ITMO20090302A1 - COMPOSITION FOR THE PRODUCTION OF A PROTECTIVE PAINT, OF A RESINOUS OR SIMILAR COATING - Google Patents

Description

â € œCOMPOSITION FOR THE PRODUCTION OF A PROTECTIVE PAINT, A RESIN COATING OR SIMILAR â €.

DESCRIPTION

The present invention refers to a composition for the production of a protective paint, a resinous coating or similar, particularly for use in the construction sector, in the treatment and storage of food, drinking water and black water, etc ... .

The protective paints and resinous coatings known to date mainly consist of a base polymer and a hardening polymer. The base polymer and the hardening polymer contain different chemical functionalities substantially attributable, respectively, to epoxy rings or alcoholic groups and to amino or isocyanate groups.

Currently known protective paints can be classified into solvent-based protective paints, 100% solid protective paints and protective paints in aqueous emulsion.

More particularly, known type solvent-based protective paints are generally of an epoxy, polyurethane and methacrylate nature; in particular, epoxies consist of a base polymer comprising: epoxy resin, plasticizers, pigments, fillers, additives and mixtures of solvents, and a hardening polymer comprising: one or more hardeners, plasticizers, pigments, fillers, additives and solvent mixtures.

The solvent mixtures, used to lower the viscosity of the paint, generally include: alcohols, esters, ketones, aromatic hydrocarbons, chlorinated solvents, etc .... These solvent mixtures, in addition to being highly flammable and dangerous for the health of the Man, they are also considerably harmful to the environment.

Also known type 100% solid protective paints can be epoxy, polyurethane and methacrylate in nature; in particular, epoxies are instead constituted by a base polymer comprising: epoxy resin, reactive diluents, plasticizers, pigments, fillers, additives and a hardening polymer of an amine nature, preferably comprising at least one hardener based on cycloaliphatic amines.

In particular, the 100% solid protective paints have therefore introduced, instead of the solvent mixtures contained in the base polymer of the solvent-based protective paints, new reactive diluents such as: Q2-C14 diglycidyl ether, O-cresyl diglycidyl ether, etc .. .. These reactive diluents are characterized by a good solvent capacity towards epoxy resins and amine hardeners and are provided with one or more epoxy rings able to react directly with the amine functionalities of the hardeners.

The use of these reactive diluents has therefore made it possible to eliminate the use of solvents and at the same time reduce the use of plasticizers.

However, the base polymer and the hardening polymer used for the 100% solid protective paints must be equally diluted on site to reach the viscosity suitable for their application. More in detail, the dilution of the base polymer and the hardening polymer before use is generally performed with solvents labeled as toxic or harmful.

The problem linked to the use of solvents dangerous for human health and harmful to the environment is therefore not solved by 100% solid protective paints but simply moved from production to use.

Protective paints in aqueous emulsion can also be, as well as solvent-based and 100% solid, epoxy, polyurethane and methacrylate ones. The composition of epoxy-based protective paints in aqueous emulsion is substantially similar to that of 100% solid paints, with the difference that both the base and hardening polymers include a percentage of water introduced by making emulsions and / or dispersions through the use of additives capable of acting effectively at the water-oil interface and such as to stabilize the resinous system which, in this case, has on average a greater polarity (due to the presence of water) than solvent-based paints or to 100% solid paints. Paints in aqueous emulsion therefore make it possible to avoid the use of toxic and dangerous solvents not only during the production phase but also during the use phase.

However, this type of protective varnish also has drawbacks. In fact, in addition to high costs, protective paints in aqueous emulsion also have lower chemical-physical properties than other types of protective paints.

The main task of the present invention is to devise a composition for the preparation of protective paints, resinous coatings and the like, which is substantially eco-compatible, and therefore such as to minimize the harmful effects on human health and the environment. , and which at the same time allows to obtain satisfactory chemical-physical properties and at least comparable with those of known products currently on the market. In addition to this aim, an object of the present invention is to devise a composition for the production of protective paints and the like, which reduces as much as possible the use of petroleum derivatives and which includes elements / compounds deriving from renewable resources and / or prepared by eco-compatible synthesis.

An object of the present invention is to devise a composition for the production of protective paints and the like which are economically competitive with the products currently present on the market and mentioned above. Another object of the present invention is to satisfy the current regulations relating to the registration and evaluation of the chemical substances used for protective paints, for resinous coatings and the like.

Another object of the present invention is to devise a composition for the production of a protective paint, a coating or the like, particularly for the building sector, which allows to overcome the aforementioned drawbacks of the prior art in the context of a simple solution , rational, easy and effective to use and low cost.

The above objects are achieved by the present composition for the production of a protective paint, a resinous coating or the like, comprising at least one base polymer and at least one hardening polymer, characterized in that said base polymer comprises one or more epoxidized compounds deriving from renewable resources and the fact that said hardening polymer comprises one or more hardeners obtained from renewable resources.

Other features and advantages of the present invention will become more apparent from the description of a preferred, but not exclusive, embodiment of a composition for the production of a protective paint, a resinous coating or the like.

The composition according to the invention for the production of a protective paint, a resinous coating or the like, comprises at least one base polymer, comprising one or more epoxidized compounds deriving from renewable resources, and at least one hardening polymer, comprising one or more hardeners (curing agents) obtained from renewable resources.

The term â € œhardenersâ € used in the present description also refers to crosslinking agents.

Preferably, both the epoxidized compounds and the hardeners are obtained from biomass.

Advantageously, at least 51% of the total carbon present in the composition according to the invention derives from biomass, and therefore does not originate from petroleum or its derivatives.

More particularly, the stoichiometric ratio between the base polymer and the hardening polymer is calculated as a function of the percentage of the different functional groups and such as to promote a degree of cross-linking that satisfies the liquid-gel-solid transition (also called cross-linking reaction) . Preferably, the stoichiometric ratio between the base polymer and the hardening polymer is comprised respectively between 100 - 20 and 100 - 80 by weight.

The epoxidized compounds obtained from biomass have the function of increasing the cross-linking density, decreasing the viscosity and increasing the share of carbon in the composition not deriving from fossil fuels and in particular from petroleum.

Advantageously, the epoxidized compounds are present in quantities ranging from 1% to 95% by weight, preferably from 50% to 70% by weight.

More particularly, the epoxidized compounds comprise epoxidized, vegetable and / or animal oils and / or fats, in quantities ranging from 1% to 95% by weight, preferably from 20 to 50%.

Epoxidized oils and / or fats have an epoxidation degree between 0.10 and 0.80 mol / 100g, preferably between 0.30 and 0.40 mol / 100g

In a preferred embodiment, the epoxidized oils and / or fats are selected from the group comprising: ESBO epoxidized soybean oils, ELSO epoxidized linseed oils, as well as differently epoxidized oils such as: castor oils, rapeseed oils, peanut oils, cotton oils, coconut oils, palm oils, etc ....

Conveniently, the epoxidized compounds are at least partly obtained by means of an epoxidation reaction, carried out according to conventional methods with the use of peracids or with further new methods, or by the reaction of oils and / or fats of vegetable origin and / or animal with at least one of the categories of compounds including: epichlorohydrin and / or its derivatives, bisphenol A, bisphenol F, epoxy derivatives, mono and polyglycidyl ether-derivatives, in order to obtain an epoxidation degree between 0.10 and 0.80 mol / 100g.

For example, the reaction between epoxidized soybean oil ESBO and bisphenol A (BPA), allows an effective cross-linking action between different ESBO units thanks to the nucleophilic attack of the phenolic hydroxyl of BPA to the carbon of the epoxy ring of the reagent oil. In this regard, it is advisable to operate in excess of ESBO in order not to excessively reduce the epoxy functionality of the final polymer obtained, which must subsequently be combined with the hardener-crosslinking agent in the cross-linking phase of the resin.

Advantageously, the epoxidized compounds also include compounds derived from alkyl-alkylene phenols.

More particularly, such compounds derived from alkyl-alkylene phenols have viscosity lower than 20,000 mPas, preferably lower than 200 mPas. Preferably, the base polymer of the composition according to the invention also comprises at least a first resin of an epoxy nature obtained from renewable resources, preferably from biomass. This first resin conveniently also includes epoxy-novolac type resins.

This first resin has the function of increasing the cross-linking density and the mechanical properties of the protective varnish or of the resinous coating thus obtained.

More in detail, the first resin is present in a variable quantity between 1% and 95%, preferably between 20% and 50%.

Advantageously, the first resin is obtained by biocatalyzing, homo and heterogeneous synthesis, and / or by polymerization reactions.

The base polymer of the composition according to the invention can also comprise a second resin, in emulsion and / or aqueous dispersion or 100% solid, of the epoxy type and not derived from biomass. As well as the first resin, the second resin also includes epoxinovolacca type resins.

More particularly, the second resin is present in a variable quantity between 1% and 80% by weight, preferably between 30% and 60%, and has an epoxy equivalent between 50 and 2000 g / eq, preferably between 150 and 500 g / eq.

Advantageously, the hardeners which make up at least part of the hardening polymer and which contribute to raising the concentration of Carbon obtained from renewable resources and therefore not deriving from petroleum, are present in a variable quantity between 1% and 95% by weight, preferably between 30% and 50%.

In a preferred embodiment, the hardeners are therefore present in lower quantities than the epoxidized compounds.

More in detail, the hardeners are selected from the group comprising: aliphatic, cycloaliphatic, aryl-amines, aromatics, polyoxyalkylenamines, polyglycolamines, ketimines, cyano-ethylates, dicyanoamides, polyamides, polyamidoamines and imidazolines, Mannich bases, anhydrides and / or mixtures of anhydrides, accelerators and crosslinkers, as well as adducts between the various compounds described above.

Preferably, the hardeners comprise compounds of saturated and unsaturated alkiphenol origin obtainable from Cashew Nut Shell Liquid. Cashew Nut Shell Liquid is an oil extracted from cashew nut (Cashew Nut Tree) and the main alkyl-phenolic compounds present in it are: Tanacardic acid, Cardol, Cardanol and 2-methyl cardol.

During the extraction and refining processes, it tends to degrade by decarboxylation in Cardanol.

Through the transformation of Cardanol, for example by aromatic aminomethylation, phenalkamine are obtained.

More particularly, aromatic aminomethylation, which is a specific case of Mannich condensation, involves the reaction, at a temperature of about 80-90 ° C, of a mixture of Cardanol, formaldehyde and a primary amine according to a defined ratio molar.

Different types of animins are used to obtain Phenalkamine, among which diamines of the type ethylenediamine (EDA), diethylenetriamine (DETA) and triethylenetetramine (TETA) are preferably used.

The compounds of alkiphenolic origin which make up the hardeners are therefore advantageously obtained from Cardanol, preferably from Phenalkamines.

Phenalkamines are in fact able to react quickly with conventional epoxy resins, generating polymeric products.

The degree of crosslinking can be controlled by introducing different polyamines into the phenalkamine and thus modifying the overall balance of the amino groups present.

From an examination of the reaction kinetics between a conventional epoxy resin (of the type DER 331 or EPIKOTE 828) and a Phenalkamine deriving from DETA and / or TETA conducted at room temperature and performed by FT-IR, it was possible to ascertain how with the proceeding of the liquid-gel-solid transition (crosslinking), the band due to the stretching of the O-H increases and at the same time the peak linked to the absorption of the epoxy ring decreases, confirming the nucleophilic substitution of the amine to the epoxy carbon with consequent formation of -OH.

It has also been observed that at low temperatures, preferably between 0 to 5 ° C, Phenalkamines have a greater reaction speed than standard amines with epoxy resins, thanks to the presence of phenolic OH which facilitates the opening of the ring. epoxy resin thus further facilitating crosslinking, better tolerance to humidity compared to the classic Mannich bases, due to the presence of the long hydrophobic aliphatic chain deriving from Cardanol, and greater flexibility and chemical resistance compared to the classic Mannich bases, due to presence of the aromatic ring.

Phenalkamines allow a high percentage of Carbon originating from renewable sources to be introduced into the composition according to the invention. Conveniently, the Phenalkamines are mixed with cycloaliphatic adducts and / or with other compounds with nucleophilic characteristics capable of reacting with the oxirane functionalities.

More in detail, the molecular structure of the hardeners comprises from 3 to 20 active hydrogens and from 2 to 50 amino functional groups, preferably from 2 to 30 amino functional groups.

Advantageously, at least one of the base polymer and the hardening polymer comprises plasticizers and / or fillers obtained from renewable resources, preferably from biomass, in quantities ranging from 1% to 50% by weight, preferably from 5% to 20%. However, it is not excluded that the plasticizers and / or fillers used in the present composition according to the invention may have a different origin, or that they may derive from fossil fuels.

The plasticizers and / or fillers have the function of reducing the viscosity of the protective paint thus obtained, reducing costs and improving chemical resistance to certain substances. These plasticizers and / or fillers generally have a modest molecular weight and a boiling point higher than 100 ° C and, more precisely, higher than 200 ° C.

Preferably, such plasticizers and / or fillers are selected from the group comprising: adipates, azelates, caprylates, abietates, acetates, benzoates, citrates, chlorinates, ethers, phosphates, phthalates, isobutyrates, oleates, oxalates, trimellitates, glycolates, sebacates, glycerol, glycerol-derivatives, alkyl-alkylene carbonates, furfuryl-derivatives, lauryl-derivatives, stearyl-derivatives, lactic-derivatives, aspartates, etc ....

At least one of the base polymer and the hardening polymer can also comprise one or more additives in a variable quantity between 1% and 25%, preferably between 1% and 5%.

More in detail, these additives are chosen from the group comprising: de-aerating, leveling, relaxing, stabilizing, anti-inflammatory, anti-inflammatory, anti-sedimenting, viscosity reducers, rheology modifiers, etc ....

Conveniently, the additives of the base polymer and / or of the hardening polymer are also obtained from renewable resources, preferably from biomass.

Advantageously, at least one of the base polymer and the hardening polymer comprises linear and / or cyclic alkyl and / or alkylene carbonates in quantities ranging from 1% to 60% by weight, preferably from 5% to 15%.

More particularly, such alkyl and / or alkylene carbonates are obtained from renewable resources, preferably from biomass, and comprise at least one of the high molecular weight carbonate polymers, preferably glycerol carbonate. Glycerol carbonate is a product labeled as non-hazardous and 75% of the carbon it contains is derived from renewable sources.

The alkyl and / or alkylene carbonates essentially perform the function of solvents, in particular as â € œreactive solventsâ €, as they reduce the viscosity of the composition, and contribute to increasing the percentage of carbon in the composition coming from renewable resources and therefore not originating from petroleum or its derivatives.

Conveniently, at least one of the base polymer and the hardening polymer comprises one or more pigments suitable for modifying the structure and the hue of the protective paint or of the resinous coating thus obtained.

More particularly, these pigments, which can be organic and / or inorganic and of synthetic and / or natural derivation, comprise at least one compound of a fluorescent and / or luminescent and / or phosphorescent and / or thermoactive and / or pearlescent and / or opalescent type. .

Furthermore, at least one of the base polymer and the hardening polymer can also include mineral compounds, fillers and fillers, capable of giving structure to the composition to obtain higher thicknesses and at the same time to contain costs.

This composition allows, through appropriate modifications in the percentages of the different compounds, easily deductible by the skilled in the art in the light of the present description, the obtaining of formulations suitable for the realization of adhesion promoters, primers, impregnants, consolidants, thin film paints and thick, self-smoothing, synthetic mortars with mineral and non-mineral fillers, trowel, decorative coatings, three-component cement-based and non-cement-based products, anticorrosive and protective paints for various types of substrates such as cement, ferrous, mineral, wood-based and polymer-based substrates .

In practice it has been found that the described invention achieves the intended aim and objects and in particular it is emphasized that the composition according to the invention allows to obtain a protective paint, a resinous or similar coating of an environmentally friendly type, i.e. in which most of the components are derived from renewable resources.

More particularly, as described above, at least 51% of the total carbon present in the composition according to the invention derives from renewable resources.

Furthermore, the composition according to the invention allows to eliminate the use of traditional dangerous solvents and at the same time to maintain a suitable workability and satisfactory chemical-physical characteristics.

In particular, from laboratory tests carried out according to the methods recognized in the specific sector of protective paints and two-component resin coatings and from DMTA (Dynamic Mechanical Thermal Analysis), DSC, TGA and FT-IR analysis, the protective paints and resin coatings obtained with the composition according to the invention they showed a high adhesion capacity to ferrous and cementitious supports, a mechanical and chemical resistance at least equal to that of the protective paints known to date, the absence of stickiness and opalescence of the hardened film , a high reactivity at low temperatures (below 10 ° C) and a high ease of application.

Furthermore, the final costs relating to the production of protective paints or resinous coatings by means of the composition according to the invention are comparable to those relating to two-component water-based systems.

Claims (10)

CLAIMS 1) Composition for the production of a protective paint, a resinous coating or similar, comprising at least one base polymer and at least one hardening polymer, characterized in that said base polymer comprises one or more epoxidized compounds deriving from renewable resources and in that said hardening polymer comprises one or more hardeners obtained from renewable resources. 2) Composition according to claim 1, wherein said epoxidized compounds are present in a variable quantity between 1% and 95% by weight, preferably between 50% and 70% by weight. 3) Composition according to claim 1 or 2, wherein said epoxidized compounds comprise epoxidized, vegetable and / or animal oils and / or fats, in quantities ranging from 1% to 95% by weight, preferably from 20 to 50%. 4) Composition according to claim 3, wherein said epoxidized oils and / or fats have an epoxidation degree comprised between 0.10 and 0.80 mol / 100g, preferably between 0.30 and 0.40 mol / 100g. 5) Composition according to claim 3 or 4, wherein said epoxidized oils and / or fats are selected from the group comprising: ESBO epoxidized soybean oils, ELSO epoxidized linseed oils, as well as different epoxidized oils such as: castor oils, rapeseed oils, peanut oils, cottonseed oils, coconut oils, palm oils, etc .... 6) Composition according to one or more of the preceding claims, where said epoxidized compounds are at least partially obtained by an epoxidation reaction or by the reaction of oils and / or fats of vegetable and / or animal origin with at least one of the categories of compounds comprising: epichlorohydrin and / or its derivatives, bisphenol A, bisphenol F, epoxy derivatives, mono and polyglycidyl ether derivatives, so as to obtain an epoxidation degree of between 0.10 and 0.80 mol / 100g. 7) Composition according to one or more of the preceding claims, wherein said epoxidized compounds comprise compounds derived from alkylalkylene phenols. 8) Composition according to claim 7, wherein said epoxidized compounds have viscosity lower than 20,000 mPas, preferably lower than 200 mPas. 9) Composition according to one or more of the preceding claims, wherein said base polymer comprises at least a first epoxy resin obtained from renewable resources. 10. Composition according to claim 9, wherein said first resin is present in a variable quantity between 1% and 95%, preferably between 20% and 50%. 1 1) Composition according to claim 9 or 10, wherein said first resin is obtained by bio-catalyzing synthesis and / or by polymerization reactions. 12) Composition according to one or more of the preceding claims, wherein said base polymer further comprises a second epoxy resin not derived from biomass in a quantity varying between 1% and 80% by weight, preferably between 30% and 60%, and which has an equivalent epoxy between 50 and 2000 g / eq, preferably between 150 and 500 g / eq. 13. Composition according to one or more of the preceding claims, wherein said hardeners are present in a variable quantity between 1% and 95% by weight, preferably between 30% and 50%. 14) Composition according to one or more of the preceding claims, where said hardeners are selected from the group comprising: aliphatic, cycloaliphatic, arylamines, aromatics, polyoxyalkylenamines, polyglycolamines, ketimines, cyano-ethylates, dicianoamides, polyamides, polyamidoamines and imidazolines , Mannich bases, anhydrides and / or mixtures of anhydrides, accelerators and crosslinkers, as well as adducts among the different compounds described above. 15) Composition according to one or more of the preceding claims, wherein said hardeners comprise saturated and unsaturated alkiphenolic origin compounds obtainable from Cashew Nut Shell Liquid, preferably from Cardando, including Phenalkamine. 16) Composition according to one or more of the preceding claims, where said Phenalkamine are mixed with cycloaliphatic adducts and / or with other compounds with nucleophilic characteristics suitable to react with the oxianic functionalities. 17) Composition according to one or more of the preceding claims, where the molecular structure of said hardeners comprises from 3 to 20 active hydrogens. 18. Composition according to one or more of the preceding claims, wherein the molecular structure of said hardeners comprises from 2 to 50 amino functional groups, preferably from 2 to 30 amine functional groups. 1 9) Composition according to one or more of the preceding claims, where at least one of said base polymer and said hardening polymer comprises plasticizers and / or fillers obtained from renewable resources in quantities ranging from 1% to 50% by weight, preferably between 5% and 20%. 20) Composition according to claim 19, where said plasticizers and / or fillers are selected from the group comprising: adipates, azelates, caprylates, abietates, acetates, benzoates, citrates, chlorinates, ethers, phosphates, phthalates, isobutyrates, oleates, oxalates, trimellitates , glycolates, sebacates, glycerol, glycerol-derivatives, alkyl-alkylene carbonates, furfuryl-derivatives, lauryl-derivatives, stearyl-derivatives, lactic-derivatives, aspartates, etc .... 21) Composition according to one or more of the preceding claims, where at least one of said base polymer and said hardening polymer comprises one or more additives, in quantities ranging from 1% to 25% by weight, preferably from 1% to 5%, selected from group including: de-aerating, leveling, stretching, stabilizing, anti-inflammatory, anti-inflammatory, anti-settling, viscosity reducers, rheology modifiers, etc .... 22) Composition according to claim 21, where said additives are derived from renewable resources. 23) Composition according to one or more of the preceding claims, where at least one of said base polymer and said hardening polymer comprises linear and / or cyclic alkyl and / or alkylene carbonates in a quantity ranging from 1% to 60% by weight, preferably between 5% and 15%. 24) Composition according to claim 23, where said alkyl and / or alkylene carbonates are obtained from renewable resources and comprise at least one of the high molecular weight carbonate polymers, preferably glycerol carbonate. 25) Composition according to one or more of the preceding claims, where at least one of said base polymer and said hardening polymer comprises one or more pigments suitable for modifying the structure and hue of said paint and comprising at least one compound of the fluorescent and / or luminescent type and / or phosphorescent and / or thermoactive and / or pearlescent and / or opalescent. 26) Composition according to one or more of the preceding claims, where at least one of said base polymer and said hardening polymer comprises mineral compounds, fillers and "fillers". 27) Composition according to one or more of the preceding claims, where at least 51% of the total carbon present in the composition itself is obtained from renewable resources and in particular from biomass. 28) Composition according to one or more of the preceding claims, wherein said renewable resources are of the biomass type.