ITMI950088A1 - PROCEDURE FOR ANCHORING A PERFLUOROPOLYMER TO A SUBSTRATE - Google Patents

Abstract

PROCESS FOR ANCHORING A LAYER OR MANUFACT OF A PERFLUOROPOLYMER TO A SUBSTRATE, CONSISTING OF BETWEEN SAID PERFLUOROPOLYMER AND THE SUBSTRATE, AN ADHESIVE MIXTURE INCLUDING: (A) A (CO) POLYMERHYLENE POLYMETER DIMETHYLENE POLYLUHURETHANE. VINYLIDENE FLORIDE, AND (C) EVENTUALLY, AT LEAST ONE INORGANIC CHARGE, A CROSS-LINKING SYSTEM OF THE ELASTOMERIC COPOLYMER (8) AND / OR A BRIDGE AGENT; AND IN SUBMITTING THE ADHESIVING MIXTURE APPLIED AT LEAST ONE HEAT TREATMENT.

Description

Description of the industrial invention

The present invention relates to a process for anchoring a perfluoropolymer to a substrate.

More particularly, the present invention refers to a process for anchoring a layer or manufactured article of a perfluoropolymer based on tetrafluoroethylene to a substrate to which it is applied or to reinforcing fillers, by means of the use of an intermediate layer which ensures its membership.

Perfluoropolymers are well-known products, characterized by a combination of chemical-physical characteristics particularly useful in various fields of application, such as anti-friction, non-stick, hydro / oil repellence, high thermal resistance, chemical agents and low dielectric constant; due to these properties, perfluoropolymers are useful as coating materials in a wide variety of applications ranging from the coating of tools in the food sector (non-stick), to the coating or coating of polymers in the mechanical sector (anti-friction or self-lubrication, seals), in the chemical one (chemical and solvent resistance), the electronic one (insulation, response of the dielectric constant to the frequency, thermal resistance) etc.

The characteristics of great chemical inertness of perfluoropolymers, together with the low surface tensoin, however, make their anchoring to surfaces difficult.

Various methods have been proposed to overcome this difficulty; they consist:

a) superficially modifying the nature of the polymer by means of chemical-physical reactions to make it bondable,

b) in treating the substrate with chemical (pickling) or physical (sandblasting) means in order to increase the contact surface and the interpenetration with the polymer which in this case must be melted on the substrate,

c) interposing between the perfluoro polymer and the substrate a layer of intermediate material (primer) which promotes the adhesion between the two otherwise incompatible materials.

The preparation of perfluoropolymer products with surfaces modified for the purpose of their bonding is, however, complex, requiring a specific plant for chemical attack, the use of aggressive substances, and produces products that have gluing characteristics that can decay over time. .

The physico-chemical modifications of the substrate, alone, are not sufficiently effective for anchoring perfluoropolymers, except for those that create dendritic chromium deposits on the surface, which however have limitations of use deriving from the toxicity of the products used.

The compositions known as "primers" are not without drawbacks; in fact, those containing water-soluble salts can cause, by diffusion of water through the perfluoropolymer, the creation of high osmotic pressure pockets with adhesion losses and the formation of bubbles (blistering). The compositions not containing water-soluble salts allow to obtain good and long-lasting adhesions but must in any case be applied to substrates that have undergone accurate pickling or sandblasting treatments. Furthermore, the application possibilities on perfluoropolymer products to make the surface of the latter glue with normal cold glues, nor the applicability to reinforcing fillers of the perfluoropolymers themselves in order to make them intimately wettable by the polymer are not known. , and, therefore, endowed with real reinforcing characteristics.

The object of the present invention is to overcome the drawbacks of the compositions known as "primers" for perfluoropolymers.

More particularly, the object of the present invention is to improve the versatility of the "primer" with respect to the different supports to which the different perfluoropolymers are adhered.

According to the present invention these for other purposes, which will emerge from the following description, are obtained by using a tackifying mixture comprising:

(A) a perfluorinated (co) polymer of tetrafluoroethylene; (B) a fluorinated elastomeric copolymer based on vinylidene fluoride, ed

(C) optionally, at least one inorganic filler, a cross-linking system of component (B) and / or a mounting agent.

Component (C) is used according to the different materials to which the perfluoropolymers adhere and may also be missing.

The above mixture can be used both as an adhesive, in a thin layer, or in bulk. It has excellent adhesive properties both for the perfluoropolymers and for the substrate to be coated. Furthermore, it has good deformability characteristics without therefore losing the adhesive characteristics due to its elastomeric component.

For these properties it can be used in various situations including some typical examples, which however cannot be considered exhaustive, include:

anchoring perfluoropolymer-based paint formulations to substrates made of different materials; anchoring of perfluoropolymer products to different supports;

treatment of fillers or reinforcements to be used in perfluoropolymers to obtain manufactured articles in which the reinforcement effect, due to the filler, is enhanced by the adhesion of the filler itself to the polymeric matrix.

The procedure necessary to obtain the best anchoring characteristics, given the breadth of the application sectors, varies in detail for each different situation; the common and qualifying point is in any case the need for a heat treatment to which the supported adhesive layer must be subjected.

Thus, for example, in the case of the application of perfluoropolymer products on metal or glass surfaces or on other materials, the process comprises the treatment of the product with the "primer" of the present invention, a thermal cycle, cooling and cold gluing with the support. medinte interposition of a conventional glue.

In the case of applying a perfluoropolymer-based paint to a metal or glass surface or to another material, the process comprises the treatment of the support with the "primer" of the present invention, a first thermal cycle, painting with perfluoropolymer and a second cycle thermal. The temperature and time of the thermal cycles are adjusted according to the substrate.

In the case of a printable or extrudable perfluoropolymer reinforced with inorganic fillers or reinforcements, the process consists in treating the filler or reinforcement with the "primer" of the present invention, in carrying out a first thermal cycle to anchor the "primer" to the reinforcement, in mixing the filler or reinforcement treated with the polymer and, therefore, in subjecting the mixture to the process of transformation into an artifact.

Therefore, the subject of the present invention is a process for anchoring a layer or manufactured article of a perfluoropolymer to a substrate, consisting in interposing between said perfluoropolymer and the substrate an adhesive mixture comprising:

(A) a perfluorinated (co) polymer of tetrafluoroethylene; (B) a fluorinated elastomeric copolymer based on vinylidene fluoride, ed

(C) optionally, at least one inorganic filler, a cross-linking system of component (B) and / or a scaffolding agent,

and in subjecting this supported tackifying mixture to at least one heat treatment.

According to the treated materials, the heat treatment has the purpose of anchoring the adhesive mixture, case by case: to the substrate so that it is not removed in case of subsequent processing necessary to obtain the product comprising the perfluoropolymer; to the perfluoropolymer product before cold gluing; or again both to the substrate and to the perfluoropolymer by means of a single heat treatment that brings the part involved in the adhesion process to a sufficient temperature.

The heat treatment is chosen according to the materials constituting the substrate and the perfluorinated (co) polymers used both as component (A) of the mixture and as perfluoropolymer to be anchored. The best results are obtained when the heat treatment reaches at least the melting temperature of the highest melting perfluoropolymer present in the area affected by the adhesion process. However, acceptable results are also obtained if it is the lowest melting perfluoropolymer of the same area that melts. Temperatures ranging from the melting point of said perfluoropolymers to 50 ° higher can be used.

From the above, it follows that a polytetrafluoroethylene (PTFE) coating can be anchored to substrates that do not resist the melting temperature of PTFE using a copolymer of tetrafluoroethylene with perfluoropropene (FEP) in the known composition as component (A) of the adhesive mixture. having a melting point of about 80 ° C lower than that of PTFE. The substrate treated with this tackifying mixture, containing this type of FEP as component (A), after the coating of the PTFE, is subjected to a heat treatment that reaches the melting temperature of the FEP; after this heat treatment, the substrate and the PTFE coating are intimately welded together.

In the event that the substrate does not even resist the melting temperature of the particular type of low-melting FEP, the anchoring can also be obtained by treating the PTFE coating with the adhesive mixture, subjecting the coating thus treated to a heat treatment sufficient to guarantee at least melting the lowest melting fluoropolymer, and cold gluing the coating to the substrate with suitable commercial adhesives.

The perfluorinated (co) polymer of tetrafluoroethylene, used as component (A) in the mixture of the present invention, comprises polytetrafluoroethylene (PTFE), the copolymers of tetrafluoroethylene with perfluoropropene (FEP) in all weight ratios between the monomer units, and the copolymers perfluorinated tetrafluoroethylene with the perfluorovinylalkyl ethers in which the alkyl group contains from 1 to 5 carbon atoms, such as for example perfluoro (methylvinylether). The latter copolymers are generally known as PFAs. Blends of these polymers can also be employed. Polymers of tetrafluoroethylene suitable for use in the present invention are PTFE and its copolymers containing up to 12 mol% of hexafluoropropene or up to 5 mol% of perfluorovinylalkyl ethers.

The perfluorinated (co) polymers of tetrafluoroethylene can be used in the form of aqueous dispersion or in the form of fine powders. Generally the dimensions of the polymeric particles are comprised between about ten micrometers to 0.05 micrometers.

The aqueous dispersions of these perfluorinated (co) polymers are preferred for obtaining adhesive mixtures to be applied in a thin layer.

The perfluorinated (co) polymers of tetrafluoroethylene have a number average molecular weight of at least 20,000, preferably between 200,000 and 1,500,000, measured according to the method described by Suwa, Takehisa and Machi in Journal of Applied Polymer Science, Vol. 17, pages 3252-3257 (1973).

The fluorinated elastomeric copolymers based on vinylidene fluoride, used as component (B) of the mixture of the present invention, comprise, in moles, from 35 to 85% of vinylidene fluoride (VDF), from 15 to 35% of hexafluoropropene (HFP ) and from 0 to 30% of tetrafluoroethylene (TFE). Such fluorinated elastomeric copolymers can have molecular weights ranging from 5,000 to 500,000. They are products widely known in the art and are described for example in Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 11 p. 64 and following (1980) and in "Polymer", 27, 906 (1986). They are available on the market in the form of aqueous dispersion or solid polymer, under different trade names, such as Tecnoflon®, Viton®, Fluorel®, Daiel®, etc.

The aqueous dispersion of these copolymers can be prepared directly by carrying out the polymerization of the monomers in an aqueous emulsion, as described in Kirk-Othmer reported above or in J. Polymer Sci., Then. Physic Ed.22, 357 (1984).

The mixture is preferably prepared by adding the elastomeric polymer (B) to the perfluorinated (co) polymer (A).

Any known technique which allows to obtain a complete and homogeneous mixing of the components can be used. Thus, for example, the aqueous dispersions of the two components (A) and (B) can be mixed; or the fluorinated elastomeric copolymer (B) can be dissolved in an organic solvent and subsequently the perfluorinated (co) polymer (A), in the form of a fine powder, is added to the solution. The solvent thus used performs a solvent and dispersing action. The solvents that can be used can be those described in US-A-4,764,431, such as esters, such as methylene or ethylene acetate; ketones, such as acetone and ethylmethylketone, ethers such as tetrahydrofuran, methylterbutyl ether, methyl isobutyl ether, optionally in admixture with a chlorofluorocarbon. The azeotropic mixture consisting of acetone and 1,1,2-trichlorotrifluoroethane (12.5: 87.5 in moles) can be used as an organic solvent.

Alternatively, a dry mixture of the two components (A) and (B) can be prepared in the form of solid polymers, for example in an open mixer such as in a calender or in Banbury and the resulting mixture optionally dissolved in an organic solvent; or the mixing of the two components (A) and (B) in the form of granular polymers can be carried out in ceramic ball mills or in microsphere mills with the help of suitable liquid vehicles.

The dry quantities of components (A) and (B) in the mixture of the present invention are not critical and can vary over a wide range. Generally, the perfluorinated (co) polymer (A) is present in an amount comprised between 5 and 95% by weight, preferably between 15 and 85% by weight, with respect to the sum of the components (A) (B). Correspondingly, the amount of elastomeric copolymer based on vinylidene fluoride (B) varies between 95 and 5% by weight, preferably between 85 and 15% by weight, with respect to the sum of components (A) (B).

As stated above, the tackifying mixture of the present invention can contain inorganic fillers, cross-linking systems and / or bridging agents. Other additives, such as swelling agents and / or porous agents, can be added to the tackifying mixture of the present invention.

The inorganic fillers possibly added to the tackifying mixture of the present invention can be colloidal silica in aqueous dispersion, conventionally stabilized at basic pH with soda, precipitated silica, silicates, aluminum-silicates, metal oxides, carbon black and other pigments. These products can be in powder form or pre-dispersed in a suitable fluid vehicle, have a particle size preferably not exceeding 10 times the maximum particle size of the polymers used and are added in quantities ranging from 0 to 50% by weight on the dry basis with respect to the total mixture.

The cross-linking system of the fluorinated elastomeric copolymer (B) can be an amine, a di-, tri- or tetra-hydroxyl derivative of benzene, naphthalene or anthracene, an organic peroxide and a quaternary compound of ammonium, phosphonium or aminophosphonium or mixtures of these. These crosslinking agents are added in an effective amount, generally comprised between 0 and 5% by weight with respect to the fluorinated elastomeric copolymer (B).

Compounds capable of establishing primary or secondary chemical bonds both with the fluorinated elastomeric copolymer (B), thanks also to the presence of the cross-linking system, and with the substrate are used as mounting agents. The mounting agent is added in an effective amount and is chosen according to the fluorinated elastomeric component and the type of substrate. Examples of mounting agents include organo-silanes, titanates, zirconates; in particular, organ silanes having amine end groups and those having acrylic end groups have proved useful.

The presence of these additives (C) allows to improve the mechanical characteristics, chemical resistance and adhesion of the adhesive mixture to the various substrates with a choice of constituents that depends on the materials used each time. The presence of this component (C) allows, in the case of particular but widely used substrates such as aluminum, to reduce the preparation of the substrate surface to simple degreasing, avoiding other treatments such as sandblasting, in-depth chemical pickling, etc.

The presence of component (C) also allows the mixture to be transformed into an article, such as for example a sheet, which can be made to adhere intimately to perfluoropolymer sheets and substrates in the press and to heat treatments satisfying the aforementioned requirements.

The tackifying mixture used in the process of the present invention can be applied in the form of an aqueous dispersion or in an organic solvent carrier when a faster drying is required or is convenient for the type of substrate used. In all cases, the mixture can be applied by means of known techniques that are more suitable each time, such as, for example, coextrusion, casting, dipping, spreading, spraying, rolling, molding, etc.

The quantity of adhesive mixture to be applied per surface unit depends on the characteristics of the surface itself, such as porosity; in general, the total amount of mixture applied, on dry matter, varies between 1 and 2000 g / m <2>.

The adhesive mixture used in the process of the present invention can constitute an intermediate layer between a perfluoropolymer and any substrate useful for its support; by way of example we cite its possible application on cookware to be subsequently painted with PTFE-based formulations, on PTFE sheets to be glued subsequently, even cold, on mechanical parts, fillers or reinforcing fibers to be used in obtaining PTFE artifacts,

After the application of the adhesive mixture, a first heat treatment is carried out with the purpose of evaporating any solvents or fluid vehicles present in it and of achieving a first anchoring of the mixture to the substrate in order to be able to subject it to any subsequent processing. The higher the temperature reached during this heat treatment, up to the maximum consisting of a temperature approximately 50 ° higher than the melting temperature of the higher melting perfluoropolymer of component (A), the greater the anchoring of the primer. This thermal treatment, which can be unique in the case in which the substrate is a perfluoropolymer manufactured article, is generally followed by the coupling of the substrate thus treated to the perfluoropolymer or of the perfluoropolymer thus treated to the substrate, with all the known means and technologies of coupling . Simultaneously or subsequently, this first heat treatment can be followed by a second definitive heat treatment which balances, thanks to the intermediate mixture, substrate and perfluoropolymer. Also in this case, the maximum temperature of the heat treatment depends on the substrates used and, in any case, the best results are obtained when the parts involved in the adhesion process remain in intimate contact at a temperature at least equal to the melting temperature of the highest melting perfluoropolymer present. , for an adequate time which generally varies from 10 seconds to 10 minutes. In the case of manufactured articles reinforced with fibers treated with the adhesive mixture of the present invention, this time can be even longer and reach 24 hours.

The anchoring process of the present invention is useful for all substrates to which a perfluorinated (co) polymer is permanently adhered. Specific examples are, among those known: non-stick kitchen dishes, · oven shelves intended for the heat treatment of sticky materials; mechanical parts such as small parts, machine parts, rollers, tanks, pipes, eco molds. to which to impart anti-friction, non-stick, chemical and solvent resistance together with the thermal resistance of the polymers used; artifacts requiring dielectric strength, constancy of the dielectric constant with respect to the signal frequency, resistance to fouling and hydro-oil repellence, such as, for example, current insulators or other details used in the electrical and electronic sector; parts of machines in which it is useful to achieve qualities of water repellency, non-adhesion or reduction of the boundary layer, such as boats, airplanes, etc.

To improve the stability, workability or filmability of the tackifying mixture used in the process of the present invention, various substances of the conventional type can be added. These substances include coalescing agents, spreading agents, dispersants, surfactants, stabilizers, antistats, etc. Examples of these substances include: diethylene glycol monomethyl ether, xylene, dimethylformamide, N-methyl pyrrolidone, etc.

The following examples are given only for illustrative and not limitative purposes of the present invention.

Example 1

In a container equipped with a stirrer, a tackifying mixture was prepared by adding, under stirring, the following components in order:

35% by volume of an aqueous dispersion of PTFE at 60% by weight of dry type D60V, produced and sold by Soc. AUSIMONT S.p.A., Milan (component A);

30% by volume of an aqueous dispersion of a fluoroelastomer terpolymer at 60% by weight of dry type FBT, produced and sold by Soc. AUSIMONT S.p.A., Milan (component B);

30% by volume of colloidal silica at 30% by weight of dry stabilized with soda at pH 9.5 approx. type KEMPROSIL 30 / ii, produced and sold by KEMPRO ITALIA, (component C);

3% by volume of diethylene glycol monomethyl ether, e

2% by volume of xylene.

The mixture thus prepared was applied by spray, in a uniform layer of about 10 microns, on a previously degreased shiny aluminum plate. The plate was allowed to dry at room temperature. A PTFE paint consisting of.

90% by volume of an aqueous dispersion of PTFE of the above type as component A;

7% by volume of diethylene glycol monomethyl ether;

3% by volume of xylene;

up to a thickness of about 8 microns on dry matter.

The substrate treated with the intermediate layer and the paint preparation was left to dry in air and was subsequently heated to a temperature of 375 ° C in 5 minutes and was kept at this temperature for 1 minute, then removed from the stove and left to cool.

The layer shown on the plate was beige in color and glossy in appearance, and gave the ASTM D3359 test results of adhesion between 5 and 4, judged to be very good (scale between 0 and 5).

This example highlights the reduction of chemical pickling treatments usually performed on the aluminum substrate in the production of manufactured articles for food use.

Example 2

Operating according to example 1, a tackifying mixture was prepared comprising: 55% by volume of the aqueous dispersion of PTFE used as component A in example 1; 41% by volume of the aqueous dispersion of fluoroelastomer used as component B of Example 1; 2% by volume of xylene, and 2% by volume of aminopropyltriethoxysilane type A 1100 (produced and sold by the UNION CARBIDE ITALIA company).

The resulting mixture was immediately sprayed on a degreased glass plate type E up to a thickness of 5 microns on the dry and left to dry in air. The PTFE-based paint preparation of Example 1 was then sprayed onto the dry layer up to a thickness of 7 microns on the dry layer. After firing with the same thermal cycle as in example 1, the slide appeared slightly darkened, with the polymer coatings adhering to the surface with a semi-gloss appearance. The adhesion value, measured by the ASTM D3359 method was level 4.

Transparent coating results can be obtained by applying the adhesive layer and the paint formulation by immersion.

The above example is applicable in the field of current insulators, lights, etc., in order to preserve these products from too rapid fouling and the formation of surface layers of unwanted characteristics (low insulation with the possibility of discharges, low transparency, etc. ). Example 3

Operating according to the modalities of example 1, a tackifying mixture was prepared comprising:

35% by volume of an aqueous dispersion of FEP type 120 (TFEM and HFP copolymer) at 55% in dry matter, produced and sold by Soc. Du Pont Italia S.p.A., Milan (component A);

30% by volume of an aqueous dispersion of the fluoroelastomer used as component B of Example 1;

30% by volume of colloidal silica of the type used as component C of Example 1;

3% by volume of diethylene glycol monomethyl ether, e

2% by volume of xylene.

The resulting mixture was sprayed (thickness approx. 10 microns) on half of a vulcanized sheet based on a copolymer fluoroelastomer TECNOFLON <®> FOR 45 from AUSIMONT S.p.A., Milan (thickness 2.5 mm) made with the following compound :

TECNOFLON <®> FOR 45: 100 parts by weight;

Magnesium oxide: 5 parts by weight;

Calcium hydroxide: 5 parts by weight,

MT carbon black: 25 parts by weight.

The vulcanization cycle was treated in a press at 170 ° C for 10 minutes, in an oven at 250 ° C for 16 hours, 8 hours of rise.

The vulcanized sheet partially covered by the adhesive mixture was left to dry in air, and subsequently, on the half already treated, a paint based on FEP 120 (copolymer of TFEM and del HFP), sold by DU PONT ITALIA, Milan, with the following formulation:

95% by volume of FEP 120 in aqueous dispersion at 55% by weight of dry material used as component A of Example 3; 3% by volume of diethylene glycol monomethyl ether;

2% by volume of xylene.

The sheet thus treated was left to dry, and subsequently surface treated with a jet of hot air at about 300 ° C until the FEP layer melted. The fusion is easily identifiable as the melting zone changes color from whitish to transparent.

Two tests were performed on the sheet thus treated: the adhesion test, ASTM D3359, which gave results at the highest level (5), and

that of diffusion of solvent consisting in depositing on both surfaces, treated and untreated, 0.5 cc of acetone, · it has been rapidly absorbed by the untreated surface, which swells evidently in the area; while, in the treated surface it spread very slowly, evaporating almost entirely and leaving the contact area only slightly altered.

Example 4

Operating according to the modalities of example 1, a tackifying mixture was prepared consisting of:

35% by weight of the aqueous dispersion of FEP used as component A in Example 3;

30% by weight of the aqueous fluoroelastomer dispersion used as component B in Example 3;

25% by weight of colloidal silica used as component C in Example 1;

5% by weight of powdered bentonite having an average particle size of about 5 microns;

2.5% by weight of xylene, e

2.5% by weight of diethylene glycol monomethyl ether.

The adhesive mixture thus obtained was applied by spray on a part of a PTFE sheet (thickness 300 microns) obtained by peeling a sintered product and allowed to dry in air. This sheet was then subjected to a heat treatment at 300 ° C for one minute.

From the sheet thus treated, 2 strips 2 cm wide were obtained. and 20 cm long, one of which is obtained from the treated part, the other from the untreated part.

The strips were covered for 2/3 of their length with a layer of bicomponent paste-like epoxy glue and kept in contact, at room temperature, with a previously degreased shiny aluminum plate for 24 hours.

The detachment test, carried out by pulling the free ends of the two specimens, led to the detachment as a whole of the untreated PTFE strip, which left a layer of shiny glue adhering to the aluminum; while it has led to the breaking of the treated strip, as it is strongly anchoring to the metal.

Claims (20)

CLAIMS 1. A process for anchoring a layer or product of a perfluoropolymer to a substrate, consisting in interposing between said perfluoropolymer and the substrate a tackifying mixture, characterized in that said tackifying mixture comprises: (A) a perfluorinated (co) polymer of tetrafluoroethylene; (B) a fluorinated elastomeric copolymer based on vinylidene fluoride, ed (C) optionally, at least one inorganic filler, a cross-linking system of the elastomeric copolymer (B) and / or a mounting agent, and that the applied tackifying mixture is subjected to at least one heat treatment. 2. Process according to claim 1, characterized in that it consists of: applying the tackifying mixture to the substrate; subjecting the substrate thus treated to a first drying and anchoring heat treatment; apply a layer of perfluoropolymer, and subject the coupled substrate-perfluoropolymer to a second anchoring heat treatment. 3. Process according to claim 1, characterized in that it consists of: apply the adhesive mixture to the perfluoropolymer product; subjecting the product thus treated to the heat treatment, e cold glue the treated product to the substrate using an adhesive. 4. Process according to claim 1, characterized in that it consists of: applying the tackifying mixture to the substrate; apply the adhesive mixture to the perfluoropolymer product; couple the substrate to the treated article, and subject the substrate-perfluoropolymer coupled to the heat treatment. 5. Process according to claim 1, characterized in that the substrate is an inorganic filler or a reinforcing material and that said process consists of: apply the tackifying mixture to the filler or reinforcing material; subjecting the filler or reinforcement material thus treated to a first drying and anchoring heat treatment; mixing the filler or reinforcement material thus treated with the perfluoropolymer, e transform the resulting mixture into an artifact. 6. Process according to any one of the preceding claims, in which the total quantity of tackifying mixture applied, on the dry basis, varies between 1 and 2000 g / m <2>. 7. Process according to any one of the preceding claims, in which the heat treatment is carried out at a temperature at least equal to the melting temperature of the highest melting perfluoropolymer present in the area affected by the adhesion process. 8. Process according to any one of the preceding claims, wherein component (A) is a copolymer of tetrafluoroethylene with perfluoropropene having a melting point of about 80 ° C lower than that of polyperfluoroethylene (PTFE) and the heat treatment is carried out at a temperature at least equal to the melting temperature of this copolymer. 9. Process according to any one of the preceding claims, in which the temperature of the thermal treatment is between the melting temperature of the perfluoropolymer and 50 ° higher than that of said perfluoropolymer. 10. Process according to any one of the preceding claims from 1 to 6, in which the perfluoropolymer is treated with the tackifying mixture and the product thus obtained is subjected to a heat treatment carried out at a temperature at least equal to the melting temperature of the lower fluoropolymer fusion point. 11. Process according to any one of the preceding claims, wherein the perfluorinated (co) polymer (A) is selected from polytetrafluoroethylene (PTFE), the copolymers of tetrafluoroethylene with perfluoropropene (FEP) in all weight ratios between the monomer units, the perfluorinated copolymers of tetrafluoroethylene with the perfluorovinylalkyl ethers in which the alkyl group contains from 1 to 5 carbon atoms (PFA) and their mixtures. Process according to any one of the preceding claims, wherein the perfluorinated (co) polymer (A) has a number average molecular weight of at least 20,000, preferably between 200,000 and 1,500,000. 13. Process according to any one of the preceding claims, wherein the perfluorinated (co) polymer (A) is selected from polytetrafluoroethylene (PTFE) and its copolymers containing up to 12% by moles of hexafluoropropene or up to 5% by moles of perfluorovinylalkyl ethers. Process according to any one of the preceding claims, wherein the perfluorinated (co) polymer (A) is in the form of an aqueous dispersion. 15. Process according to any one of the preceding claims, wherein the fluorinated elastomeric copolymer based on vinylidene fluoride comprises, by moles, from 35 to 85% of vinylidene fluoride, from 15 to 35% of hexafluoropropene and from 0 to 30% of tetrafluoroethylene and has a molecular weight between 5,000 and 500,000. 16. Process according to any one of the preceding claims, wherein the dry quantity of the perilurinated (A) (co) polymer varies between 5 and 95% by weight, preferably between 15 and 85% by weight, and, correspondingly, the quantity of elastomeric copolymer based on vinylidene fluoride (B) varies between 95 and 5% by weight, preferably between 85 and 15% by weight, with respect to the sum of components (A) (B). 17. Process according to any one of the preceding claims, in which the tackifying mixture contains from 0 to 5% by weight, with respect to the fluorinated elastomeric copolymer (B), of a cross-linking system selected from an amine, a di-, tri- or derivative tetra-hydroxyl of benzene, naphthalene or anthracene, an organic peroxide and a quaternary compound of ammonium, phosphonium or aminophosphonium and mixtures thereof. 18. Process according to any one of the preceding claims, wherein the tackifying mixture contains an effective amount of a mounting agent selected from organo-silanes, titanates and zirconates, preferably from organ-silanes having amino end groups and those having end groups acrylics. 19. Process according to any one of the preceding claims, in which the tackifying mixture contains from 0 to 50% by weight on the dry basis with respect to the total mixture of at least one inorganic filler selected from colloidal silica in aqueous dispersion stabilized at basic pH with soda, precipitated silica , silicates, aluminum-silicates, metal oxides, carbon black and other pigments. Process according to any one of the preceding claims, wherein the tackifying mixture contains coalescing, spreading, dispersing, surfactant, stabilizing and / or antistatic agents.