FI119247B - An electrically conductive plasticizer composition and a process for making it - Google Patents

Description

. 119247 An electrically conductive plasticizer composition and process for its manufacture

The present invention relates to a plasticizer composition according to the preamble of claim 1.

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Such a composition generally has a conductivity of about 10 'to 10' S / cm.

The invention also relates to a process according to the preamble of claim 8 for the preparation of an electrically conductive plasticizer composition and to a process according to the preamble of claim 17 for the production of an electrically conductive PVC film.

The fabric coated with polyvinyl chloride (PVC) can be used to make e.g. hoses. These are used as air conditioning pipes in tunnels and mines. Fabric hoses are practical for this purpose because they are easy to install and require simple support structures. However, especially in dusty mining conditions, the plastic hose easily generates static electricity, which can cause sparks. Of course, this can be very dangerous. Therefore, the hoses should be made electrically conductive so that static electricity cannot be generated.

20 It is known to manufacture electrically conductive hoses using carbon powder as a conductive component among PVC coatings. The coating is accomplished by melt processing techniques such as: *. "Calendering. An example of the prior art is U.S. Patent 6 5,066,422, which insulates carbon black-containing PVC alloys to produce • · ·: * ·· films.

··· _ _:: 25 • · · *: · *: There are significant drawbacks to prior art. Thus, the carbon powder is easily dusty and thus quite dirty. It is also difficult for the product to lurk because carbon dust gives the product a basic black color. In addition, carbon dust makes it difficult to fine tune the electrical conductive properties of the fabric without degrading the mechanical properties.

It is an object of the present invention to eliminate the drawbacks of the known solution and to provide a neat production technique for the manufacture of electrically conductive films. Especially. · · ·. It is an object of the invention to provide an electrically conductive plasticizer composition by which the electrical conductivity of a polymer composition can be modified. It is also an object of the invention to provide a composition which can be made into a film which is easy to dye and has very high conductivity values and good mechanical strength.

The invention is based on the idea of producing an electrically conductive plasticizer composition having an electrical conductivity of 10'2 to 10'9 S / cm by mixing a plasticizer with a non-conductive polyaniline to form a plasticizer blend and adding a non-conductive polyaniline anion to the plasticizer blend. to form a doped plasticizer composition. Such a plasticizer composition typically comprises about 50 to 95 parts by weight of a thermoplastic plasticizer and 50 to 5 parts by weight of polyaniline and counterions thereof, which together form a doped polyaniline complex which is dissolved or dispersed in the plasticizer.

From the plasticizer composition, an electrically conductive PVC film can be made by spraying a fluid PVC composition containing this composition to form a layer, after which the mixture is allowed to solidify to form a film. If necessary, the film may be detached from the substrate (e.g. transfer paper).

More specifically, the plasticizer composition of the invention is essentially characterized in what is set forth in the characterizing part of claim 1.

The process for preparing the plasticizer composition according to the invention has. ***. 25, in turn, is characterized in what is stated in the characterizing part of claim 8 and in the method of making the conductive PVC film according to the invention, which: 1 ": is represented in the characterizing part of claim 17.

The invention provides significant advantages. Thus, the solution can advantageously produce a conductive plasticizer composition that can be mixed with a variety of different poly (1) (, a polymer, especially a thermoplastic (plastic)) to provide a migration-free * · • j · · · polymer blend. , sheets and similar polymeric products that can be sealed by welding, for example. · · ··· 3 119247 plasticizer for easy handling and mixing of the composition with the polymer dispersions The electrical conductivity can be controlled by the amount of polyaniline and its dopant. the component does not significantly affect the strength properties of the polymer product.

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In the following, the invention will be explored in more detail by means of a detailed description and a few embodiments.

As stated above, the plasticizer composition of the invention is electrically conductive.

Its electrical conductivity is then typically in the range of 10'2 to 10'9 S / cm, typically greater than about 10-6 S / cm. The composition contains at least two components, namely a thermoplastic (thermoplastic) plasticizer and a doped polyaniline complex. The latter is dissolved or dispersed in the plasticizer so that the solid particles do not separate from the composition while standing. Typically, the polyaniline complex 15 has a particle size of less than 100 µm, usually less than 50 µm, preferably about 1 to 30 µm, in the plasticizer phase.

The plasticizer generally accounts for more than half of the weight of the plasticizer composition, although concentration limits can vary widely. Preferably, the composition contains 50 to 99 parts by weight of "*". "20 plasticizers and 1 to 50 parts by weight of a doped polyaniline complex. The composition may, however, include other components, the most important of which are the unbound dopant; possible additives and excipients, such as metal compounds used for pH adjustment.

·· * ·· • * ··· *. ♦.

:, ((: 25) The thermoplastic plasticizer is usually selected from the group consisting of dialkyl phthalate, dialkyl terephthalate, trialkyl or triaryl phosphate, ester of aliphatic acids, * * V. * such as dialkyl diacetate, dialkyl sebacate or sulfonic or benzoic acid · epoxylated oil or a mixture thereof These are typical plasticizers used as plasticizers of PVC Preferred plasticizers include dialkyl phthalates having the same or different alkyl groups, comprising a linear or branched carbon chain. are then C7 ... C9 dialkyl phthalates, i.e. mixtures of such esters, as well as dioctyl phthalate and di-isooctyl phthalate.

4, 119247

In the aniline polymer, the monomer is aniline or a derivative thereof, the nitrogen atom of which is mainly bound to the carbon of the para-position of the benzene ring of the following unit. Unsubstituted polyaniline can exist in various forms, of which the so-called "polycarbonate" is generally used for conductive polymer applications. emeraldine. Polyaniline can be doped into a conductive polyaniline complex, in particular with protic acids, examples of which are HCl, H2SO4, HNO3, HClO4, HBF4, HPF6, HF, phosphoric acids, sulfonic acids, picric acid, n-nitrobenzoic acid, dichloroacetic acid. Preferably, a functional acid is used for doping, for example a sulfonic acid, especially an aromatic sulfonic acid such as dodecylbenzenesulfonic acid (DBSA), camphorsulfonic acid, para-toluenesulfonic acid or phenolsulfonic acid. An excess of acid can be used to plasticize the mixture. A suitable metal compound such as zinc oxide may be used to compensate for the acidity. A calcium compound such as calcium carbonate may also be added. The pH of the mixture is e.g. 3-8, usually about 4-7. The preparation of polyaniline complexes is described in detail in, for example, EP-A-545 729 and 582 919 and FI-A-932557,932578 and 940626.

The polyaniline complex preferably contains polyaniline, such as emeraldine form polyaniline, from 1 to 20 wt.%, Preferably from 4 to 10 wt.%, Doping acid such as DBSA, from 50 to 90 to 20 wt.%, Preferably from 60 to 85 wt.%.

j '·· An example of a preferred plasticizer composition is a composition which is; V comprises about 3 to 8 parts by weight of polyaniline, about 70 to 90 parts by weight of plasticizer, and »*: **: about 5 to 20 parts by weight of the counter ion of polyaniline, the amount of counter ion being ... i.2 about 2-4 times the amount of polyaniline. In addition, it contains from about 1% to about 10%, based on the amount of doping agent * ··· * · *, of an inorganic compound that at least partially neutralizes the excess dopant and thereby raises the pH of the composition to a suitable level. The composition when mixed with a PVC emulsion forms a substantially non-migrated PVC mixture.

According to the invention, the above-described composition can be prepared by a two-step process. In the first step, the plasticizer is mixed with a polyaniline in a non-conductive · 9 · 9 · · ** form to form a plasticizer mixture.

«· · • * · • * • · •» »a • ·· • · 5 119247

The constituents of the plasticizer composition are usually mixed together substantially without additional heating. However, the temperature of the composition increases during mixing, whereby it varies between 25 and 50 ° C during the mixing operation.

In a second step, a counterion of a non-conductive polyaniline is added to the plasticizer mixture thus produced to dopen the polyaniline and form a doped plasticizer composition. The doped plasticizer composition is stirred for 1-48 hours at about 30-50 ° C. However, the temperature may be higher. A doping mixture comprising a polyaniline counter ion and an activator capable of accelerating doping is then added to the plasticizer mixture. The activator is preferably a volatile compound which can be removed from the plasticizer composition by evaporation. Such activators include alkanoic acids, especially formic acid and acetic acid, with formic acid being particularly preferred. Preferably, the activator is removed by vacuum and raising the temperature of the composition to about 35-150 ° C.

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According to a preferred embodiment, 3 to 8 parts by weight of polyaniline and about 70 to 90 parts by weight of plasticizer are mixed together to form a diluent mixture containing about 5 to 20 parts by weight of a polyaniline counterion and 1 to 10 parts by weight of activator.

From the above plasticizer composition, the desired electrically conductive polymer films can be prepared by coating or coating a suitable substrate with a mixture of a plasticizer composition and · ·· Senja. Coating can be done by brush or *** · roll coating.

··· ♦ · * ... · 25 '' Jointing Technique 'generally refers to coating methods in which a fluid polyaniline complex mixture is first applied to a base fabric or a substrate by means of 1' brushes or rollers, followed by matured or solidified into a film.

·· · * 1: The surfactant mixture preferably contains a flux, such as a plasticizer or solvent, to provide ···: ... 1 30 the desired fluidity. The mixture is generally heatable (i.e.; ** '; cure). Upon heating, volatile substances such as solvents are also removed.

«« «· 6 119247

Usually, some other plastic and additives are also added to the mixture. Coating is preferably done using a brush blade technique whereby the plastic blend is applied to the fabric web to form a smooth layer with a brush blade. After application, the web is preferably passed into a maturing furnace, where the mixture forms a continuous film on the fabric. After maturation, any necessary post-treatment such as smoothing or patterning and cooling is carried out.

The product surface resistance obtained varies with the amount of polyaniline complex and coating thickness. The surface resistance is e.g. about 104 to 109, preferably 105 to 10 Ω / sq.

The method according to the invention can be used to produce a firm and elastic fabric.

The fabric can be lacquered. It can be made into a hose by joining the edges of the web together. Joining together can be done using bulk sequence welding. The hose can be used especially as a ventilation pipe for mines and tunnels.

15 The fabric can also be used in other applications requiring protection against static electricity or electromagnetic radiation. Applications may include, for example, protective covers used in industrial fire or explosion sensitive situations, storage tanks (eg biogas collecting bags) and conveyor belts. Possible applications include shields for electronic devices or military applications. The fabric is best suited for • \ # 20 applications where it is not exposed to high levels of UV radiation.

♦ ♦ «· • ♦::::: ·:: · · · · amiseksi · sa amiseksi amiseksi amiseksi amiseksi amiseksi pol pol pol pol amiseksi pol pol pol amiseksi pol pol pol pol amiseksi amiseksi amiseksi pol pol pol pol pol pol pol pol Polyaniline “**: For a good mixing, it is good to first grind, for example, with a · · · Σ ... J 25 pin mill to the smallest possible particle size. A suitable particle size is, for example, 1 to 200 µm, especially 5 to 100 µm, most preferably 10 to 50 µm.

• · • «· · · · ···

In addition to the polyaniline complex, other compatible: ***: plastics, in particular PVC, are preferably used. Other useful plastics include, for example, polyacrylates, polyurethanes, polyethylene vinyl acetate, polyvinylidene chloride, polyvinyl acetate,. polyvinyl alcohol, synthetic latexes, silicones, epoxy resins and suitable mixtures thereof ··· ....: (e.g. ethyl vinyl acetate and PVC).

119247 PVC is preferably emulsion grade having a particle size of less than 60 µm. The mixture may contain a sulfonamide as an antistatic additive.

For example, the proportion of polyaniline complex in the final coating plastic composition may be from 0.1 to 30% by weight, preferably from 1 to 20% by weight, preferably from 5 to 15% by weight.

In addition, suitable additives such as plasticizers, stabilizers, flame retardants, colorants, lubricants, and modifiers may be used. The most commonly used plasticizer in PVC products is dialkyl phthalate, dialkyl terephthalate, trialkyl or triaryl phosphate, esters of aliphatic acids such as dialkyl diphatate, dialkyl sebacate or sulfonic or benzoic acid esters, or an epoxidized oil. The most commonly used stabilizers are metal soaps, inorganic salts (e.g. barium and lead salts), organotin compounds and epoxy compounds. Suitable coloring agents can be both organic and inorganic suitable materials. The lubricants may be, for example, long chain alcohols or various waxes.

For example, fabric, paper, cardboard or similar film-like and / or sheet-like substrates may be used as the substrate for the adhesive. Among the base fabrics, various fabrics and nonwovens can be mentioned. The tissue material may be, for example, polyester or polyamide.

· * · ,, 20 The base fabric is usually coated on both sides with e.g. PVC or: * · *: a halogen-free plastic such as a mixture of polyethylene methacrylic acid and polyethylene.

• * *: ··· Add a coating adhesive to the base fabric.

· · · · · · · * ·· * ί * ': A suitable base fabric can be obtained, for example, by covering the mesh with PVC- ···!, En! 25 mixture first by brushing and then calendering. If the fabric has a yarn count of more than about 6.5 threads per cm, a simple coating is sufficient.

• * • · # • · * • · • * »; When plastic other than the polyaniline complex is used in the coating composition, a: '· *; first make the plastics a dry mix, then add the desired rennet and any additives • «: *]: 30. The preparation of dry blends is described, for example, in EP-A-497 514 and a. FI applications 935889 and 941783. Alternatively, flux, plastic and desired additives may be added to the polyaniline-I complex.

8 119247

The following non-limiting examples illustrate the invention:

Example 1

Impact of the quality of DOD on the properties of the final product

Example IA Uodacyl TPB as dodecylbenzenesulfonic acid

4.68 g of polyaniline (Panipol Oy, EBR1 Lot 28) and 80.2 g of dioctyl phthalate plasticizer (Bisoflex DOP) were stirred with a magnetic stirrer for 5 min.

To the mixture was added a doping acid mixture prepared by stirring 1 S, 12 g dodecylbenzenesulfonic acid (Ufacid TPB, Unger Fabrikker A / S) and 6.5 g 85% formic acid at room temperature for 5 min. The acids were added over a period of about 10 min. During the addition, the temperature of the reaction mixture rose from room temperature to about 35 ° C, at which temperature the reaction was continued for a total of 24 h by stirring the mixture throughout the reaction with a magnetic stirrer. The product was evaporated the next day formic acid in vacuo for about 8 h. At the same time, the temperature of the product was gradually raised to 55 ° C.

When the distillation of formic acid was completed, the product was cooled. The conductive PVC film was manufactured on a laboratory scale according to the following recipe: 20 · 50 g conductive polyaniline complex, above • **: · 50 g emulsion PVC · 2 g stabilizer • *** * ... * · 3 g Carbonate paste or titanium dioxide T1O2 ( dye) • · ··· * · * ··· * 25 The materials were mixed thoroughly. After mixing, the mixture was further comminuted in a paste mill. The paste mill treatment rendered the mixture more homogeneous and • · *; [♦ * particle size minimized.

Then, 20 g of isopropanol was added to the comminuted mixture with vigorous stirring.

···: "30 After mixing, the textile fabric was coated on both sides by a coating process. The PVC film formed during the coating was kept in an oven at 165 ° C: ** for 2.5 minutes to gell the finished product.

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In the tests performed, the surface resistance was 1.2 + E5 Ω / sq.

Example IB Dodecylbenzenesulfonic acid Ufacid K

The experiment of Example IA was performed by converting only dodecylbenzenesulfonic acid grade Ufacid TPB to Ufacid K. The conductive complex had a lower viscosity and was better treated in tests performed compared to the complex of Example IA, and the surface resistance of the final product was 1.0 ... 1.2 + E5 Ω / sq.

Example 1C Uodacid KW as dodecylbenzenesulfonic acid

The experiment of Example IA was performed by converting only dodecylbenzenesulfonic acid grade Ufacid TPB to Ufacid KW. The conductive complex was lower in viscosity and better handled compared to the complex of Example IA. In the tests, the surface-15 resistance of the final product was higher than in Examples IA and IB and was about 1.5 + E6 Ω / sq.

Example 2

Effect of reaction time on final product quality · * · .. 20 1.81 kg of polyaniline (Panipol Oy, EBR1 Lot 28) and 28.96 kg of dioctyl phthalate: * · *: plasticizer (Bisoflex DOP) were stirred in the reactor for 15 min. To the mixture was added • ♦ *: **: a doping acid mixture prepared by mixing 5.46 kg of dodecylbenzene: sulfonic acid (Ufacid K) and 2.35 kg of 85% formic acid at room temperature for 15 min.

The acids were added over a period of about 20 min. During the addition, the temperature of the reaction mixture rose from room temperature ··· 25 to 40 ° C, at which temperature the reaction was continued for a total of 10 h. Stirring of the reaction mixture was intensified by turning on the homogenizer about 9 hours after reaction. The product was evaporated the next day with formic acid * ··· in vacuo for about 5 h. At the same time, the temperature of the product was gradually raised to 95 ° C.

: **]: When the distillation of formic acid was completed, the product was cooled and packaged for transport. i 30 dishes.

ΦΙ · 1 2 3 2 • · • · 3

The reaction mixture was sampled after 5 h, 8 h, 10 h. The samples were evaporated formic acid on a Rotavapor evaporator, as described above.

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The electrical conductivity values of the products were measured as surface resistance measurement after processing according to Example 1. The resistances of the conductive polyaniline complex were 5.9E + 05 Ω / sq (5h) and 5.66E + 05 Ω / sq (8h) and 1.4E + 05 Ω / sq for the final product. As a result of the measurements, the best result was obtained with the longest reaction time.

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Example 3

Preparation of a Composition on a Pilot Scale as Dodecyl Benzenesulfonic Acid Ufacid K

1.81 kg of polyaniline (Panipol Oy, EBR1 Lot 28) and 28.96 kg of dioctyl phthalate-10 plasticizer (Bisoflex DOP) were stirred in the reactor for 15 min. To the mixture was added a mixture of dental acid prepared by mixing 5.46 kg of dodecylbenzenesulfonic acid (Ufacid K) and 2.35 kg of 85% formic acid at room temperature for 15 min. The acids were added over a period of about 20 min. During the addition, the temperature of the reaction mixture rose from room temperature to about 35 ° C, at which temperature the reaction was continued for a total of 10 h. The next day, the product was evaporated off formic acid in vacuo for about 5 h.

At the same time, the temperature of the product was gradually raised to 90 ° C. When the formic acid distillation was complete, the product was cooled and used to prepare a conductive PVC film according to the following recipe: 4 · • '· * 20 · 30 kg of the conductive polyaniline complex mentioned above • V · 30 kg of PVC emulsion *!' *; · 1.2 kg of stabilizer · 1.8 kg of soot paste or titanium dioxide T1O2 (dye) «* * *» «* · ***** The substances were mixed thoroughly. After mixing, the mixture was further comminuted. In a 3 roll mill with a roll spacing of 40 to 50 µm. Roller mill treatment gave • · • · · *. I blend more homogeneous and minimize particle size.

Subsequently, 12 kg of isopropanol was added to the comminuted mixture with stirring • 1 '*; · * 30 carefully. After blending, the textile fabric was coated by a brushing or ··· *. „: Gravure printing process. The PVC film produced during the coating process was heated to about 165 ° C: ° C, whereby it was gelled to a finished product. The film was then inverted and 119247 π one side coated in the same way. In the tests performed, the finished PVC film had a surface resistance of 1.6E + 05 / sq.

Example 4

Preparation of a Composition on a Pilot Dimension of Dodecyl Benzenesulfonic Acid Ufacid TPB

1.81 kg of polyaniline (Panipol Oy, EBR1 Lot 28) and 28.96 kg of dioctyl phthalate plasticizer (Bisoflex DOP) were stirred in the reactor for 15 min. To the mixture was added dental acid mixture prepared by mixing 5.46 kg dodecylbenzene-10 sulfonic acid (Ufacid TPB) and 2.35 kg 85% formic acid at room temperature for 15 min. The acids were added over a period of about 20 min. During the addition, the temperature of the reaction mixture rose from room temperature to about 35 ° C, at which temperature the reaction was continued for a total of 10 h. The product was evaporated the next day in formic acid in vacuo for about 5 h.

At the same time, the temperature of the product was gradually raised to 90 ° C. When the distillation of formic acid 15 was completed, the product was cooled. . The product was cooled and packed in shipping containers for further processing A sample of conductive polyaniline complex was measured for electrical conductivity. The resistance value was found to be 1.76E + 07 Ω / sq. After the further process described in Example 3, the conductivity level was lower than in Example 3.

j * \. Due to the low conductivity level, the reaction was continued and M · | was added to the product. 1.8 kg of formic acid. The reaction time was 8 h. Formic acid was distilled off under vacuum: as above. The product was cooled and packed in shipping containers. The ··· :: resistance value for the product was 9.73E + 05 Ω / sq.

The quality of dodecylbenzenesulfonic acid has a significant effect on the time of preparation of the composition, but by continuing the reaction, the conductivity value can be significantly improved.

♦ «· 1 1 1 Sek 1 1 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 vaikutus Example 5« e:: ♦ Effect of Blend and Polyvinyl Quality on End Product: 30

Three batches (5a, 5b and 5c) of the composition of Example 3 were prepared. In the first two experiments (5a and b), a batch of polyaniline EBR1 Lot28 was used as polyaniline, and in the next experiment (5c) a batch of EBR Lot29 was used. The reaction was carried out as described in Example 12119247, except that in Experiment 5a, a homogenizer was used throughout the reaction at 1500 rpm and in Experiment 5b at 3000 rpm. In Experiment 5c, processing was performed as in Experiment 5b. The conductivity levels of the products were measured as resistance measurements as described in Example 1.

The resistance values of the test products were 5a: 6.02E + 04 Ω / sq, 5b: 2.35E + 04 and 5c, 86E + 06 as evaluated in Example 3. From the results it can be concluded that the efficiency of mixing slightly decreased the resistance level. Polyaniline quality was also found to have an effect on the conductivity level of the final product.

Example 6

Effect of processing temperature and pre-mixing garden 1.81 kg of polyaniline (Panipol Oy, EBR1 Lot 29) and 28.96 kg of dioctyl phthalate plasticizer (Bisoflex DOP) were stirred in the reactor for 60 min. Stirring was intensified with an IS homogenizer (3000 rpm) The temperature of the reaction mixture was raised to 45 ° C during stirring. To the mixture was added a mixture of dental acid prepared by mixing 5.46 kg of dodecylbenzenesulfonic acid (Ufacid K) and 2.35 kg of 85% formic acid at room temperature for 15 min. The acids were added over a period of about 10 min. During the addition, the rpm of the homogenizer was reduced to 1500 rpm and doubled at the end of the addition. After the addition, the temperature of the reaction mixture was raised to 50 Γ **: ° C, at which temperature the reaction was continued for a total of 10 h. The product was evaporated the next day in formic acid in vacuo for about 5 h. At the same time, the product temperature was gradually raised to 95 ° C. When the formic acid distillation was complete, the product ***** was cooled and packed in transport containers.

»« · 25

The conductive PVC film was prepared as described in Example 3 without roll mill treatment.

* »• · · '· *. * The conductivity level of the final product was determined by surface resistance measurement and was 1.25E + 04 • * Ω / sq. The result showed that the quality of the conductive complex is clearly better because no roll mill • e · treatment is required. At the same time, the result indicates a rise in processing temperature and a pre-mixing time of · ··! ...: 30 for a positive effect on product quality.

e • · • · «·· <· 13 119247

Example 7 A

Ufacid TPB as dodecylbenzenesulfonic acid

4.68 g of polyaniline (Panipol Oy, EBR1 Lot 28) and 80.2 g of C7-C9 dialkyl phthalate 5 plasticizer (Bisoflex L79P) were stirred in a magnetic stirrer for 5 min. To the mixture was added a mixture of dental acid prepared by mixing 15.12 g of dodecylbenzenesulfonic acid (Ufacid TPB) and 6.5 g of 85% formic acid at room temperature for 5 min. The acids were added over a period of about 10 min. The temperature of the reaction mixture increased from room temperature to about 35 ° C during the addition, at which temperature the reaction was continued for a total of 10 hours for 24 hours by stirring the mixture with a magnetic stirrer. The product was evaporated the next day formic acid in vacuo for about 8 h. At the same time, the temperature of the product was gradually raised to 55 ° C. When the distillation of formic acid was completed, the product was cooled. A conductive PVC film was prepared on a laboratory scale according to the following recipe: 15 • 50 g of conductive polyaniline complex above • 50 g of PVC emulsion • 2 g of stabilizer • 3 g of carbon black or titanium dioxide T1O2 (dye) 20: ***: The materials were mixed thoroughly. After mixing, the mixture was further comminuted in a *: ** paste mill. By paste mill treatment, the mixture was made more homogeneous and the particle size was minimized.

Then, 20 g of isopropanol was added to the comminuted mixture with vigorous stirring.

After blending, the textile fabric was coated on both sides by a coating method. The PVC film formed during the coating was kept in an oven at 165 ° C ··· * ”· 1 for 2.5 minutes, whereby it was gelled to a finished product.

M · • 1. · In the tests performed, the surface resistance was 1.0 + E5 Ω / sq * · 30

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* · • # ·· «14 119247

Example 7B

Dodecylbenzenesulfonic acid Ufacid K

The experiment of Example 7A was performed by converting only the dodecylbenzene-5 sulfonic acid grade Ufacid TPB to Ufacid K. The conductive complex was lower in viscosity and better treated compared to the complex of Example XA. In the final tests, the surface resistance of the final product was 1.5 + E5 Ω / sq.

Example 7C

10 Dodecylbenzenesulfonic acid Ufacid KW

The experiment of Example 7A was performed by converting only the dodecylbenzene sulfonic acid grade Ufacid TPB to Ufacid KW. The conductive complex was lower in viscosity and better treated compared to Example 7A Complex In the tests performed, the surface resistance of the final product 15 was worse than that of Examples 7A and 7B, being about 2.0 + E6 Ω / sq. • a • • a aaa • a • a aaa a aaaa «• · aaa • · • a aaa • aaaaaa * aa aaa aaaa aaa aa aaa aaa · aaa aaaa aaa aaa aaaa aaa

Claims (23)

An electrically conductive plasticizer composition having an electrical conductivity of 10'2 to 10'9 S / cm, characterized in that it comprises SO-95 parts by weight of a thermoplastic plasticizer and 50-5 parts by weight of polyaniline and its counterions together form a doped polyaniline complex dissolved or dispersed in a plasticizer. A plasticizer composition according to claim 1, characterized in that the thermoplastic plasticizer is selected from dhtalkyl ifphthalate, dialkyl terephthalate, trialkyl or triaryl phosphate, an ester of an aliphatic acid such as dialkyl diacapate, a dialkyl sebacate or an ester of a sulfonic or benzoic acid. A plasticizer composition according to claim 1 or 2, characterized in that the plasticizer is a dialkyl phthalate having the same or different alkyl groups and comprising a linear or branched carbon chain of 1-9 carbon atoms. A plasticizer composition according to claim 3, characterized in that the plasticizer is dioctyl phthalate or di-isooctyl phthalate. : *. 20 A plasticizer composition according to any one of the preceding claims, characterized by a · · •; · · · That the polyaniline counterion is derived from dodecylbenzenesulfonic acid, camphorsulfonic acid, p-toluenesulfonic acid or phenolsulfonic acid; a mixture. ···:: 25 · «· The plasticizer composition according to any one of the preceding claims, characterized in that it comprises from about 3 to about 8 parts by weight of polyaniline, from about 70 to about 90 parts by weight of plastics and about 5 to about 20 parts by weight of polyaniline. a counterion, wherein the amount of counterion is; * · *; in parts by weight about 2 to about 4 times the amount of polyaniline. • · ··· ΑΛ; ; 30 ···. ···. A plasticizer composition according to any one of claims 1 to 5, characterized in that it contains an excess of a doping agent neutralizing inorganic compound such as zinc oxide. 119247 8. A process for the preparation of an electrically conductive plasticizer composition, characterized in that the plasticizer is mixed with S polyaniline in a non-conductive form to form a plasticizer mixture, and - a counterion of non-conductive polyaniline is added to the plasticizer mixture to dopen the doped plasticizer composition. 9. A method according to claim 8, characterized in that a doping mixture comprising a polyaniline counterion and an activator capable of accelerating doping is added to the plasticizer mixture. Process according to Claim 9, characterized in that the activation is a volatile compound which is removed from the plasticizer composition by evaporation. Process according to claim 9 or 10, characterized in that the activator is formic acid or acetic acid. A method according to any one of claims 8 to 11, characterized in that φ · * · *; mixing 3-8 parts by weight of polyaniline and about 70-90 parts by weight of plastic; • · *: ··; and a doping agent mixture containing about 5 to 20 parts by weight of a polyaniline counterion and 1 to 10 parts by weight of the activator. ···: i 25 ··· The method according to any one of claims 8 to 12, characterized in that the ingredients of the · · V plasticizer composition are mixed together substantially without additional heating. · * · • · * • · • · A method according to any one of claims 8 to 13, characterized in that. the doped plasticizer composition is stirred for 1 to 48 hours at about 30 to 50 ° C. ·· ♦ • · 17 1 1 9247 Process according to any one of claims 9 to 14, characterized in that the activator is removed by vacuum and raising the temperature of the composition to about 35-150 ° C. Process according to any one of claims 9 to 15, characterized in that the polyaniline is EB (emeraldine base), the plasticizer of the thermoplastic material is dialkyl phthalate, dialkyl terephthalate, trialkyl or triaryl phosphate, ester of aliphatic acids such as dialkyldiapate, benzyl or oil or a mixture thereof, and dodecylbenzene-10 sulfonic acid, camphorsulfonic acid, p-toluenesulfonic acid or phenolsulfonic acid, or a mixture thereof, is used as the polyaniline dopant. 17. A process for the production of an electrically conductive PVC film, characterized in that 10 to 50 parts by weight of the 15 plasticizer composition according to claim 1, 1 to 90 parts by weight of a PVC emulsion and 0 to 10 parts by weight are known. and dyes to form a PVC blend, - the blend is applied to the substrate as a continuous layer, and - the layer is allowed to solidify to form a film. Process according to claim 17, characterized in that the layer is solidified by bringing it to a temperature of at least 120 ° C, preferably at least 150 ° C. · ♦ • # • ·· Γ **: Method according to claim 17 or 18, characterized in that the PVC mixture is · · ·: · *: comminuted and optionally diluted before application to the substrate. ···:: 25 · »· Process according to one of Claims 17 to 19, characterized in that the plasticizer composition, the PVC emulsion and any auxiliary and coloring agents are mixed together in a dissolver or roll mill or similar mixing device. • · • «• · * *** · * ... * 30 A process according to any one of claims 17 to 20, characterized in that: * ·: an additional PVC plasticizer which is a dialkyl phthalate, is added to the PVC mixture: * * ϊ dialkyl terephthalate, trialkyl or triaryl phosphate, an ester of aliphatic acids (Is 1 1 9247 dialkyl diacetate, dialkyl sebacate or ester of sulphonic or benzoic acid, or epoxylated oil or a mixture thereof). Method according to one of Claims 17 to 21, characterized in that the substrate 5 comprises a textile fabric or a paper substrate. A method according to any one of claims 17 to 22, characterized in that the product coated with the PVC film has a surface resistance of at least about 1 x 10 6 Ω / sq. ••••••••••••••••••••••••••••••••••••••••• * • · »··· · · · ♦ • · · · · · · ··· 119247 2 9