MXPA00007992A - Use of a composition or premix based on volatile corrosion inhibitors, composition or premix, articles comprising said composition and preparation method - Google Patents

Abstract

The invention concerns the use of a composition or premix based on volatile corrosion inhibitors comprising, in order to limit to a maximum the release and/or degradation of the volatile corrosion inhibitors when the composition or premix is being formed, either an efficient amount of a structuring agent consisting of at least one solid or pasty substance whereof the melting point ranges from 40 to 110°C, preferably from 50 to 90°C, or a liquid substance capable of forming, mixed with a mineral filler, a solid or pasty combination. The invention also concerns a composition based on volatile corrosion inhibitors comprising a composition based on volatile corrosion inhibitors comprising an efficient amount which contains an efficient amount of a solid structuring agent. The invention further concerns polymer based articles having as constituent said composition or premix;said article are useful for protecting metal parts against corrosion.

Description

UTI LIZATION OF A COMPOSITION OR MIXING BASED ON IN HI BIORES OF VOLATILE CORROSION. COMPOSITION OR MIX.

ARTICLES THAT HAVE THIS COMPOSITION AND ITS PROCEDURE OF PREPARATION The object of the invention is the use of a composition or premix based on volatile corrosion inhibitors in order to limit the degradation or liberation of volatile corrosion inhibitors as much as possible after the preparation of said composition. It also refers to a composition or premix based on volatile corrosion inhibitors. It also refers to articles based on polymers and in which one of the components is constituted by this composition or premix, as well as the process for preparing these articles, which particularly comprise packaging films, packagings constructed from plates based on polymers. It also refers to articles in the form of solid pastes, based on structuring agents, and wherein one of the compounds is constituted by said composition or premix. It finally refers to the use of said composition and articles for the protection of metal parts against corrosion. It is known to use volatile corrosion inhibitors when it comes to protecting against corrosion corrosion sensitive metal parts, particularly those that are made of mild steel based on carbon content and which, once manufactured, are issued as such its place of destination by maritime container with a view to its completion in its place, particularly of painted; the risks of corrosion are then considerable, particularly when the parts in question are routed to hot and humid areas. The volatile corrosion inhibitors offer, in these conditions, a very good protection against corrosion and have the advantage of avoiding having to resort to conventional techniques of protection of metal parts; these conventional techniques consist of the application of paints, varnishes, plastics, waxes, fats and oils that it is convenient to eliminate before finishing at the place of destination, which causes additional costs and pollution. The volatile corrosion inhibitors, generally indicated by ICV, put into operation the additives in which the vapor tension can be considered as not negligible at the temperature of use, (for example, in the order of 10"s to 10" 1 mm of Hg. , at 20 ° C), and that are able to inhibit the corrosion of metals. These ICVs act thanks to the fact that they are brought in the form of vapor to the metal surface to be protected, to be adsorbed or dissolved in an eventual condensation water. Products which are classified by extension in the ICV are also known due to the fact that one of their reaction products has an adequate vapor tension. Thus, for example, sodium nitrite, in the presence of ammonium ions, can form ammonium nitrite that is relatively volatile. The starting sodium nitrite is then considered as an ICV. It is recommended to use a mixture of different products classified by extension in the ICV in an inert liquid vehicle to obtain an optimal anticorrosion effect whatever the composition of the material to be protected (BE 702592). When the metal parts to be protected are packed in the films, the ICV are incorporated into the constituent material of these films; Given that these films can be found in direct contact with the surface of the parts to be protected, corrosion inhibitors that act by contact are also incorporated in the constituent mass of these films. The advantages of this protection technique for packing in a film containing the ICVs reside in a great facility to put in work and a global protection being given that the vapors penetrate in the most inaccessible sites of the pieces of complex forms without it being necessary have to resort to a cleaning or prior preparation, being eliminated on the other hand any operation of deprotection and all contamination. Sometimes it is necessary not to protect against corrosion but only parts of metal parts of important dimensions and complex geometry. The pasty solids conditioned by the usual techniques of the polymer industry (molding, modeling, extrusion) give the metallic pieces the necessary localized protection, minimizing the costs considerably. In order to incorporate the ICV into the constituent mass of the films or other packaging articles which are often based on thermoplastic polymers, it is known to make direct mixtures of ICV powders with the polymers and to directly form by extrusion or blowing the packing films. or massive pieces such as plates. At the extrusion temperature which is about 160 ° C for low density polyethylene and 240 ° C for polypropylene, ICVs have an extremely high volatility which leads, in the case of the manufacture of a film, to the appearance of a strong porosity and a high risk of degradation and / or decomposition with elimination of at least part of the ICV. The effectiveness from the anticorrosion point of view of such films is therefore strongly diminished as a result of the loss of active materials. To remedy this drawback, that is to limit the loss of ICV during the actual preparation of the finished articles, it has been proposed to resort to the mixtures containing the ICV, ie to the concentrates of active material dispersed in supports such as polymers. , solvents and plasticizers; the polymer-based premixes (Patent BR-A-9001035) have the general advantage of being homogeneous and easy to handle; these premixes are then incorporated into the polymers in order to prepare the packaging articles. However, since the temperatures used at the time of preparation of the premixes are often greater than 150 ° C, the degradation, at least partially, of said premixes is aided; thus, and by way of example, it is pointed out that the nitrite of dicyclohexylamine, mixed and extruded with polyethylene at 160 ° C, leads to the premix granules which have a dark yellow coloration, characteristic of a strong degradation, ie of a loss of activity . To avoid these excessive heat degradations, it has been proposed to resort to oil-based liquid premixes that do not need to go through high temperatures during their manufacture (Patent EU-A-4 913 874). But since ICVs are often poorly soluble in these oily media, there is a heterogeneity of the premixtures obtained and the appearance of difficulties due to over-concentrations or low local concentrations during their subsequent incorporation into the polymers from which the finished films are constituted. It has also been proposed to remedy this drawback by resorting to liquid premixes in the form of solutions in solvents or oily ICVs, premixes that are not incorporated during extrusion, but applied to these films by spraying, thus forming, after evaporation of the solvent, either a powder coat of ICV (Patent DE 3 417 149 A 1), or an oily layer containing the ICV (Patent GB 2 188 274). The drawback of these premixes resides in the fact that the ICVs are not imprisoned in a matrix that imposes a slow release, being therefore the protection obtained from short duration. On the other hand, the adherence of the layers deposited on the articles is weak and leads to losses during the manipulations and to the obligation to clean the pieces before being protected, which is precisely what is wanted to be avoided. The object of the invention is, above all, to remedy the drawbacks of the prior art and to provide compositions based on ICV, which respond better than those already existing to the various requirements of the practice. It also aims to provide finished articles that implement at least one ICV-based composition according to the invention. The object of the invention is finally to provide new uses of these compositions based on ICV, such as the partial and localized protection of certain metal parts of large dimensions and complex shapes. And the Applicant Society has had the merit of finding, at the end of deep investigations, that these objectives are achieved, of course, leading to a composition based on volatile corrosion inhibitors, the appropriate structuring agents to penetrate the preparation of a mixture. at temperatures sufficiently low to limit the release and / or degradation of ICVs during this preparation to the maximum. Accordingly, the invention aims to use a composition or premix based on volatile corrosion inhibitors that entail, to limit as much as possible the release and / or degradation of the ICV at the time of formation of the composition or premix , either an effective amount of a structuring agent, constituted by at least one solid or pasty substance whose melting point is 40 to 1 10 ° C, preferably 50 to 90 ° C, either a liquid substance suitable for forming, in mixture with a mineral charge, a pasty or solid unit. According to an advantageous embodiment, in the use according to the invention, the composition comprises from 1 to 90%, preferably from 20 to 60% by weight of at least one volatile corrosion inhibitor and from 10 to 99%, preferably from 40 to 80% of at least one of the structuring agents defined below. According to another advantageous embodiment, in the use according to the invention, the composition comprises at least one structuring agent selected from the group or those comprising the aliphatic and / or resinous, solid or pasty, low melting point compounds. comprised between 40 and 1 10 ° C, preferably between 50 and 90 ° C. According to another advantageous embodiment of the use according to the invention, the structuring agent of the composition is selected from the group comprising the aliphatic organic compounds mono-or polyfunctional, linear and / or slightly branched with hydrocarbon chains having at least ten carbon atoms, including, in particular: mono- or dicarboxylic acids, optionally oxidized, saturated or unsaturated, their esters or their salts , -phosphoric, sulphonic and phosphonic acids, their esters with alcohols and their alkali metal, alkaline earth salts, d zinc, aluminum and / or organic amines, - cyclic or acyclic compounds of the group comprising lactones, ketones, aldehydes, amides and acetals, - higher alcohols, primary or secondary, cyclic or acyclic, optionally polyalkoxylated, hydrocarbon-based chain having at least ten carbon atoms, - linear and / or low branched aliphatic hydrocarbons, particularly paraffins and isoparaffins, - polyolefins and their low molecular weight copolymers of 3000 to 20,000 g / mol. polyglycols, particularly polyethylene glycols of molecular weight from 2000 to 10,000 g / mol. According to another advantageous embodiment of use according to the invention, the structuring agent of the composition is selected from the group comprising the resinous compounds having a polymeric and / or cyclic structure and which may contain, in a minor proportion, derivatives aromatics and cyclic terpenes in. According to another advantageous embodiment of the use according to the invention, the structuring agent of the composition is selected from the group of those identified in Table A below and of which some are waxes of natural or synthetic origin.

TABLE A The invention also aims at a composition or premix based on volatile corrosion inhibitors, characterized in that it entails an effective amount of at least one structuring agent, constituted by a solid substance whose melting point is 40 to 1. 10 ° C, preferably 50 to 90 ° C, this is due to the fact that the release and / or degradation of the ICV at the time of formation of the composition or premix is limited to the maximum. According to an advantageous embodiment, the composition according to the invention comprises from 1 to 90%, preferably from 20 to 60% by weight of at least one volatile corrosion inhibitor and from 10 to 99% by weight, of preferably from 40 to 80% of at least one structuring agent consisting of a solid substance whose melting point is 40 to 1 10 ° C, preferably 50 to 90 ° C. According to another advantageous embodiment, the composition according to the invention comprises at least one structuring agent selected from the group of those comprising the aliphatic and / or resinous, solid, low melting point compounds comprised between 40 and 1 10 ° C, preferably between 50 and 90 C. According to another advantageous embodiment, the composition according to the invention, the solid structuring agent is selected from the group comprising the organic mono- or polyfunctional, linear and / or slightly branched aliphatic organic compounds two with hydrocarbon chains having at least 10 carbon atoms, of which particularly: - the mono- or dicarboxylic acids, optionally oxidized, saturated or unsaturated, their esters and their salts, - phosphoric, sulphonic and phosphonic acids, their esters with alcohols and their alkali metal, alkaline earth metal, zinc, aluminum and / or organic amine salts, cyclic or acyclic compounds of the group comprising lactones, ketones, aldehydes, amides and acetals, -the higher alcohols, primary or secondary, cyclic or acyclic, optionally polyalkoxylated, with a hydrocarbon chain having at least ten carbon atoms, -the linear and / or low branched aliphatic hydrocarbons, particularly paraffins and isoparaffins, -the polyolefins and their copolymers with low molecular masses of 3000 to 20,000 g / mol. -Polyglycols, particularly polyethylene glycols with a molecular weight of 2000 to 10,000 g / mol. According to another advantageous embodiment of the composition according to the invention, the solid structuring agent is selected from the group comprising the resinous compounds having a polymeric and / or cyclic structure and which may contain, in smaller proportion, the aromatic derivatives and the cyclic terpenes. According to another advantageous embodiment, the composition according to the invention and the composition used according to the invention comprises at least one volatile corrosion inhibitor selected from the group comprising: - the nitrogenous derivatives and particularly, on the one hand, the aliphatic, aromatic, acyclic or cyclic amines of which diisopropylamine and benzylamine, their organic salts such as benzoates, carbamates, laurates, caprylates, succinates or minerals such as nitrites, nitrates, carbonates, phosphates, phosphites, and, on the other hand , heterocycles such as imidazole and its derivatives, triazoles and their derivatives, as well as hexamethylenetetramine, nitrogenous oxide derivatives such as the alkali metal or alkaline earth metal salts of nitrous acid and benzoic derivatives of these metals such as the sodium benzoate. It is possible to entail the composition used according to the invention or the composition and / or the finished articles according to the invention with one or more auxiliaries selected from the group comprising: anti-oxidants and / or degradation inhibitors such as bis-phenol A, butyl-hydroxy-toluene, di-tert-butyl-phosphite, trinonyl-phenoxy-phosphite, dilauryl-thio-dipropionate, - anti-UV agents absorb odors such as benzotriazoles, triazines, hydroxybenzophenones and radicalized inhibitors such as AES or amines with a Steric Impact and HALS or "Hindered Amine Light Stabilizer" in the English language, - external antistatic agents such as phosphoric ethers of ethoxylated alcohols and ethoxylated amine chlorides, or internal ones such as ethoxylated fatty amines, ethoxylated polyols and alkylsulfonates, - external or internal lubricating agents such as paraffins, fatty alcohols, fatty acids, fatty acid esters and fatty alcohols and amides, - plasticizing agents such as dioctyl phthalate, tricresyl phosphate and diesters of aliphatic acids, - the mineral pigments among which PbSO4, PbCrO4, CdS, ZnS, the organic pigments among which the azo derivatives, phthalocy children or anthraquinones and - flame retardants, including brominated and chlorinated compounds of phosphorus, hydrides of Al, Mg and Zn compounds, as well as epoxy oligomers, - mineral fillers such as chalk and carbonates, talcs, clays, silicas. These auxiliaries can also be added only at the time of incorporation of the composition into the polymer from which the articles according to the invention are made or in the structuring agent. These articles are characterized by the fact that at least one of their components is constituted by a composition according to the invention or by using a composition according to the invention, and that they are prepared, according to a first possibility, to starting from at least one polymer that enters at least 50% by weight in its constitution. Said polymers which enter at least 50% by mass in the constitution of the packagings and / or the articles can be selected from those of the group comprising: polyolefins, among which polyethylenes, polypropylene, polybutene and their copolymers with one or more unsaturated monomers such as vinyl acetate, acrylic acid and their esters with short carbon chain alcohols, - polyvinyl chloride and its copolymers, acrylic copolymers and their derivatives, and polyamides, polystyrenes , polycarbonates, polyesters, polyurethanes, rubbers such as natural rubber, styrene-butadiene and polychloroprene. These finished articles in the constitution of which the composition according to the invention enters or which use a composition according to the invention, comprise, not only the blown or rigid films, possibly retractable, but also other elements such as the threads, the possibly shaped tubes and possibly honeycomb plates, from which it is possible to form a conditioning comprising a more or less hermetic cavity filled with a confined atmosphere containing the ICVs from the composition or premix; it is in this cavity where the metal parts to be protected against corrosion are arranged. The packagings may be constituted by simple films, but also by assemblies of several of said elements, these assemblies being carried out by implementing any appropriate procedure such as stapling, crimping, thermoforming, peli-plating (translator's note: plates made from of films) or the manufacture of ampoules. The aforementioned plates can be obtained from two films according to the invention, leaving a space between these films, this space that can be presented in the form of alveoli, or a corrugated plexus obtained from a third film, the assemble the appearance of corrugated cardboard. The packages constituted from said plates, may present communication channels from inside the cavity delimited by the packaging with the outside, these channels having a diameter of less than one millimeter in general, thus allowing the passage of a limited flow of air only. The communication channels in question are established at the time of manufacture of the packages that carry the composition according to the invention or later. According to a second possibility and more precisely in the case where it is intended to ensure the protection against corrosion of a part only of a metal part, the article alluded to by the invention is essentially based on the composition according to the invention or of the composition used according to the invention, and comprises the doughs to be shaped or molded and the putties, the article thus constituted, which, due to its plastic nature, has the advantage of easy handling and allows the best form to be made at the last moment. adapted to the geometry of the part to be protected. It is recalled that the mastics comprise the polymers and that the pastes to be modeled which are free of polymers, contain the insoluble fillers such as the mineral fillers mentioned above. In the process of preparing these articles, it comprises, in general, successively a step of preparing a composition or pre-mix according to the invention and a subsequent step in the course of which the premix is incorporated into one of said polymers, packagings and the articles themselves being obtained particularly by extrusion or blowing, or by injection from the mixture comprising the premix and the polymer. Alternatively, and in the case of pasty mixtures that do not carry polymers that require heating after manufacture, this procedure can be carried out in a single step, these articles being obtained by the mixing operations, specific for the implementation of the pasty solids and of the putties, of one or two compounds. The items in question are used for the protection of metal parts sensitive to corrosion, after transport or storage, without a complementary protection treatment being applied to these parts. The invention can be further understood with the aid of the non-limiting examples which follow and which concern the advantageous embodiments.

EXAMPLE 1 For the preparation of an ICV, 70 g of sodium nitrite are mixed, 17. 5 g of benzotriazole and 12.5 g of ammonium benzoate, then micronized in a micronizer with an air jet to give 100 g of homogeneous powder mixture designated therefor and having an average granulometry comprised between 1 and 15 μm; This powder constitutes an ICV. In a heating tank equipped with rotary and vigorous stirring, 226 g of the paraffin defined in Table A are melted at 65 ° C, then 100 g of powder are incorporated into the melt and carefully dispersed. 2 g of anti-UV agent (marketed under the trademark TI N UVI N 622 LD by Ciba Geigy), 2 g of antioxidant agent - degradation inhibitor (marketed under the trademark CH IMASSORB) are added. 944 LD by Ciba Geigy) and 3 g of yellow dye Color Index PY10401 / 70. The dispersion is carried out under agitation at a speed that is comprised between 300 and 500 revolutions / minute, during 10 minutes. The 333 g of mixture thus obtained that constitute a premix 1 b, are unloaded for cooling in a laboratory tray kept at 10 ° C, then cut into flakes with a dimension comprised between 0.5 and 10 mm. 300 g of premix 1 b are mixed cold and in a homogeneous manner with 5.7 kg of low density pbl-ethylene (d = 0.920 g / cm3 and flow index IF = 2 g / 10 min), the mixture being extruded at 140 ° C and in one minute in a single-screw extruder-laminator, which gives a tubular film designated by 1 c, transparent yellow, 90 + 10 μm thick; This film is effective against corrosion of ferrous metals. The effectiveness of this film from the point of view of protection against corrosion has been tested on specimens in the form of pieces of mild steel; the test used corresponds to the North American standard FED-STD 101, method 4031 B. This test method consists of placing a piece of steel in a confined atmosphere loaded with ICV released from the film, then causing controlled cooling a condensation on the surface of the piece in order to cause an eventual oxidation after a certain time or. The degree of winding indicates the anti-corrosion efficiency of the protective film with respect to the material constituting the piece. At the end of this test, it is verified that the piece of steel protected by the film 1 c presents in a slight staining on approximately 30% of its surface; therefore there has been no corrosion. The same test was performed as a comparison using a "control" film designated by 1 d. The control film 1 d is identical at all points to the film 1 c, except for the fact that it does not contain the ICV identified above; the 100 g of mixture there are replaced, after the manufacture of the premix, by 100 g of mineral charge based on calcium carbonate. At the end of the test, the piece protected by the control film 1 d is completely attacked: numerous pitting and rust are observed on 100% of its contact surface with the confined atmosphere.

EXAMPLE 2 For the preparation of an ICV, 50 g of ammonium benzoate, 25 g of aminotriazole and 25 g of hexamethylenetetramine are mixed, then micronized in a micronizer with air jet to give 100 g of homogeneous powder mixture designated by 2a and having an average particle size between 1 and 15 μm. In a heating tank equipped with rotating and vigorous stirring, 235 g of the carnauba wax identified in Table A are melted at 90 ° C, and 100 g of powder 2a are incorporated into the melt and carefully dispersed. The dispersion is carried out with stirring at a speed between 300 and 600 revolutions / minute, for 5 minutes. The 335 g of premix 2b thus obtained are discharged for cooling in a laboratory tray maintained at 15 ° C, then cut into flakes with a size comprised between 0.5 and 10 mm. 300 g of premix 2b are mixed cold and in a homogeneous manner with 5.1 kg of low density polyethylene (d = 0.920 g / cm3 and flow index I F = 2 g / 10 minutes), and 0.6 kg of ethylene / vinyl acetate copolymer (marketed under the brand name ESCOREN EU LTRA by Exxon), 0.1 g of anti-UV agent (marketed under the trademark TI N UVI N 622 LD by Ciba Geigy), 0.1 g of agent antioxidant - degradation inhibitor (marketed under the trademark CH IMASSORB 944 LD by Ciba Geigy) and 3 g of yellow dye Color Index PY10401.

The assembly is extruded at 120 ° C and in one minute in a single-screw extruder-laminator, which gives a tubular film designated by 2c, transparent yellow, 90 ± 10 μm thick. The effectiveness of this film against the corrosion of ferrous metals has been demonstrated by implementing the test described in Example 1. At the end of this test, the piece of steel protected by the film according to the invention has only a slight staining but acceptable on about 10% of its surface, although that protected with the control film has numerous pitting and rust on 100% of the surface. the surface.

EXAMPLE 3 For the preparation of an ICV, 75 g of benzotriazole, 15 g of tolyltriazole and 10 g of ammonium benzoate are mixed, then micronized in a micronizer with air jet to give 100 g of homogeneous powder mixture designated by 3a and having an average particle size between 1 and 15 μm. In a heating tank equipped with rotating and vigorous stirring, 230 g of the microcrystalline wax identified in FIG.

Table A at 75 ° C, and then 100 g of powder 3a are then incorporated into the melt and carefully dispersed. 3 g of Color Index PG 7 (azo pigment) green dye are added. The dispersion is carried out with stirring at a speed comprised between 300 and 500 revolutions / minute, for 10 minutes. The 333 g of premix 3b thus obtained is discharged for cooling in a laboratory tray maintained at 10 ° C, then cut into flakes with a size comprised between 0.5 and 10 mm. 300 g of premix 3b are mixed cold and in a homogeneous manner with 5.7 kg of low density polyethylene (d = 0.920 g / cm3 and flow index IF = 2 g / 10 minutes), the whole being extruded at 140 ° C and in one minute in a single-screw extruder-laminator, which gives a tubular film designated by 3c, transparent green, 90 ± 10 μm thick. This film is effective against corrosion of copper-based alloys. Its efficacy has been proven by testing with thioacetamide on electrolytic purity copper specimens, in accordance with the Swiss standard SN 289 650. To do this, a piece of copper is placed in a cavity filled with a confined atmosphere, which has a relative humidity of approximately 75%: this confined atmosphere is charged with ICV released by a piece of film 3c, also placed in this cavity, in the presence of thioacetamide which liberates the sulfur derivatives; At the end of the test, a visual evaluation of the corrosion of the surface of the piece is carried out; the degree of degradation indicates the anticorrosion efficiency of the protection film with respect to the copper constituting the piece. The piece of copper protected by the 160 cm2 film coupon 3c present, after 48 hours of testing, a slight color change on about 10% of the surface; It is a golden dye on the periphery of the piece, which shows that there is no corrosion. The same test was carried out, by way of comparison, using a "witness" 3d film: it is a film identical to 3c, except for the fact that it does not contain the ICV; The 100 g of mixture 3a was replaced, after the manufacture of the premix, by 100 g of mineral charge based on calcium carbonate. At the end of the test, the piece protected by the 3d control film presents a very important change of color over 100% of its contact surface with the confined atmosphere; It is an intense reddish gold dye that translates into an important corrosion.

EXAMPLE 4 For the preparation of an ICV, 25 g of benzotriazole, 10 g of ammonium benzoate and 25 g of dicyclohexylamine o-nitrobenzoate are mixed, then micronized in a micronizer with air jet to give 100 g of homogeneous powder mixture designated by 4a and having an average granulometry comprised between 1 and 15 μm. In a heating tank equipped with rotating and vigorous stirring, 226 g of the beeswax identified in Table A are melted at 70 ° C, and then 100 g of powder 4a are then incorporated into the melt and carefully dispersed. 2 g of anti-UV agent (marketed under the brand name) is added TINUVI N 622 LD by Ciba Geigy), 2 g of antioxidant agent - degradation inhibitor (marketed under the trademark CH I MASSORB 944 LD by Ciba Geigy). The dispersion is carried out with stirring at a speed comprised between 300 and 500 revolutions / minute, for 10 minutes.

The 330 g of premix 4b thus obtained are discharged for cooling in a laboratory tray maintained at 10 ° C, then cut into flakes with a size comprised between 0.5 and 10 mm. 300 g of premixture 4b are cold-flaked and homogenously mixed with 5.7 kg of low density polyethylene (d = 0.925 g / cm3 and flow index IF = 20 g / 10 minutes), the mixture being injected obtained at 160 ° C in the mold cooled to 40 ° C of a Battenfeld Plus 250 type machine marketed by the company Battenfeld; thus, platelets designated by 4c are obtained, colorless, translucent, of dimensions 50 x 60 x 2 mm, used for anticorrosion protection of silver. These plates are packed in a neutral polyethylene film, together with the piece of silver, for example a jewel to be protected. Thanks to the ICV that emerges from the platelets 4c, the blackening of the silver, characteristic of the aging of this material, is avoided.

EXAMPLE 5 For the preparation of an ICV, 45 g of benzotriazole, 45 g of ammonium benzoate and 10 g of potassium sorbate are mixed, then micronized in a micronizer with air jet to give 100 g of homogeneous powder mixture designated by 5a and having an average granulometry comprised between 1 and 15 μm. In a heating tank equipped with rotating and vigorous stirring, 226 g of the phosphoric ester of C.sub.6 / Ci.sub.8 fatty alcohols identified in Table A are melted at 90.degree. C., then 100 g of powder 5a are incorporated into the melt. and they scatter carefully. 2 g of anti-UV agent (marketed under the brand name) is added TI N UVI N 622 LD by Ciba Geigy), 2 g of antioxidant agent - degradation inhibitor (commercialized under the trademark CH IMASSORB 944 LD by Ciba Geigy) and 3g of blue pigment Color Index PB 1 5 (phthalocyanine pigment). The dispersion is carried out with stirring at a speed between 300 and 600 revolutions / minute, for 5 minutes. The 333 g of premix 5b thus obtained are discharged for cooling in a laboratory tray maintained at 15 ° C, then cut into flakes with a size comprised between 0.5 and 10 mm. 300 g of premix 5b are mixed cold and in a homogeneous manner with 5.7 kg of low density polyethylene (d = 0.920 g / cm3 and flow index IF = 2 g / 10 minutes), and the mass thus obtained is extruded at 140 g. ° C and in one minute in a single-screw extruder-laminator, which gives a tubular packing film designated by 5c, transparent blue, 90 ± 10 μm thick. Thanks to its content in ICV, this 5c film is effective against the corrosion of aluminum parts packed inside this film. The anti-corrosion properties of the film 5c have been tested on the pieces in aluminum alloy of shade 5052 in the ISO nomenclature, using a test that responds to the Swiss standard SN 289 650 which comprises an assay for chlorinated agents. This test consists of placing a piece of aluminum alloy that plays the role of test piece in a confined humid atmosphere, charged with a known amount of Javel water capable of releasing corrosive gaseous chlorine in the presence of the packing film 5c from from which the vapors of the ICV and content are released; the degree of degradation of the piece after a maintenance in this atmosphere for 24 hours and at a temperature of 40 ° C characterizes the effectiveness of the film 5c against the chlorine corrosion of the material constituting the piece. At the end of the test, ie after 24 hours, the surface of the piece of aluminum protected by the 160 cm2 coupon of film 5c shows no color change, nor any fogging. The same test was performed, by way of comparison, using a "witness" film 5d: it is an identical film at all points to film 5c, except for the fact that it does not contain ICV: the 100 g of mixture 5a have been replaced in effect , after the manufacture of the substitution premix in premix 5b, per 100 g of mineral filler totally ineffective for the intended use, based on calcium carbonate. At the end of the same test time, the piece protected by the control film 5d has white stings and a fogging in the whole of the contact surface with the confined atmosphere.

EXAMPLE 6 For the preparation of an ICV, 300 g of premix 1 b are mixed according to example 1 cold and in a homogeneous manner with 5.7 kg of low density polyethylene (d = 0.920 g / cm3 and flow index IF = 2 g / 10 minutes), and the assembly is extruded at 140 ° C and in a minute in a single-screw extruder-laminator, which gives a transparent tubular film, yellow in color, of 150 + 10 μm in thickness. This film is stretched with a drawing rate of 2.5 in accordance with the two orthogonal directions of the plane, before being cooled with a view to further use as a packaging film for protection against corrosion of ferrous metals. It is designated by 6c. 300 g of premix 1 b are mixed cold and in a homogeneous manner with 5.7 kg of ethylene / propylene copolymer with 5% ethylene (d = 0.895 g / cm3 and flow index IF = 4 g / 1 0 minutes-value at 230 ° C), and the assembly is extruded through three runs of plates arranged as described in French Patent FR 2 142 752 in a one-screw extruder at 180 ° C in one minute, which allows a plate to be obtained yellow alveolar having the constitution of corrugated cardboard, 3.5 mm in total thickness, and where the surface mass is 800 g / m2; This plate is effective against corrosion of ferrous metals. A classic corona surface treatment (gaseous plasma treatment) is passed over both sides, in order to facilitate a subsequent collage. It is smeared with a solid glue at room temperature, based on an ethylene / acrylic ester copolymer (15% acrylic ester content, I F = 4 g / 10 minutes). This plate is designated by 6d. From the film 6c and the plate 6d, a packaging or packaging for metal parts sensitive to corrosion is manufactured by the thermoforming technique and in the manner indicated hereinafter. It is caused to bring to the plate 6d a case assembly that has recourse to a multi-package penetration device. The packages thus obtained, of conical shape, have a diameter of less than 1 mm and are separated from each other by approximately 1 cm. A metal part is placed on the plate 6d, placed in a MECASKI N 53M brand peliplacaje machine marketed by the company SDMF. The film 6c, immobilized in a tight metal frame located above the plate 6d, is heated for 12 seconds at 90-95 ° C with the help of radiant boards. Once it is rested, then retained, covered and molded on the piece to be protected, it is deposited on the plate 6d, with the help of a partial vacuum of 680 to 720 mm Hg, secured for approximately 5 seconds. The vacuum penetrates between the two materials 6c and 6d through the packages made in the plate 6d. During this operation, the film 6c and the plate 6d are glued on a contact surface. The cavity thus formed in which the metal parts are housed contains vapors of ICV released from the film and the plate, just as if this cavity communicates with the outside atmosphere through the packages carried on the plate; the filtration of the inhibitors from inside the cavity is limited in a considerable proportion, thanks to the sieve effect played by the alveolar structure of the plate. The conditioning set is effective after a two-year long storage of the metal part.

EXAMPLE 7 For the preparation of an ICV, 150 g of paraffin and 150 g of petrolatum wax, defined in Table A, are melted and mixed at 70 ° C in a heating tank, equipped with vigorous rotating agitation. 150 g of naphthenic oil (marketed under NYTEX 810 by Nynas, density 0.901 at 15 ° C and refractive index 1.493), and incorporated into the mixture of molten waxes, are added to obtain a clean viscous liquid. homogeneous, of intense brown color. In this melt, are carefully incorporated and dispersed, with an agitation that, varies progressively from 500 to 1500 revolutions / minute, for 45 minutes, 300 g of gis marketed under the brand OMYA BL by OMYA SA, of density 2.7 and average granulometry of 10 μm ), 100 g of kaolin (marketed under the brand name SPESWH ITE by ECC International, density 2.6, average particle size 2 μm and oil intake 48 ml / 100 g) and 100 g micronised talc (marketed under the brand name "TALC") 1 0M2"by Luzenac Tales, with density 2.78, average particle size of 1 0 μm and oil intake of 48 ml / 100 g). The temperature is maintained at 65 ° C. 950 g of a smooth, fluid, beige paste is obtained, which constitutes the mixture [7a].

It is incorporated and dispersed immediately in this paste, maintained at 65 ° C, 50 g of premix [1 b], described in Example 1, with moderate agitation, comprised between 300 and 1000 revolutions / minute, for 10 minutes. The 1000 g of pasty mixture thus obtained is put to cool during 15 minutes under weak agitation, of approximately 300 revolutions / minute, at room temperature. This pasty, beige-yellow mixture, which constitutes a moldable ICV, is designated by [7c]; It is effective against corrosion of ferrous metals. The volatile anti-corrosion efficiency of this ICV paste for modeling [7c] has been tested on mild steel specimens, in the form of pieces; in the test used corresponds to the North American standard FED-STD 101, method 4031 B, described in Example 1. At the end of this test, it is verified that the piece of steel protected by the corrosion inhibiting vapors that are released from 2 g of ICV paste [7c] does not show oxidation on its surface. The same test was performed, by way of comparison, using a "control" modeling paste, designated by [7d], which is identical at all points to the paste [7c], except for the fact that it does not contain ICV identified before [1 b]; 50 g of premix [1 b] were replaced in composition [7d] by 50 g of gis. At the end of the test, the piece protected by the control modeling paste [7d] is completely attacked: numerous stings and rust are observed on 100% of its surface.

EXAMPLE 8 For the preparation of an ICV, 300 g of petrolatum wax, identified in Table A, are melted at 70 ° C in a heating tank equipped with vigorous rotating agitation. Progressively incorporated and dispersed, under a variant stirring of 500 to 2000 revolutions / minute and for 45 minutes, 350 g of gis identified in Example 7, and 300 g of kaolin identified in Example 7. There are obtained 950 g of a Smooth, fluid, beige paste, which constitutes the mixture [8a]. In this paste, 50 g of premix [2b], described in Example 2, are carefully incorporated and dispersed, with a moderate stirring comprised between 500 and 1000 revolutions / minute and for 10 minutes, The 1000 g of pasty mixture thus obtained they are put to cool during 15 minutes with smooth agitation, of approximately 300 revolutions / minute, to room temperature. This paste, of beige color, which constitutes a moldable ICV, is designated by [8c]; It is effective against corrosion of ferrous metals. The volatile anti-corrosion efficiency of this ICV paste for modeling [8c] was tested on the mild steel specimens, in the form of pieces; the test used corresponds to the North American standard FED-STD 101, method 4031 B, described in Example 1. At the end of this test, it is verified that the piece of steel protected by the corrosion inhibiting vapors that are detached from 2 g of ICV paste [8c] does not show oxidation on its surface. The same test was performed, by way of comparison, using a "witness" modeling paste, designated by [8d], which is identical at all points to the paste [8c], except for the fact that it does not contain the ICV previously identified [2b]; 50 g of premix [2b] have been replaced in the composition [8d] by 50 g of gis. At the end of the test, the piece protected by the control modeling paste [8d] is completely attacked: numerous pitting and rust are observed on 100% of its surface.

EXAMPLE 9 150 g of castor oil (marketed by Mosselman and containing 90% ricinoleic acid, replenishment index 1.48 and iodine number 90 g 12/100 g) are charged, at room temperature, in a type kneader Z arm, equipped with double wrap that allows the heating and cooling of the mixture. 650 g of gis identified in Example 7 and 150 g of kaolin identified in Example 7 are incorporated and dispersed for two hours. 950 g of a smooth, non-adhesive, crude paste forming the mixture are obtained [9a] The mixture [9a] is brought to a temperature of 65-70 ° C and 50 g of premix [3b], described in Example 3, are carefully incorporated and dispersed for 10 minutes. The 1000 g of slurry obtained in this way is they cool progressively. This paste, of green color, that constitutes a moldable ICV, is designated by [9c]; It is effective against corrosion of copper-based alloys. Its volatile anti-corrosion efficiency was tested by thioacetamide test, on electrolytic purity copper specimens, in accordance with the Swiss standard SN 289 650. The test performed is identical to that described in Example 3, except for the fact that the film [3c] was replaced by a defined amount of paste [9c]. At the end of the test, it is verified that the piece of copper protected by 2 g of paste [9c] presents, after 48 hours of test, a slight change of color on approximately 10% of the surface; It is a faint golden tint on the periphery of the piece, which shows that there is no corrosion. The same test was performed, by way of comparison, using a "control" paste, designated by [9d], which is identical at all points to the paste [9c], except for the fact that it does not contain the ICV identified above. [3b]; the 50 g of premix [3b] have been replaced in the composition [9d] by 50 g of gis. At the end of the test, the piece protected by the control modeling paste [9d] presents a very important change of color - intense reddish tint - and a fogging over 100% of its surface exposed to the confined atmosphere.

EXAMPLE 10 For the preparation of an ICV, 400 g of part A of a 2 component putty based on a hydroxylated resin (marketed under the trademark LI DEC A 223 D Partie A by means of a Z-arm horizontal kneader) is loaded. CFPI, yellow, with a mass volume of approximately 1 .47 g / cm3); 10 g of powder mixture [1 a] defined in Example 1 are carefully incorporated and dispersed for two hours. 410 g of a smooth, homogeneous paste, yellow in color, is obtained [1 0b]. 400 g of this paste [10b] are intimately mixed immediately, for crosslinking, with 40 g of part B (hardener) of the same two component putty (part sold under the brand name LIDEC A 223 D Partie B by CFPI, blue , based on isocyanate, with an approximate viscosity of 2000 m Pa.s) to obtain 400 g of viscous mixture, green in color and which, after a few hours at 23 ° C and 50% relative humidity, becomes an elastomer Shore hardness 55-60. This elastomer, which constitutes a crosslinkable ICV, is designated by [10c] and is effective against corrosion of ferrous metals. The volatile anticorrosion efficiency of this ICV elastomer [10c] was tested on pieces of mild steel, in the form of pieces; the test used brought into play 2 g of elastomer and corresponds to the North American standard FED-STD 101, method 4031 B, described in Example 1. At the end of this test, it is verified that the piece of steel protected by the corrosion inhibiting vapors that are detached from the ICV elastomer [10c] does not show oxidation on its surface.

The same test was performed, by way of comparison, using a "control" putty, designated by [10d], which is identical at all points to the elastomer [10c], except for the fact that it does not contain the ICV identified above [ 1 a]; the 10 g of powder mixture [1 a] have been replaced in the composition [10d] by 50 g of gis. At the end of the test, the piece protected by the control putty [10d] is completely attacked: numerous bites and rust are observed on 100% of its surface.

Claims (10)

1. REVIVAL NAMES 1. Packing article is presented either in the form of blown or rigid films, possibly retractable, or other elements such as threads, tubes possibly put in shape, and plates, possibly honeycombs, from which it is possible to constitute a conditioning, or pasty solids of a plastic nature, at least one of the constituents of this article of packaging that it bears. - or at least one polymer that enters at least 50% by weight in its constitution and a premix based on volatile corrosion inhibitors, said polymer being selected from those of the group comprising: - the polyolefins between which the polyethylenes, polypropylene, polybutene and their copolymers with one or more unsaturated monomers such as vinyl acetate, acrylic acid and their esters with short carbon chain alcohols, - polyvinyl chloride and its copolymers, acrylic copolymers and their derivatives, and - polyamides, polystyrenes, polycarbonates, polyesters, polyurethanes, rubbers such as natural rubber, styrene-butadiene and polychloroprene, - or at least one insoluble filler, selected from the group comprising mineral charges such as chalk and carbonates, talc, clays and silicas and a premix based on volatile corrosion inhibitors, said premix which comprises an effective amount of at least one structuring agent consisting of a solid or pasty substance, selected from the group comprising the aliphatic and / or resinous compounds, solid or pasty, with a low melting point comprised between 40 ° and 1 10 ° C, preferably between 50 ° and 90 ° C, this is because the release of volatile corrosion inhibitors at the time of premix formation is limited to the maximum.
2. 2. Packing article according to claim 1, characterized in that it consists of simple films or assemblies of several elements, these assemblies being carried out by implementing any appropriate procedure such as stapling, crimping, thermoforming, peliplacaje or the manufacture of ampoules.
3. Packaging article according to claim 1 or claim 2, characterized in that the premix comprises from 1 to 80%, preferably from 20 to 60% by weight of at least one volatile corrosion inhibitor and from 20 to 99%, preferably from 40 to 80% of at least one structuring agent consisting of a solid or pasty substance whose melting point is 40 to 1 10 ° C, preferably 50 to 90 ° C.
4. Packaging article according to one of claims 1 to 3, characterized in that the premix, the solid or pasty structuring agent is selected from the group comprising the aliphatic, mono- or polyfunctional, linear and / or little compounds branched with hydrocarbon chains having at least 10 carbon atoms.
5. Packing article according to claim 4, characterized in that the structuring agent is selected from the group comprising: - mono- or dicarboxylic acids, optionally oxidized, saturated or unsaturated, their esters and their salts. - phosphoric, sulphonic and phosphonic acids, their esters with alcohols and their salts of alkali, alkaline earth, zinc, aluminum and / or organic amines, - cyclic or acyclic compounds of the group comprising lactones, ketones , the aldehydes, the amides and the acetals, the higher alcohols, primary or secondary, cyclic or acyclic, optionally polyalkoxylated, with hydrocarbon chains having at least 10 carbon atoms, the linear and / or slightly branched aliphatic hydrocarbons, particularly the paraffins and the isoparaffins, the polyolefins and their copolymers of low molecular masses of 3000 to 20,000 g / mol, the polyglycols, particularly the polyethylene glycols with a molecular weight of 2000 to 10000 g / mol.
6. Packaging article according to claim 1, characterized in that the structuring agent is selected from the group comprising the resinous compounds having a polymeric and / or cyclic structure and which may contain, in a minor proportion, aromatic derivatives and cyclic terpenes.
7. 7. Packaging article according to any of claims 1 to 6, characterized in that the structuring agent is selected from the group of those identified in Table A below and where some are waxes of natural or synthetic origin: TABLE A
8. 8. Packaging article according to any one of claims 1 to 7, characterized in that the premix comprises at least one volatile corrosion inhibitor selected from the group comprising: - nitrogenous derivatives and particularly, on the one hand, aliphatic amines , aromatic, acyclic or cyclic such as dicyclohexylamine, cyclohexylamine, morpholine, diisopropylamine, and benzylamine, their organic salts such as benzoates, carbamates, laurates, caprylates, succinates or minerals such as nitrites, nitrates, carbonates, phosphates, phosphites and, on the other hand, heterocycles such as imidazole and its derivatives, triazoles and their derivatives, as well as hexamethylenetetramine, - nitrogenous oxide derivatives such as the alkali or alkaline earth metal salts of nitrous acid, and - benzoic derivatives of These metals such as sodium benzoate.
9. 9. The use for the realization of packaging article in pre-mix polymer material as implementation in one of claims 1 to 8. The use of packaging articles according to one of claims 1 to 8, for the protection of metal parts against corrosion. The object of the invention is the use of a composition or premix based on volatile corrosion inhibitors which comprises, in order to limit as much as possible the release and / or degradation of the ICV at the moment of the formation of the composition or premix, either an effective amount of a structuring agent consisting of at least one solid or pasty substance whose melting point is 40 to 1 10 ° C, preferably 50 to 90 ° C, or either a suitable liquid substance to form , in mixture with a mineral load, a pasty or solid group. It also refers to a composition based on volatile corrosion inhibitors that entails an effective amount of a solid structuring agent. It also refers to articles based on polymers in the constitution of which the said composition or premix enters; These items are useful for the protection of metal parts against corrosion.