Conductive plastics material and a method for its preparation

The invention relates to a conductive polymer complex which contains a polyaniline or derivative thereof doped with a protonic acid. By the method according to the invention, a conductive polymer is obtained having substantially reduced acidity, sufficiently high conductivity level, and which is suitable, for example, for being melt processed in conventional plastics processing apparatus. The acidity of the conductive polymer can be reduced by having the conductive polymer contain both a metal compound and an additionally neutralizing compound. The obtained conductive polymer material, having a pH value of approximately 3-8, can be mixed with an insulating polymer to produce a conductive plastics mixture. The invention also relates to a method of preparing a conductive polymer that is more processable by incorporating therein a plasticizing agent selected from the group consisting of water, a C.sub.1 -C.sub.3 alcohol, and mixtures thereof.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to an electrically conductive polymer 
material which contains a polyaniline or derivative thereof doped with a 
protonic acid, and a method for its production. By the method according to 
the invention, a conductive polymer material is obtained having 
substantially reduced acidity, sufficiently high conductivity, and which 
is suitable, for example, for melt-processing in conventional plastics 
processing apparatus. 
2. Description of the Related Art 
Electrically conductive polymers are at present subject to great interest 
in different parts of the world. These polymers can be used for replacing 
metal conductors and semi-conductors in a number of applications, such as 
batteries, sensors, switches, light cells, circuit boards, heating 
elements, electrostatic discharge elimination (ESD), and electromagnetic 
interference shielding (EMI). The advantages of conductive polymers over 
metals include their light weight, mechanical properties, corrosion 
resistance, and less expensive synthesis and processing methods. 
Electrically conductive plastics can be divided roughly into two 
categories: filled conductive plastics, in which a conductive filler, such 
as carbon black or soot, carbon fiber, metal powder, etc., is added to a 
thermosetting or thermoplastic resin, and intrinsically conductive 
plastics, which are based on polymers which have been rendered 
electrically conductive by oxidation, reduction or protonation (doping). 
The electrical conductivity of filled conductive polymers is dependent on 
mutual contacts between the conductive filler particles. Usually a well 
dispersed filler is needed in amounts of approximately 10-50 wt. % to 
produce composites having a good conductance. However, such conductive 
composites involve problems: their mechanical and certain of their 
chemical properties are crucially impaired as the filler content increases 
and the polymer content decreases; their conductivity is difficult to 
control, especially within the semiconductor range; and stable and 
homogenous dispersing of the filler into the matrix plastic is difficult. 
Intrinsically conductive plastics can be prepared from organic polymers 
containing long conjugated chains formed by double bonds and heteroatoms. 
The polymers can be rendered conductive by modifying the .pi.- and 
.pi.-p-electron systems in their double bonds and heteroatoms by adding to 
the polymer certain blending or doping agents which will serve as electron 
receptors or electron donors in the polymer. Thereby electron holes or 
extra electrons are formed in the polymer chain, enabling electric current 
to travel along the conjugated chain. 
An advantage of the intrinsically conductive plastics is the ease of 
varying their conductivity as a function of the amount of the doping 
agent, i.e. the degree of doping, especially within low conductivity 
ranges. On the other hand, achieving low conductivities with filled 
conductive plastics is difficult. Examples of currently known 
intrinsically conductive polymers include polyacetylene, poly-p-phenylene, 
polypyrrole, polythiophene and its derivatives, and polyaniline and its 
derivatives. 
There are two principal methods for processing polymers into the desired 
pieces, fibers, films, etc., i.e. melt processing and solution processing. 
Melt processing is a versatile processing method, whereas solution 
processing is suitable mainly for the preparation of fibers and films but 
not profiled pieces. However, the processing and doping of most 
intrinsically conductive polymers involve problems with respect to the 
handling, stability, homogeneity, etc., of the materials. 
Polyaniline, with its derivatives, is in particular a technically and 
commercially promising intrinsically conductive polymer. An aniline 
polymer or a derivative thereof is made up of aniline monomers or 
derivatives thereof, the nitrogen atom of which is bonded to the 
para-carbon of the benzene ring of the subsequent unit. Unsubstituted 
polyaniline may appear in a number of forms, including leucoemeraldine, 
protoemeraldine, emeraldine, nigraline, and toluprotoemeraldine forms. For 
conductive polymer applications, the emeraldine form is generally used, 
having the formula 
##STR1## 
wherein X is approximately 0.5. 
According to state-of-the-art technology, the doping of polyaniline is 
usually carried out by using protonic acids, which include HCl, H.sub.2 
SO.sub.4, HNO.sub.3, HClO.sub.4, HBF.sub.4, HPF.sub.6, HF, phosphoric 
acids, sulfonic acids, picrinic acid, n-nitrobenzoic acid, dichloroacetic 
acid, and polymer acids. Preferably the doping is carried out using 
sulfonic acid or its derivatives, such as dodecylbenzenesulfonic acid 
(DBSA). The protonization is focused on the iminic nitrogen atoms in the 
aniline units according to the formula presented above, which comprise 
approximately 50% of the N atoms of polyaniline. Examples of publications 
in the field include U.S. Pat. Nos. 3,963,498, 4,025,463, and 4,983,322, 
which are hereby incorporated by reference. The doping of polyaniline with 
protonic acids is also widely discussed in the literature in the field. 
U.S. Pat. No. 5,171,478, which is hereby incorporated by reference, 
discloses a method for increasing the molar mass of polyaniline by heating 
the polyaniline until its viscosity has increased. 
U.S. Pat. No. 5,232,631, Which is hereby incorporated by reference, 
discloses processible polyaniline compositions and blends that exhibit 
much lower percolation thresholds, sometimes even below 1% w/w, of 
conductive polyaniline. The patent relates to conductive polymers and 
particularly to the use of functionalized protonic acids to induce 
processibility of electrically conductive polyanilines, and to induce 
solubility of electrically conductive polyanilines in organic liquids or 
fluid (melt) phases of solid polymers. 
However, the processing a doped polyaniline having good conductivity 
properties by versatile melt-processing methods has involved problems, to 
which solutions have been sought. The mixture of polyaniline or a 
derivative thereof and a doping protonic acid is an indefinite, staining, 
strongly corrosive, viscous, fluid or paste-like, dispersion-type material 
which is difficult to handle. A significant improvement to the preparation 
of a polyaniline-based, melt-processable conductive polymer having good 
conductivity and other properties is disclosed in EP Patent Application 
545729, which is hereby incorporated by reference. According to the 
invention disclosed in the said Application, a solid, electrically 
conductive plastics material with good properties is obtained by first 
contacting the polyaniline or a derivative thereof with a doping protonic 
acid and by thereafter heat-treating the reaction product or mixture at a 
temperature of approximately +40.degree. to +250.degree. C. The heat 
treatment results in a change of the above-described preprotonized mixture 
of polyaniline or a derivative thereof and a doping protonic acid, from a 
mixture that is difficult to handle into a homogenous, solid, relatively 
inert powder or granular material that is easy to handle and is suitable 
for use in, for example, various melt processing methods. 
Polyaniline doped with a functionalized protonic acid has proved to be 
especially usable when it contains an excess of the protonic acid, such as 
the above-mentioned sulfonic acid or a derivative thereof, i.e. the 
mixture contains an amount of acid not only sufficient for the doping, but 
also for the plasticization of the mixture. When protonic acid is used in 
this manner in excess, effective doping of polyaniline is obtained and, 
additionally, the doped polyaniline becomes a material suitable for melt 
processing, since the protonic acid plays the above-mentioned two roles in 
the mixture. When protonic acid is used in this manner in excess, the 
result is a doped polyaniline which has an acidic pH value. However, 
acidity encumbers the use of the conductive polymer in most applications. 
In addition to acidic products corroding and contaminating other composite 
plastics components and the environment, acidic material to be processed 
damages the equipment, such as melt-processing apparatus, by corroding it. 
These disadvantages result in few practical applications for an otherwise 
good conductive material. 
State-of-the-art publications have almost completely overlooked the problem 
of acidity. On the other hand, it is evident in the state of the art that 
mere mixing together of a polyaniline of the emeraldine base form and a 
doping agent such as dodecylbenzenesulfonic acid will not suffice to 
produce a homogenous mixture; the result is the above-mentioned mixture or 
dispersion which is difficult to handle. In state-of-the-art publications, 
sufficient mixing and doping has in general been effected by dissolving 
the parts of the mixture in the same solvent. An example of the 
state-of-the-art publications concerning this is U.S. Pat. No. 5,006,278, 
which is hereby incorporated by reference. In addition, the methods 
disclosed in the state-of-the-art publications in general use solution 
processing, cf. WO Patents 8901694 and 9013601, in which case the acidity 
problem will not cause as much harm as in melt processing methods for 
which the polyaniline-based conductive material according to the present 
invention is especially suitable. In addition, it can be stated that 
acidity is not especially problematic in all applications, such as 
accumulators and batteries. 
One way of improving the processibility and of reducing the acidity of a 
conductive Polymer material which contains polyaniline doped with a 
protonic acid, preferably sulfonic acid and most preferably 
dodecylbenzenesulfonic acid, is disclosed in EP Patent Application 582919, 
which is hereby incorporated by reference. According to the method 
disclosed in this publication, a certain additive is used for the 
neutralization of polyaniline or its derivative doped with a protonic 
acid, and also for its plasticization and/or stabilization. According to 
the method of this publication, a mixture containing polyaniline doped 
with a protonic acid can be rendered more plastic, more stable and more 
neutral by adding to the mixture a metal compound or by treating the doped 
polyaniline with a metal compound. The metal compound can be selected from 
among numerous alternatives, according to the desired property to be 
emphasized. The compounds may be oxides, hydroxides, halides, or 
equivalent. 
In the invention disclosed, it is noted that the most advantageous are the 
compounds of zinc, of which zinc oxide (ZnO) has been found to be the most 
suitable. According to a preferred embodiment, the metal compound is 
allowed to react first with any acid which, together with the metal 
compound, forms a compound which substantially stabilizes and plasticizes 
doped polyaniline. The acid reacting with the metal compound need not be 
the same as the protonic acid to be used for the doping of polyaniline. 
However, using as the acid reacting with the metal compound the same 
protonic acid as is used for the doping of the polyaniline has proved to 
be a preferred embodiment. The mixing of the ingredients is carried out 
preferably in a melt mixing apparatus, for example by means of a kneader, 
a compounder, or a screw mixer, at a temperature of approximately 
50.degree.-200.degree. C. However, this method has the disadvantage that a 
metal compound of the type disclosed therein will strongly decrease the 
conductivity of polyaniline at higher concentrations of the metal 
compound. 
SUMMARY OF THE INVENTION 
An object of the present invention is to prepare a conductive polymer 
material which contains a polyaniline, preferably of the emeraldine form, 
doped with a protonic acid, preferably sulfonic acid, most preferably 
dodecylbenzenesulfonic acid, the acidity of the conductive polymer having 
been substantially reduced, i.e. to a pH range above 2, preferably to a pH 
range of 3-8, and most preferably to a pH range of 5-7, the conductivity 
of the polymer nevertheless remaining at a sufficiently high level. The 
conductivity remaining at a sufficiently high level in spite of the 
neutralization treatment is a significant improvement over the 
neutralization method according to the above-mentioned EP application 
582919. 
By the method of the present invention, a significant improvement is 
achieved over the method disclosed in the above-mentioned publication with 
respect to the pH range also, so that the adjustability of the pH value 
becomes possible even within a low pH range, without affecting the 
conductivity of the polymer. It has been shown that if only a metal 
compound, such as zinc oxide, is used together with an acid, the result 
may be, in spite of stoichiometric proportions of the ingredients, too 
acidic a product, the acidity of which can now be substantially reduced by 
the method according to the present invention. It is a further advantage 
of the method according to the present invention that the final product 
obtained will be of a more uniform acidity than the product obtained by 
the method according to the publication mentioned above. 
The above-mentioned advantageous acidity limits (pH 3-8) achievable by the 
method according to the invention can, however, be further widened for 
certain specialized applications. For certain purposes, conductive 
plastics mixtures having a pH even below 3 or above 8 can be used, and 
such plastics mixtures can be obtained by a suitable selection of the 
matrix polymers to be mixed with the conductive polymer material. 
The conductive polymer composition according to the present invention thus 
has wider areas of use than prior art conductive polymer compositions. 
Owing to the consistently and substantially higher pH range of the 
composition, it is considerably more suitable for use in various 
processing apparatus than previously known polyaniline conductive polymer 
compositions. Furthermore, the adjustability of the pH range and the 
conductivity of the conductive polymer concerned remaining at a 
sufficiently high level in spite of the steps it is subjected to according 
to the invention further widen the applications of the polyaniline-based 
conductive polymer composition according to the invention. Such a polymer 
material, which has a substantially higher pH value and contains a 
polyaniline doped with a protonic acid, further comprises a metal compound 
and neutralizing compound. 
The above-mentioned objects and advantages, and other objects and 
advantages of the present invention are achieved by providing a 
processable, electrically conductive polymer material comprising a 
polyaniline or derivative thereof doped with a protonic acid, a metal 
compound and a neutralizing compound. 
At least a portion of the metal compound is in the form of a reaction 
product of a starting metal compound with an acid capable of forming a 
compound with the metal. More particularly, this acid may be the same acid 
as the protonic acid used to dope the polyaniline or derivative thereof, 
such as an organic sulfonic acid, e.g., dodecylbenzene sulfonic acid. The 
metal portion of the metal compound can be selected from Mg, Ca, Ti, Zn, 
Sr, Zr, Ba, or Pb, more particularly selected from Mg, Ca, Zn, or Ba, most 
particularly Zn. For instance, ZnO can be added to the mixture of the 
conductive polymer to form a final metal compound that is, at least in 
part, the reaction product of ZnO and the acid component. 
The neutralizing compound may be a basic metal compound, preferably a metal 
carbonate, for example, CaCO.sub.3, Na.sub.2 CO.sub.3, NaHCO.sub.3, 
MgCO.sub.3, SrCO.sub.3, MnCO.sub.3, KHCO.sub.3, borax, and mixtures 
thereof, more particularly calcium carbonate or an equivalent thereof. The 
neutralizing compound may be a different compound from the metal precursor 
compound, or from the reaction product of the metal precursor compound and 
the protonic acid. This neutralizing compound may be present in an amount 
of 0.1 to 10% by weight, calculated as calcium carbonate based on the 
total composition. 
The electrically conductive material typically has a conductivity of at 
least 10.sup.-9 S/cm, more particularly at least 10.sup.-6 S/cm, most 
particularly at least 10.sup.-3 S/cm. 
The objects and advantages of the invention are also achieved by an 
electrically conductive plastics mixture containing the processable, 
electrically conductive polymer material described above in combination 
with an insulating polymer matrix, which may be a thermoset, a 
thermoplast, or an elastomeric polymer. More particularly, the insulating 
polymer matrix may be selected from the group consisting of a 
thermoplastic homo- or copolymer based on olefins, styrene, vinyl polymers 
or acrylic polymers, or a mixture thereof, and a thermoplastic 
condensation polymer. 
When the neutralizing compound is present in an amount of 0.3% by weight or 
less, based on the electrically conductive polymer material, then the 
impact strength of the conductive plastics mixture of the invention may be 
up to 30% higher than the impact strength of the corresponding plastics 
mixture without any neutralizing compound. 
The objects and advantages of the present invention are also obtained by 
providing a method for the preparation of an electrically conductive 
polymer material containing a polyaniline or derivative thereof doped with 
a protonic acid discussed above, comprising (a) contacting a polyaniline 
or a derivative thereof, a polymer-doping protonic acid, a metal compound, 
an acid capable of reacting with said metal compound to form a second 
metal compound, and a neutralizing compound, and (b) heat treating this 
mixture at a temperature of 50.degree. C. to 400.degree. C. 
The objects and advantages of the present invention are also achieved by 
providing a method for preparing the electrically conductive plastics 
mixture mentioned above, comprising combining the electrically conductive 
polymer material discussed above with an insulating polymer matrix in a 
melt mixing device at a temperature of 80.degree. C. to 350.degree. C. 
As pointed out above, it is an object of the present invention to provide a 
method for the preparation of a processable conductive polymer based on 
polyaniline or a derivative thereof, the polymer having a substantially 
improved processability, especially in the molten state. 
In another embodiment of the invention, the disadvantages of the previously 
disclosed methods mentioned above have now been eliminated and the defined 
objects and advantages of the present invention have been further achieved 
by a method for the preparation of a conductive polymer material based on 
a polyaniline or a derivative thereof and a protonic doping acid, the 
method comprising 
(a) producing a mixture which comprises 1-20 wt. % polyaniline or its 
derivative, 50-90 wt. % protonic doping acid, calculated as dodecylbenzene 
sulfonic acid, and 1-45 wt. % of a plasticizing component selected from 
the group consisting of water, a C.sub.1 -C.sub.3 alcohol, and mixtures 
thereof to form a mixture; 
(b) feeding the mixture obtained from step (a) into a melt-mixing 
apparatus, and subjecting said mixture to shear forces at a temperature of 
50.degree.-400.degree. C. to obtain a blend; 
(c) recovering the blend obtained from step (b) from the melt-mixing 
apparatus; and 
(d) optionally posttreating the blend recovered in step (c). This 
posttreatment may comprise combining the blend with another polymer, such 
as a thermoplast, in a mixing apparatus. This process may also comprise 
adding a metal precursor compound and/or a neutralizing compound, both as 
discussed above, in either step (a) or step (c), in order to achieve the 
further advantages disclosed above. 
DETAILED DESCRIPTION OF THE INVENTION 
According to the present invention it has now, surprisingly, been observed 
that, when a conductive polymer complex made up of a polyaniline doped 
with a protonic acid and a reaction product formed by a metal compound and 
an acid additionally contains an additional neutralizing compound, a 
conductive polymer material is obtained the pH range of which is 
adjustable and the pH range of which is adjusted to a substantially higher 
pH range (pH approximately 3-8, preferably 5-7), the adjusted pH value of 
which remains consistently the same throughout the entire product, and the 
level of conductivity of which remains high in spite of the additives. The 
present invention relates in particular to the neutralizing, with a 
additional neutralizing compound, of a conductive polymer complex made up 
of a polyaniline, preferably of the emeraldine form, doped with sulfonic 
acid, and of a compound formed by a zinc compound and a protonic acid. 
In practice the polyaniline or its derivative used may be any form of 
polyaniline, such as the leucoemeraldine, protoemeraldine, emeraldine, 
nigraline or toluprotoemeraldine form. The polyaniline may also be in the 
form of a derivative thereof, for example a substituted polyaniline. The 
substituted derivatives of the polyaniline forms mentioned above are, of 
course, also within the protective scope of the invention. The most 
preferred polyaniline-type conductive polymer is polyaniline, and 
preferably its emeraldine base form, the formula of which is shown above 
in connection with the description of the state of the art. 
The protonic doping acid used in the invention may be any protonic acid 
which dopes polyaniline or a derivative thereof. Typical protonic acids 
include HCl, H.sub.2 SO.sub.4, HNO.sub.3, HClO.sub.4, HBF.sub.6, HF, 
phosphoric acids, sulfonic acids, picrinic acid, m-nitrobenzoic acid, 
dichloroacetic acid, and polymeric acids. A preferred protonic doping acid 
is an organic sulfonic acid, especially-an aromatic sulfonic acid, and 
most preferably dodecylbenzene sulfonic acid (DBSA). Other usable protonic 
doping acids have been disclosed in, for example, U.S. Pat. No. 5,171,478, 
which publication is hereby incorporated by reference. 
In its most preferred embodiment the present invention relates to the 
neutralization, with calcium carbonate (CaCO.sub.3), of a emeraldine-form 
polyaniline doped with dodecylbenzenesulfonic acid and a compound formed 
by the reaction of zinc oxide (ZnO) and dodecylbenzenesulfonic acid. 
Dodecylbenzenesulfonic acid acts in the complex both as a doping agent and 
as a plasticizer of the complex. An additional plasticizing agent may also 
be used, as discussed in more detail below. This plasticizing agent may 
consist of other agents for the plasticizing of polymers. Examples of such 
plasticizing agents include water, alcohols such as methanol, ethanol, 
propanols, benzyl alcohols, etc., ethers such as diethylether, ketones 
such as acetone, acetophenone, etc., phenols, amines, esters, fluorinated 
carboxylic and sulfonic acids,.amides, phosphoramides, etc. In the final 
product obtained after the treatments carried out on the mixture made up 
of the above-mentioned complex and a additional neutralizing compound, 
i.e. mixing, solidification, etc., the proportion of the plasticizing 
agents in the resulting product may often be so small as to be difficult 
to detect. 
The metal precursor compound, which is capable of reacting with a protonic 
acid, desirably the protonic doping acid, renders the doped polyaniline a 
less acid, more easily melt-processable, better mixing, and more stable 
conductive polymer material. The metal compound may vary greatly depending 
on whether it is desired to emphasize neutralization, in which case 
compounds of metals such as magnesium, barium or calcium are possible, or 
whether it is desired to emphasize the stabilizing action, in which case 
compounds of metals such as zinc, copper, aluminum, titanium, iron or 
zirconium are preferable. Also compounds of cadmium, lead and stannium are 
possible. Mixtures of metal compounds and most metal compounds are 
suitable for this purpose according to the invention. 
The metal precursor compounds may be oxides, hydroxides, halides, or 
equivalents thereof. Also, salts of weak acids, such as stearates, 
carbonates, ricinoleates, palmetates, octoates, laurates, phenolates, 
maleates, and octylthioglycolates can be used. The metal compound may also 
be a condensation product of a metal compound and a protonic acid, having 
a melting point below about 300.degree. C. 
Particularly suitable metal compounds used in the invention are based on 
zinc, copper, calcium or magnesium, the most preferred metal compound is 
based on zinc, such as zinc stearate or zinc oxide. Preferred compounds 
are oxides and hydroxides, and the most preferred are oxides, of which 
zinc oxide ZnO is the most preferred. According to one particular 
embodiment, zinc oxide may be first reacted with a protonic doping acid, 
such as dodecylbenzene sulfonic acid, and the zinc didodecylbenzoate thus 
obtained is added to the components forming the conductive polymer. 
The use of a neutralizing compound, preferably calcium carbonate, together 
with a zinc compound, for the neutralization of doped polyaniline is thus 
advantageous not only for achieving consistent and sufficient 
neutralization and pH adjustability, but also for retaining the level of 
conductivity. It can be shown that the mere increasing of the amount of 
the zinc compound, such as zinc oxide, in order to improve the result of 
neutralization will result in a dramatic lowering of the level of 
conductivity. On the other hand, when additional neutralizing compound is 
used this does not happen; the level of conductivity unexpectedly remains 
high for a long time, and if additional neutralizing compound is added 
further, the conductivity level drops only gradually, and not suddenly and 
dramatically as it does when mere zinc oxide is used. 
According to the present invention, a neutralizing compound, for example 
calcium carbonate (CaCO.sub.3), is thus preferably used for adjusting the 
pH of the doped polyaniline. The obtained final product, a conductive 
polymer complex with a higher pH value, thus has the following 
ingredients: a polyaniline which is preferably of the emeraldine form; a 
protonic acid, most preferably sulfonic acid or a derivative thereof, used 
for the doping of the polyaniline and as a building block of a 
plasticizer; a metal compound, preferably zinc oxide, used for 
neutralization; and an additional neutralizing compound, preferably a 
carbonate or hydrogen carbonate, most preferably calcium carbonate, used 
for improving the result of neutralization. 
It is possible, when so desired, to mix a conductive polymer complex made 
up of these ingredients with an insulating polymer matrix material in 
order to produce an electrically conductive plastics mixture. Such a 
matrix material may be a thermosetting plastic, a thermoplast, or an 
elastomeric polymer. The matrix material should be compatible with the 
conductive polymer and be melt processable within the same temperature 
ranges as the conductive polymer itself. The matrix polymer is preferably 
a thermoplastic homo- or copolymer based on olefins, styrene, vinyl 
polymers or acrylic polymers, or a mixture thereof, or a thermoplastic 
condensation polymer. Examples of matrix polymers most commonly used 
include polyethylene, polypropylene, styrenebutadiene, polyester, 
polyamide, acryl-butyl-styrene, and polycarbonate. From both a 
technological and an economical viewpoint, it is preferable to aim at 
making the proportion of the conductive polymer complex in the plastics 
mixture as small as possible. A Conductive polymer complex is expensive, 
and on the other hand the mechanical properties of the entire plastics 
mixture will be better if the proportion of the conductive polymer complex 
in the mixture is as small as possible. The proportion of conductive 
polymer complex in the plastics mixture may be within a range of 
approximately 1-60 wt. %, preferably approximately 1-40 wt. %, and most 
preferably 5-15 wt. %. As regards the plastics mixtures of the conductive 
polymer material and matrix materials, reference is also made to EP 
application 582919, mentioned above. 
According to the method of the present invention, the proportion of the 
neutralizing agent, calculated as calcium carbonate, which is added in 
order to improve the result of the neutralizing of the conductive polymer 
in the final-product conductive polymer complex may vary from 
approximately 0.1 percent by weight to approximately 20 percent by weight. 
Preferably calcium carbonate is added at approximately 0.5-8 wt. % and 
most preferably at 0.5-2 wt. % of the total amount of the mixture. 
When used in accordance with the invention, the neutralizing compound has 
an advantageous effect not only on the pH values of the conductive polymer 
material and the retaining of its conductivity level, but also on its 
impact strength. In practical applications this can best be observed when 
the conductive polymer is mixed with insulating plastics materials such as 
those mentioned above. When a additional neutralizing compound, preferably 
calcium carbonate, is used, the melt-processed conductive plastic pieces 
obtained will be stronger and more durable. In other words, plastics 
mixture pieces which are made of conductive and insulating polymer and 
which contain calcium carbonate in amounts of only 0.3 wt. % or less have 
a considerably higher impact strength than pieces which do not contain 
calcium carbonate. For example, with a calcium carbonate amount of 0.3 wt. 
%, an improvement of up to 30% is obtained in the Izod impact strength 
(kJ/m.sup.2) in a plastics mixture which contains conductive polymer 
material in an amount of approximately 15 wt. % and matrix polymer in an 
amount of approximately 85 wt. %. 
The other preferred ingredients in the conductive polymer complex obtained 
as the final product were (before being mixed with the matrix polymer): an 
emeraldine-form doped polyaniline; dodecylbenzenesulfonic acid (DBSA); and 
zinc oxide. The amount of polyaniline is approximately 1-30 wt. %, 
preferably approximately 4-20 wt. %, the amount of DBSA is approximately 
50-95 wt. %, preferably approximately 70-90 wt. %, and the amount of zinc 
oxide approximately 1-10 wt. %, preferably approximately 1.5-8 wt. %. The 
amount of calcium carbonate was 0.1-20 wt. %, preferably approximately 
0.5-8 wt % most preferably 0.5-2 wt. %. If a final product having a 
composition such as this is mixed with a matrix polymer, its proportion in 
their mixture is approximately 1-60 wt. % preferably 1-40 wt %, and most 
preferably 5-15 wt. %. 
A preferred composition for a plastics mixture suitable for ESD 
applications made by injection molding may be, for example, one which 
contains conductive polymer complex in an amount of approximately 15 wt. % 
and matrix polymer in an amount of approximately 85 wt. %. Such a plastics 
mixture thus preferably contains polyaniline in an amount of approximately 
1 wt. %, DBSA in an amount of approximately 12.5 wt. %, ZnO in an amount 
of approximately 1.3 wt. % and CaO.sub.3 in an amount of approximately 0.2 
wt. %, as well as matrix polymer in an amount of approximately 85 wt. %. 
Another preferred composition for a plastics mixture suitable for EMI 
applications may be, for example, one which contains conductive polymer 
complex approximately 20-40 wt. % and matrix polymer in an amount of 
approximately 60-80 wt. %. Such a plastics mixture thus preferably 
contains polyaniline in an amount of approximately 2-5 wt. %, DBSA in an 
amount of approximately 20-30 wt. %, ZnO in an amount of approximately 
0.5-1.5 wt. % and CaCO.sub.3 in an amount of approximately 0.4-3 wt. %, as 
well as matrix polymer in an amount of approximately 60-80 wt. %. 
The ingredients of the conductive polymer material may be mixed with each 
other by using various mixers, kneaders, etc. In a preferred embodiment 
the mixing is carried out using a screw mixer. The ingredients may be 
mixed with each other in a number of different orders. Examples of these 
orders are given below. 
In one order of mixing, it is possible to introduce the ingredients, i.e. 
the polymer, the protonic acid used as the,doping agent, the metal 
compound, the acid which forms a compound with the metal compound, and the 
additional neutralizing compound which improves the result of 
neutralization, all at the same time and then to mix them preferably by 
using a screw mixer. 
In another order of mixing, it is possible to mix together the metal 
compound and the acid which forms a compound with it, and to add to this 
blend the additional neutralizing compound, and to add the mixture thus 
obtained to a mixture of the polymer and the doping acid. 
In another order of mixing, the polymer and the doping acid are first mixed 
together, and the additional neutralizing compound is added to this 
mixture. The compound formed by the metal compound and the acid is then 
added to the mixture obtained. 
Furthermore, it is also possible to carry out the mixing by adding to a 
blend of the polymer and the doping acid one portion of the compound 
formed by the metal compound and the acid and by adding the additional 
neutralizing compound to another portion of the compound formed by the 
metal compound and the acid, and adding the latter mixture thus obtained 
to the mixture containing the polymer. 
It is also possible first to mix the metal compound and the additional 
neutralizing compound and to mix this blend with the acid which forms a 
compound with the metal compound, and to add the mixture thus obtained to 
a mixture of the polymer and the doping acid. 
One further alternative order of adding the ingredients is that a portion 
of the additional neutralizing compound is added to a portion of the 
compound formed by the metal compound and the acid, and this mixture is 
added to a mixture of the polymer and the doping agent. The remainder of 
the mixture formed by the metal compound and acid and the additional 
neutralizing compound is added to the mixture thus obtained. 
In preferred embodiments, the same acid, which is preferably, for example, 
dodecylbenzenesulfonic acid, is used both as the acid which forms a 
compound with metal compound and as the doping acid. In this case it is 
possible further to carry out the mixing by mixing all of the DBSA and the 
metal compound and to add to this mixture the additional neutralizing 
compound which improves the result of neutralization. The polymer is then 
added to the mixture thus obtained, which contains DBSA in excess. In 
practice the mixings can be carried out in such a manner that some of the 
preliminary mixtures are made by using, for example, kneaders, and these 
preliminary mixtures are combined and the actual mixing, together with the 
heat treatment, is carried out, for example, in the screw mixer mentioned 
above. 
The extrusion of the conductive polymer complex is preferably carried out, 
for example, by running the mixture through the screw mixer once or 
several times, the temperatures being approximately 50.degree.-400.degree. 
C., preferably 80.degree.-300.degree. C., and most preferably 
100.degree.-200.degree. C. The same procedure is used in the extrusion as 
has been disclosed in EP patent applications 545729 and 582919.

The following examples illustrate the embodiment of the present invention 
wherein a neutralizing compound is used in greater detail. However, they 
are intended only to illustrate the invention, and they shall not be 
interpreted as limiting the invention. 
REFERENCE EXAMPLE 
(without calcium carbonate) 
A conductive polymer complex which contained 16 wt % emeraldine 
polyaniline, 64 wt % DBSA and 20 wt % ZnO was prepared by extruding the 
mixture of these components three times at 170.degree. C. with screw speed 
50 rpm. This conductive polymer complex was mixed in an amount of 25 wt % 
with high density polyethylene (NCPE 3415 produced by Neste Oy). 
The experiment was repeated by mixing the same ingredients at the same 
ratios by using the same technique. The conductivities of the resulting 
two parallel blends deviated two decades, indicating the difficulties 
encountered if conductive polymer complex is made without additional 
neutralizing agent. 
Example 1 
A conductive polymer complex which contained emeraldine polyaniline 7.6 wt 
%, DBSA 82.5 wt %, ZnO 9.1 wt % and CaCO.sub.3 0.8 wt % was prepared by 
extruding the mixture of these components three times at temperatures 
165.degree. C., 180.degree. C. and 180.degree. C. with screw speed 50 rpm. 
The pH obtained for the complex was 3.1 and its conductivity, as measured 
by the 4-probe method, was 3.5 *10.sup.-2 S/cm. 
Example 2 
A conductive polymer complex which contained emeraldine polyaniline 7.5 wt 
%, DBSA 81.9 wt %, ZnO 9.0 wt % and CaCO.sub.3 1.6 wt % was prepared by 
the procedure used in Example 1. The pH obtained for the complex was 5.2 
and its conductivity as measured by the 4-probe method was 2.0 *10.sup.-2 
S/cm. 
Example 3 
The conductive polymer complex according to Example 1 was mixed in an 
amount of 10 wt. % with HDPE (NCPE 3415, manufactured by Neste Oy), used 
as matrix polymer. The conductivity of rods injection molded from the 
polymer mixture thus obtained was 4.2 *10.sub.-5 S/cm as measured by the 
4-probe method. 
Example 4 
The conductive polymer complex according to Example 2 was mixed in an 
amount of 10 wt. % with the HDPE used in Example 3. The conductivity of 
rods injection molded from the polymer mixture thus obtained was 3.1 
*10.sup.-5 S/cm as measured by the 4-probe method. 
Example 5 
The conductive polymer complex according to Example 2 was mixed in an 
amount of 10 wt. % with a polystyrene used as matrix polymer (SB 735). The 
conductivity of rods injection molded from the polymer mixture thus 
obtained was 2.8 *10.sup.-6 S/cm as measured by the 4-probe method. 
Example 6 
A polymer mixture was prepared which contained polystyrene (SB 735) 75 wt. 
%; conductive polymer complex according to Example 2, but without 
CaCO.sub.3, 4.7 wt. %; styrene-ethylene-butadiene block polymer (SEBS, 
manufactured by Shell) 10 wt. %; and CaCO.sub.3 0.3 wt. %. The Izod notch 
impact strength of rods injection molded from the mixture was 6.4 
kJ/m.sup.2 at 23.degree. C. 
Example 7 
A polymer mixture according to Example 5 was prepared, with no calcium 
carbonate addition. The Izod notch impact strength at 23.degree. C. was 
only 4.9 kJ/m.sup.2. 
Example 8 
Three polymer mixtures were prepared which contained HDPE polyethylene 
(NCPE 3415) 85 wt % and a conductive polymer complex prepared according to 
Example 1 which contained CaCO.sub.3 in amounts of a) 0 wt. %; b) 0.8 wt. 
%; and c) 1.6 wt. %. The impact strengths measured for the mixtures were 
a) 85.6 J/m; b) 91.3 J/m; and c) 96.6 J/m. 
Example 9 
A conductive polymer complex which contained emeraldine polyaniline 7.5 wt 
% DBSA 82.0 wt %, ZnO 9.0 wt % and Na.sub.2 CO.sub.3 1.5 wt % was prepared 
according to Example 1. The pH obtained for the complex was 6.0 and its 
conductivity as measured by the 4-probe method was 2.7 *10.sup.-4 S/cm. 
Example 10 
A conductive polymer complex which contained emeraldine polyaniline 7.5 wt 
%, DBSA 81.0 wt %, ZnO 8.9 wt % and NaHCO.sub.3 2.6 wt % was prepared 
according to the Example 1. The pH obtained for the complex was 5.9 and 
its conductivity as measured by the 4-probe method was 4.0 *10.sup.-5 
S/cm. 
Example 11 
A conductive polymer complex which contained emeraldine polyaniline 7.5 wt 
%, DBSA 82.2 wt %, ZnO 9.0 wt % and MgCO.sub.3 1.3 wt % was prepared 
according to Example 1. The pH obtained for the complex was 5.6 and its 
conductivity as measured by the 4-probe method was 1.0 *10.sup.-2 S/cm. 
Example 12 
A conductive polymer complex which contained emeraldine polyaniline 7.5 wt 
%, DBSA 81.3 wt %, ZnO 8.9 wt % and SrCO.sub.3 2.3 wt % was prepared 
according to Example 1. The pH obtained for the complex was 6.2 and its 
conductivity as measured by the 4-probe method was 2.1 *10.sup.-3 S/cm. 
Example 13 
A conductive polymer complex which contained emeraldine polyaniline 7.5 wt 
%, DBSA 81.7 wt %, ZnO 9.0 wt % and MnCO.sub.3 1.8 wt % was prepared 
according to Example 1. The pH obtained for the complex was 6.1 and its 
conductivity as measured by the 4-probe method was 6.4 *10.sup.-4 S/cm. 
Example 14 
A conductive polymer complex which contained emeraldine polyaniline 7.5 wt 
%, DBSA 80.6 wt %, ZnO 8.8 wt % and KHCO.sub.3 3.1 wt % was prepared 
according to Example 1. The pH obtained for the complex was 6.0 and its 
conductivity as measured by the 4-probe method was 1.2 *10.sup.-3 S/cm. 
Example 15 
A conductive polymer complex which contained emeraldine polyaniline 7.5 wt 
%, DBSA 78.1 wt %, ZnO 8.5 wt % and Borax (Na.sub.2 B.sub.O.sub.7 *10 
H.sub.2 O) 5.9 wt % was prepared according to Example 1. The pH obtained 
for the complex was 6.1 and its conductivity as measured by the 4-probe 
method was 1.1 *10.sup.-4 S/cm. 
Example 16 
The conductive polymer complex prepared according to Example 9 was mixed in 
an amount of 10 wt % with HDPE (NCPE 3415). The conductivity of the rods 
injection molded from the polymer mixture thus obtained was 2.1 *10.sup.-6 
S/cm as measured by the 4-probe method. 
Example 17 
The conductive polymer complex prepared according to Example 10 was mixed 
in an amount of 10 wt % with HDPE (NCPE 3415). The conductivity of the 
rods injection molded from the polymer mixture thus obtained was 4.0 
*10.sup.-6 S/cm as measured by the 4-probe method. 
Example 18 
The conductive polymer complex prepared according to Example 11 was mixed 
in an amount of 10 wt % with HPDE (NCPE 3415). The conductivity of the 
rods injection molded from the polymer mixture thus obtained was 2.5 
*10.sup.-6 S/cm as measured by the 4-probe method. 
Example 19 
The conductive polymer complex prepared according to Example 12 was mixed 
in an amount of 10 wt % with HDPE (NCPE 3415). The conductivity of the 
rods injection molded from the polymer mixture thus obtained was 1.6 
*10.sup.-5 S/cm as measured by the 4-probe method. 
Example 20 
The conductive polymer complex prepared according to Example 13 was mixed 
in an amount of 10 wt % with HDPE (NCPE 3415). The conductivity of the 
rods injection molded from the polymer mixture thus obtained was 1.3 
*10.sup.-5 S/cm as measured by the 4-probe method. 
Example 21 
The conductive polymer complex prepared according to Example 14 was mixed 
in an amount of 10 wt % with HDPE (NCPE 3415). The conductivity of the 
rods injection molded from the polymer mixture thus obtained was 4.1 
*10.sup.-6 S/cm as measured by the 4-probe method. 
Example 22 
The conductive polymer complex prepared according to Example 15 was mixed 
in an amount of 10 wt % with HDPE (NCPE 3415). The conductivity of the 
rods injection molded from the polymer mixture thus obtained was 1.7 
*10.sup.-6 S/cm as measured by the 4-probe method. 
Example 23 
A conductive polymer complex which contained emeraldine polyaniline 7.5 wt 
%, DBSA 81.2 wt %, ZnO 8.9 wt % and NH.sub.4 HCO.sub.3 2.4 wt % was 
prepared according to Example 1. This conductive polymer complex was mixed 
in an amount of 10 wt % with HDPE (NCPE 3415). The conductivity of the 
rods injection molded from the polymer mixture thus obtained was 
lower-than 1 *10.sup.-9 S/cm. 
Example 24 
A conductive polymer complex which contained emeraldine polyaniline 7.5 wt 
%, DBSA 81.5 wt %, ZnO 8.9 wt % and K.sub.2 CO.sub.3 2.1 wt % was prepared 
according Example 1. This conductive polymer complex was mixed in an 
amount of 10 wt % with HDPE (NCPE 3415). The conductivity of the rods 
injection molded from the polymer mixture thus obtained was lower than 1 
*10.sup.-9 S/cm. 
Example 25 
A conductive polymer complex which contained emeraldine polyaniline 7.5 wt 
%, DBSA 82.3 wt %, ZnO 9.0 wt % and Ca(OH).sub.2 1.2 wt % was prepared 
according to Example 1. This conductive polymer complex was mixed in an 
amount of 10 wt % with HDPE (NCPE 3415). The conductivity of the rods 
injection molded from the polymer mixture thus obtained was lower than 1 
*10.sup.-9 S/cm. 
In the embodiment of the present invention wherein a plasticizing agent 
selected from the group consisting of water, a C.sub.1 -C.sub.3 alcohol, 
and mixtures thereof is used, it is advantageous if the proportion of 
polyaniline or its derivative is approx. 4-10 wt. % of the amount of the 
mixture produced in step (a). 
It is especially advantageous if the mixture obtained in step (a) of the 
present method comprises 60-85 wt. % protonic doping acid, calculated as 
dodecylbenzene sulfonic acid. 
As pointed out above, in the method according to the invention, in which a 
mixture comprising a polyaniline or a derivative thereof, a protonic 
doping acid, and water, a C.sub.1 -C.sub.3 alcohol, or a mixture thereof, 
is compounded at an elevated temperature, the water and the C.sub.1 
-C.sub.3 alcohol serve as a plasticizing agent. It can be stated that the 
idea of the invention is based specifically on the combination of such a 
plasticizing agent and compounding, whereby a conductive polymer material 
more usable than previously is obtained. The addition of a plasticizing 
agent, among other things, lowers the required mixing temperature, and 
thus the thermal decomposition of the mixture being treated decreases. In 
addition, the corroding action of the mixture on the apparatus is reduced. 
Exemplary plasticizing agents include water, methanol, ethanol, or a 
mixture of these. The most preferable component is water. 
In step (a) this embodiment of the present invention, it is advantageous if 
the produced mixture comprises approximately 1-35 wt. %, preferably 
approximately 5-20 wt. %, of water or a C.sub.1 -C.sub.3 alcohol. When the 
mixture of step (a), which has the abovementioned amount of water and/or 
C.sub.1 -C.sub.3 alcohol, is mixed by means of the shear forces of a 
melt-mixing apparatus at a temperature of 50.degree.-400.degree. C., the 
final conductive polymer material will not contain a significant amount of 
the plasticizing component used in step (a). 
According to one preferred embodiment of the invention, in connection with 
the mixing together of a polyaniline or its derivative, a protonic doping 
acid and a water or C.sub.1 -C.sub.3 alcohol component in step (a), it is 
possible to add to them also a metal compound which is preferably capable 
of reacting or has reacted with a protonic acid, such as the doping acid. 
Such a metal compound renders the doped polyaniline a less acid, more 
easily melt-processable, better mixing, and more stable conductive polymer 
material. The metal compound may vary greatly depending on whether it is 
desired to emphasize neutralization, in which case compounds of metals 
such as magnesium, barium or calcium are possible, or whether it is 
desired to emphasize the stabilizing action, in which case compounds of 
metals such as zinc, copper, aluminum, titanium, iron or zirconium are 
preferable. Also compounds of cadmium, lead and stannium are possible. 
Mixtures of metal compounds and most metal compounds are suitable for the 
purpose according to the invention. 
The metal compounds may be oxides, hydroxides, halides, or equivalent. Also 
salts of weak acids, such as stearates, carbonates, ricinoleates, 
palmetates, octoates, laurates, phenolates, maleates, and 
octylthioglycolates can be used. An important compound is a condensation 
product of a metal compound and a protonic acid, having a melting point 
below 300.degree. C. 
The preferred metal compounds used in the invention are based on zinc, 
copper, calcium or magnesium, the most preferred metal compound is based 
on zinc, such as zinc stearate or zinc oxide. Preferred compounds are 
oxides and hydroxides, and the most preferred are oxides, of which zinc 
oxide ZnO is the most preferred. According to the most preferred 
embodiment, zinc oxide is first reacted with a protonic doping acid, such 
as dodecylbenzene sulfonic acid, and the zinc didodecylbenzene sulfonate 
thus obtained is added to the components mentioned at the beginning of 
step (a). 
It is advantageous if the amount of the above-mentioned metal compound is 
approximately 3-10 wt. %, preferably approximately 5-9 wt. %, of the 
combined total weight of the compound and the components of step (a). 
It is also advantageous to combine the components of step (a) or the blend 
recovered in step (c) with a neutralizing compound, such as calcium 
carbonate or the other neutralizing compounds discussed above The use of 
calcium carbonate will neutralize the polyaniline or derivative thereof 
doped with a protonic doping agent, and will cause both sufficient 
neutralization and retaining of conductivity in the forming conductive 
polymer material. It is especially advantageous to use calcium carbonate 
together with the above-mentioned metal compound, such as zinc oxide or 
its doping acid salt. A compound of metal such as zinc also acts well as a 
plasticizer, but in high concentrations it will lead to a dramatic 
lowering of the conductivity of the material. Instead, when calcium 
carbonate is used this will not occur: the conductivity will remain at a 
high level for a long time. As was already stated, both the metal compound 
and the calcium carbonate may be added either before the compounding (in 
connection with step (a)) or thereafter (after step (c)). 
The amount of calcium carbonate used is preferably approximately 0.1-20 wt 
%, preferably approximately 0.1 to 8 wt. % and most preferably 
approximately 0.5-2%, of the combined total weight of the calcium 
carbonate and the components of step (a). The calcium carbonate acts best 
when the method according to the invention is used for preparing a 
conductive plastics mixture containing a large amount of a thermoplast in 
addition to the conductive plastic, as discussed more fully below. 
In the method according to this embodiment of the present invention, the 
conductive polymer material is prepared by first producing in step (a) a 
mixture which is then in step (b) fed into a compounder, where it is mixed 
by shear forces, and is recovered in step (c) and is possibly treated 
further in step (d). According to one preferred embodiment, step (a) is 
carried out (i) by first producing a polyaniline or derivative thereof 
which contains water or C.sub.1 -C.sub.3 alcohol 1-70 wt. %, preferably by 
polymerizing a monomer of the polyaniline or its derivative in the 
presence of said water or alcohol; (ii) mixing a protonic doping acid with 
the polyaniline or derivative thereof, obtained from step (i); and (iii) 
when necessary, adding water, C.sub.1 -C.sub.3 alcohol or mixture thereof, 
and preferably a metal compound, such as ZnO, and a neutralization agent, 
such as CaCO.sub.3, to the mixture obtained from step (ii). 
According to another, but not quite as preferred embodiment, a 
substantially dry polyaniline or derivative thereof may be mixed with a 
protonic doping acid and possibly other components, and water or C.sub.1 
-C.sub.3 alcohol or mixture thereof are added thereto. These are mixed to 
serve as the initial material for compounding. 
As was mentioned above, the components of step (a) of the method according 
to the invention, or the blend recovered in step (c) can, according to one 
embodiment, be combined with a thermoplast. A conductive polymer mixture 
is produced which has the properties of a commercial thermoplast but 
which, owing to its conductive polymer, is electrically conductive, so 
that it is suitable for being used, for example, for electrostatic 
discharge elimination (ESD), and electromagnetic interference shielding 
(EMI). 
The thermoplast used in the method according to the invention may be any 
homo- or copolymer or any mixture thereof with each other or with other 
additives. According to one embodiment the thermoplast is or contains a 
homo- or copolymer which is based on an olefin, a homo- or copolymer which 
is based on styrene or a derivative thereof, a vinyl homopolymer or vinyl 
copolymer, a thermoplastic condensation polymer, or a mixture of these. 
In general, the proportion of thermoplast in a commercial material is high, 
and according to one embodiment of the present invention, this proportion 
is approximately 50-99 wt. %, preferably approximately 70-95 wt. % of the 
combined total amount of the mixture from step (a) and a thermoplast. 
The mixing in step (b) is carried out by compounding by any standard-type 
mixing apparatus intended for a viscoelastic material. It may be an 
extruder in which the cylinder temperature and the temperature profile are 
adjustable, and quite particularly a double-screw extruder, in which the 
screw pitch and the direction of the helix and of rotation may vary. Also 
internal mixers, such as Banbury mixers, which are in wide commercial use, 
can be used. For example, heatable double-roll mills are suitable for 
small-scale production. From the viewpoint of the invention it is 
essential that the mixture of step (a) is mixed using relatively high 
shear forces in order to accomplish the desired solidification of the 
product. 
It is advantageous if the mixing in step (b) is performed at a temperature 
of 80.degree.-300.degree. C., preferably 100.degree.-200.degree. C. 
As stated above, various additives may also be added to the blend recovered 
from the melt mixing apparatus. One such additive is the above-mentioned 
metal compound, which both neutralizes and plasticizes the blend without 
the electric conductivity of the blend being substantially lowered. The 
blend obtained from step (c) may also be combined with a thermoplast of 
the types mentioned above. When the blend recovered in step (c) is 
combined with the metal compound, the calcium carbonate and/or the 
thermoplast, according to one embodiment of the invention, the combined 
composition is fed into a melt-mixing apparatus, in which it is mixed at a 
temperature of approximately 80.degree.-350.degree. C., preferably 
approximately 130.degree.-230.degree. C. In this embodiment, two mixings 
by means of shear forces and heat are carried out, one of them on the 
mixture of step (a) and the other on the blend recovered in step (c). 
Examples are of this embodiment of the present invention are presented 
below. However, these examples only illustrate, and do not limit, the 
present invention.. 
Example 26 
By the screw solidification method a conductive polymer complex was 
prepared which contained 9.7 wt. % EB wet from a water wash (dry matter 
content approximately 50%), 71.4 wt. % DBSA, 7.7 wt. % ZnO, 1.5 wt. % 
CaCO.sub.3, and 9.7 wt. % water. A mixture was prepared from the 
conductive polymer complex prepared in the manner described above and 
Neste HD polyethylene (NCPE 3415) at a mass ratio 10/90, the conductivity 
of pieces extruded from this mixture being 3.5.*10.sup.-5 S/cm measured by 
the 4-probe method. 
Example 27 
By the screw solidification method a conductive polymer complex was 
prepared which contained 9.7 wt. % EB wet from an ethanol wash (dry matter 
content approximately 50%), 71.4 wt. % DBSA, 7.7 wt. % ZnO, 1.5 wt % 
CaCO.sub.3 and, 9.7 wt. % water. A mixture was prepared from the 
conductive polymer complex prepared in the manner described above and 
Neste HD polyethylene (NCPE 3415) at a mass ratio 10/90, the four-probe 
conductivity of pieces extruded from this mixture being 1.2 *10.sup.31 4 
S/cm. 
Example 28 
A mixture was prepared from a conductive polymer complex prepared in the 
manner described in Example 27 and Neste HD polyethylene (NCPE 3415) at a 
mass ratio 8/92, the four-probe conductivity of pieces extruded from this 
mixture being 2.2 *10.sup.-5 S/cm. 
Example 29 
By the screw solidification method a conductive polymer complex was 
prepared which contained 6.2 wt. % EB dried after an ethanol wash (dry 
matter content higher than 99%), 83.4 wt. % DBSA, 8.9 wt. % ZnO, and 1.5 
wt. % CaCO.sub.3. A mixture was prepared from the conductive polymer 
complex prepared in the manner described above and Neste HD polyethylene 
(NCPE 3415) at a mass ratio 8/92, the four-probe conductivity of pieces 
extruded from this mixture being lower than 1 *10.sup.-9 S/cm. 
Example 30 
A complex which contained 7.5% EB dried after an ethanol wash (dry matter 
content higher than 99%), 82.2 wt. % DBSA, 8.8 wt. % ZnO, and 1.5 wt. % 
CaCO.sub.3 was solidified by heating it in a dielectric analyzer at a rate 
of 3.degree. C./min. The solidification temperature (determined as the 
maximum point of the tangent of loss) was 160.degree. C. 
Example 31 
A complex which contained 6.5 wt. % EB dried after an ethanol wash (dry 
matter content higher than 99%), 72.6 wt. % DBSA, 7.9 wt. % ZnO, 1.5 wt. % 
CaCO.sub.3, and 12 wt. % water was solidified by heating it in a 
dielectric analyzer at a rate of 3.degree. C./min. The solidification 
temperature was 110.degree. C. 
Example 32 
The procedure used was that of the preceding examples, but the mixing 
proportions were those set forth in Table 1. The results are also shown in 
Table 1. 
TABLE 1 
__________________________________________________________________________ 
Proportionate amounts of additives 
Exp. 1 
Exp. 2 
Exp. 3 
Exp. 4 
Exp. 5 
Exp. 6 
Exp. 7 
Exp. 
Exp. 
__________________________________________________________________________ 
9 
PANI EB 6.0% 6.0% 6.8% 7.2% 6.0% 6.0% 6.0% 6.0% 6.0% 
DBSA 66.3% 66.3% 
63.8% 62.6% 
66.3% 66.3% 66.3% 66.3% 66.3% 
ZnO 7.1% 7.1% 6.6% 6.4% 7.1% 7.1% 7.1% 7.1% 7.1% 
Water 19.4% 19.4% 
21.9% 23.1% 
19.4% 19.4% 19.4% 19.4% 19.4% 
CaCO3 1.2% 1.2% 0.9% 0.7% 1.2% 1.2% 1.2% 1.2% 1.2% 
Matrix plastic and its 
proportionate amount 
Matrix PVC PVC PVC PVC PP/SB PVC HDPE PP PS 
Amount % 90 85 90 90 80 85 80 80 85 
Conductivity 
1.00e-04 
5.00e-03 
1.00e-04 
6.00e-07 
3.00e-04 
5.00e-03 
1.00e-03 
1.00e-05 
5.00e-04 
__________________________________________________________________________ 
Example 33 
The procedure used was that described in the preceding examples, but the 
proportions of ingredients and the results were in accordance with Table 
2. 
TABLE 2 
______________________________________ 
Proportionate amounts of additives 
Exp. 1 Example 8 Example 9 Example 10 
______________________________________ 
6.0% 5.1% 4.4% 4.4% PANI EB 
66.3% 55.5% 47.8% 47.8% DBSA 
7.1% 5.9% 5.1% 5.1% ZnO 
19.4% 32.4% 41.9% 41.9% water 
1.2% 1.0% 0.9% 0.9% CaCO3 
Matrix 
plastic and 
its propor- 
tionate 
amount 
PVC PVC PVC PVC Matrix 
90 90 90 90 Amount % 
1.00e-04 
as in as in as in Conductivity 
Example 1 Example 1 Example 1 
______________________________________ 
The invention being thus described, it will be obvious that the same may be 
varied in many ways. Such variations are not to be regarded as a departure 
from the spirit and scope of the invention, and all such modifications as 
would be obvious to one skilled in the art are intended to be included 
within the scope of the claims.