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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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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.

Licowax, Licolub and Licocenefor PVC processing


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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


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



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


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 12 0.2

TiO2 1.0

CaCO3 5.0

Sn siding profile (twin screw)

Parts

S-PVC, k-value 67 100.0



PMMA processing aid 0.5


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


Phosphite (e.g. TNPP) 0.4


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



Glycerol monostearate 0.5


Licolub WE 4 0.4

Licowax PE 520 0.1

TiO2 8.0

CaCO3 3.0


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29

Sn sheet formulation Sn shrink-wrapping film

Parts

S-PVC, k-value 58-62 100.0


Impact modifier 8.0


Epoxidized soya bean oil 1.0

Lauryl stearate 0.6

Licolub WE 40 0.5

Licowax PED 191 0.1

Parts





Glycerol dioleate 0.8

Licolub H 12 0.3

Sn cosmetic/oil bottle formulation I

(Fatty acid ester as internal lubricant)

Parts



Impact modifier 8.0


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



Impact modifier 10.0



Licolub WE 4 / Licolub WM 31 0.3Licowax PED 191 0.2

Sheets/blow molded parts/blown films



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30

Parts


Tribasic lead sulfate 4.0

Dibasic lead stearate 0.4



Stearyl stearate 0.6


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








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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31

Parts



PMMA processing aid 7.0Calcium stearate 0.8




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



Phosphite (e. g., TNPP) 0.4



Hydroxystearic acid 0.1Distearyl phthalate 0.4


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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32

Parts



Impact modifier 2.0




Parts




Neutral lead stearate 0.1




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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33

Parts


Phthalate plasticizer 60.0



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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34

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



Phthalate plasticizer 8-11.0



Impact modifier 6.0


Licowax OP 0.2

Parts



Phthalate plasticizer 8-11.0



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


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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35

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



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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.

aditivos clariant

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