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BU AdditivesBU Additives
Licowax, LicolubandLicocene for PVC processingProduct leaflet
Exactly your chemistry.
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Contents
Introduction 3
Mode of action and uses 5
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
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3
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 trouble-
free processing. They are called lubricants or waxes.
These lubricants (waxes) are added to the PVC to fulfillthe 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)
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 monitor-
ing. 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.
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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 polarityThe 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 PVCThe 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 (f ig.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.
VolatilityIn 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 pro-
duction, 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 meltsurfaces, 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)
100 m
Globules
(microparticles)
1 m
Nodules
(submicroparticles)
10 nm
Plasticization, up to approx. 190 C
Gelation, after approx. 180C
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Mode of action of lubricants
Viscosity reductionLubricants 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 effectGelation 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.
Figure 2:
Mode of action of lubricants
Plasticization Shear dependentviscosity control
Reduction of friction
Viscosity reduction Release effect Slip effect
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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 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.
Figure 3:
Classification of various lubricants
by their effect in tin-stabilized PVC
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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 com-
pressed. 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.
Apparentviscosity[log
*]
Apparent shear speed [log *]
Newtonian behavior PVC with viscosity-reducing lubricant
(fatty acid ester)
PVC without lubricant PVC with shear dependent viscosity control
lubricant (montan wax)
Model
Spring
Damper
Melt
Elasticity
Viscosity
Figure 5:
Spring-damper model
of viscoelastic behavior
Figure 4:
Viscosity in relation to modulus
of shear deformation
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* = part by weight (parts per hundred resin)
Dieswell[%]
50
45
40
35
30
25
20
+ 0.5phr*
Licowax E
+ 1.0phr
High-molecular
release agent
+ 0.5phr
High-molecular
release agent
+ 0.5phr
Fatty acid
complex ester
+ 0.5phr
Licolub WE 4
Conditions: Extrusiometer screw 4:2; 20 rpmTemp.: 150/170/185/195/195CNozzle: 4 mm
Formulation: S-PVC, k-value 60 100.0 parts
Sn stabilizer 1.5 phr Glycerol dioleate 0.5 phr
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.
Figure 6:
Die swell in PVC through various
additives
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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.
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Characteristics of the end products
Thermostabilityis 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 printabilityof 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 glossof 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 moldingtoo, 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 transparencyof 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.
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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 waxesThe montan wax esters Licowax E, Licowax OP, Licolub WE 4, Licolub WM 31 and
Licolub WE 40are 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 montanicacids result in low volatility for these products.
Licowax E, Licolub WE 4, andLicolub WE 40are 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 31is 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
esterscombine internal and primarily external lubrication effects in PVC:
n Maintenance of transparency
n Low volatility
n Low migration tendency
n Intrinsic viscosity
n Melt strength
n High processing safety
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KEY DATA FOR LICOWAX, LICOLUB AND LIC OCENE
Name Chemical characteristics Physical and chemical properties
Drop point Acid value Density Viscosity Color
[C] [mg KOH/g] 23 C [g/cm3] [mPas]
Licowax E Montan wax-based ~ 81 ~18 ~ 1.02 ~30a pale yellowish
ester wax
Licowax OP Partially saponified, montan ~ 99 ~ 12 ~ 1.02 ~ 300b yellowish
wax-based ester wax
Licolub WM 31 Montan wax and long chain ~ 75 ~ 12 ~ 1.00 ~ 26a yellowish
aliphatic acid based ester wax
Licolub WE 4 Montan wax-based ~ 80 ~ 26 ~ 1.01 ~ 60a yellowish
ester wax
Licolub WE 40 Complex ester of ~ 76 ~ 20 1.02 ~ 150a yellowish
montanic acids
Licowax C Amide wax ~ 142 ~ 6 ~ 1.00 almost white
Licolub H 12 Polar polyethylene wax ~ 104 ~ 17 ~ 0.95 ~ 300b almost white
Licowax PED 191 Polar polyethylene wax ~ 123 ~ 17 ~ 0.98 ~ 1,800d almost white
Licowax PE 190 Non-polar polyethylene wax ~ 135g 0 ~ 0.96 ~ 25,000
d white
Licowax PE 520 Non-polar polyethylene wax ~ 120 0 ~ 0.93 ~ 650d white
Licolub H 4 Modified hydrocarbon wax ~ 110 0 ~ 0.92 ~ 13b white
Licocene PP 6102 Non-polar polypropylene wax ~ 145f 0 ~ 0.90 ~ 60
e white
Licocene PE 4201 Non-polar polyethylene wax ~ 127 0 ~ 0.97 ~ 60d white
Ca 2+
n
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
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Overview of applicationsOverview of the main uses for Licolub and Licowax in various types of PVC processing
Product Calendering Extrusion Injection Foam Flexible
molding applications applications
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
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Waxes for calendering films
Tin stabilizationAs already mentioned, lubricants serve many purposes in PVC during various processing
steps (fig. 7).
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 Licolub WE 4 n Licowax OP
n Licolub WE 40* n Licowax En Licolub WM 31* n Licowax C
From a technical point of view, these are the highest-quality additives for the production of
PVC calender films (fig. 8).
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
(Viscosity) PrintabilityRelease effect Gloss
Transparency
Thermostability
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
Less condensation
Universal compatibility Surface properties (smoothness)
Transparency
No plateout
Figure 8:
Advantages and effects
of the montan waxes in PVC
Figure 7:
Calender film production as
an example of the influence
of lubricants on the individual
processing steps
* = with limitations due to the absence of food approvals
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Figure 10:
Comparison of the effect of fatty
acid complex esters (FACE) and
montan wax on tack-free time for
formulations with and without MBS
Tack-freetime[min]
40
35
30
25
20
15
10
5
0Licowax E Fatty acid
complex esterLicolub WE 4
Formulation: S-PVC, k-value 60 100.0 partsOctyltin stabilizer 1.5 phr
Glycerol dioleate 0.3 phrTest product 0.3 phr
Without MBS
Formulation: S-PVC, k-value 60 100.0 partsMBS impact modifier 8.0 phr
PMMA processing aid 1.0 phr Octyltin stabilizer 1.5 phr
Glycerol dioleate 0.5 phrTest product 0.5 phr
Tack-freetime[min]
40
35
30
25
20
15
10
5
0Licowax E Fatty acid
complex esterLicolub WE 4
With MBS
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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.
Figure 11:
Differentiation of lubricants
on a measuring rolling mill
Figure 12:
Release effect of Licolub WE 4 in
comparison to fatty acid complex
ester/fatty acid ester (FACE/FAE)
mixture
Adhesiveforce[%]
60
50
40
30
20
10
0
0 200 400 600 800
Time [sec]
1,000 1,200 1,400
Fatty acid complex ester
Licolub WE 4
Formulation: S-PVC, k-value 60 100.0parts Octyltin stabilizer 1.2 phr Glycerol dioleate 0.5 phr
MBS impact modifier 6.0 phr
Processing aid 0.5 phr
Lubricant 0.3 phr
Tack-freetime[min]
40
35
30
25
20
15
10
5
0Mixture ofFACE/FAE
0.5 phr high-molecular-weightrelease agent
without high-molecular-weightrelease agent
Licolub WE 4Mixture ofFACE/FAE
Licolub WE 4
23
Two-roll mill (190 C, 15/20 rpm)
34
19
32
Formulation: S-PVC, k-value 60 100.0parts Octyltin mercaptide 1.5 phr MBS impact modifier 8.0 phr
PMMA processing aid 1.0 phrGlycerol dioleate 0.6 phrTest product 0.5 phr
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* = epoxidized soya bean oil
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 OPis 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 timethan the corresponding fatty acid ester containing
calcium, and the gelation timeis shorter. For results with Licolub WM 31please 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.
Tra
nsparency[%]
90
89
88
87
86
85
84
83Licowax E FACELicolub WE 40Licolub WE 4
Formulation: M-PVC, k-value 57 100.0 partsMBS impact modifier 8.0 phr
PMMA processing aid 1.2 phr
Octyltin stabilizer 1.6 phr
ESBO* 1.0 phrGlycerol dioleate 0.3 phrTest product 0.6 phr
20
18
16
14
12
10
8
6
4
2
0
134
129
124
119
114
109Ca-FAE/FACE Licowax OP
Tack-freetime[min]
(two-rollmill,1
90C,1
6.7/20rpm)
Gelationtime[sec]
(Haake
Kneader;40rpm,
140C,
63g)
Formulation: S-PVC, k-value 60 100.0 parts
Octyltin stabilizer 1.5 phrMBS impact modifier 8.0 phr
PMMA processing aid 1.0 phr
Glycerol dioleate 0.6 phrTest product 0.5 phr
Figure 13:
Influence of various montan waxes
vs. fatty acid complex ester on
transparency (0.5 mm pressed
sheets)
Figure 14:
Release effect and gelation
behavior of fatty acid esters
containing calcium (Ca-FAE/FACE)
in comparison to Licowax OP
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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
n Licocene PE 4201 n Licolub H 12 n Licolub WM 31
n Licolub H 4 n Licowax PED 191 n Licowax E
n Licowax PE 520 n 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.
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The hydrocarbon wax Licolub H 4also acts as an external lubricant. Licolub H 4and
Licocene PE 4201are 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 OPor the montan wax ester Licowax Eand 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.
Figure 15:
Energy input of oxidized PE waxes
in the PVC extrusion (Pb-stabilized)
En
ergyinput[Wh/kg]
60
55
50
45
40Licolub H 12 Licowax PED 191
Formulation: S-PVC, k-value 60 100.00parts
PMMA processing aid 2.00 phr
CaCO3 5.00 phr
Lead stabilizer mixture 4.75 phr
Hydrostearic acid 0.20 phr
Distearyl phthalate 0.60 phr
Lubricant combination 0.35 phrTest product 0.20 phr
Conditions: Weber CE 3; 20 1/min screw speed
Material direct from dosing hopper
Cylinder temperature:
175/185/190C
Tool temperature:
185/185/190/200 C
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Calcium/zinc stabilization
n Licocene PE 4201 n Licolub H 4 n Licolub WE 40
n Licocene PP 6102 n Licolub H 12
n Licowax PE 520
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 estersis recommended.
In these compounds too the non-polar and thus incompatible waxes Licowax PE 520,
Licolub H 4, Licocene PE 4201and
Licocene PP 6102act 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
oxidized PE wax in the PVC
extrusion (Ca/Zn-stabilized)
EnergyInput[Wh/kg]
70
65
60
55
50Without + 0.1 phr
Licolub H 12
+ 0.2 phr
Licolub H 12
Conditions: Weber CE 3; 20 1/min screw speed
Material direct from dosing hopper
Cylinder temperature:175/185/190C
Tool temperature:185/185/190/200C
Formulation: S-PVC, k-value 68 100.0partsPMMA impact modifier 6.0 phrCaCO3 5.0 phrTiO2 3.0 phrCa/Zn-stabi. compoundwithout lubricant 3.0 phrHydroxystearic acid 0.3 phrLicolub WE 40 0.3 phrLicowax PE 520 0.3 phr
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Tin stabilization
n Licocene PE 4201 n Licowax PE 520 n Licolub WE 4
n Licolub H 4 n Licolub WM 31
n Licolub H 12
n Licowax PED 191
PVC compounds produced with tin stabilizerstend 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 andLicowax 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.
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Ca/Zn pipe formulation
Parts
S-PVC, k-value 65-68 100.0
Ca/Zn stabilizer compound 2.2
Phosphite (e.g. TNPP) 0.4
PMMA impact modifier 1.0
Distearyl phthalate 0.4
Hydroxystearic acid 0.2
Licolub H 4 / Licocene PE 4201 0.5
Licowax PE 520 0.2
Basic Formulations
Pipes/profiles
Sn pipe formulation (twin screw)
Parts
S-PVC, k-value 65-68 100.0
Sn stabilizer (containing sulfur) 0.4
Calcium stearate 0.8
MBS impact modifier 1.0
Licolub H 4 / Licocene PE 4201 1.2
Licolub H 12 0.2
TiO2 1.0
CaCO3 5.0
Sn siding profile (twin screw)
Parts
S-PVC, k-value 67 100.0
Sn stabilizer (containing sulfur) 1.2
MBS impact modifier 5.0
PMMA processing aid 0.5
Calcium stearate 1.2
Licolub H 4 / Licocene PE 4201 1.0Licolub H 12 0.2
TiO2 10.0
Ca/Zn window profile formulation
Parts
PVC copolymer, impact mod.
(e. g. k-value 64; 7 % acrylate copolymer) 100.0
Ca/Zn stabilizer compound 3.4
Phosphite (e.g. TNPP) 0.4
PMMA processing aid 2.0
Hydroxystearic acid 0.2Licolub WE 40 0.3
Licocene PP 6102 0.2
TiO2 7.0
CaCO3 4.0
Sn window profile formulation
Parts
PVC copolymer, impact mod.
(e. g. k-value 64; 7 % acrylate copolymer) 100.0Sn stabilizer (containing sulfur) 1.5
PMMA processing aid 1.0
Calcium stearate 1.0
Glycerol monostearate 0.5
Licolub H 4 / Licocene PE 4201 0.6
Licolub WE 4 0.4
Licowax PE 520 0.1
TiO2 8.0
CaCO3 3.0
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Sn sheet formulation Sn shrink-wrapping film
Parts
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
Parts
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 cosmetic/oil bottle formulation I
(Fatty acid ester as internal lubricant)
Parts
S-PVC, k-value 58 100.0
Sn stabilizer (containing sulfur) 1.5
Impact modifier 8.0
PMMA processing aid 1.0
Glycerol monooleate 0.6
Licowax E / Licolub WM 31 0.3Licowax PED 191 0.2
Sn cosmetic/oil bottle formulation II
(Epoxidized soya bean oil as internal lubricant)
Parts
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 0.3Licowax PED 191 0.2
Sheets/blow molded parts/blown films
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Parts
S-PVC, k-value 60 100.0
Tribasic lead sulfate 4.0
Dibasic lead stearate 0.4
PMMA processing aid 6.0
Calcium stearate 0.8
Stearyl stearate 0.6
Distearyl phthalate 0.4
Licolub H 12 0.5
Foaming agent (e. g., azodicarbonamide, hydrogen carbonate) 2.0
TiO2 5.0
CaCO3 3.0
Pb sheet, Celuka process
Parts
S-PVC, k-value 60 100.0
Tribasic lead sulfate 2.2
Dibasic lead stearate 0.7
PMMA processing aid 5.0
Calcium stearate 0.3
Distearyl phthalate 0.2
Licolub H 4 / Licocene PE 4201 0.1
Licowax E / Licolub WM 31 0.2
Licolub H 12 0.2
Foaming agent (e. g., azodicarbonamide) 1.0
TiO2 4.0
CaCO3 2.0
Pb sheet, free-foamed
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: n Improvement in lubrication between the surface of the metaland the expandable melt (containing a foaming agent)
n Prevention of plateout
Waxes for extrusion of PVC foam
Lead stabilization
n Licocene PE 4201 n Licolub H 4 n Licowax E
n Licolub H 12 n Licolub WM 31
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Parts
S-PVC, k-value 60 100.0
Sn stabilizer (containing sulfur) 1.5
PMMA processing aid 7.0Calcium stearate 0.8
Epoxidized soya bean oil 0.5
Distearyl phthalate 0.5
Licowax E / Licolub WM 31 0.3
Licowax PED 191 0.6
Foaming agent (e. g., azodicarbonamide, hydrogen carbonate) 1.0
TiO2 4.0
CaCO3 2.0
Ca/Zn sheet, free-foamed
Sn sheet, free-foamed
Parts
S-PVC, k-value 60 100.0
Ca/Zn stabilizer compound 3.0
Phosphite (e. g., TNPP) 0.4
PMMA processing aid 7.0
Epoxidized soya bean oil 0.8
Hydroxystearic acid 0.1Distearyl phthalate 0.4
Licolub H 4 / Licocene PE 4201 0.2
Licowax OP 0.2
Foaming agent (e. g., azodicarbonamide) 1.0
TiO2 4.0
CaCO3 2.0
Calcium/zinc stabilization
n Licocene PE 4201 n Licolub H 4 n Licowax OP
Tin stabilization
n Licowax PED 191 n Licowax E
n Licolub WM 31
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Parts
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 0.5
Parts
S-PVC, k-value 60 100.0
Tribasic lead sulfate 2.5
Dibasic lead stearate 0.6
Neutral lead stearate 0.1
Calcium stearate 0.4
Glycerol monostearate 0.5
Licowax E / Licolub WM 31 0.5
Lead stabilization
Tin stabilization
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 31and Licowax OP.
Licowax E n High heat distortion temperature
Licowax OP n High flowability
Licolub WM 31 n High mold filling
n Less charring due to shear
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Parts
S-PVC, k-value 70 100.0
Phthalate plasticizer 60.0
Tribasic lead sulfate 6.0
Calcium stearate 0.4
Licowax E / Licolub WM 31 0.5CaCO3 30.0
Pb cable sheathing formulation
Waxes for flexible PVC
Hoses, wire and cable sheathing
n Licowax E
n 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.
Calender and blown films
n Licolub WE 4 n Licowax C
n Licolub WM 31
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 4or Licolub WM 31 displays optimal performance with regard to anti-
sticking 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.
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REFERENCES
n Plastics Additives Handbook, 5thEdition, Hanser Publishers, Munich
n Kunststoff Handbuch (Becker/Braun) Polyvinylchlorid, Carl Hanser Verlag, Munich
n
Gleitmittel fr die Folienherstellung, Dr. Eric Richter/Clariant Gersthofen,Lecture at the meeting PVC Folien und Alternativen, SKZ/Wrzburg (07/1999)
n Various technical wax brochures for plastics processing, Clariant
Parts
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 0.2
Licowax OP 0.2
Parts
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
Parts
S-PVC, k-value 70 > 55.0
Calcium stearate + zinc stearate 1.0
Plasticizer, here DOP 40.0
Epoxidized soya bean oil 10.0
Licowax C 1.0
Ca/Zn shrink-wrapping film formulation, calendered
Ca/Zn shrink-wrapping film formulation, blown film extrusion
Ca/Zn blood bag formulation
Calcium/zinc stabilization, semi-rigid
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Safety informationFor each Clariant product there is a material safety data sheet available with comprehensive information regarding safety.
Storage, shelf lifeThe products mentioned should be stored dry at room temperature. Under these conditions a shelf life of at least 2 years
is ensured.
Shipping and transportationOur products mentioned are not dangerous goods under following regulations:
ADR, RID, ADN, GGVSEB, IMDG-Code, ICAO TI/IATA-DGR
Status under food legislationFor each Clariant product there is a technical Product Data Sheet (PDS) available with respective information.
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
Licocene PE 4201 Granules PE bag 20 kg Powder Pallet 1000 kg
Licocene PP 6102 Granules PE bag 15 kg PE bag 20 kg
Fine grain Pallet 750 kg
Pallet 1000 kg
Bigbag 1000 kg
Licolub H4 Fine grain PE bag 25 kg Pallet 750 kg
Licowax PE 520 Granules Paper bag 25 kg
Fine grain Pallet 1000 kg
Powder Bigbag 1000 kg
Licowax PE 190 Powder PE bag 20 kg Pallet 1000 kg
Bigbag 500 kg
Granules Paper bag 25 kg
Pallet 1000 kg
Bigbag 1000 kg
Licolub H 12 Powder, fine grain PE bag 20 kg Pallet 1000 kg
Bigbag 450 kg3
Licowax PED 191 Flakes Paper bag 20 kg Pallet 800 kg
Bigbag 600 kg
Powder PE bag 20 kg
Pallet 1000 kg
Product Delivery form Packaging
Licowax C Powder PE bag 25 kg Pallet 1000 kg
Bigbag 500 kg
Micropowder Paper bag 25 kg
Pallet 300 kg
Licowax E Flakes, powder PE bag 20 kg Pallet 1000 kg
Bigbag 450 kg1
Bigbag 500 kg2
Powder fine Paper bag 25 kg
Pallet 600 kg
Licowax OP Flakes, powder PE bag 20 kg Pallet 1000 kg
Bigbag 450 kg1
Bigbag 500 kg2
Licolub WE 4 Flakes, powder PE bag 20 kg Pallet 1000 kg
Bigbag 450 kg1
Bigbag 500 kg2
Licolub WE 40 Powder PE bag 20 kg Pallet 1000 kg
Bigbag 500 kg
Licolub WM 31 Flakes, powder PE bag 20 kg Pallet 1000 kg
Bigbag 450 kg
Pallet 900 kg
1 = Flakes 2 = Powder 3 = Fine grain
Licowax, Licolub and Licocenefor PVC processing
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DA8
293E_
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 inthis 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, pleaset t Cl i t
www.additives.clariant.com
Headquarters:
Clariant International Ltd
Business Unit Additives
Marketing and Operations Waxes
Rothausstrasse 61
4132 Muttenz
Switzerland
Phone: +41-61- 469 -7912
Fax: +41-61-469-7550
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: +49-821-479-2693Fax: +49-821-479-2968
Exactly your chemistry.