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BU Additives

Exactly your chemistry.

Licowax, Licolub and


Licocene for PVC processing
Product leaflet

Contents

Introduction

Mode of action and uses

Characteristics of the end products

11

Product description

13

Key data for Licowax, Licolub and Licocene

15

Overview of applications

16

Waxes for calendering films

17

Waxes for extrusion of compact PVC

23

Lead stabilization

23

Calcium/zinc stabilization

26

Tin stabilization

27

Basic Formulations

28

Waxes for extrusion of PVC foam

30

Waxes for PVC injection molding

32

Waxes for flexible PVC

33

Packaging, Safety, Storage, Transportation and


Food legislation

35

Licowax , Licolub and Licocene for PVC processing

Introduction
As a rule, thermoplastics are usually processed in a melt.
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 the polymer melt are therefore indispensable for troublefree processing. They are called lubricants or waxes.

For these requirements Clariant offers a variety of different


waxes. Furthermore, Clariant has a wide assortment of
additives such as light stabilizers and antistatic agents
for PVC. Additional details on these products are available
in the respective leaflets Clariant Light stabilizers
and Clariant Antistatic agents. In addition to the
most important PVC applications mentioned here, the
waxes described in this leaflet can be used successfully in
almost all other PVC applications. Unfortunately, a complete
description is not possible within the scope of this leaflet.
For consulting and for development of tailor-made customer
solutions, our experienced and well-trained team of technical
service consultants is available to you.
Our specifications are contained in the product data sheets.
The specifications are secured through continuous monitoring. This quality control ensures the safety in the processing
and use of our products Licowax , Licocene and Licolub .
The quality assurance system (DIN ISO 9001) was already
certified by the DQS (Deutsche Gesellschaft zur Zertifizierung
von Management Systemen mbH) in November 1992 and has
been reviewed regularly since then.

These lubricants (waxes) are added to the PVC to fulfill


the following requirements:
n Improvement of the flow behavior of the melt, i. e.,
reduction of internal and external friction, which
means less damage to the material
n Achievement of certain characteristics in the end
product (e. g. gloss, smoothness, anti-blocking)

Licowax , Licolub and Licocene for PVC processing

Mode of action and uses of lubricants in PVC


The mode of action of the waxes in PVC can be illustrated using the chemical structure
of the lubricants and the morphology of PVC:

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 processing
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 m 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.

Volatility
In everyday 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 undesirable. Low-molecular fatty acid esters are viewed as particularly critical in
this context.

Figure 1:
Morphological structure of PVC

Secondary particle
(particles)

Globules
(microparticles)

Nodules
(submicroparticles)

100 m

1 m

10 nm

Plasticization, up to approx. 190 C


Gelation, after approx. 180 C

Mode of action of lubricants


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.

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 remnants also display an external
lubrication effect and form a lubricating film.

Plasticization

Shear dependent
viscosity control

Reduction of friction

Viscosity reduction

Release effect

Slip effect

Figure 2:
Mode of action of lubricants

Licowax , Licolub and Licocene for PVC processing

Lubricants with long hydrocarbon remnants 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 remnants, such as montanic acid
esters, display 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 dependent 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 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.

Lubrication effect in PVC


Internal

External
Fatty acid ester
Fatty acid amide (Licowax C)

Figure 3:
Classification of various lubricants
by their effect in tin-stabilized PVC

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)

Figure 4:
Viscosity in relation to modulus
of shear deformation

Apparent viscosity [log *]

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.

Apparent shear speed [log *]


Newtonian behavior

PVC without lubricant

PVC with viscosity-reducing lubricant


(fatty acid ester)
PVC with shear dependent viscosity control
lubricant (montan wax)

Model

Melt

Spring

Elasticity

Damper

Viscosity

Figure 5:
Spring-damper model
of viscoelastic behavior

Licowax , Licolub and Licocene for PVC processing

Put simply the plastic melt has a memory: if the material is compressed 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.

50

Die swell [%]

45
40
Figure 6:

35

Die swell in PVC through various

30

additives

25
20
+ 0.5

phr*
Licowax E

Formulation: S-PVC, k-value 60



Sn stabilizer

Glycerol dioleate

+ 0.5

phr
Licolub WE 4

100.0 parts
1.5 phr
0.5 phr

+ 0.5

phr
Fatty acid
complex ester

+ 0.5

phr
High-molecular
release agent

+ 1.0

phr
High-molecular
release agent

Conditions:  Extrusiometer screw 4:2; 20 rpm


Temp.: 150/ 170/185/195/195 C
Nozzle: 4 mm

* = part by weight (parts per hundred resin)

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
coatings. It is a very complex topic, which 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.

10

Licowax , Licolub and Licocene for PVC processing

Characteristics of the end products


Thermostability is an important parameter for many applications. 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)
temperature. 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 are suspected of having a negative effect. However,
print technology and printing ink quality are certainly of greater importance.
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 important. However, in
this case, external lubricants do have an effect.
In profile extrusion, however, the gloss is created primarily in the nozzle by the slippage
of the melt along the wall. External lubricants are predestined for this application.
Primarily hydrocarbon waxes with high softening points are used.
The transparency of an end product is often used as a measure of the compatibility of
the additives used. Internal lubricants 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 preparation is produced as a
dust-free powder that is optimal for further processing.

11

12

Licowax , Licolub and Licocene for PVC processing

Outlook
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.
Unfortunately, there is no ideal lubricant. Instead, based on the customers 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.

Product description
Based on their chemical structure, Licowax, Licolub and Licocene can be divided into
5 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 montanate, and it thus displays additional effects (binds acid).
Licolub WM 31 is an ester based on montanic acids and 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

Intrinsic viscosity

Low volatility

Melt strength

Low migration tendency

High processing safety

13

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, 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 metallocene 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 lead-stabilized or calcium / zinc-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.

Polypropylene wax
Licocene PP 6102 is a 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 more moderate buildup of pressure in the
extruder in comparison to Licowax PE 520.

Hydrocarbon wax
Licolub H 4 is a modified hydrocarbon wax with an external lubricating effect, which is used
primarily in extrusion (Pb-/Sn-stabilized) and in injection molding of opaque PVC products.

Amide wax
Licowax C is an amide wax of type N,N-bis-stearyl ethylenediamine with particularly good
thermostability. It provides 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 it acts predominantly as an internal lubricant to improve flow.

Test methods
Drop point
Acid value
Density (23 C)
Viscosity

14

[C]
[mg KOH/g]
[g/cm 3]
[mPas]

ISO 2176
ISO 2114
ISO 1183
DIN 53018

Licowax , Licolub and Licocene for PVC processing

Key data for Licowax, Licolub and Licocene


Name

Chemical characteristics



Licowax E

Montan wax-based

ester wax

Licowax OP

Partially saponified, montan

wax-based ester wax

Physical and chemical properties


Drop point
[C]

Acid value
[mg KOH/g]

Density
23 C [g/cm 3]

Viscosity
[mPas]

~ 81

~18

~ 1.02

~30

~ 99

~ 12

~ 1.02

~ 300

~ 75

~ 12

~ 1.00

~ 26

~ 80

~ 26

~ 1.01

~ 76

~ 20

1.02

Color
pale yellowish

yellowish

Ca 2+

Licolub WM 31

Montan wax and long chain

aliphatic acid based ester wax

Licolub WE 4

Montan wax-based

ester wax

Licolub WE 40

Complex ester of

montanic acids

yellowish

~ 60

yellowish

~ 150

yellowish

almost white

Licowax C

Amide wax

~ 142

~ 6

~ 1.00

Licolub H 12

Polar polyethylene wax

~ 104

~ 17

~ 0.95

~ 300

almost white

Licowax PED 191 Polar polyethylene wax

~ 123

~ 17

~ 0.98

~ 1,800

almost white

Licowax PE 190

Non-polar polyethylene wax

~ 135

~ 0.96

~ 25,000

Licowax PE 520

Non-polar polyethylene wax

~ 120

~ 0.93

~ 650

Licolub H 4

Modified hydrocarbon wax

~ 110

~ 0.92

~ 13

white

white

white

white

white

Licocene PP 6102 Non-polar polypropylene wax

~ 145

~ 0.90

~ 60

Licocene PE 4201 Non-polar polyethylene wax

~ 127

~ 0.97

~ 60

a = at 100 C, b = at 120 C, c = at 150 C, d = at 140 C, e = at 170 C, f = softening point according to DIN 51920, ASTM D 3104

15

Overview of applications
Overview of the main uses for Licolub and Licowax in various types of PVC processing

Product
Calendering
Extrusion

Licowax C
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

16

Injection
molding

Foam
applications

Flexible
applications

Licowax , Licolub and Licocene for PVC processing

Waxes for calendering films


Tin stabilization
As already mentioned, lubricants serve many purposes in PVC during various processing
steps (fig. 7).
Mixing

Extruder

Homogenization

Viscosity reduction

Phase compatibilizing

Regulation of gelation time

Dispersion

Increasing intrinsic viscosity

Calender

Finished article properties

Improved bank behavior

Anti-blocking effect

an example of the influence

(Viscosity)

Printability

of lubricants on the individual

Release effect Gloss

Figure 7:
Calender film production as

processing steps

Transparency
Thermostability
With the waxes from Clariant, Licowax and Licolub, you can get the job done. The montanic
acid esters in particular provide a high degree of processing safety and result in good
product characteristics:
n
n
n

Licolub WE 4
Licolub WE 40*
Licolub WM 31*

n
n
n

Licowax OP
Licowax E
Licowax C

* = with limitations due to the absence of food approvals

From a technical point of view, these are the highest-quality additives for the production of
PVC calender films (fig. 8).
Advantages

Effects

Comprehensive lubricant effect

Improved flow

(internal and external) Dispersion

Release effect
Demolding properties
High melt strength

Dimensional stability

Low volatility Less mold deposits


Figure 8:
Advantages and effects
of the montan waxes in PVC

Less condensation

Universal compatibility Surface properties (smoothness)


Transparency

No plateout

17

18

Licowax , Licolub and Licocene for PVC processing

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. 9) 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. For one thing, the addition of MBS impact modifiers
(methacrylic styrene-butadiene copolymers) can increase tackiness. For another, 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.
Licolub WE 4 displays a better release effect, in formulations both with and without MBS,
i. e. a longer tack-free time than the fatty acid complex ester and Licowax E (fig. 10). The
latter in turn offers advantages regarding rapid gelation and high transparency (see below)
in comparison to the other lubricants.

30

Tack-free time [min]

25
Figure 9:
20

Influence of release-effective

15

lubricants in comparison to
high-molecular release agents

10
5
0
Licowax E
0.5 phr

Licolub WE 4
0.5 phr

Formulation: S-PVC, k-value 60


100.0 parts

Sn-stabilizer
1.5 phr

MBS impact modifier
8.0 phr

PMMA processing aid
1.0 phr

Glycerol dioleate
0.5 phr

High-molecular
release agents
0.5 phr

High-molecular
release agents
1.0 phr

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

19

Without MBS

40
35

Figure 10:
Comparison of the effect of fatty
montan wax on tack-free time for
formulations with and without MBS

30
Tack-free time [min]

acid complex esters (FACE) and

25
20
15
10
5
0
Licowax E

Licolub WE 4

Formulation: S-PVC, k-value 60



Octyltin stabilizer

Glycerol dioleate

Test product

Fatty acid
complex ester
100.0 parts
1.5 phr
0.3 phr
0.3 phr

With MBS

40
35

Tack-free time [min]

30
25
20
15
10
5
0
Licowax E

Licolub WE 4

Formulation: S-PVC, k-value 60



MBS impact modifier

PMMA processing aid

Octyltin stabilizer

Glycerol dioleate

Test product

20

Fatty acid
complex ester
100.0 parts
8.0 phr
1.0 phr
1.5 phr
0.5 phr
0.5 phr

Licowax , Licolub and Licocene for PVC processing

With the help of a measuring rolling mill, it is possible to quantify not only the tack-free time
but also the adhesive force. In addition, it is possible to track the tackiness of a formulation
relative to time, which can produce interesting results (fig. 11).
Here the advantage of Licolub WE 4 compared to fatty acid complex ester is obvious too.
After longer processing time, the FACE deviates from Licolub WE 4, i. e., the adhesive force
of WE 4 remains at the desired level throughout the duration of processing.
When using mixtures of fatty acid complex esters and fatty acid esters (FACE/FAE) it is
common to use 0.5 -1.0 phr high-molecular-weight, release agent, too in order to improve
tack-free time. By replacing FACE/FAE with Licolub WE 4 this release agent can be
significantly reduced (fig. 12), wich leads to cost minimization.

60

Adhesive force [%]

50
Fatty acid complex ester

40

Figure 11:

30

Licolub WE 4

20

Differentiation of lubricants
on a measuring rolling mill

10
0
0

200

400

600

800

1,000

1,200

1,400

Time [sec]
Formulation: S-PVC, k-value 60
parts
Octyltin stabilizer

Glycerol dioleate

100.0
1.2 phr
0.5 phr

0.5 phr high-molecular-weight


release agent

MBS impact modifier


Processing aid
Lubricant

6.0 phr
0.5 phr
0.3 phr

without high-molecular-weight
release agent

40

Tack-free time [min]

35

34

32

Figure 12:
Release effect of Licolub WE 4 in

30
25

comparison to fatty acid complex

23

ester/fatty acid ester (FACE/FAE)

19

20

mixture

15
10
5
0

Mixture of
FACE/FAE

Licolub WE 4

Mixture of
FACE/FAE

Licolub WE 4

Two-roll mill (190 C, 15/20 rpm)


Formulation: S-PVC, k-value 60
parts
Octyltin mercaptide

MBS impact modifier

100.0
1.5 phr
8.0 phr

PMMA processing aid


Glycerol dioleate
Test product

1.0 phr
0.6 phr
0.5 phr

21

In comparison to Licowax E, Licolub WE 4 has a better release effect under slight loss of
transparency (fig. 13), although Licolub WE 4 is still better than the fatty acid complex ester.
Licowax OP is used primarily for film formulations that contain acetate copolymers, since
the calcium montanate it contains has a co-stabilizing effect. Here too the advantages of the
montan waxes compared to fatty acid complex ester mixtures are seen (fig. 14). Licowax OP
clearly offers longer tack-free time than the corresponding fatty acid ester containing
calcium, and the gelation time is shorter. For results with Licolub WM 31 please regard our
flyer Licolub WM 31.
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 these films are to be further processed (e. g., printed,
metalized, etc.), the strong migration tendency of this type of wax to the film surface
should be taken into consideration and the dosage adjusted accordingly. Upon request,
our Marketing / Technical Service Department of the Business Line Waxes will be happy
to provide you with model formulations for a wide variety of film applications.

90

Figure 13:
Influence of various montan waxes
vs. fatty acid complex ester on

Transparency [%]

89

transparency (0.5 mm pressed

88
87
86
85
84

sheets)

83
Licowax E
Formulation: M-PVC, k-value 57
MBS impact modifier
PMMA processing aid
Octyltin stabilizer

Licolub WE 4
100.0 parts
8.0 phr
1.2 phr
1.6 phr

Licolub WE 40
ESBO*
Glycerol dioleate
Test product

FACE
1.0 phr
0.3 phr
0.6 phr

* = epoxidized soya bean oil

Figure 14:
Release effect and gelation
behavior of fatty acid esters
containing calcium (Ca-FAE/FACE)
in comparison to Licowax OP

Tack-free time [min]


(two-roll mill, 190 C, 16.7/20 rpm)

18
16

129

14
124

12
10
8

119

6
4

114

2
0

109
Ca-FAE/FACE

Formulation: S-PVC, k-value 60


Octyltin stabilizer
MBS impact modifier

22

Licowax OP
100.0 parts
1.5 phr
8.0 phr

PMMA processing aid


Glycerol dioleate
Test product

1.0 phr
0.6 phr
0.5 phr

Gelation time [sec]


(Haake Kneader; 40 rpm, 140 C, 63 g)

134

20

Licowax , Licolub and Licocene for PVC processing

Waxes for extrusion of compact PVC


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.

Lead stabilization
Licocene PE 4201
n Licolub H 12
Licolub H 4
n Licowax PED 191
n Licowax PE 520

n

n
n

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 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.

23

24

Licowax , Licolub and Licocene for PVC processing

The hydrocarbon wax Licolub H 4 also acts as an external lubricant. Licolub H 4 and
Licocene PE 4201 are used predominantly in the production of pipes. Dosage: 0.2-0.6 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. 15). 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 montan wax ester Licowax E and Licolub WM 31
(0.3-0.5 phr wax) is recommended. The profiles then have a smooth surface even at high
pigment and filler contents, without impairing weldability or thermostability.

Energy input [Wh/kg]

60

55

Figure 15:
Energy input of oxidized PE waxes

50

in the PVC extrusion (Pb-stabilized)

45

40

Licolub H 12

Formulation: S
 -PVC, k-value 60
parts
PMMAprocessing aid
CaCO3
Lead stabilizer mixture
Hydrostearic acid
Distearyl phthalate
Lubricant combination
Test product

Licowax PED 191


Conditions: Weber CE 3; 20 1/min screw speed

100.00
2.00
5.00
4.75
0.20
0.60
0.35
0.20

phr
phr
phr
phr
phr
phr
phr

Material direct from dosing hopper

Cylinder temperature:
175/185/190 C
Tool temperature:
185/185/190/200 C

25

Calcium / zinc stabilization


n
n

Licocene PE 4201
Licocene PP 6102

n
n

Licolub H 4
Licolub H 12
Licowax PE 520

Licolub WE 40

In Ca/Zn-stabilized systems, depending on the chain length of the Ca/Zn compound, the
stabilizer has hardly any self-lubricating effect. Therefore somewhat higher quantities of
lubricants and processing aid are needed. To reduce friction fatty acid esters are used,
or, in profile applications, the use of montanic acid esters is recommended.
In these compounds too the non-polar and thus incompatible waxes Licowax PE 520,
Licolub H 4, Licocene PE 4201 and Licocene PP 6102 act as external lubricants, which
regulate gelation behavior. In comparison to Licowax PE 520, the Licocene waxes causes
a later and lower build-up of pressure in the extruder as well as stronger nozzle lubrication.
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.
An example of how oxidized PE wax increases energy input is shown in figure 16.

Figure 16:
Increase in energy input through

Energy Input [Wh/kg]

70

65

60

55

oxidized PE wax in the PVC


extrusion (Ca/Zn-stabilized)

50

Without

+ 0.1 phr
Licolub H 12

Formulation: S
 -PVC, k-value 68
100.0
parts
PMMAimpact modifier
6.0 phr
5.0 phr
CaCO3
3.0 phr
TiO2
Ca/Zn-stabi. compound
without lubricant
3.0 phr
Hydroxystearic acid
0.3 phr
Licolub WE 40
0.3 phr
Licowax PE 520
0.3 phr

26

+ 0.2 phr
Licolub H 12

Conditions: Weber CE 3; 20 1/min screw speed


Material direct from dosing hopper

Cylinder temperature:
175/185/190 C
Tool temperature:
185/185/190/200 C

Licowax , Licolub and Licocene for PVC processing

Tin stabilization

n

Licocene PE 4201

Licowax PE 520
Licolub H 4
Licolub H 12
Licowax PED 191

n
n

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.

27

Basic Formulations
Pipes /profiles
Ca/Zn pipe formulation

S-PVC, k-value 65-68
Ca/Zn stabilizer compound
Phosphite (e. g. TNPP)
PMMA impact modifier
Distearyl phthalate
Hydroxystearic acid
Licolub H 4 / Licocene PE 4201
Licowax PE 520

Sn pipe formulation (twin screw)


Parts
100.0
2.2
0.4
1.0
0.4
0.2
0.5
0.2

Parts
100.0
0.4
0.8
1.0
1.2
0.2
1.0
5.0

Sn siding profile (twin screw)

Ca/Zn window profile formulation



PVC copolymer, impact mod.
(e. g. k-value 64; 7 % acrylate copolymer)
Ca/Zn stabilizer compound
Phosphite (e. g. TNPP)
PMMA processing aid
Hydroxystearic acid
Licolub WE 40
Licocene PP 6102
TiO2
CaCO3


S-PVC, k-value 65-68
Sn stabilizer (containing sulfur)
Calcium stearate
MBS impact modifier
Licolub H 4 / Licocene PE 4201
Licolub H 12
TiO2
CaCO3

Parts
100.0
3.4
0.4
2.0
0.2
0.3
0.2
7.0
4.0


S-PVC, k-value 67
Sn stabilizer (containing sulfur)
MBS impact modifier
PMMA processing aid
Calcium stearate
Licolub H 4 / Licocene PE 4201
Licolub H 12
TiO2

Parts
100.0
1.2
5.0
0.5
1.2
1.0
0.2
10.0

Sn window profile formulation



PVC copolymer, impact mod.
(e. g. k-value 64; 7 % acrylate copolymer)
Sn stabilizer (containing sulfur)
PMMA processing aid
Calcium stearate
Glycerol monostearate
Licolub H 4 / Licocene PE 4201
Licolub WE 4
Licowax PE 520
TiO2
CaCO3

28

Parts
100.0
1.5
1.0
1.0
0.5
0.6
0.4
0.1
8.0
3.0

Licowax , Licolub and Licocene for PVC processing

Sheets/blow molded parts /blown films


Sn sheet formulation

S-PVC, k-value 58-62
Sn stabilizer (containing sulfur)
Impact modifier
PMMA processing aid
Epoxidized soya bean oil
Lauryl stearate
Licolub WE 40
Licowax PED 191

Sn shrink-wrapping film
Parts
100.0
2.0
8.0
1.0
1.0
0.6
0.5
0.1

Sn cosmetic/oil bottle formulation I


(Fatty acid ester as internal lubricant)

S-PVC, k-value 58
Sn stabilizer (containing sulfur)
Impact modifier
PMMA processing aid
Glycerol monooleate
Licowax E / Licolub WM 31
Licowax PED 191


S-PVC, k-value 60
Sn stabilizer (containing sulfur)
MBS impact modifier
PMMA processing aid
Glycerol dioleate
Licolub H 12

Parts
100.0
1.5
5.0
1.5
0.8
0.3

Sn cosmetic/oil bottle formulation II


(Epoxidized soya bean oil as internal lubricant)
Parts
100.0
1.5
8.0
1.0
0.6
0.3
0.2


S-PVC, k-value 58
Sn stabilizer (containing sulfur)
Impact modifier
PMMA processing aid
Epoxidized soya bean oil
Licolub WE 4 / Licolub WM 31
Licowax PED 191

Parts
100.0
1.7
10.0
1.5
1.2
0.3
0.2

29

Waxes for extrusion of PVC foam


Foamed PVC places special requirements upon rheological behavior (melt strength)
and makes the selection of suitable lubricants especially important. Improper selection or
an increased dosage can lead to undesired effects. These include formation of bubbles,
resulting in a higher volumetric weight; delay of the necessary fast gelation and thus
impairment of welding of the individual filaments of the melt after passing the mandrel,
the strainer plate, or the torpedo carriers.

Requirements:


Improvement
in lubrication between the surface of the metal
and the expandable melt (containing a foaming agent)
Prevention of plateout

Lead stabilization
n

Licocene PE 4201

n
n

Licolub H 4
Licolub H 12

n
n

Licowax E
Licolub WM 31

Pb sheet, free-foamed

S-PVC, k-value 60
Tribasic lead sulfate
Dibasic lead stearate
PMMA processing aid
Calcium stearate
Distearyl phthalate
Licolub H 4 / Licocene PE 4201
Licowax E / Licolub WM 31
Licolub H 12
Foaming agent (e. g., azodicarbonamide)
TiO2
CaCO3

Parts
100.0
2.2
0.7
5.0
0.3
0.2
0.1
0.2
0.2
1.0
4.0
2.0

Pb sheet, Celuka process



S-PVC, k-value 60
Tribasic lead sulfate
Dibasic lead stearate
PMMA processing aid
Calcium stearate
Stearyl stearate
Distearyl phthalate
Licolub H 12
Foaming agent (e. g., azodicarbonamide, hydrogen carbonate)
TiO2
CaCO3

30

Parts
100.0
4.0
0.4
6.0
0.8
0.6
0.4
0.5
2.0
5.0
3.0

Licowax , Licolub and Licocene for PVC processing

Calcium/zinc stabilization
n

Licocene PE 4201

Licolub H 4

Licowax OP

Ca/Zn sheet, free-foamed



S-PVC, k-value 60
Ca/Zn stabilizer compound
Phosphite (e. g., TNPP)
PMMA processing aid
Epoxidized soya bean oil
Hydroxystearic acid
Distearyl phthalate
Licolub H 4 / Licocene PE 4201
Licowax OP
Foaming agent (e. g., azodicarbonamide)
TiO2
CaCO3

Parts
100.0
3.0
0.4
7.0
0.8
0.1
0.4
0.2
0.2
1.0
4.0
2.0

Tin stabilization
n

Licowax PED 191

n
n

Licowax E
Licolub WM 31

Sn sheet, free-foamed

S-PVC, k-value 60
Sn stabilizer (containing sulfur)
PMMA processing aid
Calcium stearate
Epoxidized soya bean oil
Distearyl phthalate
Licowax E / Licolub WM 31
Licowax PED 191
Foaming agent (e. g., azodicarbonamide, hydrogen carbonate)
TiO2
CaCO3

Parts
100.0
1.5
7.0
0.8
0.5
0.5
0.3
0.6
1.0
4.0
2.0

31

Waxes for 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 and Licowax OP.

Licowax E
Licowax OP
Licolub WM 31

n
n
n
n

High heat distortion temperature


High flowability
High mold filling
Less charring due to shear

Lead stabilization

S-PVC, k-value 60
Tribasic lead sulfate
Dibasic lead stearate
Neutral lead stearate
Calcium stearate
Glycerol monostearate
Licowax E / Licolub WM 31

Parts
100.0
2.5
0.6
0.1
0.4
0.5
0.5

Tin stabilization

S-PVC, k-value 60
Sn stabilizer (containing sulfur)
Impact modifier
PMMA processing aid
Glycerol monostearate
Licowax E / Licolub WM 31

32

Parts
100.0
2.0
2.0
1.0
1.0
0.5

Licowax , Licolub and Licocene for PVC processing

Waxes for flexible PVC


Hoses, wire and cable sheathing
n
n

Licowax E
Licolub WM 31

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. For the most part, phthalate plasticizers are used. The stabilization system
utilized depends on the application. Usually lead stabilizers are used; or for transparent
applications tin (or formerly barium/cadmium/zinc). 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 quite useful especially for small cross-sections.
Pb cable sheathing formulation

S-PVC, k-value 70
Phthalate plasticizer
Tribasic lead sulfate
Calcium stearate
Licowax E / Licolub WM 31
CaCO3

Parts
100.0
60.0
6.0
0.4
0.5
30.0

Calender and blown films


n
n

Licolub WE 4
Licolub WM 31

Licowax C

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).
There is less need for internal lubricants, primarily for semi-rigid settings.

33

Calcium/zinc stabilization, semi-rigid


Ca/Zn shrink-wrapping film formulation, calendered

S-PVC, k-value 60
Ca/Zn stabilizer compound
Phthalate plasticizer
Epoxidized soya bean oil
PMMA processing aid
Impact modifier
Glycerol monostearate
Licowax OP

Parts
100.0
2.0
8-11.0
2.5
1.0
6.0
0.2
0.2

Ca/Zn shrink-wrapping film formulation, blown film extrusion



S-PVC, k-value 60
Ca/Zn stabilizer compound
Phthalate plasticizer
Epoxidized soya bean oil
PMMA processing aid
Impact modifier
Glycerol monostearate (or GDO)
Licowax OP

Parts
100.0
2.0
8-11.0
2.5
1.0
6.0
0.2
0.3

Ca/Zn blood bag formulation



S-PVC, k-value 70
Calcium stearate + zinc stearate
Plasticizer, here DOP
Epoxidized soya bean oil
Licowax C

Parts
> 55.0
1.0
40.0
10.0
1.0

References
n
n
n

34

Plastics Additives Handbook, 5 th Edition, Hanser Publishers, Munich


Kunststoff Handbuch (Becker/Braun) Polyvinylchlorid, Carl Hanser Verlag, Munich
Gleitmittel fr die Folienherstellung, Dr. Eric Richter/Clariant Gersthofen,
Lecture at the meeting PVC Folien und Alternativen, SKZ/Wrzburg (07/1999)
Various technical wax brochures for plastics processing, Clariant

Licowax , Licolub and Licocene for PVC processing

Packaging, Safety, Storage, Transportation and Food legislation


Our products are delivered in the following packaging units (delivery in full pallets only,
smaller amounts on request via our business partners):

Product

Delivery form

Packaging

Product

Licocene PE 4201 Granules



Powder

PE bag
Pallet

20kg
1000kg

Licocene PP 6102 Granules




Fine grain

PE bag
PE bag
Pallet
Pallet
Bigbag

15kg
20kg
750kg
1000kg
1000kg

Licolub H4
Fine grain

PE bag
Pallet

25kg
750kg

Licowax PE 520

Granules
Fine grain
Powder

Licowax PE 190
Powder



Granules

Paper bag 25kg


Pallet
1000kg
Bigbag 1000kg
PE bag
20kg
Pallet
1000kg
Bigbag
500kg
Paper bag 25kg
Pallet
1000kg
Bigbag 1000kg

Licolub H 12
Powder, fine grain PE bag

Pallet

Bigbag
Licowax PED 191 Flakes



Powder

20kg
1000kg
450kg3

Paper bag 20kg


Pallet
800kg
Bigbag
600kg
PE bag
20kg
Pallet
1000kg

Delivery form

Packaging

Licowax C
Powder



Micropowder

PE bag
25kg
Pallet
1000kg
Bigbag
500kg
Paper bag 25kg
Pallet
300kg

Licowax E
Flakes, powder




Powder fine

PE bag
20kg
Pallet
1000kg
Bigbag
450kg1
Bigbag
500kg2
Paper bag 25kg
Pallet
600kg

Licowax OP
Flakes, powder

PE bag
Pallet
Bigbag
Bigbag

20kg
1000kg
450kg1
500kg2

Licolub WE 4
Flakes, powder


PE bag
Pallet
Bigbag
Bigbag

20kg
1000kg
450kg1
500kg2

Licolub WE 40
Powder

PE bag
Pallet
Bigbag

20kg
1000kg
500kg

Licolub WM 31
Flakes, powder


PE bag
Pallet
Bigbag
Pallet

20kg
1000kg
450kg
900kg

1 = Flakes

2 = Powder

3 = Fine grain

Safety information
For each Clariant product there is a material safety data sheet available with comprehensive information regarding safety.

Storage, shelf life


The products mentioned should be stored dry at room temperature. Under these conditions a shelf life of at least 2 years
is ensured.

Shipping and transportation


Our products mentioned are not dangerous goods under following regulations:
ADR, RID, ADN, GGVSEB, IMDG-Code, ICAO TI/IATA-DGR

Status under food legislation


For each Clariant product there is a technical Product Data Sheet (PDS) available with respective information.

35

www.additives.clariant.com
Headquarters:
Clariant International Ltd
Business Unit Additives
Marketing and Operations Waxes
Rothausstrasse 61
4132 Muttenz
Switzerland
Phone: +41- 61-4 69 -7912
Fax: +41- 61-4 69 -7550
Global Marketing and Technical Center:
Clariant Produkte (Deutschland) GmbH
Business Unit Additives
Marketing and Operations Waxes
Technical Marketing Waxes
Ludwig-Hermann-Str. 100
86368 Gersthofen
Germany
Phone: +49-8 21-4 79-2693
Fax: +49-8 21-4 79-2968

NO EXPRESS OR IMPLIED WARRANTY IS MADE OF THE MERCHANTABILITY, SUITABILITY, FITNESS


FOR A PARTICULAR PURPOSE OR OTHERWISE OF ANY PRODUCT OR SERVICE.

= Product and service marks


protected by Clariant in many
countries
= Clariant International Ltd, 2010

DA 8293 E_10/2010

* For sales to customers located within the United States and Canada the following applies in addition:

DA 8293 E_02/04

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 informations accuracy, adequacy, sufficiency or freedom from defect and assumes
no liability in connection with any use of this information. Any user of this product is responsible for
determining the suitability of Clariants products for its particular application. * Nothing included in
this information waives any of Clariants General Terms and Conditions of Sale, which control unless it
agrees 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 with applicable law. You should obtain and review the applicable Material
Safety Data Sheet information before handling any of these products. For additional information, please
contact Clariant.

Exactly your chemistry.