WO1991011479A1

WO1991011479A1 - Polyurethane-type compositions cross-linkable with ionizing radiation for use as finishing coatings on metal or metallized surfaces

Info

Publication number: WO1991011479A1
Application number: PCT/FR1991/000050
Authority: WO
Inventors: Jean Godde
Original assignee: Societe Celliose Lobo Entreprise
Priority date: 1990-02-01
Filing date: 1991-01-29
Publication date: 1991-08-08
Also published as: IE910327A1; FR2657613A1; FR2657613B1; EP0466880A1; PT96595A

Abstract

Polyurethane acrylate-type compositions which can be cross-linked with ionizing radiation to form coatings on metal or metallized surfaces, said compositions being obtained by mixing two liquid and/or pasty phases, of which the first (A) contains polyols and the second (B) polyisocyanates, and characterized in that they mainly comprise the following as dry materials: in phase (A): A1) at least one hydroxylated vinyl polymer and/or copolymer; A2) at least one acrylic monomer having at least two ethylene functions; A3) at least one acidic acrylic derivative; A4) at least one cross-linking initiating agent. In phase (B): B1) at least one polyisocyanate. Once they have been cross-linked by ionizing radiation, these compositions have remarkable properties such as excellent adhesion on metal and/or metallized surfaces without the need for an adhesive underlayer and with complete immunity to moist and/or alcohol atmospheres.

Description

CROSS-LINKABLE COMPOSITIONS OF THE TYPE

IONIZING RADIATION POLYURETHANE FOR THE FINISH COATING OF METALLIC OR METALLIC SURFACES

The invention relates to crosslinkable compositions. of the polyurethane acrylate type by ionizing radiation, for the finishing coating of metallic or metallized surfaces.

The invention also relates to the application of the compositions crosslinkable by ionizing radiation, as a finishing coating, on metallic or metallized surfaces.

Thereafter, the expression “metallic or metallized surfaces” intends to define all the metallic or non-metallic substrates, the latter having undergone a metallization treatment by known means of metallization, such as, in particular, vacuum metallization, sputtering (sputtering) or others.

BACKGROUND OF THE INVENTION

For a long time now, protective varnishes intended for the finishing coating of metallic or metallized surfaces have been the subject of numerous researches and even of industrial developments, these varnishes having to possess essential qualities of adhesion to the substrate, of high hardness and a excellent resistance to aqueous or alcoholic media. Such substrates to be treated are, for example, metallic objects or other materials, such as metallized polymers, which it is desirable to coat with a finishing layer, to provide them with a transparent coating, protecting them against attack by the environment. All these substrates, when they are poorly protected, are the site of chemical transformation actions which cause a loss of adhesion of the film, or of modification of appearance, especially when said substrates are exposed, even naturally, to humid atmospheres. , or even simply atmospheric.

To date, and depending on the substrates to be protected from their environment, various ways have been proposed in an attempt to provide the finishing varnishes (deposited on said substrates), with the qualities previously stated: namely excellent adhesion, high hardness and good resistance to aqueous or alcoholic media.

A first proposed route consists in placing between the metallic or metallized surface and the finishing varnish, an intermediate undercoat subsequently promoting the adhesion of the finishing varnish. This route, considered to be relatively advantageous by the qualities which it provides to the varnish deposited on the surface to be treated, however has major drawbacks which make its industrial operation difficult. Indeed, this route requires the realization of two successive operations, one concerning the adhesion sublayer, its deposition and its formation by reaction of its compounds, the other relating to the deposition of the finishing varnish, therefore that said sub-layer is capable of receiving it.

A second way proposed and exploited, consists in incorporating within the finishing varnish, an adhesion promoter such as, for example, acrylic and methacrylated derivatives of an acidic nature, which should promote the adhesion of the film of finish on the metallic or metallized surface to be treated. However, it has been experimentally found that this route leads to annoying inconveniences since the adhesion promoter (which has a hydrophilic tendency) must be introduced in a major amount to be effective. Therefore, and for this reason, the characteristics of the film of the finishing varnish are compromised (because adhesion, hardness and resistance to water or alcohol, turn out to be poor) making this route technically unusable for the finishing of metallic or metallized surfaces to be protected. Another way, finally, was directed towards the research of chemical compositions of finishing varnish, adapted to each case of application, these compositions being source of polymerization reactions between hydroxylated functions (-OH) and isocyanate functions ( -NCO) and acrylic derivatives and monomers. Such compositions, which acquire a reputation for their propensity to solve the specific problems with which they are confronted, are described in the specialized literature.

In this regard, the German patent 2,601,408 describes compositions for varnishes intended for the manufacture of printing inks, the compositions resulting from the mixture:

- a hydroxylated ethylenic compound originating from the condensation reaction between an epoxy resin and an unsaturated carboxylic acid, - a polyisocyanate compound obtained by addition reaction between an aromatic polyisocyanate (Toluylene diisocyanate TDI), and an unsaturated carboxylic acid .

At least one acrylic monomer and one photoinitiator are added to the adduct obtained by ionic reaction of these two compounds, the radical reaction being carried out by ultraviolet irradiation. Another patent, Japanese Patent JP 59-080473, describes compositions for varnishes intended for the protection of electrical insulators. These compositions are obtained (a) by the addition reaction between a polyol and an aromatic polyisocyanate, leading to a compound with free -NCO function and (b) by the reaction of the addition compound with -NCO functions originating from (a ) with various hydroxylated acrylic compounds. The reaction product obtained can be polymerized under ultraviolet irradiation in the presence of a photoinitiator.

However, although this third path could give rise to possible hopes for improving the behavior of photocrosslinkable varnishes intended for the finishing coating of metallic or metallized surfaces of substrates to be treated, it has been experimentally verified that this path leads after photocrosslinking, with certain disadvantages since, the adhesion, hardness and resistance to water and / or alcohol of the film deposited on a metal surface, remain poor.

This is why a first object of the invention aims to obtain crosslinkable compositions for the finishing coating of metallic or metallized surfaces requiring neither the use of a bonding prelayer, nor the introduction into the compositions of finishing varnishes, of a large amount of adhesion promoter.

Another object of the invention is to obtain crosslinkable compositions for the finish coating of metallic or metallized surfaces having, after crosslinking, excellent adhesion characteristics on the metallic or metallized surface, hardness and resistance to l water and / or alcohol by immersion. Finally, another subject of the invention aims at the new application of finishing compositions, crosslinkable by ionizing radiation to the protection of metallic and / or metallized surfaces of substrates to be protected.

SUMMARY OF THE INVENTION

Strong of the aforementioned drawbacks, the applicant continued, through its research, the establishment of crosslinkable compositions of the polyurethane acrylate type for the finishing coating of metallic or metallized surfaces meeting the objectives it has set itself.

According to the invention, the compositions of the polyurethane acrylate type, crosslinkable by ionizing radiation, for the finishing coating of metallic or metallized surfaces, obtained by the mixture of two liquid and / or pasty phases, one (A) containing the polyols , and the other (B) polyisocyanates, are characterized in that the two phases mainly comprise dry matter:

- in phase (A):

A1) at least one vinyl hydroxylated polymer and / or copolymer;

A2) at least one acrylic monomer having at least two ethylenic functions;

A3) at least one acrylic derivative having an acidic character;

A4) at least one crosslinking initiating agent.

- in phase (B):

B1) at least one polyisocyte. DETAILED DESCRIPTION OF THE INVENTION

While the prior art recommends:

- or processes making use of intermediate sublayers for hanging the finishing varnish;

- Or the incorporation in said varnish of adhesion promoter, in large quantity (from 3 to 10% by weight, for example, relative to the mass of dry matter);

- or compositions of the polyurethane acrylate type, obtained by the polymerization reaction between the hydroxylated functions and the isocyanates, the invention is distinguished by the fact that the compositions of the polyurethane acrylate type developed contain among the components at least a hydroxylated vinyl polymer, at least one at least difunctional acrylic monomer, and at least one polyisocyanate.

Under these conditions, the crosslinkable compositions of the polyurethane acrylate type for the finishing coating of metallic and / or metallized surfaces according to the invention, in contrast to known art, have the qualities sought and hitherto not acquired, which are those of adhesion to the substrate, hardness and resistance to aqueous or alcoholic media. The crosslinkable compositions according to the invention comprise at least one hydroxylated vinyl homopolymer and / or copolymer (component A1) taking advantage of their advantageous hydrophobic properties. These hydroxylated vinyl homopolymers and / or copolymers are chosen from those known having an average molecular weight of between 4000 and 35000 and preferably between 5000 and 30000.

Among the homopolymers and / or copolymers concerned, mention may be made of hydroxylated polyvinyl halides, such as hydroxylated polyvinyl chloride, or alternatively vinyl esters, such as polyvinyl acetate, hydroxylated vinyl copolymers, such as acetochloride. hydroxylated polyvinyl chloride, polyvinyl chloride hydroxylated acrylic ester, as well as terpolymers based on vinyl chloride / acrylic ester / ester of hydroxy carboxylic acid.

Such hydroxylated vinyl polymers and / or copolymers are for example known under the trade names such as UCAR VAGH, UCAR VAGF, UCAR VAGD, UCAR VROH, UCAR VYES, from SOCIETE UNION CARBIDE, or also VINNOL E15 / 40 A, E15 / 48 A, E20 / 55 A, E22 / 40 A, E22 / 48 A, from WACKER CHEMIE or HOSTAFLEX CM 158, HOSTAFLEX VCM 1550, from the company HOECHST.

The acrylic monomer having at least two ethylenic functions (component A2) is chosen from di or trifunctional acrylates having the property of being crosslinked according to any of the methods known to those skilled in the art, such as for example , chemical crosslinking, or crosslinking by ionizing radiation, ensuring the "in situ" polymerization of said monomer. Such acrylic monomers are, for example, 1,6 hexane diol diacrylate, tripropylene glycol diacrylate, 1,3 butane diol diacrylate, trimethylol propanetriacrylate, pentaerythritol triacrylate, triethylene glycol diacrylate, glyceryl propoxy triacrylate ethyl trimethylol triacrylate, dipenta erythrytol penta acrylate, polyethylene glycol 200 or 400 diacrylate.

The acrylic derivative having an acidic nature (constituent A3) is chosen from the group consisting of acrylic and methacrylated derivatives of acidic nature. Such constituents are known, for example, under trade names such as EBECRYL 169 or EBECRYL 170 PA, from SOCIETE U. C.B.

Unlike the prior art, the acrylic derivative having an acidic nature is introduced into the photocrosslinkable compositions of the polyurethane acrylate type according to the invention, at very low doses, ranging from 0.5% to 3% by weight relative to in total of dry matter of said compositions, the doses being from 3% to 10% in the known art.

At least one crosslinking initiating agent (constituent A4) can also be introduced into the compositions according to the invention to promote crosslinking thereof.

This crosslinking initiating agent can be chosen from those known, such as, for example, hydroxy 1 - cyclohexyl phenylketone, 2 hydroxy - 2 methyl 1 - phenyl propane 1 one, (4 isopropylphenyl) - 2 - hydroxy 2 methyl propane 1 - one, the derivatives of Thioxanthone, acetophenone, benzophenone, or benzyl dimethyl ketal. Such photoinitiators are known, for example, under the trade names of: IRGACURE 184 (CIBA GEIGY), DAROCUR 1173 or DAROCUR 1116 (MERCK), LUCIRIN BDK (BASF). The polyisocyanates used according to the invention (constituent B1) are compounds of the aliphatic and / or aromatic type, alone or mixed, such as for example, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), diphenyl methane diisocyanate 4 - 4 'and its counterparts (MDI), naphthalene diisocyanate 1 - 5 (NDI), or still appearing as prepolymers obtained by the combination of isocyanates between them or with reactive compounds.

Finally, various other adjuvants of known type can also be introduced into the compositions according to the invention. These various possible adjuvants belong to the groups of dispersing agents, dyes, biocidal agents, anti-scratching agents or tensioning agents or the like.

The phases (A) and (B) of the compositions which can be crosslinked according to the invention by ionizing radiation, appear in the form of solutions and / or dispersions in suitable organic liquids, compatible with each other and with the various constituents involved in the formation of the finishing coating of metallic and / or metallized surfaces.

Such organic liquids are for example: ethyl acetate, methyl isobutyl ketone, toluene, xylene, ethyl glycol acetate, methoxy propyl acetate, diacetone alcohol, cyclohexanone, used alone or as a mixture.

In general, the coating compositions according to the invention obtained by mixing the two phases (A) and (B) in solution and / or dispersion, consist of quantities expressed as percent by weight of the various main constituent substances, it being understood that both phase (A) and (B) may also contain other specific agents well known in the field of surface finishing coatings metallic and / or metallized.

The coating compositions according to the invention comprise, expressed in percent by weight of dry matter relative to the total mass of said material:

- in phase (A)

(A1) from 10% to 60% and preferably from 15% to 50% by weight of at least one vinyl hydroxylated polymer and / or copolymer.

(A2) from 15% to 65% and preferably from 20% to 45% by weight of at least one acrylic monomer having at least two ethylene functions.

(A3) from 0.5 to 3% and preferably from 1.0% to 2.8% by weight of at least one acrylic derivative having an acidic character.

(A4) from 3% to 8% and preferably from 4% to 8% by weight of at least one crosslinking initiating agent.

- in phase (B)

(B1) from 10 to 30% and preferably from 10% to 25% by weight of at least one polyisocyanate.

The mixing of the two phases, both of which are dispersed and / or dissolved in at least one suitable organic liquid, is desirably carried out by a person skilled in the art at the time when the coating compositions are used, to coat the metallic or metallized substrates to be protected.

The mixing can be carried out in a time interval preceding its use which can reach even up to 10 days.

To allow the easiest application of the compositions according to the invention, phases (A) and (B) are prepared dissolved and / or dispersed in the appropriate organic liquid and the viscosity of said mixture is adjusted, by introducing additional amounts of the organic liquid. The coating compositions according to the invention can be applied to the substrate according to any of the known methods such as, for example, the methods of compressed air spraying, spraying by electrostatic field, hot spraying or airless spraying.

These application methods make it possible to obtain layers with a thickness in the dry state of between 5 and 15 micrometers. As soon as they are deposited on the substrate to be protected, the coating compositions according to the invention are crosslinked according to methods known to those skilled in the art, which are chemical crosslinking, and crosslinking by ionizing radiation ensuring the elimination of the residual monomers by grafting and / or polymerization, and the possible formation of free radicals, the presence of which promotes the creation of internal defeats and granted to said compositions the desired characteristics. Sources usable for such treatment of ionizing radiation consist of radioactive isotopes emitting gamma radiation such as, for example, Co 60 and Cs 137, in X-ray generators, or in electron accelerators generating beta radiation , and UV sources The irradiation treatment of the compositions according to the invention can be carried out in air, in vacuum, or in suitable gas atmospheres, according to methods known and practiced by those skilled in the art.

Thus, the compositions according to the invention are particularly remarkable because of the exceptional qualities which they develop in comparison with the compositions of the prior art.

Among these exceptional qualities, an excellent adhesion to metallic and / or metallized surfaces can be mentioned more particularly, in the absence of an adhesion sublayer and their insensitivity to any humid and / or alcoholic atmosphere.

The invention will be better understood thanks to the illustrative examples developed below. In all of these examples, the crosslinkable compositions used, whether they are subject of the invention or whether they belong to the closest prior art, were the subject of tests for assessing their respective qualities. adhesion, hardness, water resistance and alcohol resistance. Adhesion test

This test, described in French standard NFT 30038, consists in incising, up to the support, the film of the composition used, then in tearing off the incised film by means of an adhesive tape. The quality of the adhesion is expressed by a score ranging from 0 to 5, (0 when the film has perfect adhesion and 5 when the adhesion is zero).

Pencil hardness test

The pencil hardness of a film is determined using pencils (with graphite lead) of increasing hardness (ranging from 6 B to B, HB to F and from H to 9 H). According to the test, the pencil hardness designates that of the pencils which leaves a trace of writing on the film, while the next in gradation of hardness penetrates the film by scratching it.

This test is carried out using a device allowing the pencil to move slowly over the film, at an angle of 45 degrees and a load of 750 g.

PERSOZ hardness test This test is described in French standard NFT 30016. It consists in measuring the damping time of the pendulum ostillations resting on the film to be checked by two steel balls. Water resistance test This test consists in immersing, for 24 hours, the film of the composition tested in water maintained at 40 degrees C. At the end of this immersion, the film must neither peel off nor whiten .

Alcohol resistance test

This test is carried out according to the same protocol as that of water resistance, the immersion medium being ethanol.

TABER abrasion resistance test

This test, described in French standard NFT 30015, consists in evaluating the abrasion resistance (measurement of the weight loss) of a film, of the composition to be checked, applied to a disc (made of aluminum), a diameter of 100 mm.

The tests are carried out on a TABER abrasimeter (from the company Télédyne TABER), under a load of 500 g according to a cycle number equal to 5 A 0. Examples 1 to 8:

These examples illustrate the preparation of compositions of the polyurethane acrylate type, according to the invention, crosslinkable by ionizing radiation and their applications to metallized surfaces.

To do this, the two phases (A) and (B) of these compositions were prepared by mixing the components necessary for one and the other phase in qualitative and quantitative conformity with the invention (compositions 1 to 8).

The amounts of each component are expressed in percent by weight of dry matter relative to the total mass of each phase, and in percent by weight of dry matter relative to the total mass of dry matter present in the cumulative phases ( A) and (B).

All the compositions (that is to say the components and the solvents) 1 to 8 have been combined in Table I below.

RETURNS

1 UCAR VROH) Vinyl hydroxylated copolymers marketed by

(CARBID UNION

2 UCAR VAGH)

3 PETIA Pentaerythritoltriacrylate

4 TMPTA Trimethylolpropane triacrylate

5 EBECRYL 169 marketed by UCB RADCURE SPECIALITES

6 IRGACURE 184 marketed by CIBA GEIGY

7 DAROCURE 1173 marketed by MERCK

8 IPDI T 1890 S marketed by HULS

9 DESMODUR L 75 marketed by BAYER

10 EBECRYL 1290 urethane aliphatic acrylate marketed by UCB

RADCURE SPECIALTIES

11 EBECRYL 264 urethane aliphatic acrylate marketed by UCB

RADCURE SPECIALTIES

12 TPGDA tripropylene glycol diacrylate

13 HDDA 1,6 hexanediol diacrylate

14 DOWANOL PM propylene glycol methyl ether marketed by

DOW CHEMICAL

15 BYK 341 marketed by BYK CHIMIE

All the compositions were applied to metallic or metallized surfaces, the application being carried out by spraying, using a pneumatic gun and in such a way that the deposited monolayer has, after hardening, approximately

10 micrometers.

After pre-drying under infrared and crosslinking under ultraviolet radiation

(power 80 Watts / cm, distance 12 centimeters and forward speed 10 m / min), the compositions according to the invention have undergone tests of adhesion, hardness and resistance to water and alcohol such as previously described.

All the results relating to these tests have been collated in Table II below.

Examples 9 and 10

These examples illustrate the preparation of compositions belonging to the prior art undergoing finishing by ionizing radiation by means of an ultraviolet source and their applications to metallized surfaces.

To do this :

- Example 9 illustrates the case of a two-layer protection according to the prior art, comprising an intermediate sublayer between the metallic or metallized surface and the finishing varnish, this sublayer having the property of promoting the adhesion of the latter.

- Example 10 illustrates the case of a monolayer protection according to the prior art, comprising a large amount of adhesion promoter, much greater than in the case of the invention.

These two compositions were deposited on metallic or metallized surfaces, in accordance with the application protocol practiced in Examples 1 to 8, it being understood that the composition of Example 9 was deposited according to two successive operations, one concerning the adhesion undercoat, the other the topcoat.

After pre-drying and crosslinking under ultraviolet radiation, the compositions of the prior art have undergone the same tests as those carried out in the case of the compositions according to the invention.

The formulas of the two compositions of the prior art and the results of the quatity tests have been collated in Table III below.

The comparison of the results obtained with the compositions according to the invention and those of the prior art shows that:

- the monolayer compositions according to the invention prove results much superior to those of the monolayer compositions of the prior art;

- the monolayer compositions according to the invention provide results equivalent to those acquired by the bilayer compositions of the prior art.

Claims

CLAIMS 1 - Crosslinkable compositions of the polyurethane-acrylate type by ionizing radiation for coating metallic or metallized surfaces obtained by the mixture of two liquid and / or pasty phases, one (A) containing polyols, and the other (B ), polyisocyanates characterized in that they mainly contain dry matter:

- in phase (A):

A1) at least one hydroxylated vinyl polymer and / or copolymer.

A2) at least one acrylic monomer having at least two ethylenic functions.

A3) at least one acrylic derivative having an acidic character.

A4) at least one crosslinking initiating agent.

- in phase (B):

B1) at least one polyisocyanate. 2 - Compositions according to claim 1 characterized in that the vinyl hydroxylated polymers and / or copolymers (components Al) are chosen from the group consisting of polymers and / or hydroxylated copolymers, halogenated or not, and vinyl esters. 3 - Compositions according to claims 1 or 2 characterized in that the vinyl hydroxylated polymers and / or copolymers are preferably chosen from the group consisting of hydroxylated polyvinyl chloride, polyvinyl acetate, hydroxylated polyvinyl acetochloride, chloride polyvinyl: hydroxylated acrylic esters. 4 - Compositions according to any one of claims 1 to 3, characterized in that the vinyl hydroxylated polymers and / or copolymers have an average molecular weight of between 4000 and 35000 and preferably between 5000 and 30000. 5 - Compositions according to any one of claims 1 to 4, characterized in that the acrylic monomer having at least two ethylenic functions (component A2) is preferably chosen from the group consisting of 1, 6 hexane diol diacrylate, tripropylene glycol diacrylate, 1,3 butane diol diacrylate, trimethylol propanetriacrylate, pentaerytrhritol triacrylate triethylene glycol diacrylate, glyceryl propoxy triacrylate, trimethylol propane ethoxylated triacrylate, dipenta erythritol penta acrylate. 6 - Compositions according to any one of claims 1 to 5, characterized in that the acrylic derivative having an acidic character (component A3) is chosen from the group consisting of acrylic and methacrylated derivatives having an acidic character.

7 - Compositions according to any one of claims 1 to 6, characterized in that the crosslinking initiating agent (component A4) is preferably chosen from the group consisting of hydroxy 1 - cyclohexyl phenylketone, 2 hydroxy - 2 methyl 1 - phenyl propane 1 one, (4 isopropylphenyl) - 2 - hydroxy 2 methyl propane 1 - one, Thioxanthone derivatives, acetophenone, benzophenone, or benzyl dimethyl ketal.

8 - Compositions according to any one of claims 1 to 7, characterized in that the polyisocyanates (components B1) used are of the aliphatic or aromatic type, taken alone or as a mixture. 9 - Compositions according to claim 8 characterized in that the polyisocyanates are preferably chosen from the group consisting of hexamethylene dusocyanate (HDI) isophorone dusocyanate (IPDI), toluene dusocyanate (TDI), diphenylmethane dusocyanate 4 'and its counterparts (MDI), naphthalene diisocyanate 1 - 5 (NDl), and the prepolymers obtained by combining isocyanates together or with reactive compounds.

10 - Compositions according to any one of claims 1 to 9, characterized in that they contain known adjuvants of the dispersing agent, biocidal agent, anti-scratch agent, tensioning agent, dye type. 11 -Compositions according to any one of claims 1 to 10, characterized in that they comprise expressed in percent by weight of dry matter relative to the total mass of said matter: - in phase (A)

A1 - from 10% to 60% by weight of at least one vinyl hydroxylated polymer and / or copolymer.

A2 - from 15% to 65% by weight of at least one acrylic monomer having at least two ethylenic functions.

A3 - from 0.5 to 3% by weight of at least one acrylic derivative having an acidic character.

A4 - from 3% to 8% by weight of at least one crosslinking initiating agent. - in phase (B)

B1 - from 10 to 30% by weight of at least one polyisocyanate. 12 -Compositions according to any one of claims 1 to 11, characterized in that they preferably comprise expressed in percent by weight of dry matter relative to the total mass of said matter:

- in phase (A)

A1 - from 15% to 50% by weight of at least one vinyl hydroxylated polymer and / or copolymer.

A2 - from 20% to 45% by weight of at least one acrylic monomer having at least two ethylenic functions.

A3 - from 1.0% to 2.8% by weight of at least one acrylic derivative having an acidic character.

A4 - from 4% to 8% by weight of at least one crosslinking initiating agent.

- in phase (B)

B1 - from 10 to 25% by weight of at least one polyisocyanate. 13 - Compositions according to any one of claims 1 to 12, characterized in that they are used in a dissolved or dispersed form in organic liquids. 14 -Compositions according to claim (13) characterized in that the organic liquids are preferably ethyl acetate, methyl isobutyl ketone, toluene, xylene, ethyl glycol acetate, metoxy propyl acetate , alcohol diacetone, cyclohexanone, used alone or as a mixture. 15 - Application of the compositions according to any one of claims 1 to 14, to the protection of metallic and / or metallized surfaces of various substrates.

16 -Application according to claim (15) characterized in that the compositions deposited on the metallic and / or metallized surfaces are subjected to crosslinking by ionizing radiation.

17 - Application according to claim (16) characterized in that the treatment of ionizing radiation is carried out by means of a source chosen from the group consisting of radioactive isotopes emitting gamma radiation, X-ray generators, accelerators of electrons generating beta radiation, and UV sources

18 -Application according to claims 16 or 17 characterized in that the treatment of ionizing radiation of the compositions is carried out in air, in vacuum or in suitable gaseous atmospheres.