 to 1, pre-
ferably from 5 to 2, minutes. Observations to date have shown
that the use of a solvent is optional.
The vinylaromatic monomers (component (cl)) used are styrene,
45 substituted styrenes of general formula (I), which have already
been stated as component (a21), or the C1-C8-alkyl esters of
methacrylic or acrylic acid, stated under component (a21).
2i4513~
Styrene, alpha-methylstyrene and p-methylstyrene are preferably
used.
If desired, monomers Which have already been stated as component
5 (a22) may be used as monofunctional comonomers (cG.,.ponent (c2)).
If desired, the Cl-Cg-alkyl esters of methacrylic and acrylic
acid, stated under component (a21), may furthermore be mixed with
the monomers stated under component (a21) and the mixture used as
component (c2).
In a preferred embodiment, a mixture of styrene (S) and acryloni-
trile (AN), S and a-methylstyrene, optionally mixed with methyl
methacrylate or maleimides, or methyl methacrylate, if desired
with methyl acrylate, is used.
The polymers of component (C) are as a rule known and are obtain-
able by methods known per se (cf. Runststoff-Handbuch, Vieweg-
Daumiller, Volume V (Polystyrol), Carl-Hanser-Verlag, Munich
1969, page 124, lines 12 et seq.). The polymerization i8 carried
20 out as a rule by free radical emulsions, suspension, solution or
mass polymerization. In general, the polymers (C) have viscosity
numbers (VN) (measured in a 0.5 % strength by weight solution in
dimethylformamide at 23 C [~spec/C in cm3/g]) of from 40 to 160,
which corresponds to average molecular weights Mw of from 40,000
25 to 2,000,000.
The novel thermoplastic molding materials may contain, as further
component D), up to 50, in particular from 0.1 to 20, % by
weight, based on the total material (A) + (B) + (C), of fibrous
30 or particulate fillers or of mixtures thereof. These are prefer-
ably commercially available products. Processing assistants and
stabilizers, such as UV stabilizers, lubricants and antistatic
agents, are usually used in amounts of from 0.01 to 5 % by
weight, but reinforcing agents, such as carbon fibers and glas~
35 fibers, in general in an amount of from 5 to 40 % by weight.
Fillers or reinforcing materials, such as glass beads, mineral
fibers, whiskers, alumina fibers, mica, quartz powder and wollas-
tonite, may also be added.
The novel molding materials may also contain further additives
which are typical and conventionally used for styrene/acryloni-
trile (SAN) polymers and graft copolymers based on acrylonitrile/
styrene/acrylates (ASA) or mixtures thereof. Examples of such ad-
45 ditives are dyes, pigments, antistatic agents, antioxidants andin particular the lubricants which are required for further pro-
cessing of the molding material, for example in the production of
`` 214513~
11
moldings or shaped articles, in particular up to 10 ~ by weight
of plasticizers and, if desired, polar copolymers having anti-
static activity, such as ethylene oxide/propylene oxide copoly-
mers.
The novel thermoplastic molding materials are usually prepared by
processes known per se, by mixing the components (A), (B) and, if
desired, (C) and/or (D). It may be advantageous to premix indi-
vidual components. It is also possible to mix the components in
lO solution and remove the solvents. However, mixing of the compo-
nents is preferably carried out at from 200 to 320 C by extruding
or kneading the components together or treating them in a roll
mill, if necessary the c~l"~onents having been isolated beforehand
from the solution obtained in the polymerization or from the
15 aqueous emulsion.
The novel thermoplastic molding materials can be processed by the
known methods for processing thermoplastics, for example by ex-
trusion, injection molding, calendering, blowmolding, pressing or
20 sintering.
In a further preferred embodiment, halogen-free films having a
leather-like appearance, stable to aging and containing only a
small amount of volatile c~ ~_nents are produced by, usually,
25 calendering and, if desired, subsequent deep drawing of the
films, by using, as component (~), a copolymer prepared from
45-S5 % by weight of ethylene,
11-15 % by weight of carbon monoxide and
30 30-36 % by weight of n-butyl acrylate
according to US 2,897,183 or US 5,057,593, and, as component (C),
a copolymer prepared by continuous solution polymerization of
35 65 % by weight of styrene and
35 % by weight of acrylonitrile,
having a viscosity number of 80 ml/g (measured in a 0.5 %
strength by weight solution in dimethylformamide at 23 C. A graft
40 copolymer having a core comprising essentially n-butyl acrylate
which is crosslinked with tricyclodecenyl acrylate and a graft
shell prepared from 60-90 % by weight of styrene and 40-10 % by
weight of acrylonitrile, according to DE-A 3,149,358, is prefer-
ably used as component (A). Such novel films are preferably used
45 for the interior trim of commercial vehicles, such as auto-
mobiles, aircraft, ships and trains.
`` 214513~
~_ 12
The films~which can be prepared from the novel thermoplastic
molding materials have a balanced ratio of tensile strength,
elongation at break, tear propagation strength, hardness and col-
or stability during processing, compared with those of the prior
5 art.
Examples
The mean particle size and the particle size distribution were
lO determined from the integral mass distribution. In all cases, the
mean particle sizes are the weight average of the particle sizes,
as determined by means of an analytical ultracentrifuge using the
method of W. Scholtan and H. Lange, Kolloid-Z., and Z. Polymere
250 (1972), 782-796. The ultracentrifuge measurement gives the
15 integral mass distribution of particle diameter of a sample. From
this it iQ possible to determine the percentage by weight of the
particles which have a diameter equal to or smaller than a cer-
tain size. The mean particle diameter, which i8 also referred to
as the d50 value of the integral mass distribution, is defined as
20 the particle diameter at which 50 ~ by weight of the particles
have a diameter smaller than the diameter which corresponds to
the d50 value. Likewise, 50 % by weight of the particles then have
a diameter larger than the d50 value. To characterize the width of
the particle size distribution of the rubber particles, the dlo
25 and dgo values obtained from the integral mass distribution are
used in addition to the d50 value (mean particle diameter). The
dlo and dgo values of the integral mass distribution are defined
similarly to the d50 value, except that they are based on 10 and
90 % by weight, respectively, of the particles. The quotient
dgo - dlo
= Q
d50
35 is a measure of the width of the particle size distribution.
The following components were used:
A. A coarse-particled graft polymer which was prepared as fol-
lows:
1.5 g of the finely divided butyl acrylate latex prepared ac-
cording to EP-~ 6503, page 12, line 55, to page 13, line 22,
were initially taken, 50 g of water and 0.1 g of potassium
persuflate were added and then, in the course of 3 hours, a
mixture of 49 g of butyl acrylate and 1 g of tricyclodecenyl
acrylate on the one hand and a solution of 0.5 g of the
` 2i4~134
_ 13
sodium~salt of a C12-C1g-paraffinsulfonic acid in 25 g of wa-
ter on the other hand were introduced at 60 C. Polymerization
was then continued for 2 hours. The resulting latex of the
crosslinked butyl acrylate polymer had a solids content of 40
~ by weight. The mean particle size (d50) (weight average of
the latex) was determined as 430 nm, and the particle size
distribution was narrow (Q = 0.1).
150 g of the latex prepared above were mixed with 20 g of
styrene and 60 g of water, a further 0.03 g of potassium per-
sulfate and 0.05 g of lauroyl peroxide were added and the
mixture was then heated at 65 C for 3 hours while stirring.
The emulsion obtained in this graft copolymerization was then
polymerized with 20 g of a mixture of styrene and acrylo-
nitrile in a weight ratio of 75:25 for a further 4 hours. The
reaction product was then precipitated from the emulsion by
means of a calcium chloride solution at 95 C, isolated,
washed with water and dried in a warm air stream. The degree
of grafting of the graft copolymer was determined as 35 ~.
The mean particle size (d50) of the latex particles was
510 nm.
Bl) A copolymer prepared from ethylene, carbon monoxide and 30 %
by weight of n-butyl acrylate (Elvaloy0 HP-40Sl from DuPont
prepared similarly to Example 2 in US 5,057,593).
B2) An ethylene/vinyl acetate copolymer (Luwax0 EVAl (BASF); melt
viscosity at 140C 1500 mm2/sec).
30 A copolymer prepared from styrene and acrylonitrile in a weight
ratio of 65:35 (S:AN) and having a viscosity number of ôO ml/g
(measured in a 0.5 ~ strength by weight solution in dimethylform-
amide at 23 C) was used as component C. The polymerization was
carried out by continuous solution polymerization similarly to
35 Kunststoffe-Handbuch, Vieweg-Daumiller, Volume V (Polystyrol),
Carl-Hanser-Verlag, Munich 1969, page 124, line 12 et seq.
The films were produced in a thickness of 0.5 mm, by mixing in a
roll mill heated at 200-C. Moldings were punched out from these
40 films, and the tensile test according to DIN 53504 and the tear
propagation test according to DIN 53515 were carried out.
The Shore hardness was determined according to DIN 53505.
45 The Vicat A heat distortion resistance was determined (in C) ac-
cording to DIN 53460.
214513~
-
lg
, _
V ., ~ ~ X X X X ", o X `
o, o , , o ,~, o
_,
o U~ o
Ul ,
~ o a~ O
.. ~ o~ '
o O I I ~ ~1 a~
o
'U~ , ",, ~ o~
~ n
Q ~ ~
Q J U' _~ ~ _ a~ ~ O ~ U
~ Q ~ z, ~ d~ Q~ ~ Z S ~ -~ O
m m u E~ n ~ ~ n-- rn.c ~--
214513~
_ 15
In order to determine the volatile components in leather-like
films, 2 g of each of the films to be tested, from Examples 2, 3
and 4, were heated in a glass cylinder for 1 hour at 280 C in a
5 stream of nitrogen. The masses used were determined before and
after the experiment. The difference between the masses corre-
sponded to the amounts of volatile components. The values ob-
tained also provide information about the fogging behavior: the
greater the loss of mass, ie. the higher the content of volatile
10 components, the greater is the fogging.
Table 2
Example Loss of mass [~ by weight]
15 2 0.67
3 0.75
4 0.82
for comparison
Vl 1.08
V2 2.82
The following were used as comparative films:
Vl: Film comprising 80 parts by weight of c~ ,onent ~A), 10 parts
by weight of component (C) and 10 parts by weight of a
copolymer prepared from 90.5 ~ by weight of ethylene and
9.5 ~ by weight of vinyl acetate (melt viscosity at 120C:
1700 mm2/sec; Luwax~ EVA2 (BASF)),
V2: Baymoflex~ A VPKU 3-2069 A (Bayer AG); polymer blend based on
acrylonitrile/styrene/acrylate resin:
35 Softening temperature:above about 90C
Density: about l.0 g/cm3 at 20C (DIN 53479)
Bulk density: about 250-350 kg/m3
Solubility in water: insoluble
Ignition temperature: above 400C (DIN 51794)
