Note: Descriptions are shown in the official language in which they were submitted.
~C53~37~
AQUEOU~ VULCANIZING ADHE8IV~
This invention relates to an improved water-based
binder for vulcanizing various types of rubber onto vul-
canization-stable substrates.
It is becoming increasingly desirable to avoid the
presence of volatile substances, such as solvents, in ad-
hesives of the type in question. Accordingly, efforts have
been made to formulate solventless systems. Thus, it is
proposed in applicants' European patent 21 186 to synthe-
size a homopolymer or copolymer of vinylidene chloride
and/or of butadiene/acrylonitrile copolymers, aromatic
nitroso compounds, blocked isocyanates, polyvinyl pyrroli-
done and other auxiliaries. Although products such as
these were useful, there was still a need to improve bond
strength with respect to all types of rubbers, including
apolar rubbers, such as natural rubber, and to increase the
2C~3!37~
economy of the binders.
A terpolymer latex consisting of a 2,3-dihalo-1,3-
butadiene, an aromatic monoalkenyl alkyl halide and other
monomers is known from DE-OS 34 25 381. This terpolymer
may be processed together with polyfunctional aromatic ni-
troso compounds, the solids typically used in this field
and a film-forming agent to form an adhesive composition.
The film-forminq agents mentioned also include homopolymers
and copolymers of vinyl acetate. Although binders on this
basis for vulcanizing rubber onto metals and the like pro-
duce useful results, it has now been found that major im-
provements can be obtained when the copolymers of vinyl
acetate or the vinyl acetate are/is subjected to partial
saponification to the corresponding polyvinyl alcohols.
Water-based binders for vulcanizing rubber onto vul-
canization-stable substrates are already known from Euro-
pean patent 161 373. However, these known binders contain
masked polyfunctional isocyanates. The use of masked iso-
cyanates is undesirable because they can cause stability
problems in storage. The known binders according to Euro-
pean patent 161 373 may also contain polyvinyl alcohol, al-
though there is no reference to the type or quantity of
polyvinyl alcohol used. The function of the polyvinyl al-
cohol in formulations such as these is merely to stabilize
the constituents, i.e. polyvinyl alcohol is used as a stab-
ilizer and not as a reactive component which contributes
essentially to the composition of the binder.
Accordingly, the present invention relates to a water-
based binder dispersion for vulcanizing rubber onto vulcan-
ization-stable substrates consisting of
- a halogenated copolymer containing an alkylating
aromatic monoalkenyl alkyl halide in addition to other
constituents,
- polyfunctional aromatic nitroso compounds,
- pigments, carbon black, foam inhibitors, emulsifiers
and other auxiliaries,
characterized in that partially saponified homopolymers or
2c53a74
copolymers of vinyl acetate and, if desired, other standard
additives are present for increasing bond strength.
The most important constituent of the binder according
to the invention is a halogen-containing polymer based on
an alkylating aromatic monoalkenyl alkyl halide. Preferred
halogenated copolymers of this type are terpolymers of
- 60 to 97% by weight of a 2,3-dihalo-1,3-butadiene,
- 2 to 33% by weight of an aromatic monoalkenyl alkyl
halide corresponding to the formula:
0 I.
~ CX2=CX~
_
--C--R
and
.
~25 tx2=cx
Y--C--Z ~--C--R
1 _ ~ _
b b
in which X is hydrogen, chlorine, bromine or iodine;
Y is hydrogen, chlorine or bromine; Z is hydrogen,
chlorine or bromine and A is hydrogen, chlorine,
bromine or a Cl_3 alkyl group, with the proviso that,
of Y, Z or A, at least one is chlorine or bromine and,
where A is an alkyl group, at least one of Y or Z is
chlorine or bromine, and a = 1 or 2 and b = 0, 1 or 2,
with the proviso that at least one b is at least 1;
and
0.5 to 10% by weight of at least one olefinically un-
saturated monomer, the monomer being at least copol-
ymerizable with the conjugated diene monomer and di~-
ferent from the aromatlc alkyl halide.
With regard to the 2,3-dihalo-1,3-butadiene as con-
jugated diene monomers, which are known commercial prod-
ucts, the halogen substituent is selected from a groupconsisting of chlorine, bromine and iodine, chlorine pres-
ently being the preferred halogen substituent.
With regard to the mixture of at least two different
unsaturated monomers which are copolymerizable at least
with the conjugated diene monomer, it is pointed out that
these monomers are selected from a first group, which con-
sists of ~-haloacrylonitrile, ~-haloacrylic acid, ~-halo-
acrylic acid ester, ~-halovinyl ketone, ~-halovinyl ace-
tate, vinyl halide, vinylidene halide, styrene and aromatic
monoalkenyl alkyl halides, and from a second group consist-
ing of monomeric compounds containing at least one olefin-
ically unsaturated group, the monomers of the second group
being different from the monomers of the first group.
At present, compounds corresponding to formula I are
preferred. Representative aromatic monoalkenyl alkyl ha-
lides include vinylbenzyl chloride, p-trichloromethyl vin-
ylbenzene, p-(~-chloroethyl)-vinylbenzene, p-(~-chloro-
butyl)-vinylbenzene, ~-chlorovinylbenzene chloride, 2,3-
di-(~-chloroethyl)-vinylbenzene, 4-chloromethyl vinyl naph-
thalene, the corresponding bromine and iodine analogs andthe like. At present, the preferred aromatic monoalkenyl
alkyl halide is vinylbenzyl chloride (4-chloromethyl vinyl-
benzene).
With regard to the second group of copolymerizable
monomeric compounds, the ethylenically unsaturated com-
pounds of the second group are those which can be polymer-
ized by addition of unsaturated bonds, providing they do
not crosslink, i.e. either only one unsaturated ethylene
group is present in the compound or, where more than one
group is present, they are conjugated as such or crosswise.
~he ethylenically unsaturated monomers which may be used in
the terpolymers according to the invention are those which
2C53874
which contain either one or several CH2 = C groups.
The ethylenically unsaturated compounds containing one
or more CH2 = C = groups include such compounds as styrene,
p-chlorostyrene, 3,5-dichlorostyrene, p-methoxystyrene, ac-
rylonitrile, methacrylonitrile, vinyl bromide, vinyl fluor-
ide, vinyl iodide, vinyl acetate, vinyl propionate, vinyl
butyrate, vinyl benzoate, vinylidene bromide, vinylidene
chlorofluoride, methyl methacrylate, butyl methacrylate,
methacrylamide, vinyl methyl ketone, vinyl pyridine, vinyl
carbazole, vinyl methyl ether, isobutylene, ethylene, vinyl
chloride, vinylidene chloride, alkyl acrylates, including
methyl, ethyl, propyl, butyl and octyl acrylates, acrylic
acid and methacrylic acid and other similar monoolefinic
polymerizable compounds. Other unsaturated compounds con-
taining more than one olefinic group which may be copolym-
erized to form the terpolymers according to the invention
are conjugated dienes, such as l,3-butadiene, isoprene and
other 1,3-butadiene hydrocarbons, chloroprene and also 3-
cyano-1,3-butylidene, trienes, such as myrcene, and com-
pounds containing olefinic and acetylenic bonds, such as
vinyl acetylene, vinyl ethynyl, diethyl carbonyl and the
like.
The terpolymer latex used in accordance with the in-
vention may be prepared by emulsion polymerization of the
halogenated conjugated diene with at least two different
unsaturated comonomers in an aqueous medium in the presence
of an ionic or a mixed ionic/nonionic surface-active sys-
tem, ionic surface-active systems presently being prefer-
red. It has been found that the terpolymer products which
are most suitable for carrying out the invention contain 60
to 97% by weight, preferably 75 to 97% by weight and opti-
mally 93 to 97% by weiqht halogenated conjugated diene and,
in addition, 2 to 33% by weight, preferably 3 to 25% by
weight and optimally 3 to 7% by weight of the monomer of
the first group and 0.5 to 10% by weight and preferably 2
to 7% by weight of the monomer of the second group. Of
particular value are terpolymer products which have ~een
produced from 2,3-dihalo-1,3-butadiene, more particularly
2,3-dichloro-1,3-butadiene, in a quantity of 80 to 95% by
weight, based on polymer, aromatic monoalkenyl alkyl ha-
lides, more particularly vinylbenzyl chloride, in quanti-
ties of 2 to 10% by weight and also olefinically unsatur-
ated monomers, more particularly monomers containing at
least one -COoH group, acrylic acid, methacrylic acid and/
or 2-hydroxyethyl methacrylate monophosphate in quantities
of 2 to 10% by weight. Part of the aromatic monoalkenyl
alkyl halides, for example 10 to 90 mol-%, may also be
saponified to the corresponding hydroxyalkyl compounds.
The emulsion polymerization is carried out in a closed
vessel in which space that is not occupied by the reaction
mixture is kept free from oxygen, preferably a layer of
inert gas, such as nitrogen, because the induction period
for the polymerization reaction is prolonged by the pres-
ence of oxygen and because it is desirable to carry out the
reaction in the substantial absence of oxygen. Generally
speaking, the emulsion polymerization is carried out by
mixing the monomeric constituents with one another, emulsi-
fying the mixture and subjecting the emulsion to moderate
polymerization conditions until substantially the entire
monomeric batch is polymerized. However, for various prac-
tical reasons which need not be discussed here, it has beenfound that the emulsion polymerization of the tertiary mon-
omeric system is carried out more effectively by a semi-
continuous process which comprises adding an emulsion of a
halogenated conjugated diene and the monomers of the first
and second group at constant speed to a polymerization zone
containing an aqueous solution or dispersion of the poly-
merization initiator. The polymerization conditions are
otherwise substantially the same as in batch polymerization
processes and need not be discussed here. The polymeriza-
tion reaction is exothermic and the reaction temperatureshould be kept below about 75C and preferably below about
60C. Virtually any catalyst or initiator which forms free
ZC~5387~
radicals, including the known redox catalyst systems, such
as ammonium persulfate/sodium metabisulfite, benzyl perox-
ide, hydrogen peroxide, di-t-butyl peroxide, azo-bis-(iso-
butyronitrile), alkali metal persulfates and alkyl metal
ammonium perborates, may be used in the copolymerization
reaction to ensure rapid initiation of the reaction and
reproducible results. After the polymerization reaction,
unreacted volatile constituents may be removed by vacuum
treatment at elevated temperature or by steam distilla-
tion, the particular method being a matter of choice.
The choice of the surface-active agent is of major
importance to the production of a latex which ensures
satisfactory adhesion. It has been found that anionic
surfactants or mixtures of anionic and nonionic surfactants
have to be used, the mixtures presently being preferred.
Whereas cationic surfactants as such are effective emulsi-
fiers, their use in the production of the elastomeric ter-
polymer latex according to the invention either individu-
ally or in combination with either an anionic or a non-
ionic surfactant or with both adversely affects the adhes-
ive properties. The surface-active systems are used in
quantities of 0.01 to 15% by weight and preferably in
quantities of 1 to 10% by weight, based on the weight of
the monomers used. At present, it is preferred to use a
mixed anionic/nonionic surface-active system with a ratio
of anionic to nonionic surfactant of 1.2 to 2.1:1 and pref-
erably 1.3 to 2.0:1. Representative anionic surfactants
are carboxylates, such as fatty acid soaps of lauric,
stearic and oleic acid and also acyl derivatives of sarco-
sine, such as methyl glycine; sulfates, such as sodiumlauryl sulfate; sulfatized natural oils and esters, such as
turkey red oil and alkylaryl polyether sulfates; alkylaryl
polyether sulfonates; isopropyl naphthalene sulfonates and
sulfosuccinates and also sulfosuccinamates; phosphate
esters, such as partial esters of complex phosphates with
short-chain fatty alcohols; and orthophosphate esters of
polyethoxylated fatty alcohols. Representative nonionic
2C53874
surfactants include ethoxylated (ethylene oxide deriva-
tives), monohydric and polyhydric alcohols, ethylene oxide/
propylene oxide block copolymers; esters, such as glycerol
monostearate; dehydration products of sorbitol, such as
sorbitan monostearate and polyethylene oxide sorbitan mon-
olaurate; and amines, such as lauric acid, isopropenyl ha-
lide. At present, a 1.8:1 mixture of sodium dodecyl di-
phenyl ether disulfonate as the anionic surfactant and
nonylphenol polyethylene glycol as the anionic surfactant
is preferred. Anionic and anionic/nonionic surface-active
systems which have to be used in accordance with the inven-
tion are described in detail in Em~lsions: Theory and Prac-
tice, by Paul Becher, Chapter 6 (Reinhold Publishing Cor-
poration, New York, 196S), and in McCutcheon's Detergents
and Emulsifiers, 1972 Annual.
The terpolymer latex obtained in accordance with the
invention by the emulsion copolymerization of halogenated
dienes and unsaturated monomers of the first and second
group generally has a pH value in the range from 2 to 3.
It is possible, but not preferred, to adjust the pH to a
value in the range from about 4 to 11 and preferably 6 to
10 using acid acceptors or buffers, such as zinc oxide,
dibasic lead phosphate, sodium acetate/acetic acid mixtures
or the like, dibasic lead phosphate presently being the
preferred acid acceptor. Stabilizers of this type are of
course used in a quantity sufficient to maintain the de-
sired pH value because excesses can be problematical.
The binders according to the invention contain aroma-
tic nitroso compounds as another key constituent. The aro-
matic nitroso compounds which are suitable for carrying outthe invention are any aromatic hydrocarbons, such as ben-
zene, naphthalene, anthracene and diphenyl, which contain
at least two nitroso groups attached directly to non-adja-
cent ring carbon atoms. Nitroso compounds such as these
are known as aromatic poly-C-nitroso compounds containing
1 to 3 aromatic nuclei, including aromatic nuclei fused to
one another containing 2 to 6 nitroso groups which are at-
2C53874
tached directly to non-adjacent ring carbon atoms. At
present, preferred poly-C-nitroso materials are aromatic
nitroso compounds, more particularly dinitrosobenzenes and
dinitrosonaphthalenes, such as meta- or para-dinitrosoben-
zenes and meta- or para-dinitrosonaphthalenes. The ring
hydrogen atoms of the aromatic nucleus may be replaced by
alkyl, alkoxy, cycloalkyl, aryl, arylnitroso, halogen and
similar groups. The presence of such substituents at the
aromatic nucleus has little effect on the activity of the
poly-C-nitroso compounds according to the invention. As
far as it has hitherto been possible to tell, there are no
limitations in regard to the nature of the substituent
which may be organic or inorganic. Accordingly, any refer-
ence to the "aromatic" poly-C-nitroso comopound, "benzene"
or "naphthalene" is understood to encompass both substi-
tuted and unsubstituted nitroso compounds, etc., unless
otherwise stated.
A partial non-limiting list of suitable poly-C-nitroso
compound suitable for carrying out the invention includes
m-dinitrosobenzene, p-dinitrosobenzene, m-dinitrosonaph-
thalene, p-dinitrosonaphthalene, 2,5-dinitroso-p-cymol, 2-
methyl-1,4-dinitrosobenzene,2-methyl-5-chloro-1,4-dinitro-
sobenzene, 2-fluoro-1,4-dinitrosobenzene, 2-methoxy-1,3-
dinitrosobenzene, 5-chloro-1,3-dinitrosobenzene, 2-benzyl-
1,4-dinitrosobenzeneand2-cyclohexyl-1,4-dinitrosobenzene.
The binders according to the invention contain partly
saponified homopolymers or copolymers of vinyl acetate as
another characteristic constituent. Compounds such as
these are referred to herein as polyvinyl alcohol. They
are used in quantities of 1 to 15% by weight and preferably
in quantities of 1.5 to 5% by weight, based on binder. The
degree of saponification of the polyvinyl alcohols used,
i.e. the percentage number of hydroxyl groups, based on the
acetate groups originally present, is between 40 and 98~.
Particularly favorable results are obtained with degrees of
saponification of 80 to 90%.
Suitable polyvinyl alcohols are derived on the one
2C53874
hand from vinyl acetate homopolymers and on the other hand
from copolymers thereof. Suitable copolymers are copoly-
mers of vinyl acetate with olefins, halogenated olefins,
vinyl ethers, olefinically unsaturated mono- or dicarbox-
ylic acids and/or - to a limited extent - esters thereof.
In addition to the saponification products of polyvinyl
acetate, therefore, preference is attributed to saponifi-
cation products of polyvinyl acetate-co-vinyl butyrate,
saponification products of vinyl acetate/ethylene/vinyl
chloride copolymers, saponification products af vinyl
acetatelacrylates, of vinyl acetate/maleic acid dibutyl
ester copolymers, of vinyl acetate/styrene acrylate co-
polymers and of vinyl acetate/methyl acrylate copolymers.
Copolymers of vinyl acetate, ethylene and vinylidene chlor-
ide having the degrees of saponification mentioned are also
suitable. In the copolymers mentioned, the vinyl acetate
content in mol-% of the copolymer as a whole is more than
30 mol-%, preferably more than 50 mol-% and, more prefer-
ably, more than 70 mol-%.
Although no theoretical explanation for the effects
observed in accordance with the invention can be given at
the present time, the hydroxyl groups of the polyvinyl al-
cohols which must be present in accordance with the inven-
tion would appear to react with the other constituents dur-
ing establishment of the bond under vulcanizatiqn condi-
tions.
According to the invention, favorable results are ob-
tained with polyvinyl alcohols having a molecular weight
in the range from 14,000 to 100,000. It has been found in
this regard that the molecular weight is only of minor im-
portance to the result obtained. However, the expert can
increase the viscosity by increasing the molecular weight
and, hence, can vary the processing properties of the bind-
er. However, it has been found that binders based on rela-
tively high molecular weight polyvinyl alcohols show better
adhesion of the uncured binder film to metals or primers
which is often desirable for automated application proces-
2C53874
ses. Binders in which the polyvinyl alcohol has molecular
weights in the ran~e from 30,000 to 75,000 have proved to
be successful for this purpose, so that this molecular
weight range may be regarded as preferred.
Quantitatively, the binders according to the invention
preferably contain 5 to 20% by weight halogenated polymer,
2 to 20% by weight of at least one polyfunctional aromatic
nitroso compound, 0.2 to 15% by weight polyvinyl alcohols
and 0.2 to 6% by weight auxiliaries. The balance to 100%
~ by weight is water. The total solids content of the prepa-
rations is between 10 and 50% by weight and preferably be-
tween 20 and 30% by weight.
The dispersions according to the invention may also
contain typical adhesion-improving fillers, more particu-
larly carbon black in quantities of 0.2 to 10% by weight,zinc oxide in quantities of 0.1 to 10% by weight or, if
desired, basic lead phosphite and the like. Pigments may
also be incorporated. Another advantage of the binders
according to the invention is that the masked isocyanate
compounds, which are described as essential in preparations
of the type in question, for example in the binder accord-
ing to DE-PS 29 23 651 and in German patent application ~E
34 00 851, need not be used. Technically, the presence of
masked isocyanates is generally critical to the stability
of the binders, particularly at elevated temperatures such
as can occur in warehouses in summer. To prepare the bind-
ers according to the invention, a latex of the halogenated
polymer based on an alkylating aromatic monoalkenyl alkyl
halide is initially prepared by emulsion copolymerization.
The other constituents and, if desired, water are added to
the latex. After preliminary dispersion in a suitable
unit, the latex is then ground in a ball mill to a fineness
of less than 2 mils.
The water-based binders according to the invention are
suitable for bonding vulcanizable elastomers to a number of
substrates, including for example numerous metals, such as
iron, stainless steel, lead, aluminium, copper, brass,
2CS3874
bronze, monel metals, nickel, zinc and the like. They are
also suitable for treated metals, such as phosphated steel,
galvanized steel, and may also be used for glass and cer-
amic materials and for high-melting plastics, such as ara-
mide fibers for example. Emphasis is placed on their fav-
orable effect in particular in the vulcanization of polar
rubbers, for example nitrile rubber, onto aramide fibers or
metals.
The binders are conventionally applied to the sub-
strate surfaces, for example by dip coating, spray coating,
brush coating and the like. It may be advisable in some
cases to carry out a pretreatment with a primer of chlorin-
ated rubber, phenolic resin or the li~e. After coating,
the substrate surfaces are left to dry before being fitted
together. After the surfaces have been fitted together,
the composite structures are conventionally heated to bring
about vulcanization.
~ x am p 1 e s
In the tests, the product according to the invention
was investigated for its basic adhesive properties and
tested for comparison with known products.
Standard test methods, such as ASTM-D 429, Method A or
Method ~, were used for the tests.
The metals were pretreated in the usual way.
Vulcanization was carried out in a press under the
vulcanization conditions indicated in the Tables. After
vulcanization, all the composites were stored for approxi-
mately 24 hours and then subjected to the individual tests.
Of the formulations listed in Table 1, Nos. 1 to 3
correspond to the water-based binders according to the
invention while formulation No. 4 is a product correspond-
ing to EP 161 373.
For all the tests, the water-based binder was applied
over a primer (based on a phenolic resin).
~t~n~ard a~hesion an~ corrosion test
This test determines the shear strength of the bond
and, at the same time, evaluates the failure pattern
12
~C53874
formed.
In the corrosion test, the composite elements are
stored for 2 h in water at 95 to 98C while a load of 2
kg/in is applied to the bond line.
The results expressed as 100 R (100 R = 100% failure
in the rubber) in Table 2 show satisfactory adhesion and
strength both in the adhesion test and in the corrosion
test for all the rubber mixtures used.
Tensile test
The test according to ASTM-D 429, Method A, determines
the tensile shear strength of a rubber/metal composite.
The result of this test (see Table 3) shows that 100~
failure in the rubber is always obtained in the tensile
test as well, irrespective of the rubber mixture. The dif-
lS ferences between the strength values are due to mixing.
Preheating resistanc~
To test preheating resistance, the coated test plates
are placed in the vulcanizing mold for the preheating time
at 153C and are then directly vulcanized onto the NR mix-
ture.
The failure patterns indicated in Table 4 show a dis-
tinctly better preheating resistance for binder No. 3 than
for binder No. 4. Even after heating for only 8 minutes,
binder No. 4 i3 no longer able to establish a firm bond.
Binder No. 3 performs satisfactorily after preheating for
14 minutes.
~ydrolysis stability
The automotive industry requires a resistance to Gly-
santin~/water (1:1) at 135C of more than 42 hours for EPDM
composite elements used in the vicinity of radiators.
A resistance to damper liquid (Glykosafe~610, a prod-
uct of BASF) of 7 days at 130C is required for engine
bearings (NR composite).
Different EPDM or NR mixtures were bonded with binders
Nos. 3 and 4 and subjected to the described stability
tests.
Table 5 shows the distinct superiority of binder No.
13
2c5387
3 to binder No. 4.
Boiling w~t-r resi~tance
In addition to the hydrolysis tests mentioned, the
boiling water test (as already described) clearly shows to
what extent a safe bond is established.
As shown in Table 6, all NR mixtures are bonded so
firmly with binder No. 3 that satisfactory boiling water
resistance is achieved. Binder No. 4 fails completely.
The described tests showed that only limited adhesion
and very poor stability are achieved with the hitherto
known binder according to European patent o 161 373.
In contrast, the binder according to the invention
performs satisfactorily in all the tests. The resistance
to Glysantin0 and Glykosafe~610 achieved with the binder
according to the invention is particularly remarkable.
In addition, the binder according to the invention is
also satisfactory in regard to spraying behavior, spray
pattern, sedimentation or substrate adhesion and stripping
resistance.
Binders Nos. 1 and 2 in Table 1 correspond in their
adhesion and resistance behavior to binder No. 3 which has
been described in detail. They are only inferior to binder
No. 3 in viscosity or thixotropic behavior so that a broad
account is not necessary.
The chemical names of the commercial products are
given after the Tables.
ZC53874
Formulation of the NR mixtur-
Mixture constituents
_
NR SMR 5 CV 60 100 parts
Stearie acid 2 parts
Vulkanox~HS 1 part
Zno RS 10 parts
Pine tar 2 parts
CK 3 25 parts
VulkacitL 0.33 part
Vulkacit~DM 0.58 part
Sulfur 2.75 parts
Vuleanization: 153C/10 mins.
Formulation of the BBR mixture
Mixture eonstituents
.
Buna H~ls~1500 100 parts
Stearie aeid 1 part
Zno RS 5 parts
Corax03 50 parts
ParafluxO 8 parts
Vulkaeit~CZ 0.95 part
Sulfur 1.6 parts
Vuleanization: 153C/30 mins.
2C53874
For~ul~tion of NBR ~ixtur-
Mixture constituents
Perbunan0 N 3807 lOO parts
Hycar0 1312 lO parts
Alnovol0 Ph 809 15 parts
VulkanoxO MB 1 part
Vulkanox0 AP 1 part
Zno active 5 parts
Arovel0 FEF 20 parts
Regal0 R 35 parts
Stearic acid 1 part
Winnofil S 20 parts
Vulkacit CZ 1 part
Vulkacit Thiuram 3 parts
Sulfur 0.2 part
Vulcanization: 153C/15 mins.
Foruul~tio~ of th- IIR ~ixtur-
Mixture constituents
Esso-butyl0 325 lOO parts
Stearic acid 1 part
Zno RS 5 parts
Corax 3 50 parts
Vulkacit0 DM 1 part
Ethyl-Tellurac 1.5 parts
Sulfur 1 part
Vulcanization: 160C/30 mins.
16
Formulation of the CR mixtUro ZC53874
Mixture constituents
_
Baypren~ 110 50 parts
Baypren0 210 50 parts
Stearic acid 0.5 part
MgO light 4 parts
Vulkanox~ MB 0.5 part
Vulkanox~ 4010 NA 1 part
Antiozonant AFD 0.5 part
Antiozonant wax 1111 part
Thermax~ MT 140 parts
Ingraplast~ S 10 parts
Rhenosorb0 C 5 parts
Zno RS 5 parts
Vulkacit Thiuram~MS1 part
Vulkacit~ DOTG 1 part
Sulfur 0.5 part
Vulcanization: 160C/20 mins.
17
2~53874
Formulatlon o~ EPDN mixture No. 1
Mixture constituents
Keltan0 512 lOO parts
Stearic acid 0.5 part
Vulkanox0 HS 1.5 parts
ZnO RS 5 parts
Corax~ 3 9O parts
Gulf security032050 parts
BDMA0 1.5 parts
Perkadox0 14/40 8.5 parts
Vulcanization: 160C/25 mins.
ZC5387A
_ .
U q~
o\ o~o o~o o~o o~o ~ o U
.,~ o
. . . . . . ,,
~r 1` 1 ~1 1 ~1 0
In U~ 0
~ ,,
'~5 h
.,_
~o ~o o\ d~o`.P 0\ ~
O C~ _~
. . . . . . .
I o ~ ,~ o ~ u ~
~ m _I h
_ N
~ C)
o\ o\ o\ o\,o\ o\d~ R
~D ~ ~ ~ X ~:0
~1 . . . . . . . ~
r~ I o ~ ~ o~1 ~ ~ O
) _ h -- ~q
a) . a~ ~
.. ~ h
~ O ~ ~
~ ~ ~ o
_ ~
_ _ 0 I ~ ~ O
. . 0 ~ rl ~ q~
O O --
1 0 Ul 0 ~ O o
S .C 0 h ~
.!C U U :~ ~3 O o
,C ~1 ~1 In
o o ~ o o a~ a~ ~ x ~
.) O ~: 3
_ _ _ _ _ _ _ .,~
I ~ I~
_ ` ~ ~0 _,
~ ~ ~ ~o
_ ~ O O _l
0 O ~ ,1
_ _ h X a) ~ O h E~
o~O ~ ~ ~D N ~a .C ~I)
_ O X ~ ~ ~ O P~ O
1 X a~ 1~ ~ ~ u
~ _ ~ ~5 'I .q :,~, ,, ~rl
O _ ~r h 10 O O t~ 'CS t~
,~ _ ~ --~ o o In h ~ O
.-1 o ~1 U ~: ~ o In _I h ~1
_ O ~ 13 h ~ ~ O ~
~1 ~~ 1 _ ~ h
:~ _ X ~ ~ ' _l .,1 ~ ,1 ~. O
~ _ a t~ ~ ~ o ~
o o~ n ~ ~I X ~ o
O r~ ~1 0 ~ 1 h ~ ~n ~1
I I -- ,C .~:1 rl ~ ~ I ~ O O
o~ m 0 ~ X -- E-l ~ X P~ O h
r~ h ~ O
a~ ~ ~r o o ,1 o h
~1 C ~n 3 3 h C J~
,~ C~ C~ O O ~ ~ ~ _ _ _ ,~
~ m 1~ ~ N ~ V N 3 ~
E~
2C53874
Table 2
_tand~r~ adheslon and aorros~on test
Substrate: steel
Test method: ASTM-D 429, Method B
Binder: No. 3 over primer
Mixture Adhesion test Boiling water
test
Adhesion Failure
value pattern
_
NR 42 daN/in lOO R lOO R
SBR 80 daN/in lOO R lOO R
CR 35 daN/in lOO R lOO R
EPDM 55 daN/in lOO R lOO R
IIR 48 daN/in lOO R lOO R
NBR 45 daN/in lOO R lOO R
Rey to raw materials
Vulkacit0L (zinc-N-dimethyl dithiocar-
bamate)
Vulkacit0DM (dibenzothiazyl disulfide)
Vulkacit~CZ (benzothiazyl-2-cyclohexyl sul-
finamide)
Vulkacit0 Thiuram MS (tetramethyl thiuram monosul-
fide)
Vulkacit0 Thiuram (tetramethyl disulfide)
Vulkacit0DOTG (di-o-tolyl guanidine)
Ethyl-Tellural0 (tellurium diethyl dithiocar-
bamate)
Vulkanox0HS (2,2,4-trimethyl-1,2-dihydro-
quinoline, polymeric)
Vulkanox0MB (2-mercaptobenzimidazole~
2C538~4
Vulkanox04010 NA (N-isopropyl-N'-phenyl-p-phenyl-
enediamine)
Vulkanox0AP (co~densation product of aldol/
naphthylamine)
Antiozonant wax III (mixture of various hydrocar-
bons)
Antiozonant AFD (unsaturated ether)
Corax03 (carbon black ASTM N 330)
CK03 (carbon black ASTM S 300)
Arovel0FEF (carbon black ASTM N 550)
Regal0R (carbon black ASTM N 774)
Thermax0MT (carbon black ASTM N 99O)
Gulf security0320 (paraff. mineral oil)
Pine tar (pinewood tar)
Paraflux0 (saturated polymerized petroleum
hydrocarbons)
Ingraplast0S (naphthenic mineral oil)
Winnofil0S (calcium carbonate coated with
calcium stearate)
Rhenosorb0C (calcium oxide)
BDMA0 (butyl glycol dimethacrylate)
Perkadox014/40 (1,3-bis-(t-butylperoxyisopro-
pyl)-benzene)
2C538~4
Table 3
Ton~ile test
Substrate: steel
Test method: ASTM-D 429, Method A
Binder: No. 3 over primer
MixtureAdhesion valueFailure pattern
_
NR 6.2 MPa 100 R
SBR10.2 MPa 100 R
CR 5.8 MPa 100 R
EPDM4.9 MPa 100 R
IIR8.9 MPa 100 R
NBR6.4 MPa 100 R
Table 4
Preheating re~istan¢e
Substrate:steel
Test method: ASTM-D 429, Method B
Binder: either No. 3 or No. 4 over
primer
Binder layer thickness: approx. 18 - 20
Mixture: NR
Vulcanization: 153C
Preheating time Binder No. 3 Binder No. 4+)
8 mins.100 R 90 R
10 mins.100 R 40 R
12 mins.100 R 10 R
14 mins.100 R 0 R
16 mins.80 R 0 R
+) Comparison Example according to EP 161 373
Table 5 2CS3874
~ydrolys~ J~a,bi~
Substrate: steel
Test method: ASTM-D 4 2 9, method B
Binder: No. 3 or No. 4 over primer
Glysant~n~/water ~1:11, 3 days/135C
Mixture Binder No. 3Binder No. 4+)
EPDM No. 1 100 R 10 R
EPDM No. 2 100 R 0 R
EPDM No. 3 100 R 0 R
Gly~osafe~C10. 7 ~a~s/130C
Mixture Binder No. 3Binder No. 4
NR No. 1 100 R 90 R
NR No. 2 100 R 90 R
NR No. 3 100 R 20 R
NR No. 4 100 R 30 R
) Comparison Example according to EP 161 373
Table 6 ZC53874
90il~g water resistanc~
Substrate: steel
Test method: ASTM-D 429, method B
Binder: No. 3 or No. 4 over primer
..
Mixture Binder No. 3 Binder No. 4+)
NR No. 1 100 R 0 R
NR No. 2 lOo R o R
NR No. 3 100 R 0 R
NR No. 4 100 R 0 R
) Comparison Example according to EP 161 373
24
