CHAPTER 4

Elementary Principles of pvc Formulation

W. V. TITOW

4.1 INTRODUCTION

As has been mentioned in Chapter 1, PVC resins-whether homo-

polymers or copolymers-must be modified by the incorporation of
appropriate additives for satisfactory processing and end-use perform-
ance. The necessary modifications are more varied and extensive than
those practised with any other polymer of major industrial importance,
but so also is the applicational versatility of PVC in the form of the
resulting materials.
In this chapter the terms 'composition' and 'compound' are used
generically for the material which results when PVC resin is combined
with the necessary additives, and the operations involved in making a
composition are collectively called 'compounding'.

Note: Compounding may consist of, or include as one of its stages,

mixing and/or melt-compounding. The former term applies
either to the blending together of the constituents to produce a
solid composition in the form of a free-flowing powder or
powder agglomerate (either of these may be referred to as
'pre-blend' or 'dry blend', depending on the context), or to
their mixing to form a liquid composition, i.e. a paste, latex,
or solution. Melt-compounding is the operation (commonly
carried out on a mixed pre-blend) whereby the constituents of
a composition are intimately combined with the resin in the
melt, under heat and shear: the resulting compound is
normally pelletised (granulated).
79

W. V. Titow, PVC Technology

© Elsevier Applied Science Publishers Ltd 1984
80 w. V. Titow

A composition is processed by the appropriate method to make a

PVC product (e.g. sheet, film, pipe, injection-moulded component,
blow-moulded container, coating on a fabric, etc.): some of the
products may be used to fabricate secondary products by further
processing (e.g. mouldings thermoformed from sheet, wall coverings
made by laminating calendered films). A general outline of this
sequence may be schematically represented as in Fig. 4.1.
The material (and thus, of course, the formulation) of a product is
that of the composition used to make it, but in the product the material
will have had a more extensive 'heat history', having undergone at
least one processing operation after the original compounding. The
basic, general principles of formulating a PVC composition (Le.
deciding on the nature and proportions of its constituents) are
relatively straightforward: however, successful practice calls for a great
deal of specialist knowledge and experience.
A formulator normally designs a composition in response to a stated
need for a product, Le. he starts with the knowledge of the nature and
intended end-use of the product into which the composition will be
processed (these factors will also determine the process to be used): in
the light of this knowledge three main considerations will govern his
choice of the formulation's components and their proportions, viz.

1------ --------,
Compounding : Physical forms: :
r---..L---, JSolid: (a) Fr(l(l-flowlng powd(lr or 1
Composition powd(lr agglom(lrat(l I
L..-_.,....----J-- ------1 (pr(lbl(lnd; dry bl(lndJ I
: (b) P(lII(lts; granulat(l I
Proc(lssing I Liquid: (a) Past(l 1

IProd"~
I (b) Lat(lx I
I
1- (c) Solution l
_

I
I
Furth(lr proc(lsslng
I
• t.I ,
IS(lcondary product 1
----------J
Fig. 4.1 Stages in the manufacture of PVC products-general outline.
 4 Elementary Principles of pvc Formulation 81

(i) Processing requirements: To meet these the composition must

be in the right form (e.g. pellets for most injection mouldings,
paste for spread-coating of a fabric), have the necessary heat
stability under the processing conditions, and other properties
appropriate for the particular process (e.g. the right melt
rheology for injection moulding or extrusion, right viscosity
characteristics in a paste for spread-coating, correct lubricity in
a calendering compound to prevent 'plate-out').
(ii) Service requirements: These will be dictated by the end-use, and
will normally include stability to the service environment.
(iii) Material and process cost economy: Save in certain special cases
(e.g. some military applications) this is always an important
consideration, influencing the design of a formulation.

4.2 THE COMPONENTS, AND BASIC TYPES, OF A

PVC FORMULATION

As already mentioned in Chapter 1, PVC materials and products fall

into two broad categories: rigid (uPVC) and plasticised (pPVC).
Materials of the latter group with low plasticiser content (up to about
30 phr) are often referred to as 'semi-rigid': the softest pPVC materials
may contain over 100 phr of plasticiser(s).
With the partial exception (not important in the context of the
present discussion) of certain liquid compositions (some solutions and
lattices-see Chapters 23 and 24), virtually all PVC compositions
undergo heat treatment-and most experience 'internal' (frictional)
heat generated by mechanical shearing-in the course of processing
(including the initial compounding). Many end-uses also involve
exposure to heat (albeit usually at temperatures somewhat lower than
those encountered in processing) either as a normal condition of
service (e.g. for flexible PVC insulation on electric wire, or rigid PVC
products exposed to direct sunlight outdoors, as with, say, guttering,
cladding or window frames), or as an occasional hazard. For all these
reasons, the PVC polymers-which are inherently prone to heat
degradation (see Chapters 1, 9, and 12)-have to be protected by the
incorporation of heat stabilisers. Thus the PVC resin itself and a heat
stabiliser are two essential components of virtually every PVC
formulation.
A simple, basic formulation for a solid uPVC composition will also
82 W. V. Titow

normally contain a processing aid (a polymeric additive, to improve

fusion characteristics and melt flow), an impact modifier (also a
polymeric additive, to impart toughness to the relatively brittle PVC
resin), and a lubricant to counteract sticking to hot equipment surfaces
in processing ('external' lubrication) and/or to reduce the frictional
effects within the melt ('internal' lubrication): more than one lubricant
is often used to discharge these functions. Similarly, more than one
processing aid and/or impact modifier may be incorporated for best
results in a particular composition, but-on the other hand-a single
additive may serve in both capacities in some cases (e.g. chlorinated
polyethylene in certain formulations-see Chapter 11).
In a basic formulation for a pPVC composition the plasticiser (or
plasticiser system, if more than one plasticiser is used) is the essential
component in addition to the PVC resin and heat stabiliser. Apart
from its effects on the finished material properties (imparting softness,
flexibility, extensibility, toughness) it plays an important role in heat
processing, combining the functions of processing aid with lubricant
action (particularly internal lubrication; although some plasticisers-
and especially extenders-can provide external lubrication, it is not
unusual to include lubricants with good 'external' effect in pPVC
formulations) .
In addition to the basic constituents most PVC formulations contain
other components incorporated mainly to impart properties required in
the PVC product for particular end-uses. The most widely used of
these additives are colourants and fillers. The colourants include
pigments (which impart opacity as well as colour to the PVC material)
and dyes (colourants fully soluble in the composition and thus suitable
for transparent materials). Fillers are often included to cheapen the
cost of PVC compositions, although even when this is the primary
purpose the attendant effects on some properties may also be useful,
e.g. reduced shrinkage, increased hardness and stiffness, which are
often brought about by the presence of a substantial proportion of
finer. Some fillers have a purely functional role-e.g. glass fibres and
fine-particle calcium carbonate act as reinforcements in uPVC
compositions. The uses and effects of fillers are discussed in Chapter 8.
Other formulation components with specific end-use functions in the
PVC material are the following:

Antioxidants and UV absorbers: Used to improve the resistance of

PVC products (especially those for outdoor use) to photochemical
degradation and weathering generally (see Chapters 11 and 12).
 4 Elementary Principles of pvc Formulation 83

Antistatic agents: Incorporated to counteract the build-up of

electrostatic charges (with the consequent risk of sparks in some cases,
and the nuisance of dust pick-up) on the surface of PVC products-
e.g. pPVC conveyor belts, or uPVC mouldings.

Flame retardants: Included, especially in some flexible PVC

materials, to reduce their flammability (enhanced by the presence of
substantial amounts of many plasticisers). uPVC is among the least
flammable plastics materials (see Chapters 7, 8, 11 and 12).

Smoke suppressants: Incorporated to reduce the amount of smoke

generated by burning PVC materials (some additives in this category
also cut down the evolution of HCI in burning)-see Chapters 8, 11
and 12.

Biostats: Included in PVC compositions (especially some flexible

materials) to counteract attack by micro-organisms (bacteria and
fungi)-see Chapters 7 and 12.

Odour control agents: Such additives are used in some formulations

to impart a smell (e.g. leather-like odour to PVC handbags or
upholstery) or to mask odour of another formulation component.
According to their function in a particular composition they may be
referred to as 'reodorants' or 'deodorants'.

Two kinds of functional components included in certain formulations

to act in the processing rather than the service stage are blowing agents
(which, in the production of PVC foam, create the cellular structure by
evolution of gases at the processing temperature) and surface active
agents used to facilitate the mechanical whipping-in of air into PVC
pastes, and to control the resulting bubble formation, in the
air-entrainment method of PVC foam production-see Chapters 11
and 25.

4.3 FORMULATION COSTING-BASIC POINTS

It is usual to express the formulation of a composition on the basis of

100 parts by weight of the PVC resin, using the abbreviation 'phr'
(parts per hundred of resin) for the content of each of the other
components present. For costing purposes the volume cost is usually
84 w. V. Titow
required, and for this the volume content of each component of the
formulation is worked out from the weight content and density values.
These points are illustrated by the following example of a simple
plasticised compound (an extrusion compound of BS softness about
20):

Component Parts by weight Density Parts by volume

(g) (gem- J ) (em3)

PVC polymer 100·0 1·40 71·43

Plasticiser 50·0 0·99 50·50
Stabiliser 7·0 3·81 1·84
Lubricant 1·0 0·93 1·08
158·0 124·85

Since, by definition, density = weight/volume, the parts by volume are

obtained by dividing the parts by weight by the density in each case.
Similarly, the density of the compound is given by 158/124·85 = 1·266
gcm- 3 .
The density of a PVC composition is important for costing purposes
since, although it is convenient to formulate it on a weight basis, the
composition will ultimately be used (and sold) on a volume basis, as a
given weight will produce a certain number of mouldings or a certain
volume of extrudate (e.g. a certain length of pipe of given dimensions).
Thus the volume cost is of direct interest, as is the fact that, in a
comparison of two formulations, it may be higher for the one cheaper
on a weight basis. For example, consider two compounds, A and B, of
which B is 10% more expensive on a weight basis but has lower
density:

Weight eost Volume cost

per kg perg (perem3)

Compound A 1·35 n O·OOln 1·35 x O·OOln = 0·00135n

Compound B 1-10 1-1n O·OOlln 1·10 x O·OOlln = 0·001 21n

Thus, in this general example, because of the density difference, the

compound which is 10% more expensive on a weight basis is cheaper
in roughly the same proportion on a volume basis.
 4 Elementary Principles of pvc Formulation 85

The simple extrusion compound cited at the beginning of this section

may be costed as illustrated below (the component prices used in the
illustration are roughly in line with those applicable to tonne-lot
purchases in the first half of 1980 in the UK).

Formulation A B C
component Weight Cost per kg Cost in formulation
proportion (£) (A x B)
(kg) (£)

PVC polymer 100 0·40 40

Plasticiser 50·0 0·50 25
Stabiliser 7·0 0·40 2·8
Lubricant 1·0 0·25 0·25
158·0 68·05

The weight cost of this compound will therefore be

68·05/158 = £0·4307 per kg,
and the volume cost (given the density as 1·266 g cm- 3-see above)
1·266 x 0·0004307 = £0·000545 26 per cm3.

4.4 MAIN GENERAL CONSIDERATIONS IN THE

SELECflON OF PRINCIPAL FORMULATION
COMPONENTS

Each component of a particular PVC formulation (i.e. the PVC resin,

stabiliser, plasticiser, etc.) is selected from a large group of available
materials of its type. The choice is made-in the light of the
requirements mentioned in Section 4.1-on the basis of the known
characteristics of the individual candidate materials within the group,
in conjunction with certain other relevant considerations (including the
mutual compatability, interactions, and side effects of the formulation
components when compounded into a composition). The purpose of
this section is to give a general indication of the main factors concerned
in the choice: a comprehensive discussion of the complex subject of the
properties and effects of PVC formulation components would be far
beyond its scope. Further relevant information will be found in various
86 w. v. Titow

parts of this book (especially Chapters 2, 3, 6 to 12, and 21 to 25). A

useful summary of some important considerations has been provided
by K. Regan in the Buss-Hamilton Compounding Manual. *

4.4.1 Nature and Characteristics of Individual Components of a

Formulation

(a) PVC Polymer

MOLECULAR WEIGHT
In general, the higher the molecular weight of the polymer (and hence
its K value and viscosity number-see Chapters 1 and 2) the better
many mechanical properties of the composition but the more difficult
its processing (because the ease of fusion and melt flow decreases with
increasing molecular weight). The choice of the molecular weight
grade (K value) of a commercial polymer to be used in a particular
formulation is normally a compromise between what is the most
desirable for processing on one hand and service properties on the
other. The processing considerations become less critical with
adequately plasticised compositions, so that polymers of higher K
value can be used in those-typically 65 to 71 t (ICI range 60-65, Fig.
4.2), as against 54 to 65t (ICI range 50-60) in uPVC (with the lowest
molecular weight polymers used in those rigid compositions where the
easiest melt flow is required, e.g. in some injection-moulding and
bottle-blowing compounds). The molecular weight distribution of the
polymer also affects physical properties and processing: it is normally
maintained within certain limits in a given commercial polymer grade.

KIND (PROCESS TYPE)

Except for the special case of formulating PVC solutions for surface
coatings, for which polymer produced by the solution process will
normally be used (see Chapters 2 and 24), the choice will be between
suspension polymers, mass (bulk) polymers or emulsion polymers (i.e.
PVC resins produced by those three polymerisation processes-see
Chapter 2). For PVC paste compositions emulsion polymers are used
* Edited and published by Buss-Hamilton Ltd, Cheadle Hulme, Stockport,
England.
t K values from viscosity determinations on 0·5 g per 100 ml (polymer/cyc-
lohexanone) solutions. Corresponding ISO viscosity number ranges are, re-
spectively, about 105-125 and 70-105-see Table 2.1 in Chapter 2.
 4 Elementary Principles of pvc Formulation 87

80

70

50

60 70 80
K value (0·59 resin In 100ml cyclohexanone)

Fig. 4.2 The relationship between ICI K value and K value determined by
viscosity measurement on a solution of 0·5 g PVC resin in 100 ml cyclohex-
anone (ct. Chapter 1, Fig. 1.2, and Chapter 2, Table 2.1)

because of their particle size and structure characteristics, although

suspension resins are sometimes added as 'extender' ('filler') polymers
to modify the viscosity of pastes: the use of PVC polymers in pastes is
discussed in Chapter 21. Solid compositions (sometimes referred to as
'general purpose' compounds in contradistinction to pastes) for
injection moulding, extrusion, or calendering are commonly formu-
lated with suspension or mass polymers, although mixtures of one of
these with an emulsion resin, or even emulsion resins alone, are
occasionally used in Europe in some uPVC compositions for better
melt flow.
Note: Emulsion resins are not used in electrical insulation composi-
tions, because the residues of additives from the polymerisa-
tion process (especially emulsifying agents) which they contain
lower electrical resistivity.
Suspension and mass polymers are, broadly speaking, roughly
88 W. V. Titow

equivalent from the point of view of the final material properties,

although a mass polymer may contain fewer impurities than an
otherwise comparable suspension polymer and hence give compounds
of better clarity (see 'quality' below). The differences between the two
types of polymer are more strongly manifested in processing. Mass
polymers tend to have higher bulk densities than suspension polymers
(for comparable polymer molecular weight and particle porosity), with
greater uniformity of particle porosity and shape (and hence more
uniform and rapid plasticiser absorption), as well as greater ease of
gelation (i.e. ease and completeness of fusion in heat processing) which
is of particular interest in the production of large mouldings. All these
characteristics can offer processing advantages in certain circumstances
and processes, but the fact should not be overlooked that-whilst the
optimum conditions for a suspension and a mass polymer may be
different in a particular process-if they are properly optimised in each
individual case either polymer can be processed satisfactorily.

CHEMICAL NATURE
The PVC resin on which a formulation is based may be a
homopolymer, or a copolymer, or sometimes a mixture of both. The
general differences between the two, their main respective applications
and uses, and the copolymers of the greatest practical interest, have all
been mentioned in Chapters 1 and 2. In broad summary it may be said
that homopolymers have better thermal stability and impart better
physical properties to the composition, whilst copolymers make for
easier melt processing at relatively lower temperatures, and improve
extensibility and filler acceptance in some compositions: copolymers
are also normally used in PVC-based solution formulations for surface
coatings-see Chapter 24. The melt-processing advantages of copoly-
mers versus homopolymers, like those of lower versus higher
molecular weight polymers (see above), are more important in rigid
formulations, as in adequately plasticised compositions the fusion and
melt flow characteristics are primarily governed by the plasticiser.
Vinyl chloride/acetate copolymers form the basis of uPVC compounds
for gramophone records and certain types of sheeting; they are also
used in flooring compositions. In Europe they are sometimes included
with a homopolymer to improve the ease of processing of some rigid
formulations. Vinyl chloride/vinylidene chloride copolymers are em-
ployed, alone or in admixture to homopolymer, in some specialised
calendering compounds (for uPVC sheeting), and as viscosity-
 4 Elementary Principles of pvc Formulation 89

reducing extender polymer in some paste formulations (see Chapter

21).

QUALITY
It is clearly desirable that the PVC resin used in any formulation
should be of reasonable quality, and the standard grades supplied by
the manufacturers are, generally speaking, reliable and acceptable in
this respect for most purposes. However, some applications call for
particularly high quality (and special high-grade resins are available)
whilst in certain cases a lower than standard quality may be acceptable
in the formulation. Apart from the molecular weight spread (which
should be within appropriate limits for the given nominal K value of
the polymer grade) the factors making up quality in the present context
are: polymer particle size and size distribution (with special reference
to coarse particle content); colour; 'fish-eye' content; and level of
particulate contamination ('speck count').
Note: ISO 472-1979 defines 'fish-eye' as 'a small globular mass which
has not blended completely into the surrounding material and
is particularly evident in a transparent or translucent mate-
rial'. In PVC polymer fish-eyes (also called gels) are hard,
particulate specks of polymer which are not dispersed in
processing and thus remain as discrete inhomogeneities in the
finished product. A standard method of determining the
number and size of fish-eyes in general-purpose PVC resins is
given in ASTMD3596-77 (see also ASTMD3351-74: Gel
count of plastic film).
Low-grade polymer can be used, in admixture with a standard grade
or even alone, in formulations for the cheaper kinds of injection-
moulding compositions, usually fairly heavily filled, used for the
production of cheap moulded footwear (sandals, slipper soles) and
toys. High-grade polymer is necessary for such uPVC products as
transparent ('clear') packaging film and bottles, and in plasticised
compositions for clear medical products (e.g. containers and tubing for
saline drip sets), clear, flexible hose and packaging film (e.g.
'clingwrap') .

(b) Heat Stabilisers

Whilst the main mechanisms involved in the complex process of
thermal degradation of PVC and its counteraction by stabilisers are
90 W. V. Titow

understood in general terms, the stabilisation of PVC formulations is

still largely a practical art, relying on the specialist interpretation and
application, in the specific context of a particular composition, of
information and principles stemming mainly from practical experience.
For this reason, and also because a great variety of stabilisers is
available (many of which are not single chemicals but compositions
specially developed for particular types of formulations and end-uses)
even a skilled formulator will normally seek the advice of a reputable
supplier when formulating a composition of which he has no previous
experience. The proportion of stabiliser(s) in a PVC formulation will
vary-in broad, general terms between about 0·5 and 8 phr-
depending on the nature and purpose of the composition, the nature of
the stabiliser itself, and the processing (including the kind of
compounding to be undergone--e.g. completeness of dispersion
achievable with modern compounding machinery reduces stabiliser
requirement). Heat stabilisers and their effects are discussed in some
detail in Chapters 9 and 10; only the most basic, general points are
mentioned here.
There is no rigid, standard classification of stabilisers, but-for the
purposes of a brief general discussion-they may conveniently be
considered under the following headings.

LEAD COMPOUNDS
Several lead salts and some lead 'soaps' (notably lead stearates) are
widely used as stabilisers in PVC (the soaps partly for their lubricant
properties). Lead compounds are the oldest general-purpose stabilis-
ers, comparatively cheap, and capable of imparting good long-term
stability. They have always dominated the electrical insulation
applications of pPVC compounds, because lead chloride, formed when
a lead stabiliser reacts with HCl (a principal decomposition product of
PVC-see Chapter 9), is insoluble and non-ionisable, so that the
electrical resistivity remains unimpaired as the stabiliser discharges its
function. In uPVC compositions lead stabilisers are used in many
formulations for extruded cladding and profiles: dibasic lead phos-
phite is of particular interest for opaque products for outdoor use, as it
imparts very good light stability. In Europe lead stabilisers are also
used in uPVC pipes, although in the USA tin stabilisers (see below)
are favoured for this area of application. The main limitations and
disadvantages of lead stabilisers as a group are toxicity (hazards in
processing, as distinct from potential risks in compounds, are reduced
 4 Elementary Principles of pvc Formulation 91

to some extent by various means-see Chapter 9), opacity (or at least

translucency) imparted to PVC compositions, and susceptibility to
staining (through the formation of black lead sulphide) in contact with
sulphur-containing materials (e.g. 'cross-staining' with certain rubbers)
and atmospheres.

BARIUM/CADMIUM AND BARIUM/CADMIUM/ZINC SYSTEMS

The former type of stabiliser system may consist of barium and
cadmium soaps (e.g. laurates, stearates, or myristates) mixed or
co-precipitated, or a liquid salt combination (e.g. barium and cadmium
phenates). The zinc-containing systems incorporate in addition an
organic salt of that met.al (often zinc octoate). Both types of system are
extensively used-and can be considered by the formulator-for a
variety of applications in both flexible and rigid PVC compositions: for
example, most of the flexible calendered film and sheeting compounds
are formulated with these stabilisers, as are many paste products (e.g.
coatings, rotational mouldings), as well as numerous flexible and rigid
extrusion compositions (including, e.g. wire-coating compounds,
profiles), and injection-moulding compounds (e.g. for footwear). Both
types of stabiliser system are quite widely used in conjunction with
synergistic co-stabilisers-an organic phosphite and/or an epoxy
compound (often an epoxidised oil) which enhance the main stabilising
action and improve the weathering resistance of the composition. The
epoxy compound also has a plasticising action, which may be
significant in some rigid formulations, e.g. bottle compounds. Some
proprietary BalCd and BalCd/Zn stabilisers include the synergistic
co-stabilisers as part of the system. Both types of basic system offer
good heat stability and colour control, and good light stability (when
the co-stabilisers are incorporated). Clear compounds can be formu-
lated with the liquid BalCd systems; the soap-based and zinc-
containing systems have an opacifying effect and are thus more suited
to translucent or opaque compositions. Although effective and
versatile, the systems are not without their limitations: the presence of
cadmium makes them susceptible to sulphide-staining (through the
formation of yellow cadmium disulphide on contact with sulphur
compounds) although this is counteracted by the presence of zinc in
those of the systems which contain it: 'plate-out' can occur in the
processing of compositions stabilised with these systems (i.e. the
formulation of sticky deposits on the working surfaces of processing
equipment-see Chapter 9); cadmium-containing systems are not
92 W. V. Titow

suitable for food-contact applications and other end-uses (e.g. medical

equipment) where potential toxicity is a problem-other combined
metal salt systems (usually in conjunction with epoxy compounds) are
used in such cases (see below).

TIN STABILISERS
These are organotin compounds, comprising methyl, butyl, octyl and
lauryl tin derivatives, and including also the relatively recent 'estertins'
(see Chapter 9); some contain mercaptan or thio groups (and hence
are usually referred to as 'tin mercaptides' or 'thiotins'), and others
sulphur-free groups derived from carboxylic acids (the tin 'carboxy-
lates'). The tin compounds (and, within this group, especially the
thiotins) are the most effective heat stabilisers for PVC, both flexible
and rigid, imparting a high degree of initial and long-term stability, and
outstanding clarity to transparent compounds (particularly important
in, for example, packaging film and bottles). Their limitations are:
relatively high cost, comparatively poor light stability of thiotin-
stabilised compounds, and toxicity, although a few tin stabilisers are
permitted for food-contact uses (see Chapter 9). The thiotins can also
impart odour to PVC compositions and cause sulphide cross-staining
with heavy-metal stabilisers or pigments.
Note: Some antimony mercaptide stabilisers are also available.
Whilst generally similar in their action (and limitations) to the
tin stabilisers, they can be more economical in some
formulations, but also make compositions somewhat more
prone to sulphide cross-staining, and less stable to photo-
degradation. The use of calcium stearate in conjunction with
antimony mercaptide stabilisers increases heat stability
through a strong synergistic effect.

NON-TOXIC STABILISERS
These must be used in products for food-contact and medical
applications, e.g. flexible and rigid PVC packaging films, PVC bottles,
flexible PVC medical tubing, and hose used in food processing. The
relevant regulations and directives (and-in cases of doubt-the official
bodies concerned) should always be consulted when formulating
non-toxic compositions, as the requirements and restrictions applicable
can differ with the application, and from country to country. As has
been mentioned, some tin stabilisers are permitted (with limitations, in
 4 Elementary Principles of pvc Formulation 93

some countries, on the percentage present in the formulation, and the

amount extractable) for food-contact uses (see Chapter 9). Systems
consisting of combinations of organic salts of calcium and magnesium,
calcium and zinc, or calcium, magnesium and zinc, may also be used,
commonly in conjunction with an epoxy compound (which here
improves heat as well as light stability, and provides some plasticisa-
tion) and-where appropriate-also permitted antioxidants. Some
esters of aminocrotonic acid are permitted food-contact stabilisers in
several countries.
Note: Calcium stearate, regarded for some purposes as a non-toxic
stabiliser, is used in certain compositions (e.g. pastes for
dip-coating applications) which are not primarily intended for
non-toxic end-uses.

NON-METALLIC (ORGANIC) STABILISERS

The materials which may be grouped under this heading are the
already mentioned epoxy compounds and organic phosphites, most
commonly used as auxiliary, synergistic stabilisers with some metal
stabiliser systems. The epoxy compounds are very often epoxidised oils
(e.g. epoxidised soyabean oil), but epoxidised esters and some epoxy
resins can also be used (see also Chapter 9).

(c) Plasticisers
As has been mentioned, plasticisers convert the hard, inherently brittle
PVC resin into compositions of varying degrees of softness and
flexibility, processable into a variety of products with divers properties
and uses (determined to a large extent by the nature and amount of
plasticiser(s) present). Plasticisers and their effects in PVC are
discussed in several chapters of this book (in particular Chapters 5 to
7): because these chapters cover the subject thoroughly, and because
of its complexity and extent, only the most basic, general pointers are
given in the present section.
The proportion of plasticiser in a pPVC composition is always fairly
substantial, and may be very high in very soft materials. For this
reason cost considerations are particularly important in plasticiser
selection. In the absence of special processing and/or service
requirements which may dictate the choice (see below) the formulator
will normally consider first a relatively inexpensive, general-purpose
plasticiser. In most cases this will be a phthalate, very often dioctyl
94 W. V. Titow

phthalate (DOP) which offers good all-round compound properties.

Several phthalates (including DOP) are primary plasticisers, that is
they are highly compatible with PVC resins (in proportions of 100 phr
and over). The cost of phthalate-plasticised formulations (and some
containing other plasticisers) can often be reduced by replacing part of
the main plasticiser by an extender: This is frequently a chlorinated
hydrocarbon which, additionally, has a flame-retardant effect-a useful
feature because substantial plasticisation with phthalates increases the
flammability of PVC compositions (cf. Chapters 11 and 12). Triaryl
phosphate plasticisers (which also act as flame retardants) are the
second most important group of common, primary plasticisers;
however, a triaryl phosphate will rarely be used as the sole plasticiser,
since the low-temperature properties (cold flex, toughness) of its
compounds with PVC resins are comparatively poor. This may be
corrected by the inclusion of a phthalate plasticiser (in adequate
proportion) or-where a stronger effect is required-of an aliphatic
diester plasticiser which imparts particularly good low-temperature
properties. In general, when more than one plasticiser is used, the
properties of the PVC composition will represent a combination of
those normally conferred by each individual plasticiser when present
alone. This is an important feature of plasticiser action, widely utilised
in formulating PVC compositions.
Even within the phthalate group (the largest both in terms of
number of members and usage volume) some plasticisers are
particularly associated with the special properties they promote in the
compound. For example, butyl benzyl phthalate (BBP) is one of the
best solvating, quickest fusing, plasticisers for PVC (and thus promotes
rapid and easy processing of its compositions); it also imparts
particularly good stain resistance to PVC films and surfaces. Ditridecyl
phthalate has a particularly low volatility (for a phthalate) and hence a
high degree of permanence in compounds (useful, for example, in
high-temperature cable coverings). For particularly high levels of
certain properties, beyond what is available even with the best among
general-purpose plasticisers, recourse must be had to other, special
plasticiser types. Selected representatives of these types (all more
expensive, as a rule, than general-purpose plasticisers) are used in
PVC compositions where the particular property or group of properties
they contribute is of special importance. Such special uses are
indicated, in a general way, in the outline summary of plasticiser
effects in Table 4.1. Table 6.1 in Chapter 6 provides a guide to the
 4 Elementary Principles of pvc Formulation 95

main advantages and limitations of major types of plasticiser relevant

to their usage.

(d) Lubricants
The functions of lubricants in PVC compositions are:
(i) to reduce the friction at, and adhesion to, working surfaces
when the composition is being processed (external lubrication);
and/or
(ii) to lower the inter-particle and inter-molecular friction in
processing (internal lubrication); this reduces the effective melt
viscosity and heat build-up.
Some lubricants discharge only, or mainly, one of these two
functions and are, accordingly, referred to as internal or external
lubricants; others act in both ways. The main factor determining the
type of lubricant action is the lubricant's compatibility with PVC: a
true external lubricant is poorly compatible, and a good internal
lubricant highly compatible with the resin. Chemical compounds used
as lubricants include paraffins, paraffin oils, polyethylene waxes, fatty
acids, fatty acid amides and esters, fatty alcohols, and metal soaps.
Lubricants must be used in uPVC compositions (for both internal and
external effects: two or even more lubricants are often combined, up to
a total content of about 3 phr) , and are beneficial in many plasticised
compositions (in amounts within the range O· 2-1' 5 phr) mainly for
external lubrication, as much of the internal function is discharged by
the plasticiser. The nature and amount of lubricant(s) used in a
formulation depend critically and in a complex way on several factors,
viz. the other components (see below), the processing to be undergone
by the composition (the correct choice is particularly important in
many calendering compositions), and any subsequent treatments (e.g.
films to be printed must have no exuded external lubricant on the
surface). Possible interaction or co-action with other constituents of
the formulation, especially the stabiliser(s), is a most important
consideration in the choice of lubricant(s) and the amount(s) to be
used. For example, some stabilisers have a lubricant action, and/or
benefit from synergistic co-action with certain lubricants, whilst some
lubricants also exert a stabilising effect; more lubricant may be
necessary in compositions highly loaded with fine-particle fillers
(because of absorption effects), but relatively less if the filler is
surface-coated with a stearate (see Chapter 8); the degree of
 ~

TABLE 4.1
Some General Features of Plasticiser Usage
Characteristics required Typically relevant plasticiser type(s) Examples of application ~
:<:::
Price economy Selected phthalates, extenders Wide range of cheaper-grade com- :::J
positions for various purposes o~
Important features of behaviour of plasticiser
in composition:
(a) High compatability with PVC resin Many phthalates, triaryl phosphates Very soft, flexible products, including
(i.e. suitability for use in high propor- paste mouldings and coatings
tions in a composition)
(b) Permanence (low volatility, resistance Polymeric plasticisers; Shower curtains, upholstery; gaskets
to extraction and migration in com- for some purposes:
positions) trimellitates,
high molecular weight
phthalates,
solid blending resins (e.g.
chlorinated PE, EVA
copolymers, nitrile rubber)
Processing properties:
(a) Ease of solvation, fusion, and gelation BBP,DBP, Foamed coatings
triaryl phosphates,
phthalates
(b) Effect on viscosity of pastes:
low viscosity Aliphatic diesters and extenders
high viscosity BBP, DBP, triaryl phosphates,
~
polymeric plasticisers
End-use properties imparted to compositions:
(a) Good colour Phthalates Clear compositions
(b) Good chemical resistance Polymeric plasticisers Protective clothing f
is
(c) Good low-temperature properties Aliphatic diesters (sebacates, Tarpaulins, flexible tubing for use in ~
adipates, AGS esters) cold conditions
(d) Electrical properties ?-
(")

high resistivity Triaryl phosphates ~

~
low resistivity Sebacates
(e) Food-contact applications Individual plasticisers (high purity Packaging films .5;,
grade) as permitted by relevant
authorities ~
(f) Mechanical properties ~
high tensile strength Triaryl phosphates ~
I::
high extensibility Sebacates i:>
5'
;::s

~
98 W. V. Titow

compatibility of a lubricant with the processing aid and/or impact

modifier in a uPVC composition will affect the choice of type and
proportion of the lubricant. Suppliers provide lubricant systems,
including 'single-pack' stabiliserllubricant combinations, for most types
of PVC compositions, and even a highly skilled formulator can benefit
from their advice.
Lubricants and their uses are discussed in more detail in Chapter 11,
Section 11.1.

(e) Polymeric Modifiers

The polymeric additives used in PVC compositions fall into two broad
functional groups: processing aids and impact modifiers.

PROCESSING AIDS
The polymers used in this capacity improve the melt-processing
characteristics of PVC compositions (rapidity of homogenisation and
fusion) and the properties of the melt (melt strength, cohesion and
elongation are increased; in many cases the melt modulus is reduced),
but they also usually increase the melt viscosity (which is already high
in uPVC compositions): some can also have an external lubricant effect
(lubricating processing aids). At their usual levels of incorporation
(1-6 phr) processing aids do not significantly affect the end-use
properties of the composition.
The processing aids in commercial use may be broadly grouped
under the following headings:
(i) acrylic polymers (acrylates and methacrylates);
(ii) styrene copolymers (with acrylonitrile or certain methacrylates).
Both these general groups contain many proprietary products with
varying applicability in different types of composition. The recom-
mendations of a reputable supplier should, therefore, always be
considered. Poly-a-methylstyrene and some ABS terpolymers are also
used as processing aids (the former can, inter alia, actually reduce the
melt viscosity of a uPVC composition).

IMPACT MODIFIERS
The main function of these additives is to improve the toughness
(resistance to impact at room and low temperatures) of uPVC
compositions, in which they are usually incorporated in proportions of
5 to about 15 phr (the use and effects of impact modifiers are discussed
 4 Elementary Principles of pvc Formulation 99

in more detail in Chapter 11, Section 11.2). In most cases there is also
some processing-aid action, but this may be significant only at
processing temperatures higher than those at which regular processing
aids exert their effect. Some types of impact modifier (e.g. (iv), (v),
and certain kinds of (vii) below) are highly compatible with PVC and
may be incorporated in high proportions, to act as plasticisers (see
Chapter 11, Section 11.2). Commercially available impact modifiers
are polymers of the following types:
(i) acrylonitrile/butadiene/styrene terpolymers (ABS);
(ii) methacrylate/butadiene/styrene terpolymers (MBS);
(iii) modified acrylic polymers;
(iv) ethylene/vinyl acetate copolymers (EVA) and graft copolymers
of vinyl chloride and EVA (EVAIVC);
(v) nitrile rubber (butadiene/acrylonitrile copolymers);
(vi) polyurethane elastomers;
(vii) chlorinated polyethylene (various degrees of chlorination).
While the impact modifiers find their main application in uPVC
compositions (although some, as just mentioned, may be used-in
large proportions-to act as plasticisers), some (notably certain ABS
types) may be incorporated in semi-rigid and even flexible compounds,
not primarily to contribute to toughness, but to improve melt strength
in processing, emboss retention and thermoforming properties of sheet
(where they can also reduce post-forming shrinkage).
In some types of composition very high proportions of a polymeric
modifier are included. Thus up to about 100 phr of particular
processing aids, or modified ABS or MBS impact-modifier systems,
may sometimes be used to improve the heat distortion properties of
the material (the heat deflection temperature under load at 1·82 MPa
may be raised by about 15°C in comparison with that of an unmodified
lkt otherwise similar uPVC composition). Some flexible compositions
may actually contain more of an ABS polymer than PVC resin, so that
the latter may be regarded as a modifier for the former (see Chapter
11, Section 11.2).

(f) Fillers
The use of fillers in PVC is discussed in some detail in Chapter 8, and
referred to in other parts of the book in connection with various filled
compositions and products. Only the most basic points relevant to the
role and application of fillers in PVC formulations are briefly
100 W. V. Titow

TABLE 4.2
Effect of Particulate FiBer Content on Tensile Strength (Ibfin- z) of pPVC

Parts by weight
Filler 0 10 20 30 40 50 60
Precipitated
whiting 1700 1420 1350 1200 920 750 510
Hard clay 1700 1780 1710 1450 1200 890 1110
Carbon black 1700 1900 1920 1550 1750
Omya BSH 1700 1615 1590 1580 1370 1250 1070

mentioned here. In many compositions a filler is included principally to

reduce material cost: in such 'extender' applications the filler is
nowadays normally some form of particulate calcium carbonate. When
present in a substantial amount this filler will-as will virtually all
mineral fillers in plastics generally-affect some physical properties of
the PVC composition: the common effects are reduced tensile strength
(see Table 4.2), elongation at break, moulding shrinkage and thermal
expansion coefficient, and increased hardness. A particularly important
point concerning the general effects of mineral fillers in plastics
compositions, including PVC, is that even at loadings which in many
cases do not bring about substantial changes in other properties, the
density of the composition may increase significantly; it will also
continue rising with further increases in filler content. Since the
compositions are sold on a weight basis (whilst ultimately used, in the
form of products, on a volume basis-see Section 4.3 above), the
overall material cost saving may drop progressively (in some cases
quite rapidly) with increased filler loading.
Note: e.g., if a given volume of product (say a moulding) weighs
1 kg when produced from a compound of density 1·1 gcm- 3 ,
the weight of compound of density 1·4 g cm -3 needed to
produce it will be 1·4/1·1 = 1·27 kg (to the second decimal
place).
Typical applications of calcium carbonate in plasticised PVC include
its use in electrical cable coverings (insulation and sheathing), moulded
footwear (especially the cheaper qualities), moulding compounds for
toys, some grades of sheeting and fabric coatings (in the latter two
applications plasticiser exudation can be reduced, and some improve-
ment in weathering promoted, by the presence of the filler). In
 4 Elementary Principles of pvc Formulation 101

unplasticised PVC products calcium carbonate fillers are used at

relatively lower loadings in most cases. The biggest outlets are in rigid
pipes and profiles, and in flooring.
Over the years, calcium carbonate fillers have largely displaced clay
fillers in most applications primarily because of the cost advantages
they offer in virtually every case. Clays are still used, however, in
certain special electrical insulation compounds, where-at loadings of
about 5-15 phr-they benefit the insulation properties. Their generally
low pigmentation effect (due to a refractive index closely approaching
that of many PVC compositions) can also be an advantage in some
cases. Some effects of an electrical grade of clay filler on the properties
of a PVC composition are shown in Table 4.3.

TABLE 4.3
Some effects of a Clay Finer in a pPVC Composition
Resin
Di-2-ethyl hexyl phthalate 100
50 } Parts by
Filler Composition a Tribasic lead sulphate 7 weight
content Paraffin wax 1
and Filler: M 501 b As stated
properties
M501 (phr) Nil 5 10 15 20 30 40 50
T~nsile strength 2500 2500 2500 2500 2400 2500 2400 2500
(lbfin- 2)
Modulus 100%
extension (lbf in -2) 1500 1700 1800 1900 2000 2200 2300 2400
Elongation at break
(%) 300 280 270 250 230 170 170 120
Tear strength (lb in-I) 1200 1300 1400 1400 1400 1400 1500 1500
BS softness No. 38 32 32 30 29 28 26 23
Volume resistivity,
conditioned x 1014
(23°C, 65% RH) 0·3 11 13 15 13 12 8 6
Volume resistivity
(Qcm x 1014 ,
24 h immersion) 0·2 3 6 7 7 6 4 2
Volume resistivity at
60°C x 1012 0·6 50 90 110 100 90 70 60
a Compounding and testing was carried out according to the procedure laid
down in BS 2571: 1955.
b Calcined clay for electrical applications: English China Clays International
Ltd.
102 W. V. Titow

In so far as a generalisation can be made, it is useful to remember

that with particulate fillers the larger the particle size the greater the
reduction of surface gloss of the composition, the higher the water
absorption and the tendency to 'stress whitening' (see Chapter 8).
However, the finer the filler the greater the plasticiser demand and the
tendency to absorb lubricants except where t.he particles are effectively
surface-coated (see Chapters 8 and 11).

(g) C%urants
A colourant must be able to discharge its function-Leo to impart the
desired colour, in adequate strength, to the PVC-when present in a
relatively low proportion (normally up to a few phr at most). The
colourants used in PVC may be broadly divided into pigments and
dyes. The pigments are fine-particle materials, intimately dispersible-
but not soluble-in the PVC composition: for this reason they have an
opacifying effect and are resistant to migration (with the partial
exception, in some circumstances, of certain lake pigments and organic
pigments appreciably soluble in plasticisers-see below). Dyes are
colourants soluble (Le. dispersible on a molecular level) in PVC
compositions: they are thus non-opacifying (and hence suitable for
transparent compounds) but, in general, rather prone to migration.
From the standpoint of their chemical nature, dyes are organic
compounds, whilst the pigments fall into three main groups: inorganic
compounds (mainly metal oxides), lakes (dyestuffs precipated onto
inorganic compounds, which act as bases or carriers in this combina-
tion), and organic compounds. In addition carbon black may be
regarded as forming a 'group' on its own; metal powders (usually
aluminium) are also occasionally used to impart a metallic colour
effect. The chemical composition, classification and properties of
colourants are discussed in Chapter 11, Section 11.3.
Colourants of the inorganic pigment group are the most widely and
commonly used in PVC: many of these combine good all-round
resistance and high colour value with relatively moderate cost. Inter
alia the group includes titanium dioxide ('Titanium White'), the
pigment universally employed for white compositions, and also
frequently incorporated to enhance the colour in coloured PVC
materials.
Completeness of colourant dispersion is of paramount importance
for optimum colour effect in a PVC composition, whilst ease of
handling and dispersibility of the colourant in compounding are equally
 4 Elementary Principles of pvc Formulation 103

important from the point of view of operational efficiency and

economy. Colourants are available in forms particularly suited to these
requirements, viz. as premixed concentrates, or as integral components
of multicomponent 'single-pack' additive systems in which they are
intimately interdispersed with other additives, for direct, joint addition
in the course of compounding a particular type of PVC composition
(See Section 4.4.2 below). A colour concentrate may be a masterbatch
(in which a high proportion of colourant is dispersed in PVC
composition of the same kind as that to be coloured), or a colour paste
in plasticiser(s) suitable for colouring solid plasticised compositions or
pastes, or a concentrated dispersion of colourant in a carrier other than
a plasticiser, compatible with (or useful in) the PVC composition to be
coloured (e.g. a fatty acid, which may serve as lubricant). The
compounding of colourants into PVC, including the preparation of
colour concentrates, is discussed in Chapter 13, Sections 13.4.1(c),
13.4.2(a) and 13.4.3.
It is self-evident that the colourant(s) chosen for a particular
formulation must be suitable for (stable in) the conditions of
processing and ultimate service. The chemical stability of the
colourant, and its colour fastness, to heat and to any potentially
aggressive constituents of the service environment are of particular
importance. Mutual compatibility with, and stability to, the other
components of the formulation (at room as well as elevated
temperatures) is an equally important consideration: in some circum-
stances inorganic pigments (notably iron and zinc compounds) may
promote degradation of the PVC resin-this can happen in the
presence of an acid (even trace quantities remaining in the pigment
itself as residues from the manufacturing process). The dyestuff
components of some lakes, as well as some organic pigments, may be
sufficiently soluble in plasticisers for migration or blooming to occur in
some plasticised compositions. Colourant manufacturers are, as a rule,
very technically minded and their advice on specific formulation
problems is both readily available and worth having.

4.4.2 Interactions and Mutual Effects of Formulation Components

Most PVC compositions are complex, multicomponent systems. In

addition to the interactions involved in the components' exercising
their primary functions in accordance with the formulation (i.e.
plasticisation of the PVC resin by the plasticiser(s) and its stabilisation
104 W. V. Titow

by the stabiliser(s); lubrication of the composition by the lubricant(s);

etc.), the components can also interact in certain other ways. This
section gives a brief, general indication of the kinds of such secondary
interactions which the formulator should take into account: more
detailed discussion of some of their aspects will be found in other
chapters.

(a) Compatibility Effects

As has been mentioned, it is a cardinal general requirement that the
components of a formulation should be compatible with one another in
both processing and service conditions.
Possible effects of one component on the mutual compatibility of
some of the others should also be borne in mind. For example, the
compatibility of an external lubricant with the PVC resin (which should
be relatively limited, for the lubricant to exercise its function properly)
may be increased by the presence of plasticisers or certain polymeric
modifiers: more external lubricant will then be required in the
particular formulation than in a comparable one where the effect does
not arise (cf. Chapter 11, Section 11.1.2). Similarly, the presence in the
composition of an appreciable quantity of fine-particle filler (or
pigment) able to absorb plasticisers or lubricants may necessitate the
inclusion of these additives in proportions higher than would otherwise
be required, whilst the use of a surface-coated grade of the same filler
(with absorptivity reduced by the coating) would obviate the need for
such compensatory increase (cf. Chapter 8, Section 8.3.3., and Chapter
11, Section 11.1.2).

(b) Synergism
The action of some stabilisers can be synergistically enhanced by
certain other stabilisers or lubricants. Examples are: the effect of
organic phosphite and epoxy co-stabilisers on the heat stability and
resistance to weathering of PVC stabilised with certain stabilisers
(especially BalCd-see Section 4.4.1(b) above, and Chapters 9 and
10), and the synergism of glycerol ester lubricants with sulphur-
containing tin stabilisers, or that of calcium stearate lubricant with
antimony mercaptide stabilisers (see Chapter 11, Section 11.1.2(a)).

(c) Other Mutual Effects

Noteworthy examples are: the activating effect of some stabilisers on
blowing agents in the production of cellular PVC materials (see
 4 Elementary Principles of pvc Formulation 105

Chapter 25, Section 25.3), and discoloration which may result through
interaction of some lead stabilisers with impurities in lubricants of the
glycerol ester type (cf. Chapter 11, Section 11.1.2(a)), or through the
interaction of sulphur-containing tin stabilisers with lead-containing
pigments (due to formation of coloured sulphides).

4.4.3 Side Effects of Formulation Components

Some constituents of a PVC composition can, in addition to the

function for which they are incorporated, also exert effects which are
the primary functions of other constituents; undesirable side effects
may also arise. The following examples illustrate some of the effects in
each category.

(a) 'Secondary Functionality' Effects

Such effects are illustrated and exemplified by the following:

(i) Stabilising action of some lubricants and lubricant action of

certain stabilisers (both permitting the use of the other
component in proportions lower than would otherwise be
necessary-see Section 4.4.1(d) above and Chapter 11, Section
11.1.2(a)).
(ii) Flow-promoting action (Le. processing-aid effect) of some
polymeric impact modifiers (see Section 4.4.1(e) above and
Chapter 11, Section 11.2).
(iii) Internal lubrication by plasticisers, and their impact-modifying
effects.
(iv) External-lubricant effect of some plasticisers and extenders (see
Chapter 11, Section 11.1.2).
(v) Flame-retardant effect of phosphate plasticisers and chlorin-
ated compounds used as plasticiser extenders (d. Section
4.4.1(c) above; Chapter 7, Section 7.6; Chapter 11, Section
11.5; and Chapter 12, Section 12.10).
(vi) Stabilising action of epoxy plasticisers (cf. Section 4.4.1(b)
above; Chapter 6, Section 6.10.1; and Chapter 9, Section 9.6)
(vii) Light-stabilising effect of carbon black, the universal black
pigment in many plastics compositions, including some PVC
materials (see e.g. Chapter 8, Section 8.4.3 or Chapter 11,
Section 11.3).
106 w. V. Titow

(b) Undesirable Side-effects

Examples of such effects include:

(i) Opacification effects of fillers, many impact modifiers and other

formulation components, which must be considered when
formulating clear compositions.
(ii) Susceptibility to 'sulphide staining' (through formation of
coloured sulphides) associated with the presence of stabilisers
which are heavy-metal compounds (especially lead and cad-
mium-see, for example, Section 4.4.1(b) above, and Chapter
9).
(iii) Detrimental effect of emulsion PVC polymer on the electrical
resistance of compositions based on this type of polymer (cf.
Section 4.4.1(a) above and Chapter 2).
(vi) Lowering of heat stability of PVC compositions by most
antistatic agents (ct. Chapter 11, Section 11.4).
(vii) Tendency to 'stress whitening' promoted by the presence of
some fillers (see Chapter 8, Section 8.3.3) and polymeric
modifiers (see Chapter 11, Section 11.2).

4.5 SOME SPECIAL END-USE REQUIREMENTS

Some end-use requirements may be described as special in that they

dictate, or preclude, the incorporation of certain components in a PVC
formulation. This kind of requirement may be illustrated by the
following examples.

4.5.1 Food-contact Applications (e.g. food-packaging films; bottles)

Non-toxicity of all formulation components is a prime requirement in

such applications. Stabiliser choice will in practice be limited to
selected di-n-octyl tin stabilisers (especially where the highest clarity is
a requirement) and stabiliser systems comprising compounds of
calcium, zinc and magnesium. Plasticisers, and all other components,
should be checked with current lists of permitted materials published
by organisations concerned with the health and safety aspects of
 4 Elementary Principles of pvc Formulation 107

plastics products (ct. Chapter 7, Section 7.12 and Chapter 12, Section
12.9), or-in cases of doubt-directly with such organisations.

4.5.2 Resistance to Weathering

This is of paramount importance in such PVC products as rainwater

goods, window frames, cladding, fencing, films for reservoir or
swimming-pool lining, tarpaulins and the like. Particular heat stabiliser
systems, normally incorporating synergistic co-stabilisers of the epoxy
type with chelators, are highly relevant here (see Section 4.4.1(b)
above; Chapter 9; and Chapter 12, Section 12.6), and-among lead
stabilisers-dibasic lead phosphite (see Chapter 9). Ultra violet
absorbers are also widely used in weathering-resistant formulations.
Polymeric modifiers in rigid products (e.g. rain guttering and
down-pipes, window frames) should be of the type which detracts least
from good weatherability, such as VClEVA copolymers or selected
acrylic modifiers (alternatively the PVC resin used may be a VClEVA
graft copolymer-see Chapters 1 and 2).

4.5.3 Electrical Insulation

The use of emulsion PVC polymer is precluded in this application (see

Section 4.4.3(b)(iii) above, and Chapters 1 and 2) because of the
deleterious effect of the trace impurities it contains upon electrical
resistivity (and hence insulation value). Lead stabilisers are the first
choice (for the stabilisation of all but transparent compositions)
because they are electrically non-conductive. For insulation and cable
covering resistant to high temperature selected plasticisers must be
used (ct. Chapter 7, Section 7.5.3 and Chapter 12, Section 12.3).

4.6 EXAMPLES OF BASIC FORMULATIONS

The following examples illustrate something of the principal features of

basic outline formulations for some PVC products of the main groups
listed in Table 1.1, Chapter 1.
108 W. V. Titow

4.6.1 Film and Sheeting

(i) Calendered clear uPVC: food packaging grade:

PVC polymer (S* or Mt, K value 60) 100
Stabiliser: a di-n-octyl tin (e.g. Irgastab 17 MOL- 1·1-1·5 phr
Ciba-Geigy)
Lubricants:
Internal: fatty alcohol type (e.g. Irgawax 365- 1·2-2·0phr
Ciba-Geigy)
Internal/external: fatty acid ester type (e.g. 0·2-0·5 phr
Irgawax 370)
If an impact modifier is included it should be of the MBS type (and
fully compatible with the lubricant system) to maintain transparency.
For maximum clarity the polymer should be of high-purity, fish-eye free
grade.

(ii) Calendered clear or pigmented uPVC with good stability to light:

technical grade:
PVC polymer (M or S, K value 60) 100
Stabiliser: a dibutyl tin maleate chosen for both l'5-2'Ophr
good heat and light stability (e.g.
Irgastab 1'9)
UV absorber: (light stabiliser, e.g. Tinuvin 320- 0·2-0·3phr
Ciba-Geigy)
Lubricants:
Internal: fatty alcohol type 1·0-1·2 phr
Internal/external: fatty acid ester type 0·2-0·4phr
If titanium dioxide pigment is included its presence may further
improve stability to light.

(iii) Extruded (blown) clear uPVC film: non-toxic grade:

PVC polymer (M or S, K value 57-60) 100
Stabiliser: a di-n-octyltin (e.g. Irgastab 17 MO) 1·1-1·5 phr
Lubricants:
Internal: a glycerol monoester (e.g. Irgawax 361) 0·5-0·8 phr
Internal/external: fatty acid ester type (e.g. 0·5-0'8 phr
Irgawax 370)
* Suspension type. t Mass type.
 4 Elementary Principles of pvc Formulation 109

Processing aid: an acrylic polymer (e.g. Aeryloid 0·8-2·0 phr

K-120N-Rohm and Haas)
(iv) Calendered, clear pPVC with good stability to light: general-
purpose and horticultural applications:

PVC polymer (S or M, K value 69-72) 100

Stabiliser: BalCd liquid (e.g. Irgastab BC 26) 1·3-1·6 phr
Co-stabilisers: epoxidised soyabean oil 5 phr
an organic phosphite (chelator) 0·4-0'5 phr
Plasticisers: DOP 55 phr
triaryl phosphate 10 phr
UVabsorber: (light stabiliser, e.g. Tinuvin P) 0·2-0·3 phr
External lubricant: stearic acid 0·2-0·4 phr
(v) Extruded (blown) filled pPVC film: industrial grade:
PVC polymer (S or M, K value 68-71) 100
Stabiliser: a BalCd soap complex (e.g. Irgastab 0,9-1,8 phr
BC 247)
Co-stabiliser: an organic phosphite (e.g. Irgastab 0'3-0'6phr
CH301)
Plasticiser: DOP 42phr
Plasticiser extender: chlorinated paraffin 13phr
(50-52% CI)
Filler: whiting (a coated grade) 40phr

The barium/cadmium soap stabiliser has some external lubricant action

in this composition, so additional external lubrication may not be
necessary. Otherwise about 0·3 phr of stearic acid may be added. It is
good practice to use a chelating co-stabiliser with solid Ba/Cd
stabilisers (in the respective proportions of 1 to 3) to improve the
initial colour and light stability of the composition.

4.6.2 Calendered Plasticised Vinyl/Asbestos Flooring (Tiles)

Vinyl chloride/acetate copolymer (K value 55, 100

13-15% VA)
Stabiliser: a CalZn complex powder (e.g. Irgastab 2'0-4'Ophr
CZ45M)
Co-stabiliser: epoxidised soyabean oil 6·0-8·Ophr
Plasticiser: DOP 15 phr
External lubricant: stearic acid 1·0-2·Ophr
110 w. V. Titow

Pigment: titanium dioxide 10-15 phr

Fillers: asbestos (chrysotile) 100phr
whiting 160phr
Special grades of solid calcium/zinc complex stabilisers are produced by
most manufacturers for vinyl/asbestos flooring compositions. These
stabilisers combine good compatibility with VCNA copolymer and
asbestos, with very good heat stabilisation (even when a substantial
proportion of scrap is added to the compound) and freedom from
sulphide staining of the flooring in contact with rubber objects in
service. They have no appreciable lubricating action; an external
lubricant should, therefore, be included in the formulation; stearic acid
is particularly useful since, in addition to its lubricant effect it can also
enhance stabilisation. The amount required will normally increase with
increasing calcium carbonate filler loading (as well as when substantial
amounts of pigment are incorporated): 0·1 phr stearic acid per 8 phr
filler may be taken as a general guideline (but with surface-coated filler
grades the effect of the presence of the coating should be taken into
account-see Chapter 11, Section 11.1.2).

4.6.3 Pipe and Tubing

(i) Rigid pipe:

PVC polymer (S or M, K value 66) 100
Stabiliser: a thiotin complex 2phr
Lubricants:
Internal: glycerol monoester of a fatty acid (e.g. 1·2 phr
a mono-oleate, Loxiol Glo-Henkel)
External: ester wax (e.g. Irgawax 360) 0·6phr
Pigment, colourant and calcium carbonate filler (a precipitated, coated
grade) may be included.

(ii) Clear, ftexibile tubing (non-toxic-for medical use):

PVC polymer (S or M, K value 65-70) 100
Stabiliser: Ca/Zn type 1·5-2·0 phr
Co-stabiliser: epoxidised soyabean oil 2 phr
Plasticisers: DOP 10 phr
high molecular weight polyester (e.g. 37 phr
Reoplex 43O-Ciba-Geigy)
Lubricant: a glycerol monoester (e.g. Loxiol GIO) 0·0-0·6 phr
 4 Elementary Principles of pvc Formulation 111

4.6.4 Cable Covering and Insulation

(i) General-purpose cable sheathing:

PVC polymer (S or M, K value 68) 100
Stabiliser: basic lead carbonate 5phr
Plasticiser: DIOP 52phr
Plasticiser extender: chlorinated paraffin (50- 32phr
52% CI)
External lubricant: dibasic lead stearate 0·5-1·0phr
Filler: whiting (a coated grade) 40phr

(ii) High-temperature cable compound:

PVC polymer (S or M, K value 68) 100

Stabiliser: dibasic lead phthalate 7phr
Plasticiser: tri-Linevol 79 trimellitate (e.g. Reomol 70phr
LTM-eiba-Geigy)
External lubricant: calcium stearate 1phr
Flame retardant: antimony trioxide 6phr

In this composition calcium stearate contributes to heat stabilisation

whilst acting as lubricant. Di-tridecyl phthalate (DTDP) may be used
as plasticiser instead of the more expensive trimellitate for all but the
most severe conditions (but the efficiency of the latter is better, so that
a lower proportion is required, and trimellitate-plasticised composi-
tions retain their properties better after heating at high temperatures).
An antioxidant is desirable, especially if the compound is to be used in
thin sections. Reomol LTM already contains 0·2% of an effective
antioxidant (Irganox 1010).

(iii) General-purpose insulation:

PVC polymer (S or M, K value 68) 100
Stabiliser: basic lead carbonate 7phr
Plasticiser: DIOP 30phr
Plasticiser extender: chlorinated paraffin (50- 30phr
52% CI)
External lubricant (with stabilising action): 1·3 phr
calcium stearate
Filler: whiting (a coated grade) 70phr
112 W. V. Titow

4.6.5 Gramophone Records

Vinyl chloride/acetate copolymer (K value 47-S0, 100

lS% VA)
Stabiliser: tetrabasic lead fumarate 1·S-1·7phr
Lubricant: a compound or system with mainly 0·2-0·3 phr
external action
Pigment: carbon black 1·0-1·S phr
A copolymer resin is used for ease of processing, with low K value for
the best surface-detail reproduction (associated with ease of flow). The
carbon black should be of a sufficiently fine and readily dispersible
grade to meet this important requirement. An antistatic agent is
usually incorporated in the composition: this should be selected inter
alia for minimum effect on thermal stability.

4.6.6 Blow-moulded Bottles

(i) For mineral water:

PVC polymer (S or M, K value S8) 100
Stabilisers: zinc octoate 0·IS-0·20 phr
calcium stearate O·OS-O·lO phr
Co-stabilisers: distearyl pentaerythritol diphosphite 0·4-0·S phr
epoxidised soyabean oil 3·0 phr
Impact modifier: MBS type 10·0 phr
Processing aid: acrylic type O·S-1·0 phr
All additives in a formulation for this purpos~ must be of special purity
grade (as well as permitted for food contact) because mineral water
picks up taints easily. For the same reason the use of permitted
organotin stabilisers is not recommended. The epoxy co-stabiliser has
some plasticising action. If the lubricating effect of the calcium stearate
is not sufficient in a particular moulding process lubricant(s), best
suited to the conditions, should be incorporated.

(ii) General purpose, clear:

PVC polymer (S or M, K value 54-58) 100
Stabiliser: liquid thiotin 1·4-1·6phr
Impact modifier: MBS type 10-12 phr
 4 Elementary Principles of pvc Formulation 113

Processing aid: acrylic type 1-2 phr

Lubricant (internal/external): fatty acid ester type 1·0-1·5phr

4.6.7 Injection Mouldings

(i) uPVC pipe fitting:

PVC polymer (S or M, K value 55-60) 100
Stabiliser: a solid dialkyl tin mercaptide (e.g. l'0-2'Ophr
Irgastab 1'270)
Impact modifier: ABS type 8-lOphr
Processing aid: acrylic type 1·5-2·5 phr
Lubricants:
Internal/external: calcium stearate 0·8-1·0 phr
fatty acid ester type O·5-1·0 phr
External: polyethylene wax 0·05-0·1 phr
Pigment: titanium dioxide 3 phr
Colourant: phthalocyanine type 0·02-0·03 phr
In rigid injection-moulding formulations for components which may be
stressed in service it is advisable to keep liquid additives to a minimum,
as they can lower heat distortion temperature.

(ii) Clear, plasticised compound:

PVC polymer (S or M, K value 65-67) 100
Stabiliser: liquid Ba/Cd/Zn (e.g. Irgastab BC 206) 1,5-2·5 phr
Co-stabiliser: epoxidised soyabean oil 5phr
External lubricant: liquid, non-polar type (e.g. 0·3-0·5 phr
Irgawax 360)
The lubricant used should be chosen, inter alia, for its suitability in a
clear formulation.

(iii) Oil-resistant soling compound:

PVC polymer (S, K value 66-70) 100
Stabiliser: solid Ba/Cd 4phr
Co-stabiliser: epoxidised soyabean oil 5phr
Plasticiser: DIOP 80phr
Polymeric modifier: nitrile rubber 33phr
114 w. V. Titow

4.6.8 Extruded Profile

(i) High-impact uPVC:

PVC polymer (S or M, K value 60) 100
Stabilisers: tribasic lead sulphate 6phr
dibasic lead stearate 1 phr
Lubricants (internal/external): fatty acid ester l'9-2'Ophr
type
calcium stearate 0'4-0'8phr
Impact modifier: ABS type 6-10 phr
Processing aid: acrylic type 1·8-2·2phr

(ii) Flexible composition:

PVC polymer (S or M, K value 68-70) 100
Stabiliser: a BalCd soap complex (e.g. Irgastab 1·2-1·5 phr
BC 247)
Co-stabiliser: an organic phosphite (e.g. decyl 0·4-0·5 phr
diphenyl phosphite, Irgastab CH 301)
epoxidised soyabean oil 5 phr
Plasticiser: DOP 47 phr
External lubricant: stearic acid 0'1-0·4 phr
This is a non-transparent composition which may be pigmented. The
BalCd stabiliser provides some lubrication, reinforced as necessary by
the stearic acid.

4.6.9 Paste Formulations

(i) Cold-dipping paste:

PVC polymer (E, * K value 69-72) 100
Stabiliser: basic lead carbonate 2phr
Plasticisers: DOP 65 phr
DOS 17phr

(ii) Conveyor belting:

PVC polymer (E, K value 69-72) 100
Stabiliser: tribasic lead sulphate 2·0-3·0phr
* Emulsion type.
 4 Elementary Principles of pvc Formulation 115

Plasticiser: triaryl phosphate 40phr

Plasticiser extender: chlorinated paraffin (45% CI) 35phr
Flame retardant: antimony trioxide 5 phr
Antistatic agent: e.g. Lankrostat LA3 (Lankro lOphr
Chemicals)

(iii) Composite coating for upholstery fabric:

Base coat
PVC polymer (E, K value 70) 100
Stabiliser: liquid Ca/Zn (e.g. Irgastab CZ 57) 1·5-3·0 phr
Co-stabiliser: epoxidised soyabean oil 5·0 phr
Plasticiser: Dap 85phr
Filler: whiting 20phr
Intermediate (expanded) coat
PVC polymer (E, K value 68-70) 100
Stabiliser/activator: liquid, zinc-containing (e.g. 1·5-2·5 phr
Irgastab ABC 2)
Co-stabiliser: epoxidised soyabean oil 6'0-8'Ophr
Plasticisers: Dap 45phr
BBP 30phr
Blowing agent: azodicarbonamide (paste, 1: 1 2·5-4·5 phr
in Dap)
Filler: fine ground whiting 5phr
The zinc-based stabiliser is selected to act also as an activator ('kicker')
for the blowing agent in this foaming composition. The BBP (butyl
benzyl phthalate) is a highly solvating plasticiser, widely used in PVC
foam formulations for rapid, uniform fusion of the composition.
Top coat
PVC polymer (E, K value 70-72) 100
Stabiliser: liquid BalCd/Zn complex (e.g. Irgastab 1·5-2·5 phr
BC206)
Co-stabiliser: epoxidised soyabean oil 5·0 phr
Plasticiser: DDP 52phr
Pigment: titanium dioxide 0'0-3'Ophr
Filler: whiting 0·0-10·0 phr
Colourant: as required
The stabiliser is one suitable for clear PVC to enable the formulation
to be used for unpigmented, unfilled compositions.