Waxes for

PVC LUBRICATION
Waxes for
PVC Lubrication

Contents

Theory of lubrication PVC 4

Action mode of lubricants 6

Requirements of the final articles 10

Lubricants for PVC 11

Product description 12

Product characteristics 14

Overview of PVC applications 15

Waxes for calendering films 16

Waxes for PVC extrusion 20

Basic formulations 24

PVC foam extrusion 26

PVC injection molding 28

Flexible PVC 29

Semi-rigit PVC 30

Technical information 31

2 waxes for PVC lubrication

Many plastics are not chemically stable enough at the necessary
processing temperatures. The results are oxidation, cross-linking,
chain scission, etc. The thermal sensitivity of PVC is well known.
Hydrogen chloride already begins to split off above 120 °C and is
associated with dramatic losses in the optical, mechanical, and
rheological characteristics of the polymer. The rapid discoloration
(»charring«) and the formation of corrosive fragmentation
products (HCl) are the main problems in this context.

Thermostabilizers make it possible to eliminate or reduce

substantially the splitting off of hydrogen chloride. In addition
to the thermal stress, the plastic melt is also subject to strong
mechanical stress (shear and friction) during processing.
Depending on the processing method, 80 % of the heat energy
is brought into the polymer via friction and only about 20 %
through direct heating.

Additives that have a favorable effect on the flow behavior of For these requirements Clariant offers a variety of different waxes.
the polymer melt are therefore indispensable for troublefree Furthermore, Clariant has a wide assortment of additives such
processing. They are called lubricants or waxes. as light stabilizers and antistatic agents for PVC. Additional details
on these products are available in the respective leaflets.
These lubricants are added to the PVC to fulfill the following
requirements: For consulting and for development of tailor-made customer
solutions, our experienced team of technical service consultants
· Improvement of the flow behavior of the melt, i. e., reduction is available to you.
of internal and external friction, which means less damage to
the material
· Achievement of certain characteristics in the end product
(e. g. gloss, smoothness, anti-blocking)
· Extrernal lubrication like anti-sticking and die-lubrication

3
Theory of lubrication
Impact on PVC
The mode of action of the waxes in PVC
can be illustrated using their chemical
structure and the morphology of PVC:
4 waxes for PVC lubrication
Chemical structure and polarity
The structure and above all the polarity of the lubricant are decisive
for the effect during PVC processing. External lubricants, which are
less compatible with the plastic matrix, act as a »lubricating film«
between the polymer melt and the hot metal parts of the process-
ing machine. Internal lubricants take effect primarily between the
particles (polymer chains). However, very few lubricants can be
classified purely in the one group or the other. Their effects usually
overlap and also depend on the dosage (solubility limit).
Morphological structure of PVC
The PVC particle (secondary particle) is made up of so-called
primary particles or globules, which are about 1 μm in size.
They consist of nodules about 10 nm in size. At processing
temperatures up to 190 °C the secondary particles break down
into globules, a process normally referred to as plasticization.
After about 190 °C these in turn break down into nodules, which
is called gelation (fig.1). Thus there is not a pure melt during
PVC processing. Instead one speaks of particle flow. Suitable
lubricants are able to delay or accelerate this process.
Figure 1: Morphological structure of PVC
Secondary particle Globules
(Particles) (Microparticles)
100 µm 1 µm
Plasticization, up to approx. 190 °C
Gelation, after approx. 180 °C
5
Volatility
In plastics processing, the volatility of lubricants plays an important
role. The formation of vapors and condenses on machines and
equipment parts not only impairs production, but also working
conditions for the personnel. In extrusion processes the effect is
seen in the form of deposits on the nozzles. In calendering films,
with their large open melt surfaces, formation of vapors is especially
critical. In injection molding too, deposits on the tools are un-
desirable. Low-molecular products like fatty acid esters are viewed
as particularly critical in this context.
Nodules
(Submicroparticles)
10 nm
Action mode of
lubricants
Figure 2: Action mode of lubricants
Plasticization Shear dependent
viscosity ­control
Viscosity reduction Release effect
Viscosity reduction
Lubricants with high polarity and short C-chains have a relatively
high ability to penetrate the PVC particle. The extreme case is
represented by plasticizers, which permeate the entire particle
and thus change not only the viscosity, but also the hardness
of the final product. However, internal lubricants penetrate the
particle to only a limited extent and reduce friction between the
globules. The characteristics of the final particles are not affected
by the quantities that are normally used. Typical representatives
are internal lubricants, such as glycerol monooleate (GMO),
glycerol monostearate (GMS), and stearyl stearate.
6 waxes for PVC lubrication
Reduction of friction
Slip effect
Influencing gelation behavior and release effect
Gelation of PVC is delayed primarily by the reduction of wall
adhesion. As the non-polar remnants of the lubricant molecules
become longer, they are less able to penetrate the PVC particle,
and the external proportion of the lubrication effect increases.
The polyolefine and paraffin waxes represent an extreme case.
They do not dissolve in PVC, are displaced from the melt, and are
deposited between the metal and the melt. As a result, however,
they are also susceptible to incompatibility reactions, such as
plateout.
Between the two extremes mentioned, polar/internal and non-
polar/external lubricants, there is a wide range (fig. 3). Oxidation
of polyethylene waxes can produce polar wax oxidates. Ester
waxes made up of long-chain nonpolar chains also provide an
external lubrication effect and form a lubricating film.
 Figure 3: Classification of various lubricants by their effect in tin-stabilized PVC

Lubrication effect in PVC

Internal External
Fatty acid ester
Fatty acid amide (Licowax C)
Montanic acid diol ester (Licowax E)
Montanic acid diol ester, partially saponified (Licowax OP)
Montanic acid triol ester (Licolub WE 4)
Montanic acid complex ester (Licolub WE 40)
Oxidized polyethylene wax (Licowax PED 191)
Polypropylene wax (Licocene PP 6102)
Polyethylene wax (Licowax PE 520)

Lubricants with long hydrocarbon backbone protect the globules
and prevent degradation into nodules. However, viscosity is lower
when there are fewer nodules. Experience has shown that ester
lubricants with long (C26 – C32) non-polar chains, such as montanic
acid esters, allow a wide processing range and are less susceptible
to variations in shear speeds (fig. 4). In practice the use of montan
waxes is said to provide a »wider processing window« (shear de-
pendent viscosity control).
Montanic acid esters in particular are typical examples of such ester
waxes. They delay slightly the gelation of the PVC mass, but thanks
to their polar groups, they are anchored to the globules adequately
enough that no plateout occurs. This provides optimal prevention
of adhesion to the hot machine parts. In addition, there is almost no
negative effect upon melt strength and Vicat softening temperature.
Influence on intrinsic viscosity
and melt strength of PVC
Intrinsic viscosity is understood as the drop in viscosity of a
melt with increasing shear. For example, lubricants that increase
the intrinsic viscosity of PVC are especially useful in extrusion
processes, in which there are areas of different shear speed.
In especially shear-intensive zones in the extruder, a less viscous
melt exerts less resistance, thus lessening the danger of local
thermal overload (i. e., charring). In zones of reduced shear, the
melt is thicker, and it is easier to introduce heat energy. In addition,
the melt displays higher firmness where there is low shear, e. g.,
in the shaping area (nozzle) or when drawing a calender film.

Figure 4: Viscosity in relation to modulus of shear deformation

internal method
Apparent viscosity [log η*]

Apparent shear speed [log γ*]

Newtonian behavior PVC with viscosity-reducing lubricant

(fatty acid ester)
PVC without lubricant PVC with shear dependent viscosity
control lubricant (montan wax)

7
Action mode of
lubricants

Formation of flow line and die swell in PVC

In the calendering process in particular, the formation of flow lines
is undesirable. The quality of the film depends decisively on the
running behavior of the kneading mass and therefore must always
be viewed in conjunction with lubricants. In addition, however,
the viscoelastic characteristics of plastic melts must also be taken
into consideration. In addition to flow (non-Newtonian flow),
every plastic melt also displays elastic behavior, i. e., it can be
compressed. The spring-damper model (fig. 5) describes the
phenomenon well. The spring effect ensures that the melt returns
to its original state after short-term stress, once that stress has
been released. The damper effect ensures flow, i. e., the mass
evades long-term stress.

Figure 5: Viscosity in relation to modulus of shear deformation

Model Melt

Spring Elasticity

Damper Viscosity

8 waxes for PVC lubrication


Figure 6: Die swell in PVC through various additives
50
Die swell ø [ % ]
40
30
20
+ 0.5 phr* + 0.5 phr + 0.5 phr
Licowax E Licolub WE 4 Fatty acid High-molecular
complex ester
Put simply the plastic melt has a memory: if the material is com-
pressed for only a short time (e. g., in a very short nozzle), it tends
to relax and resume its original form immediately after leaving the
pressure zone. If the kneading mass does not run optimally through
the roll gap and displays waves and deformation, these waves will
also appear again as flow lines on the other side of the gap. This
behavior can also be quantified via the die swell, which, for example
in injection molding, represents an undesirable effect (fig. 6).
Basically there are two ways to influence
viscoelastic behavior
First: Improve the flowability of the melt by adding internal
lubricants or by selecting a suitable type of PVC. However, the
former have the disadvantage of lowering melt strength.
Second: Control swelling behavior through suitable additives.
While PMMA copolymers (processing aids, high-molecular release
agents) have a great influence on swelling, lubricants with release
properties have practically no such effect.
9
Formulation (phr)*:
S-PVC, k-value 60 100.0
internal method
Sn stabilizer 1.5
Glycerol dioleate 0.5
Conditions:
Extrusiometer screw 4:2; 20 rpm
Temp.: 150/170/185/195/195 °C
Nozzle: ø 4 mm
* Parts per hundred resin
+ 0.5 phr + 1.0 phr
High-molecular
release agent release agent
Plateout, formation of condensed precipitates
Precipitates on calender rolls or cold machine parts are an
unpleasant phenomenon in continuous production. Many
components in the formulation of the PVC compound can cause
this phenomenon. An analysis of such precipitates usually detects
all the components of the formulation. In addition to the quality
of the PVC, the compatibility of the additives plays an important
role. For example, the individual additives can be very compatible,
but in a formulation the additives can displace each other, react
with each other, or lead to plateout. Very incompatible lubricants
with low affinity to PVC, such as polyethylene waxes, have a strong
tendency toward plateout.
Oxidized polyethylene waxes also have a strong tendency toward
cross-linking upon contact with oxygen and thus to formation
of deposits on the rolls that are difficult to remove. As already
mentioned, the volatility of internal lubricants plays a role, and
lubricants that contain metallic soaps are suspected of promoting
the formation of deposits. It is a very complex topic, which
generally cannot be reduced to a particular component of the
formulation. Solving the problem or improving the situation
requires that the PVC formulation is examined precisely.
Certain non-polar PO waxes however seem to be more sensitive
than others. Especially Licocene PP 6102 has a beneficial behaviour
showing less plate out than standard PE waxes.
Requirements of
the final articles
Thermostability is an important parameter for many appli-
cations. The end product must not deform or soften at its service
temperature or any possible temperature peaks (e. g., inside
automobiles). A suitable measurement for this characteristic is
the Vicat (softening) templerature or heat distortion temperature
(HDT). The more polar, i. e. more compatible a lubricant (internal
lubricant), the more it is able to penetrate the PVC particle and to
soften the polymer. The Vicat temperature decreases. On the other
hand, in a deep-drawing sheet, this effect can be quite desirable.
Unlike internal lubricants, external lubricants do not lower the
Vicat temperature.
The printability of a finished product depends mainly upon
its surface tension. Here the migration of additives can play an
important role. Additives that are not very compatible and also
have a low molecular weight, are inclined, especially at higher
temperatures, to migrate to the surface and can thus decrease
printability. In this context, mainly metallic soaps and amide
waxes based on fatty acids are suspected of having a negative
effect. However, print technology and printing ink quality are
certainly of higher importance.
10
The gloss of finished parts is determined substantially by the
type of processing. With calender films, for example, the last two
calender rolls, the embossing rolls, if present, and the draw-off rolls
play the decisive role. External lubricants have hardly any effect.
In injection molding too, the tool and its surface are extremely im-
portant. However, in this case, external lubricants do have an effect.
In profile extrusion, however, the gloss is created primarily in the
nozzle / die by by the slippage of the melt along the wall. External
lubricants are predestined for this application. Primarily hydro-
carbon waxes with high softening points are used like Licowax
PE 520 or Licocene PP 6102.
The transparency of an end product is often used as a
measure of the compatibility of the additives used. Internal lubri-
cants usually have very little effect on transparency. As the effect
of external lubricants increases, transparency is impaired more.
Of course the presence of other additives that affect transparency
also plays an important role. When impact modifiers are present,
primarily methacrylic styrene-butadiene copolymer (MBS),
the influence of the lubricant on transparency is very slight.
Pigment dispersion, especially organic colored pigments
in thin-walled PVC applications, can be improved markedly by
pre-dispersion of the pigments with montan wax, e. g. Licowax OP.
When rubbed off on a triple roll mill, the pigment-wax prepara-
tion is produced as a dust-free powder that is optimal for further
processing.
waxes for PVC lubrication
Lubricants for
PVC

Lubricants are present in formulations in only small quantities,

but they have a decisive effect on the rheology and, in part, on
the characteristics of the PVC.

Based on the customer’s requirements profile and the equipment

conditions, an optimal formulation must be developed, which, as
a rule, cannot be finalized until a production test is done. An
important parameter in the selection of the components of the
formulation is price, which also applies to the lubricant. However,
price means the effective price, i. e. the price/performance ratio.
The following information will show that high-quality lubricants
based on montan wax can have a positive influence on many
characteristics, help avoid problems, and thus have an optimal
price/performance ratio.

11
Product
Description
Based on their chemical structure,
Licowax®, Licolub®, Licocene® and Licocare®
can be divided into 6 groups:
Montan waxes
The montan wax esters Licowax E, Licowax OP, Licolub WE 4,
Licolub WM 31 and Licolub WE 40 are secondary products of the
oxidative refinement of raw montan wax.
The montanic acids contained in raw montan wax are unbranched,
even-numbered monocarboxilic acids with chain lengths in the
range of C26-C32. These long-chain montanic acids result in low
volatility for these products.
Licowax E, Licolub WE 4, and Licolub WE 40 are esters of
montanic acids with ethylene glycol and glycerol, in which the
latter are complex esters. Licowax OP differs from these products in
that the montanic acids are only partially esterified with butanediol
and that the rest is saponified with calcium hydroxide. Licowax OP
thus contains not only montanic acid esters but also calcium mon-
tanate, and it thus displays additional effects (binds acid).
Licolub WM 31 is an ester based on montanic acids and other long
chain aliphatic acids.
Due to its polar centers and the long, non-polar hydrocarbon chains,
the montanic acid esters combine internal and primarily external
lubrication effects in PVC:
· Maintenance of transparency
· Low volatility
· Low migration tendency
· Intrinsic viscosity
· Melt strength
· High processing safety
12
Polyethylene waxes
The low molecular weight PE waxes from Clariant are waxes
polymerized using the Ziegler and the Metallocene process,
with especially high thermostability. They thus differ from
decomposition waxes, which are usually produced through
thermal decomposition of polyethylenes.
Licowax PE 520 is a medium-molecular, slightly branched
polyethylene wax with low density and is marked by high resistance
to oxidation and thus high color and viscosity stability.
Licowax PE 520 and Licowax PE 190 have a strong external
lubricating effect in PVC.
Licowax PE 190 is a high-molecular, linear PE wax with high
density and is used preferably in the production of transparent
PVC articles.
Licocene PE 4201 is a medium-molecular, low branched metal-
locene polyethylene wax with even stronger external lubricating
effect in PVC than Licowax PE 520 and Licowax PE 190.
Licowax PED 191 is a high-molecular, oxidated, and thus polar PE
waxes, which is used primarily in tin-stabilized rigid PVC due to
its strong nonstick effect and high transparency for sheet extrusion
and the production of blow molded parts. In addition it promotes
gelation in calcium/zinc stabilized or lead-stabilized PVC.
Licolub H 12, a polar PE wax based on Licowax PE 520, also has
a strong antisticking effect. Important areas of applications are
pipe and profile extrusion and extrusion blow molding, especially
when the final product does not require high transparency.
waxes for PVC lubrication
Polypropylene wax
Licocene PP 6102 is an isotactic metallocene polypropylene wax
and has a strong external lubricating effect in PVC. It is suitable
for regulation of gelation behavior of Pb-stabilized and Ca/Zn-
stabilized PVC mixtures and provides a lower buildup of pressure
in the extruder in comparison to Licowax PE 520. Especially in the
field of pipe extrusion it can be used as FT-paraffin replacement.
Hydrocarbon wax
Licolub H 4 is a modified hydrocarbon wax with an external
lubricating effect, which is used primarily in extrusion of opaque
PVC products.
13
Amide wax
Licowax C and Licolub FA 1 vegetable based are amide waxes
of type N,N-bis-stearyl ethylenediamine with particularly good
thermostability. They provide PVC film with slip (rigid sheets) and
anti-blocking characteristics (flexible films) as well as good release
properties in injection molding applications (flexible PVC).
During processing they act predominantly as an internal lubricant
to improve flow.
Renewable Wax
Licocare SBW 11 TP* is a natural based, chemically modified wax,
which is produced by metathesis of soya bean oil. Due to the good
external lubrication effect and excellent color behavior, this test
product is perfectly suitable for rigid PVC processing.
TP * = Test product
Product
characteristics

product Name Chemical characteristics Physical and chemical properties

Drop point Acid value Density Viscosity Color

[ °C ] [ mg KOH/g ] 23 °C [ g/cm3 ]  at 100°C [ mPa·s ]
Licowax E Montan wax-based ester wax ~ 81 ~ 18 ~ 1.02 ~ 20 Pale yellowish

Licowax OP Partially saponified, ~ 99 ~ 12 ~ 1.02 ~ 300 (120 °C) Yellowish

montan wax-based ester wax

Ca2+

Licolub WM 31 Montan wax and long chain aliphatic ~ 74 ~ 12 ~ 1.00 ~ 26 Pale yellowish
acid based ester wax
Licolub WE 4 Montan wax-based ester wax ~ 80 ~ 26 ~ 1.01 ~ 60 Yellowish

Licolub WE 40 Complex ester of montanic acids ~ 76 ~ 20 ~ 1.02 ~ 150 Yellowish

Licowax C Amide wax ~ 142 < 8 ~ 1.00 – White

LICOLUB FA 1 Amide wax ~ 142 < 8 ~ 1.00 – White

vegetable based

Licolub H 12 Polar polyethylene wax ~ 104 ~ 17 ~ 0.95 ~ 350 Almost white

Licowax PED 191 Polar polyethylene wax ~ 123 ~ 17 ~ 0.98 ~ 1800 (140 °C) Almost white

Licowax PE 190 Non-polar polyethylene wax ~ 135 – ~ 0.96 ~ 25000 (140 °C) White

Licowax PE 520 Non-polar polyethylene wax ~ 120 – ~ 0.93 ~ 650 (140 °C) White

Licolub H 4 Modified hydrocarbon wax ~ 111 – ~ 0.92 max. 10 (120 °C) White

Licocene PP 6102 Non-polar polypropylene wax ~ 145±± – ~ 0.90 ~ 60 (170 °C) White

Licocene PE 4201 Non-polar polyethylene wax ~ 128 – ~ 0.97 ~ 60 (140 °C)

LICOCARE SBW 11 TP* Modified soya bean wax ~ 55 Typical 0 – – Off-white
TP* Test product ** Softening point according to DIN 51920, ASTM D 3104
Test methods: Drop point [ °C ] ISO 2176, Acid value [ mg KOH/g ] ISO 2114, Density (23 °C) [ g/cm3 ] ISO 1183, Viscosity [ mPa · s ] DIN 53018
  

14 waxes for PVC lubrication

Overview of
PVC Applications

product Name Calendering Extrusion Injection Foam Flexible

molding applications applications

Licowax C

Licolub FA 1 vegetable based

Licowax E

Licowax OP

Licowax PE 190

Licowax PE 520

Licocene PE 4201

Licowax PED 191

Licocene PP 6102

Licolub H 4

Licolub H 12

Licolub WE 4

Licolub WE 40

Licolub WM 31

Licocare SBW 11 TP*

TP* Test product   Recommended   Applicable

TP * = Test product

15
Waxes for
calendering films

Tin stabilization Waxes from Clariant, Licowax, Licolub and Licocare, fulfill above
As already mentioned, lubricants serve many purposes mentioned requirements. The montanic acid esters in particular
in PVC during various processing steps. provide a high degree of processing safety and result in good
product characteristics:
Mixing
· Homogenization Licolub WE 4
· Phase compatibilizing Licolub WE 40*
· Dispersion Licolub WM 31*
Licowax OP
Extruder Licowax E
· Viscosity reduction
· Regulation of gelation time Licowax C
· Increasing intrinsic viscosity Licolub FA 1 vegetable based

Calender Licocare SBW 11 TP*

· Good bank behavior
· (Viscosity) * For technical applications
· Release effect

Finished article properties From a technical point of view, these are the highest-quality
· Anti-blocking effect additives for the production of PVC calender films.
· Printability
Advantages and effects of the montan waxes in PVC
· Gloss
Transparency
Advantages Effects
· Thermostability
Comprehensive lubricant effect Improved flow
(internal and external) Dispersion
Release effect
Demolding properties
High melt strength Dimensional stability
Low volatility Less mold deposits
Less condensation
Universal compatibility Surface properties (smoothness)
Transparency
No plateout

TP * = Test product

16 waxes for PVC lubrication

 The release effect of various lubricants is usually
determined on the two-roll mill by measuring the time it takes
for the melt to stick to the roll. The longer the tack-free time, the
better the release effect. The following test (fig. 7) shows that high-
molecular release agents have a corresponding effect, but only at
much higher dosages and without an additional lubricating effect.

In assessing lubricants, however, one must always consider the

entire formulation. It is known that various additives can influence
each other. Thus, as a rule, higher amounts of release agents have
to be used in formulations with impact modifiers. There can be
two different causes for this situation. The addition of MBS impact
modifiers (methacrylic styrene-butadiene copolymers) can increase
tackiness. It is also possible that the lubricants will dissolve
preferably in the MBS phase and thus no longer be available to
reduce tackiness on the surface of the PVC.

Figure 7: Influence of release-effective lubricants in comparison to high-molecular release agents Formulation (phr):
S-PVC, k-value 60 100
internal method Sn-stabilizer 1.5
30 MBS impact modifier 8.0
PMMA processing aid 1.0
Glycerol dioleate 0.5
Tack-free time [ min ]

20 Conditions:
Two-roll mill, 190 °C 25/30 rpm

10

0
Licowax E Licolub WE 4 High-molecular High-molecular
0.5 phr 0.5 phr release agents release agents
0.5 phr 1.0 phr

17
Waxes for
calendering films

With the help of a measuring rolling mill, it is possible to quantify Figure 8: Differentiation of lubricants on a measuring rolling mill
not only the tack-free time but also the adhesive force. In addition, internal method
60
it is possible to track the tackiness of a formulation relative to time,
which can produce interesting results (fig. 8). 50
Adhesive force [ % ]

40
Here the advantage of Licolub WE 4 compared to fatty acid
complex ester (FACE) is obvious too. After longer processing time, 30

the FACE deviates from Licolub WE 4, i. e., the adhesive force

20
of WE 4 remains at the desired level throughout the duration of
processing. 10

0
When using mixtures of fatty acid complex esters and fatty acid 0 200 400 600 800 1000 1200 1400
esters (FACE/FAE) it is common to use 0.5 – 1.0 phr high-molecular- Time [ sec ]
weight, release agent, too in order to improve tack-free time. By Licolub WE 4 Fatty acid complex ester

replacing FACE/FAE with Licolub WE 4 this release agent can

Formulation (phr):
be significantly reduced (fig. 9), wich leads to cost minimization. S-PVC, k-value 60 100.0
Octyltin stabilizer 1.2
Glycerol dioleate 0.5
MBS impact modifier 6.0
Processing aid 0.5
Lubricant 0.3

Formulation (phr):
Figure 9: Release effect of Licolub WE 4 in comparison to fatty acid complex
S-PVC, k-value 60 100.0
ester/fatty acid ester (FACE/FAE) mixture
Octyltin mercaptide 1.5
internal method MBS impact modifier 8.0
40 PMMA processing aid 1.0
Glycerol dioleate 0.6
Test product 0.5
Tack-free time [ min ]

30

20

10

0
Mixture of Licolub WE 4 Mixture of Licolub WE 4
FACE/FAE FACE/FAE
0.5 phr high-molecular-weight Without high-molecular-weight
Release agent Release agent

18 waxes for PVC lubrication

In comparison to Licowax E, Licolub WE 4 has a better release Figure 10: Sticking power (Collin Two Roll Mill, 220 g, 195 °C, 15/20 rpm)
effect under slight loss of transparency, although Licolub WE 4 is internal method
30
still better than the fatty acid complex ester. Licowax OP is used
primarily for film formulations that contain acetate copolymers, 25
since the calcium montanate it contains has a co-stabilizing effect. Sticking power
20
Here too the advantages of the montan waxes compared to fatty
acid complex ester mixtures are seen. 15

10
If slip effects are needed for rigid PVC films, then amide waxes
are used, i. e., Licowax C (dosage 0.1 – 0.3 phr). However, in case 5

these films are to be further processed (e. g., printed, metalized, 0

etc.), the strong migration tendency of this type of wax to the film 0 200 400 600 800 1000 1200 1400
surface should be taken into consideration and the dosage adjusted Time [ sec ]
accordingly. Fatty acid complex ester Licowax E Licocare SBW 11 TP

Figure 11: Sticking behavior of Licolub WM 31 vs. Fatty Acid Complex Ester
Mixture (GL 2), (Collin two roll mill, 195 °C, friction 25 %)
internal method
30

25
Sticking power

20

15

10

0
0 50 100 200
Time [ sec ]
Mixture of fatty acid complex esters Licolub WM 31

Formulation (phr):
S-PVC, k60 100
Octyl tin stabilizer 1.2
MBS impact modifier 8.0
PMMA Processing aid 1.2
Glycerol dioleate 0.3
Test product 0.3

19
Waxes for
PVC extrusion

As already mentioned, the slip of the melt along

the walls plays a decisive role in the processability
and the characteristics of the final products in
extrusion. External lubricants, especially PE
waxes and hydrocarbon waxes are used here.

In more demanding applications, such as extruded

profiles for windows, the use of montanic acid
esters has a very positive effect on processing
and performance. Depending on the type of
stabilization and the end product, different
waxes are used.

TP * = Test product

20 waxes for PVC lubrication

Calcium/zinc stabilization

Licocene PE 4201, Licocene PP 6102,

Licolub H 4, Licolub H 12,
Licowax PE 520, Licolub WE 40,
Licocare SBW 11 TP*

In Ca/Zn-stabilized systems the stabilizer has hardly any self-lub- Figure 13: Waxes in Ca/Zn stabilized PVC window profiles –
ricating effect. Therefore somewhat higher quantities of lubricants FACE versus Licolub WE 40
and processing aid are needed compared to Pb-stabilized systems. internal method
250 20
To reduce friction internal lubrications like fatty acid esters are
used. In profile applications, the use of montanic acid esters or the

■ Fusion time [ min ]

■ Output [ g/min ] 200 16
renewable wax, Licocare SBW 11 TP*, is recommended.
150 12

In these compounds too the non-polar and thus incompatible waxes

100 8
Licowax PE 520, Licocene PP 6102, Licocene PE 4201 and Licolub
H4 act as external lubricants, which regulate gelation behavior. In 50 4
comparison to Licowax PE 520, the Licocene waxes causes a later
0 0
and lower build-up of pressure in the extruder as well as stronger 0.3 phr FACE + 0.3 phr Licolub WE 40 +
nozzle lubrication. Especially the metallocene wax Licocene 0.2 phr Licowax PE 520 0.2 phr Licowax PE 520

PP 6102 shows a beneficial behavior regarding less mold deposits.
The polar and thus partially compatible lubricants Licolub H 12
(oxidized PE wax) and Licolub WE 40 (montanic acid complex
ester) fulfill the same functions already described for the lead-
stabilized compounds. As a rule, the additive quantities are from
0.2 – 0.4 phr.
Formulation (phr): S-PVC, k value 64, impact mod, Ca-Stearate: 100.0,
Zn-Stearate: 0.5, Hydrotalcit: 1.0, ß-Diketone: 1.0, Di-Trimethylol Propane: 0.6,
Phenolic Antioxidant: 0.5
Figure 14: Waxes in Ca/Zn stabilized PVC pipes - Energy consumption
at different screw speeds
internal method

0.105

Figure 12: Metallocene wax in Ca/Zn-stabilized PVC window profiles – 0.100

Pressure formation along the single screw extruder
E-value [ KWh/kg ]

internal method
300 0.095

0.090
Pressure [bar]

200
0.085

100 0.080

0.075
0 50 60 70 80 90 100
p1 p2 p3 p4 p5 Screw speed [ l/min ]

0.3 phr standard PE wax 0.2 phr PP 6102 0.3/0.05 phr C80/H1 0.35 phr Licocene PE 4201
0.3 phr PP 6102 0.35 phr Licocene PP 6102

Formulation (phr): S-PVC k-value 68, Ca/Zn-Stabilizer compound: 100, Formulation (phr): S-PVC k-value 68: 100, CaCO3 (90T): 15.0,
Impact modifier: 2.4, Processing aid: 7, TiO2: 1 Ca/Zn Core stabilizer: 1.18, Test products: 0.35

21
Tin stabilization

Licocene PE 4201, Licocene PP 6102,

Licowax PE 520, Licolub H 4,
Licolub H 12, Licowax PED 191,
Licolub WE 4, Licolub WM 31

PVC compounds produced with tin stabilizers tend to stick to hot

metal parts on the processing equipment. Therefore the use of
external and internal lubricants is indispensable. Calcium stearate
is normally used in large quantities, acts as a co-stabilizer, and
supports gelation. The build-up of pressure in the extruder and
the lubricating effect are controlled by non-polar hydrocarbon and
PE waxes (Licolub H 4, Licowax PE 520 and Licocene PE 4201).

For higher requirements concerning anti-sticking, oxidized PE

waxes (Licolub H 12, Licocene PE 4201 and Licowax PED 191)
are preferred. Furthermore, the use of montan waxes (Licolub
WE 4 and Licolub WM 31), e. g., in the production of high-quality
profiles, offers a large number of technical (and economical)
advantages, which have already been described in detail in the
preceding sections.

Formulation (phr):
Figure 15: Metallocene Waxes in Sn-Stabilized PVC
S-PVC, k-value 57 100.00
internal method Sn-butyl-stabilizer 1.3
300 TiO2 8.0
Chalk 6.0
Impact modifier 5.0
Pressure [bar]

Processing aid 1.0

200
Ox. PE-wax 0.5
Test products 1.25 – 0.7

100 Conditions:
Extrusiometer E 30 M: D = 30 mm, 25 L/D, n = 30 rpm,
180-185-190-200-210 °C, round-section die: 215 °C

0
p1 p2 p3 p4 p5

1.0 phr Hydrocarbon wax 0.7 phr mPP 6102

1.0 phr mPE 4201  1.0 phr mPP 6102

22 waxes for PVC lubrication

Lead stabilization

Licocene PE 4201, Licocene PP 6102,

Licolub H 4, Licowax PE 520,
Licolub H 12, Licowax PED 191,
Licolub WM 31, Licowax E, Licowax OP

Due to the relatively strong lubricating effect of lead stabilizers,
the addition of a certain amount of external lubricants is usually
sufficient in these systems. The lead salts are combined with neutral
and/or dibasic lead stearate and calcium stearate. The lead salts
provide acceptable flowability, and stearic acid (which reacts on
the surface of the lead oxides) and hydrocarbon waxes can be added
in order to delay gelation. These provide also good slippage along
the walls in the extruder head and nozzle. However, if the dosage is
too high, there is a danger that deposits will form on the nozzles.
Licowax PE 520 (PE wax) and even more Licocene PE 4201 /  montan wax ester Licowax E and Licolub WM 31 (0.3 – 0.5 phr wax)
Licocene PP 6102 are used to regulate gelation behavior, i. e.,
they delay gelation and improve the surface, especially the gloss
of Pb-stabilized PVC compounds. The amounts added range from
0.05 to 0.2 phr.
Oxidized PE waxes, such as Licolub H 12, increase energy input in
the extruder and thus provide optimal, early gelation. Its positive
influence on gelation can be strengthened through the use of high-
molecular, oxidized PE waxes, i. e. Licowax PED 191 (fig. 10). As a
result of the even faster gelation, the better homogeneity of the melt
leads to improved physical characteristics and higher surface gloss.
Dosage: 0.1 – 0.4 phr.
For high-quality profiles, e. g., profiles for windows, combination
with the partially saponified montan wax ester Licowax OP or the
is recommended. The profiles then have a smooth surface even at
high pigment and filler contents, without impairing weldability or
thermostability.

The metallocene waxes, Licocene PE 4201 and Licocene PP 6102

as well as the hydrocarbon wax Licolub H 4 act as strong external
lubricants. They are used predominantly in the production of pipes
in the dosage 0.1 – 0.4 phr.

Figure 16: Energy input of oxidized PE waxes in the PVC extrusion Formulation (phr):
(Pb-stabilized) S-PVC, k-value 60 100.00
internal method PMMA processing aid 2.00
60 CaCO3 5.00
Lead stabilizer mixture 4.75
Hydrostearic acid 0.20
Tack-free time [ min ]

55 Distearyl phthalate 0.60

Lubricant combination 0.35
Test product 0.20
50
Conditions:
Weber CE 3; 20 1/min screw speed
45
Material direct from dosing hopper
Cylinder temperature: 175/185/190 °C
40 Tool temperature: 185/185/190/200 °C
Licolub H 12 Licowax PED 191

23
Basic formulations
Pipes/profiles

Ca/Zn pipe formulation Sn pipe formulation (twin screw)

phr phr
S-PVC, k-value 65 – 68 100.0 S-PVC, k-value 65 – 68 100.0
Ca/Zn stabilizer compound 2.2 Sn stabilizer (containing sulfur) 0.4
Phosphite (e. g. TNPP) 0.4 Calcium stearate 0.8
PMMA impact modifier 1.0 MBS impact modifier 1.0
Distearyl phthalate 0.4 Licocene PE 4201 / Licocene PP 6102 / Licolub H 4 0.7 – 1.2
Hydroxystearic acid 0.2 Licolub H 12 0.2
Licocene PE 4201 / Licocene PP 6102 / Licolub H 4 0.5 TiO2 1.0
Licowax PE 520 0.2 CaCO3 5.0

Ca/Zn window profile formulation Sn siding profile (twin screw)

phr phr
PVC copolymer, impact mod.
(e. g. k-value 64; 7 % acrylate copolymer) 100.0 S-PVC, k-value 67 100.0
Ca/Zn stabilizer compound 3.4 Sn stabilizer (containing sulfur) 1.2
Phosphite (e. g. TNPP) 0.4 MBS impact modifier 5.0
PMMA processing aid 2.0 PMMA processing aid 0.5
Hydroxystearic acid 0.2 Calcium stearate 1.2
Licolub WE 40 0.3 Licocene PE 4201  / Licocene PP 6102 / Licolub H 4 1.0
Licocene PP 6102 / Licowax PE 520 0.2 Licolub H 12 0.2
TiO2 7.0 TiO2 10.0
CaCO3 4.0

Sn window profile (twin screw)

phr
PVC copolymer, impact mod.
(e. g. k-value 64; 7 % acrylate copolymer) 100.0
Sn stabilizer (containing sulfur) 1.5
PMMA processing aid 1.0
Calcium stearate 1.0
Glycerol monostearate 0.5
Licocene PE 4201 / Licocene PP 6102 / Licolub H 4 0.6
Licolub WE 4 0.4
Licowax PE 520 0.1
TiO2 8.0
CaCO3 3.0

24 waxes for PVC lubrication

Basic formulations
Sheets/blow molded parts/
blown films

Sn sheet formulation
phr
S-PVC, k-value 58 – 62 100.0
Sn stabilizer (containing sulfur) 2.0
Impact modifier 8.0
PMMA processing aid 1.0
Epoxidized soya bean oil 1.0
Lauryl stearate 0.6
Licolub WE 40 0.5
Licowax PED 191 0.1

Sn shrink-wrapping film
phr
S-PVC, k-value 60 100.0
Sn stabilizer (containing sulfur) 1.5
MBS impact modifier 5.0
PMMA processing aid 1.5
Glycerol dioleate 0.8
Licolub H 12 0.3

Sn bottle formulation
phr
S-PVC, k-value 58 100.0
Sn stabilizer (containing sulfur) 1.7
Impact modifier 10.0
PMMA processing aid 1.5
Epoxidized soya bean oil 1.2
Licolub WE 4 / Licolub WM 31 0.3
Licowax PED 191 0.2

25
PVC
foam extrusion

Foamed PVC places special requirements upon rheological behavior Requirements:

(melt strength) and makes the selection of suitable lubricants · Improvement in lubrication
especially important. Improper selection or an increased dosage
can lead to undesired effects.
between the surface of the
metal and the expandable melt
These include formation of bubbles, resulting in a higher volumet- (containing a foaming agent)
ric weight; delay of the necessary fast gelation and thus impairment · Prevention of plateout
of welding of the individual filaments of the melt after passing the
mandrel, the strainer plate, or the torpedo carriers.

26 waxes for PVC lubrication

Calcium/zinc Tin stabilization
stabilization

Licocene PE 4201, Licocene PP 6102, Licowax PED 191, Licowax E

Licolub H 4, Licowax OP Licolub WM 31

Ca/Zn sheet, free-foamed Ca/Zn sheet, free-foamed

phr phr

S-PVC, k-value 60 100.0 S-PVC, k-value 60 100.0

Ca/Zn stabilizer compound 3.0 Sn stabilizer (containing sulfur) 1.5
Phosphite (e. g., TNPP) 0.4 PMMA processing aid 7.0
PMMA processing aid 7.0 Calcium stearate 0.8
Epoxidized soya bean oil 0.8 Epoxidized soya bean oil 0.5
Hydroxystearic acid 0.1 Distearyl phthalate 0.5
Distearyl phthalate 0.4 Licowax E / Licolub WM 31 0.3
Licocene PE 4201 / Licocene PP 6102 / Licolub H 4 0.2 Licowax PED 191 0.6
Licowax OP 0.2 Foaming agent (e. g., azodicarbonamide, hydrogen carbonate) 1.0
Foaming agent (e. g., azodicarbonamide) 1.0 TiO2 4.0
TiO2 4.0 CaCO3 2.0
CaCO3 2.0

Lead stabilization

Licocene PE 4201, Licocene PP 6102,

Licolub H 4, Licolub H 12,
Licowax E, Licolub WM 31

Pb sheet, free-foamed Pb sheet, Celuka process

phr phr

S-PVC, k-value 60 100.0 S-PVC, k-value 60 100.0

Tribasic lead sulfate 2.2 Tribasic lead sulfate 4.0
Dibasic lead stearate 0.7 Dibasic lead stearate 0.4
PMMA processing aid 5.0 PMMA processing aid 6.0
Calcium stearate 0.3 Calcium stearate 0.8
Distearyl phthalate 0.2 Stearyl stearate 0.6
Licocene PE 4201 / Licocene PP 6102 / Licolub H 4 0.1 Distearyl phthalate 0.4
Licowax E / Licolub WM 31 0.2 Licolub H 12 0.5
Licolub H 12 0.2 Foaming agent (e. g., azodicarbonamide, hydrogen carbonate) 2.0
Foaming agent (e. g., azodicarbonamide) 1.0 TiO2 5.0
TiO2 4.0 CaCO3 3.0
CaCO3 3.0

27
PVC
injection molding

Usually in injection molding, S-PVC or M-PVC with

k-values between 55 and 65 are used, with k-values of 58 to 60
being most frequent. Flowability and mechanical stability
are the most important criteria in injection molding.
Therefore in this case, the montanic acid esters are
particularly suitable as lubricants; here Licowax E,
Licolub WM 31, Licowax OP and Licocare SBW 11 TP*.

Licowax E · High heat distortion temperature

Licowax OP · High flowability
Licolub WM 31 · High mold filling
Licocare SBW 11 TP*
· Less charring due to shear

Ca/Zn – stabilization Lead stabilization

phr phr

S-PVC, k-value 57 100.0 S-PVC, k-value 60 100.0

Ca/Zn-stabilizer compound 2.8 Tribasic lead sulfate 2.5
PMMA processing aid 1.0 Dibasic lead stearate 0.6
Licowax E / Licocare SBW 11 TP 0.9 Neutral lead stearate 0.1
Calcium stearate 0.4
Glycerol monostearate 0.5
Tin stabilization Licowax E / Licolub WM 31 0.5
phr

S-PVC, k-value 60 100.0

Sn stabilizer (containing sulfur) 2.0
Impact modifier 2.0
PMMA processing aid 1.0
Glycerol monostearate 1.0
Licowax E / Licolub WM 31 / Licocare SBW 11 TP* 0.5

TP * = Test product

28 waxes for PVC lubrication

Flexible PVC
Hoses, wire and cable sheathing,
Calender and blown films

Licowax E Licolub WE 4, Licolub WM 31,

Licolub WM 31 Licowax C,
Licolub FA 1 vegetable based

These profiles are usually produced on linear, horizontal extrusion
equipment. The k-values preferred lie between 65 and 70, with
S-PVC and also E-PVC being used, depending on the application.
Phthalate plasticizers are used. The stabilization system depends
on the application. Lead stabilizers have been widely used.
Now it is Calcium/Zinc or Barium/Zinc and tin. For cost reasons
one often incorporates natural or precipitated calcium carbonate
as fillers in dosages of up to 80 phr (coating mixtures).
The resulting impairment of processing characteristics is not
inconsiderable. Therefore in this area too, montanic acid esters,
i. e., Licowax E, Licolub WM 31, have proven useful especially
for small cross-sections.
Glass-clear flexible PVC films are usually produced using a
suspension PVC (but M-PVC is also used) with k-values between
65 and 75. Depending on the requirements, however, k-values of
55 to 80 are applied. For pigmented films E-PVC is preferred
(higher filler capacity, better antistatic behavior). The phthalate
plasticizer content is between 20 and 100 phr.
For processing flexible PVC on the calender or in extrusion
blow molding, external lubricants are needed in order to prevent
sticking to the hot machine parts. Here the montanic acid ester
Licolub WE 4 or Licolub WM 31 displays optimal performance with
regard to antisticking effect, processing window, and final product
characteristics (dosage: 0.3 – 0.5 phr). Here also the renewable wax,
Licocare SBW 11 TP* can be successfully used. There is less need
for internal lubricants, primarily for semi-rigid settings.

Ca/Zn cable sheathing

phr

S-PVC, k-value 57 100.0

Plasticizer (e. g. DIDP) 50.0
Ca/Zn-stabilizer compound 3.7
CaCO3 60.0
Ester waxes 0.3
Pigment x

29
Semi-rigit PVC
Calcium/zinc stabilization

Ca/Zn shrink-wrapping film formulation, Ca/Zn blood bag formulation

calendered phr phr

S-PVC, k-value 60 100.0 S-PVC, k-value 70 > 55.0

Ca/Zn stabilizer compound 2.0 Calcium stearate + zinc stearate ≤ 1.0
Phthalate plasticizer 8 – 11.0 Plasticizer, here DOP ≤ 40.0
Epoxidized soya bean oil 2.5 Epoxidized soya bean oil ≤ 10.0
PMMA processing aid 1.0 Licowax C / Licolub FA 1 vegetable based ≤ 1.0
Impact modifier 6.0
Glycerol monostearate 0.2
Licowax OP / Licolub WM 31 / Licocare SBW 11 TP* 0.2

Ca/Zn shrink-wrapping film formulation,

blown film extrusion phr

S-PVC, k-value 60 100.0

Ca/Zn stabilizer compound 2.0
Phthalate plasticizer 8 – 11.0
Epoxidized soya bean oil 2.5
PMMA processing aid 1.0
Impact modifier 6.0
Glycerol monostearate (or GDO) 0.2
Licowax OP 0.3

References
·P
 lastics Additives Handbook, 5th Edition,
Hanser Publishers, Munich
·K
 unststoff Handbuch (Becker/Braun)
Polyvinylchlorid, Carl Hanser Verlag, Munich
·G
 leitmittel für die Folienherstellung,
Dr. Eric Richter/Clariant Gersthofen,
Lecture at the meeting »PVC Folien und
Alternativen«, SKZ/Würzburg (07/1999)
·V
 arious technical wax brochures for
plastics processing, Clariant

TP * = Test product

30 waxes for PVC lubrication

Technical
Information
Technical Data
For further information on the physical and
chemical properties, detailed application
and packaging of our products please refer
to our product data sheets, our various
application brochures and product flyers.
31
Safety information Storage
The usual precautions to be taken when The products described in this leaflet have
handling chemicals should be observed. A a minimum shelf life of two years from date
safety data sheet will be supplied for each of delivery when stored in a dry place at
individual product upon request. When room temperature.
handling organic powders, the domestic
regulations must be observed in order to
prevent dust fires and dust explosions.
Toxicological and ecological properties
For data on the toxicological and ecological
properties of the product groups mentioned,
please refer to the relevant safety data sheet
or the corresponding product data sheet.
Status according to the European
chemicals law ( REACH )
The products mentioned in this leaflet or
the monomers are either pre-registered,
registered, or exempt from registration as
polymers ( EC 1907/2006 ).
Clariant International Ltd
Rothausstrasse 61
4132 Muttenz
Switzerland

Business Unit Additives

Business Line Waxes
Phone + 41 (0) 61 469 79 12
Fax + 41 (0) 61 469 75 50

www.additives.clariant.com
www.clariant.com

This information corresponds to the present state of our knowledge and is intended as a general
description of our products and their possible applications. Clariant makes no warranties, express or
implied, as to the information’s accuracy, adequacy, sufficiency or freedom from defect and assumes
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determining the suitability of Clariant’s products for its particular application. * Nothing included in this
information waives any of Clariant’s General Terms and Conditions of Sale, which control unless it agrees
DA 8293 E | 09.2013

otherwise in writing. Any existing intellectual/industrial property rights must be observed. Due to possible
changes in our products and applicable national and international regulations and laws, the status of our
products could change. Material Safety Data Sheets providing safety precautions, that should be observed
when handling or storing Clariant products, are available upon request and are provided in compliance
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before handling any of these products. For additional information, please contact Clariant.

* For sales to customers located within the United States and Canada the following applies in addition:
NO EXPRESS OR IMPLIED WARRANTY IS MADE OF THE MERCHANTABILITY, SUITABILITY,
FITNESS FOR A PARTICULAR PURPOSE OR OTHERWISE OF ANY PRODUCT OR SERVICE.

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