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Title:
PROCESS FOR OBTAINING CURED THERMOSET POLYMERIC COMPOSITES
Document Type and Number:
WIPO Patent Application WO/2010/124352
Kind Code:
A1
Abstract:
The present invention refers to cured thermoset polymeric composites comprising the steps of dissolution of organic polymers and/or mixtures of organic polymers in monomers and/or mixtures of monomers and/or addition of photo-thermo-reactive diluents and/or mixtures of photo-thermo-reactive diluents, contemplating thermo and/or photo-thermo-initiators, and/or mixture of photo-thermo-initiators and/or mixed curing systems, as well as, eventually, any agents and/or fillers, application of the resulting composite on the surface of a substrate, followed by curing of said composite, performed by means of radiation (CSR) and/or by means of temperature (FCR). The invention also relates to thermoset polymeric composites obtained according to the aforementioned process, as well as the use of the said cured thermoset polymeric composites in paintings, coatings, inks, printing, lacquers, enamels, varnishes, sealers and adhesives.

Inventors:
COGHI, Marco Fabio (Rua Antônio de Macedo Soares, 1212 apto. 141-, Campo Belo -001 São Paulo, 04607, BR)
SILVA, Naraci Cristina da (Av. Bunduki, 88Bairro Assunção, -580 São Bernardo do Campo - SP, 09812, BR)
Application Number:
BR2010/000137
Publication Date:
November 04, 2010
Filing Date:
April 26, 2010
Export Citation:
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Assignee:
COMPANHIA NITRO QUÍMICA BRASILEIRA (Av. Dr. José Artur Nova, 951São Miguel Paulista, -000 São Paulo - SP, 08090, BR)
COGHI, Marco Fabio (Rua Antônio de Macedo Soares, 1212 apto. 141-, Campo Belo -001 São Paulo, 04607, BR)
SILVA, Naraci Cristina da (Av. Bunduki, 88Bairro Assunção, -580 São Bernardo do Campo - SP, 09812, BR)
International Classes:
B41M7/00; C08L1/18; G03C1/73
Foreign References:
US20050202247A9
US20050156522A1
US20030187087A1
US20060240246A1
US20030138733A1
US20060078742A1
Attorney, Agent or Firm:
KUNG, Angela Fan Chi (Pinheiro Neto - Advogados, Rua Hungría 1.10, Jardim Europa -000 São Paulo - SP, 01455, BR)
Download PDF:
Claims:
CLAIMS

1. A process for obtaining cured thermoset polymeric composites comprising the steps of dissolving 0.1 to 90% of organic polymers and/or mixtures of organic polymers in 0.1 to 90% of monomers and/or mixtures of monomers, and/or 0.0 to 90% of photo-thermo-reactive diluents and/or mixture of photo-thermo-reactive diluents and/or 0.0 to 50% of photo-thermo- initiators and/or mixtures of photo-thermo-initiators, followed by the application of the composite on the surface of a substrate and curing by radiation and/or temperature of said composite.

2. The process of claim 1, wherein the organic polymer comprises organic polymer of nitrocellulose.

3. The process of claims 1 or 2, wherein it comprises organic polymer of nitrocellulose with a molecular mass ranging from 10,000 to 800,000 Daltons.

4. The process of claim 3, wherein the organic polymer of nitrocellulose presents a molecular mass between 500 and 7,000 Daltons, and functionality between 1 and 70.

5. The process of any of claims 1 to 4, wherein it comprises between 0.0 to 99% of polymers or polymer mixtures.

6. The process of any of claims 1 to 5, wherein the polymer comprises pre-polymer and oligomer.

7. The process of claim 6, wherein the oligomer comprises epoxy acrylate oligomer.

8. The process of any of claims 6 or 7, wherein the epoxy acrylate oligomer comprises a mono or multifunctional aromatic, modified with bisphenol A or other modifying agent, aromatic epoxy modified with phenolic resin, aliphatic epoxy acrylate, or other acrylic resin modified with fatty acid, vegetable oils, aliphatic and/or aromatic urethane acrylate, polyester acrylate as the conventional ones based on polyols and diacids or those modified with fatty acids, and/or other modifiers, polyether acrylate, polyester modified with chlorinated or fatty acids among others, acrylic acrylate, amino acrylates, silicone acrylates and other specialty polymers.

9. The process of any of claims 1 to 8, wherein the monomers and/or mixtures of monomers and/or photo-thermo-reactive diluents and/or mixtures of photo-thermo-reactive diluents from the dissolution step comprise organic compounds in general, but not exclusively monomers, unsaturated organic compounds of functionality ranging from mono, bi, tri up to hexafunctional or even greater functionality, of low and medium molecular mass, aliphatic and cycloaliphatic alkanes, ethers derived from ethylene oxide or propylene oxide and/or their mixture, aromatic compounds, unsaturated aliphatic derivatives of butadiene, polyesters and their derivatives, derivatives of fatty acids acrylates.

10. The process of claim 9, wherein the monomers and/or photo-thermo-reactive diluents and/or mixtures of monomers and/or mixtures of photo-thermo-reactive diluents from the dissolution step comprise isobomyl acrylate, tripropylene glycol diacrylate, 1.6 hexanediol 4.1.3.3 diacrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate.

11. The process of any of claims 1 to 10, wherein the photo-thermo-initiators comprise mono, di, tri or polyaromatic compounds.

12. The process of claim 11, wherein the photo-thermo-initiators comprise benzyl dimethyl ketal, phenylglyoxalate, benzophenone, alpha-hydroxy ketone, bisacylphosphine oxide, monoacylphosphine oxide and alpha-amino ketones.

13. The process of any of claims 1 to 12, wherein comprises the addition of agents in any steps, such as pigments, finishing, plasticizers, solvents, diluents, fillers, additives, waxes, fibrous and particulate organic and/or inorganic materials, products unsaturated or not.

14. The process of any of claims 1 to 13, wherein the cure by radiation comprises exposure of the composition to ultraviolet radiation, visible light spectrum, infrared radiation, electron beam or thermal radiation, alone or in combination.

15. The process of claim 14, wherein the cure by ultraviolet radiation comprises exposing the composition to the power source comprising light bulbs with or without electrodes, of high or medium pressure.

16. The process of claim 14, wherein the cure by electron beam comprises exposure of the composition to equipments that accelerate electrons.

17. The process of claim 14, wherein the cure by infrared radiation comprises exposing the composition to electrical resistance, light bulbs, fuel combustion and other sources of heating.

18. The process of claim 14, wherein the cure by visible radiation comprises exposing the composition to sunlight.

19. The process of claim 14, wherein curing is done by temperature.

20. The cured thermoset polymeric composites obtained of any of claims 1 to 19.

21. An use of the cured thermoset polymeric composites of claim 20 in paintings, coatings, inks, printing, lacquers, enamels, varnishes, sealers and adhesives.

22. The use of the cured thermoset polymeric composites of claim 21, wherein comprises the application by roll, spray, brush and curtain.

23. The products obtained by any of claims 21 and 22.

Description:
PROCESS FOR OBTAINING CURED THERMOSET POLYMERIC COMPOSITES

FIELD OF THE INVENTION

[0001] The present invention relates to a new process of obtaining cured thermoset polymeric composites.

[0002] The invention also relates to the polymer obtained in the form of pellicle or film, as well as its various applications and uses.

BACKGROUND OF THE INVENTION

[0003] Systems for radiation curing are often used for painting systems, coatings, serigraphic inks, rotogravure and flexography ink, printing ink, offset inks, lacquers, electrical insulating enamels, automotive enamels, finishing varnishes, sealers, adhesives etc., and can be applied in various ways, such as roll, spray with or without air, brush, roller printing, curtain, among others.

[0004] Brazilian Patent Application PI0604199-0, filed September 20, 2006, entitled "Tinta liquida para impressao de dupla cura-secagem termica e por radiacao ultravioleta ou feixe de electrons-tinta hfbrida" refers to the invention of a liquid ink for printing of dual cure-drying by UV or EB. The composition of these paints, with double drying process, has solvents and eventually resins common to both solvent systems and polymers, monomers and photo-initiators for UV systems.

[0005] Brazilian Patent Application MU8400153-4, filed January 30, 2004, entitled "Disposicao aplicada em unidade secadora de tintas para impressao e escrita" describes a single equipment that combines the three drying technologies of induction by radiation, ultraviolet (UV) radiation, radiation from a heat source of electrical power.

[0006] Brazilian Patent Application PI9300471-0, filed February 03, 1993, entitled "Composicao de polimero de latex curavel por radiacao, processo para formar a mesma e composicao de revestimento" teaches the composition of latex polymer curable by radiation and a process for forming the same. Coating compositions are described based on a composition of functionalized latex polymer curable by radiation.

SUMMARY OF THE INVENTION

[0007] The present invention relates to a new process of obtaining cured thermoset polymeric composites. The above process involves the dissolution of organic polymers, and/or mixtures of organic polymers in monomers and/or mixtures of monomers, and/or photo-thermo-reactive diluents and/or mixtures of photo- thermo-reactive diluents, and/or including photo-thermo-initiators, and/or mixture of photσ-thermo-initiators in the presence or not of polymers, or mixture of polymers, and/or mixed systems of curing and, as well as, eventually, any agents and/or additives and/or fillers, the application of the obtained composite on the surface of a substrate, followed by curing of said composite, carried out by radiation (SCR) and/or by temperature (FCR).

[0008] The invention also relates to the polymer obtained in the form of pellicle or film, as well as to its various applications and uses.

DETAILED DESCRIPTION OF THE INVENTION

[0009] Curing by radiation and/or by temperature causes nitrocellulose insoluble in organic solvents, water-resistant, forming high gloss films, controllable hardness according to the system composition and excellent spreading. It also presents low content of Volatile Organic Compounds (VOC, ASTM D-5403), that can be used in putties, sealers, adhesives, paints and varnishes. Such compositions comprise nitrocellulose alone or in combination with one or more organic resins and/or photo-reactive polymers and/or thermosets of many types, mono, di, tri and/or multifunctional photo-reactive diluents, thermo-reactive and/or photo-reactive initiators, with or without the addition of additives, fillers, pigments, dyes, plasticizers, solvents, diluents and other photo-reactive components, that are thermo-reactive or not, being these components usually employed in the formulation and production of putties, primers, sealers, adhesives, paints and varnishes in general.

[0010] Paints, varnishes, putties, sealers, adhesives, printing inks and other formulations made with nitrocellulose alone or mixed with other organic resins, are dried by the solvents evaporation mechanism and present a large amount of solvent in their composition. Paints, varnishes, sealers, adhesives and putties based on nitrocellulose are products whose composition has a high VOC content. Nitrocellulose also forms films of average brightness (60% at 60° measured in Glossmeter), with low resistance to water and to alcohol, low resistance to polar solvents and rigid structure, requiring the use of plasticizers. It is used traditionally in the manufacture of products for wood protection and finishing, plastic packaging, adhesives, leather, automotive paint for re-painting and nail polish.

[0011] Nitrocellulose is an organic polymer obtained industrially by the nitration reaction of a mixture of sulfuric acid, nitric acid, water, nitric and nitrous oxides usually but not exclusively, with chemical wood cellulose or cotton linter (dissolving pulp) cellulose. Therefore, the obtained nitrocellulose has the molecular mass adjusted by a thermal process of acid hydrolysis (digestion), followed by processes of thermal stabilization, dehydration and wetting in various wetting agents (water, ethanol, isopropanol, butanol and/or various plasticizers, such as phthalates, citrates, organic phosphates, among others). Nitrocellulose incorporates nitro groups to its molecule by reaction of the nitric acid with cellulose hydroxyls, the amount of those nitro groups being expressed by the content of nitrogen, ranging between 10.0 and 12.5%. The molecular mass of nitrocellulose is controlled in the process of acid hydrolysis under pressure, and is expressed by viscosity. The viscosity is determined in a solution of nitrocellulose dissolved in a mixture of solvents, according to national and international technical standards (ASTM D-301, DIN 53179, ISO 14446 or other similar or equivalent) and varies from 5 to 650,000 centiPoise. The digestion process results in nitrocellulose polymers whose molecular mass ranges from 10,000 to 800,000 Dal tons or more.

[0012] The cure by radiation (CR) is an industrially used technique to provide the polymerization of resins, oligomers, organic polymers and monomers, it comprises curing by ultraviolet (UV) radiation, curing by radiation in the spectrum of visible light (VL), electron beam (EB) or thermal radiation (IV), alone or in combination. The main systems and technologies of curing by radiation are:

• Curing by UV radiation uses as a source of radiant energy electric light bulbs with or without electrodes, with high or medium pressure (mercury with or without gallium iodide and/or iron iodide); containing hydrogen gas, mercury steam or other chemical element(s), doped or not with metals or semi-metals;

• Electron beam curing uses equipment that involves acceleration of electrons with energy up to 300 kV. When accelerated electrons collide with the reactive organic molecules present in suitable formulated systems form free radicals. Organic molecules and free radicals formed react with each other and undergo polymerization, regardless of the presence of photo-initiators;

• Curing by radiation (IV) produces infrared radiation by means of electrical resistance, light bulbs, fuel combustion and other sources of heating, where the wavelength of the emitted radiation by these devices is within the infrared spectrum; and • Curing by visible light (VL) is performed by exposure of the composition to direct or indirect sunlight. The wavelength of the radiation is situated within the spectrum of visible light.

[0013] The curing systems by radiation (CSR) are chemical compositions that produce thermosetting (cured) polymeric composites when adequately exposed to one or more of such radiations. The CSR is based on the property that certain chemicals become chemically reactive when subjected to UV, VL, EB and IV radiation sources. These radiations promote in one or more chemical compounds, that make up the formulation of the CSR, the production of highly reactive free radicals or ions in the presence (or not) of photo- initiators and/or thermo-initiators, that will promote the polymerization of the active components. The CSR can also be mixed whereby there is the use of thermal energy together with or separately to the UV, VL and EB systems. As soon as the photo-reactive and/or thermo-reactive composition (CSR) - e.g. paint, varnish, lacquer, adhesive or other photo-curable/thermo-curable CSR - is adequately irradiated during the necessary and sufficient time by the suitable source(s) of radiation(s), with adequate amount of energy and appropriate temperature, a process of polymerization begins between the unsaturated compounds: resins and/or unsaturated polymers with other unsaturated chemical compounds that act like photo-reactive diluents (monomers). The obtained chemical reaction originates strong covalent bonds between the film-forming substances. Such film consists of the product resulting from the reaction between resins and/or unsaturated photo/thermo-curable polymers, photo-reactive diluents - mono, di or multifunctional photo-reactive monomers, photo-initiators and/or thermo-initiators and other components (photo-reactive or not) that will be present in the referred formulation. The polymerization reaction (cure) occurs until a final step of polymerization is obtained, with the conversion of 20% to 100%, preferably 60% to 100% or better, between 80% and 100% of unsaturated into saturated bonds. The conversion means that the saturated bonds existing in the CSR become covalent saturated bonds, with the formation of a polymer with high molecular mass and insoluble in common solvents. The chemical reactions triggered by UV, VL, IV and EB radiations are of free radicals type or cationic, and occur in polymers and/or unsaturated polymers (not exclusive), of the following types: epoxy acrylate, aliphatic and/or aromatic urethane acrylate, polyester acrylate, polyether acrylate, acrylic acrylate, amino acrylates, silicone acrylate and other- specialty polymers, or cationic, in the later the polymerization takes place preferably through epoxy groups. Parallel to the reaction via free radicals, there is also the formation of polymer with crossed networks in proportions of 0 to 100% of the polymers formed by crosslinking of the reactive monomers (reactive diluents) in which resins and polymers are retained in its polymeric chains, the chains are obtained by radiation polymerization, forming mono, bi and three-dimensional reticles. The curing systems by radiation may also be water based, where the resin is emulsifiable, dispersible or soluble in water and water is removed just before the curing process by radiation (mixed systems IV/UV).

[0014] The CSR can be based exclusively on compositions where the viscosity of the system is reduced by photo-reactive monomers (reactive diluents), organic solvents or water in the systems well-known as solvent based or water based (soluble, dispersible or emulsifiable in water).

[0015] The CSRs are products obtained by mixing, dispersion or homogenization by means of electromechanical mixers, cowless, dispersers, sand or metallic spheres mills, ball mills or other suitable equipment to prepare dispersions, emulsions, solutions, mixtures in general.

[0016] The application of such CSR compositions is performed by any of the methods of application, not limited to, roll, printing roll, pad, rotogravure, flexography, offset, brush, curtain, vacuum, spray, airless spray, immersion, etc. and cured by ultraviolet radiation (UV), electron beam (EB) or Light Emission Diode (LED) or still other ionizing radiation and/or generating free radicals. Parallel to the reaction via free radical there is also the formation of Interpenetrating Network Polymer (INP), in proportions of 0% to 100% of the polymers formed by crosslinking of the reactive monomers (reactive diluents) in which resins and oligomers are retained in its polymeric chains, the chains are obtained by radiation polymerization, forming mono, bi and three-dimensional reticles. The application of CSR is done on different substrates, such as thermoplastic and thermoset polymers, metals, glass, massive wood, MDF, OSB, plywood and particle boards, fiber plate, hard plates, wooden veneer, paper and cardboard, parquet, polymer reinforced with organic and/or inorganic fibers, textile, electro-electronic devices, among other organic and/or inorganic materials.

[0017] The organic polymers referred to in this patent of invention are saturated or unsaturated compounds that react with reactive monomers in the presence of photo- and/or thermo- initiators when subjected to UV, VL, IV and/or EB radiations to form a compound of higher molecular mass than resins and individual polymers, and that belong to the chemical classes, though not exclusively, commercially known as nitrocellulose with nitrogen content «12.5% epoxy acrylate polymers (aromatic mono or multifunctional, modified with bisphenol A, or other modifying agent, aromatic epoxy modified with novolac resin, aliphatic epoxy acrylate, or other modified acrylic epoxy resin with fatty acid, vegetable oils, e.g. soybean, linseed, rice, among others), aliphatic and/or aromatic urethane acrylate (mono, di, tri, tetra, penta, hexa or greater degree of acrylation), polyester acrylate (conventional on the base of polyol and diacids or modified with fatty acids, and/or other modifiers), polyether acrylate, modified polyesters (chlorinated, modified with fatty acids, among others), acrylic acrylate, amino acrylates, silicone acrylates and other specialty polymers, with molecular mass ranging from 10,000 to 800,000, preferably from 500 to 7,000 Daltons and functionality from 1 to 70, preferably functionality of 2 to 10.

[0018] The polymers referred to in this application may be pure, dissolved or diluted in reactive diluents in any proportion, from 0.0 to 99%, preferably from 0 to 90% concentration of polymer in reactive diluents.

[0019] The photo-reactive monomers or diluents referred to in this invention are organic chemicals, in general, but not exclusive, unsaturated organic compounds with functionality ranging from mono, bi, tri up to hexa-functional or even greater functionality, low and medium molecular mass, whose main function is to reduce the viscosity of the CSR, to improve the wettening of substrates and pigments, to provide some final physical properties of the cured film, and to control the curing velocity. The reactive diluents belong to the chemical classes, but not limited to: aliphatic and cycloaliphatic alkanes, ethers derived from ethylene oxide or propylene oxide and/or their mixture, aromatic compounds, unsaturated aliphatic derivatives of the type of butadiene, polyesters and their derivatives, derivatives from acrylates of fatty acids, among others. As not limiting examples of commercial photo-reactive solvents can be cited: isobornyl acrylate (IBOA), tripropylene glycol diacrylate (TPGDA), 1.6 hexanediol 4.1.3.3 diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), trimethylolpropane tiϊacrylate (TMPTA), and the other photo-reactive monomers.

[0020] As described herein, photo-initiators belong to the group, but not limited to, of mono, di, tri or polyaromatic compounds, including the benzyl dimethyl ketal (BDK), phenylglyoxalate, benzophenone, alpha-hydroxy ketone, bisacylphosphine oxide (BAPO), monoacylphosphine oxide (MAPO), alpha-amino ketones and other photo- initiators.

[0021] The other components of the CSR herein described belong to the classes of pigments usually used in formulations and preparations of paints, synthetic enamels and other products formulated for paintings, coatings, printing inks, paints and finishes for plastics, among others, as well as plasticizers, solvents, diluents, fillers, additives, waxes, fibrous and particulate organic and inorganic materials, unsaturated or not.

[0022] Advantageously the present invention comprises a process of getting cured thermoset polymeric composites comprising the steps of dissolving 0.1 to 90% of organic polymers and/or mixtures of organic polymers, in 0.1 to 90% of monomers and/or mixtures of monomers and/or adding 0.0 to 90% of photo-thermo-reactive diluents and/or mixtures of photo-thermo-reactive diluents, and 0.0 to 50% of photo-thermo-initiators, and/or mixture of photo-thermo-initiators, followed by application of the compound on a substrate surface and cure by radiation and/or temperature of said compound.

[0023] More advantageously this invention refers to a process comprising organic polymer including nitrocellulose.

[0024] Still more advantageously the present invention relates to nitrocellulose organic polymer presenting molecular mass between 10,000 and 800,000 Daltons.

[0025] Preferably the invention refers to a process for nitrocellulose organic polymer presenting molecular mass ranging from 500 to 7,000 Daltons, and functionality between 1 and 70.

[0026] More preferably the invention relates to a process comprising between 0.0 and 99.0% of polymers or mixtures of polymers.

[0027] Still more preferably the invention relates to a process comprising polymer, including prepolymer and/or oligomer.

[0028] Advantageously the invention refers to a process comprising polymer including epoxy acrylate oligomer.

[0029] More advantageously the invention relates to a process for the epoxy acrylate oligomer comprising mono or multifunctional aromatic, modified with bisphenol A, or other modifying agent, aromatic epoxy modified by phenolic resin, aliphatic epoxy acrylate, or other acrylic resin modified with fatty acid, vegetable oils, aliphatic and/or aromatic urethane acrylate, polyester acrylate like the conventional polyols and diacids based or those modified with fatty acids and/or other modifiers, polyether acrylate, polyesters modified by chlorinated or fatty acids among others, acrylic acrylate, amino acrylates, silicone acrylates and/or other specialty polymers.

[0030] Still more advantageously the present invention refers to a process relative to monomers and/or photo-thermo-reactive diluents and/or mixtures of different monomers and/or mixtures of different photo-thermo-reactive diluents of the dissolution step comprising organic compounds in general, but not exclusively monomers, unsaturated organic compounds with functionality ranging from mono, bi, tri and up to hexafunctional or even greater functionality, with low and medium molecular mass, aliphatic and cycloaliphatic alkanes, ethers derived from ethylene oxide or propylene oxide and/or their mixture, aromatic compounds, aliphatic unsaturated derivatives of butadiene, polyesters and their derivatives, derivatives from acrylates of fatty acids.

[0031] Preferably the invention relates to a process relative to monomers and/or photo-thermo-reactive diluents and/or mixtures of different monomers and/or different pholo-thermo-reactive diluents from the dilution step comprising isobornyl acrylate, tripropylene glycol diacrylate, 1.6 hexanediol 4.1.3.3 diacrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate.

[0032] More preferably the present invention refers to a process relative to photo-thermo-initiators comprising mono, di, tri or polyaromatic compounds.

[0033] Preferably this invention refers to a process related to photo-thermo- initiators comprising benzyl dimethyl ketal, phenylglyoxalate, benzophenone, alpha-hydroxy ketone, oxide of bis acyl phosphine, oxide of monoacyl phosphine and alpha-amino ketones.

[0034] More preferably the present invention refers to a process relative to the addition of agents in any steps such as pigments, coatings, plasticizers, solvents, diluents, fillers, additives, waxes, fibrous and particulate organic and/or inorganic materials, unsaturated or not.

[0035] Even more preferably the invention refers to a process related to radiation cure by exposure of the curing composition to ultraviolet light, visible light spectrum, electron beam.

[0036] Advantageously the present invention relates to a process of curing by ultraviolet radiation comprising the exposure of the composition to a power source comprising electric light bulbs with or without electrodes, with high or medium pressure.

[0037] More advantageously this invention refers to a curing process using electron beam comprising the exposure of the composition to equipments that accelerate electrons.

[0038] Still more advantageously the invention relates to a curing process by infrared radiation comprising exposure of the composition to heat generated by electrical resistance, light bulbs, fuel combustion and other sources of heating.

[0039] Preferably the invention refers to a process related to curing by visible radiation comprising the exposure of the composition to direct or indirect sunlight. [0040] More preferably the present invention relates to a process for curing by temperature.

[0041] Even more preferably the present invention relates to a process of curing by radiation and temperature.

[0042] Advantageously the present invention relates to cured nitrocellulose thermosetting polymeric composites obtained by the mentioned process.

[0043] More advantageously the present invention relates to the use of the cured thermoset polymeric composite obtained by that process in paintings, coatings, inks, printing, lacquers, enamels, varnishes, sealers and adhesives.

[0044] Still more advantageously the present invention relates to the use of the cured thermoset polymeric composites obtained by that process in their application by rolls, spray, electrostatic, pad, brush and curtain.

[0045] Preferably the invention relates to the obtained products and the uses of the cured thermoset polymeric composites obtained by that process.

[0046] To better illustrate the present invention following are examples of its formulation and execution as merely and exclusively illustrative, not limiting.

Examples of typical formulations currently in use for the application on cellulosic and non-cellulosic substrates:

1. Wood putty:

• Epoxy acrylate Polymer 25 to 40%

• Fillers 40 to 70%

• Monomers 5 to 10%

• Photo-initiator 1.5 to 3%

2. Primer for wood:

• Epoxy acrylate polymer 15 to 30%

• Polyester polymer 0 to 25%

• Pigments 10 to 30%

• Photo-initiator 3 to 5%

• Filler 0 to 10%

• Additives 1 to 2%

3. Sandable formulation for primer: • Epoxy acrylate polymer 40 to 60%

• Reactive Monomers 20 to 40%

• Fillers 10 to 20%

• Photo-initiator 1.5 to 3%

• Additives 0.5 to 3%

4. Formulation of finishing primer for wood:

• Acrylic polymer 40 to 60%

• Photo-reactive monomers 20 to 40%

• Photo-initiator 1.5 to 3%

• Additives 0,5 to 1,5%

5. Texture printing

• Epoxy acrylate polymer 30 to 50%

• Photo-reactive monomers 20 to 40%

• Pigments/dyes 15 to 25%

• Photo-initiator 3 to 10%

• Additives 0.5 to 5%

6. Formulation for Finishing:

• Epoxy acrylate polymer 40 to 60%

• Photo-reactive monomers 20 to 40%

• Photo-initiator 2 to 5%

• Matting agent 0 to 12%

Formulations developed according to the present invention:

[0047] Use of nitrocellulose of «12.5% of nitrogen and low, medium and/or high viscosity (degree of polymerization from 20 to 3,000 or more), in compositions with or without other organic polymers, resins, polymers, unsaturated or not, with mono, bi, tri, and/or polyfunctional monomers, with or without photo and/or thermo-initiators, other constituents of paints, varnishes and adhesives (pigments, dyes, reactive or non-reactive plasticizers, solvents, fillers, additives, etc.) curable by radiation.

Example 1 [0048] Nitrocellulose lacquer made from mixtures of trifunctional photo- reactive monomer trimethylolpropane triacrylate, and photo-initiator hydroxy methyl phenil propanone.

Components Percent by weight

• Nitrocellulose, alcoholized in ethanol 26.3%

• Photo-reactive monomer 67.2%

• Photo-initiator 6.4%

[0049] The nitrocellulose was solubilized in the photo-reactive monomer. After dissolution photo-initiator was added. The resulting varnish was applied on glass, plastic, metal and wood as substrate and cured by mercury lamp under a mat. The cured film presented the following properties:

• Conversion rate: 97%

• Adhesion: High adhesion to the substrate

• Brightness at 60°: 90 ub (units of brightness)

• Pencil hardness (HB series): 2H

• Solvent resistance: The cured film showed resistance to the main functional solvents, such as: ketones, alcohols, aromatic hydrocarbons and glycols. It did not show staining, changes in brightness, blistering, adhesion loss, bloating or other adverse effect.

Example 2

[0050] Nitrocellulose lacquer made from the mixture of trimethylolpropane triacrylate trifunctional photo-reactive monomer and smaller amount of hydroxy methyl phenyl propanone photo-initiator.

Components Percent by weight

• Nitrocellulose 27.1%

• Photo-reactive monomer 69.3%

• Photo-initiator 3.6%

[0051] The nitrocellulose was solubilized in TMPTA monomer. After dissolution the photo- initiator was added. The resulting varnish was applied to glass, plastic, metal and wood as substrates, and cured under mercury lamp under a mat. The cured film presented the following properties:

• Conversion rate: 90% • Adhesion to substrate: grade 0 (high adhesion to substrate)

• Brightness at 60° (Glossmeter): 85 ub (units of brightness)

• Pencil hardness (HB series): 3H

• Solvent Resistance: The film showed resistance to the main solvents such as ketones, alcohols, aromatic and aliphatic hydrocarbons, esters, glycols esters and glycols. It did not show staining, changes in brightness, blistering, adhesion loss, bloating or other deleterious effects to the film.

Example 3

[0052] Nitrocellulose lacquer made by mixture of tripropylene glycol diacrylate (TPGDA) difunctional photo-reactive monomer, and hydroxy methyl phenyl propanone photo-initiator.

Components Percent by weight

• Nitrocellulose 26.3%

• TPGDA photo-reactive monomer 67.2%

• Photo-initiator 6.4%

[0053] Nitrocellulose was solubilized in TPGDA monomer. After dissolution photo-initiator was added. The resulting varnish was applied on glass, cardboard, plastics and wood as a substrate, cured by mercury lamp under a mat. The cured film presented the following properties:

• Conversion rate: 100%

• Adhesion to substrate: High adhesion

• Brightness at 60°: 77 ub (units of brightness)

• Pencil hardness (HB series): F

• Resistance to solvents: The film showed resistance to the main functional solvents, ketones, alcohols, aromatics and glycols. It did not showed staining, changes in brightness, blistering, adhesion loss, bloating or other adverse effect or harm to the film.

Example 4

Components Percent by weight

• Nitrocellulose 27.1%

• TPGDA monomer photo-reactive 69.3%

• Photo-initiator 3.6% [0054] Nitrocellulose was solubilized in TPGDA monomer. After dissolution photo- initiator was added. The resulting varnish was applied on glass and wood as a substrate, cured by mercury lamp under a mat. The cured film presented the following properties:

• Conversion rate: 100%

• Adhesion: High adhesion to the substrate

• Brightness at 60° (Glossmeter): 74 ub (units of brightness)

• Pencil Hardness (HB series): F

• Solvent Resistance: The film showed resistance to the main functional solvents, ketones, alcohols, aromatics and glycols. It did not showed staining, changes in brightness, blistering, adhesion loss, bloating or other adverse effect or harm to the film.

Example 5

[0055] Nitrocellulose lacquer is produced by mixture of tripropylene glycol diacrylate (TPGDA) difunctional photo-reactive monomer, trimethylol propane triacrylate trifunctional and hydroxy methyl phenyl propanone photo-initiator.

Components Percent by weight

• Nitrocellulose 25.1%

• Photo- reactive monomer 35.1%

• TPGDA photo-reactive monomer 35.1%

• Photo-initiator 4.6%

[0056] Nitrocellulose was solubilized in TPGDA and TMPTA photo-reactive monomers. After dissolution of the nitrocellulose photo-initiator was added. The resulting varnish was applied to glass, plastic, metal and wood as a substrate and cured by mercury lamp under a mat. The cured film showed the following performance:

• Conversion Rate: 99%

• Adhesion: High adhesion to the substrate

• Brightness at 60°: 85%

• Pencil hardness (HB series): 2H

• Solvent Resistance: The film showed resistance to the main functional solvents, ketones, alcohols, aromatics and glycols. It did not showed staining, changes in brightness, blistering, adhesion loss, bloating or other adverse effect or harm to the film.

Example 6

[0057] Nitrocellulose vamish made from mixture of polyester acrylate oligomer in 60% of the oligomer in 40%, trimethylolpropane triacrylate (TMPTA) trifunctional photo-reactive monomers, and hydroxy methyl phenyl propanone photo- initiator.

Components Percent by weight

• Acrylate polyester oligomer 36.9%

• Nitrocellulose 21.1%

• TMPTA photo-reactive monomer 36.9%

• Photo-initiator 5.2%

[0058] Nitrocellulose was solubilized in TMPTA monomer. After dissolution the polyester resin and photo-initiator were added. The resulting vamish was applied on glass and wood as substrate, and cured by mercury lamp under a mat. The cured film showed the following properties:

• Conversion rate: 99%

• Adhesion: Level 0 (high adhesion to substrate)

• Brightness at 60° (Glossmeter): 85 ub (units of brightness)

• Pencil hardness (HB series): 2H

• Solvent Resistance: The film showed resistance to the main functional solvents, ketones, alcohols, aromatics and glycols. It did not showed staining, changes in brightness, blistering, adhesion loss, bloating or other adverse effect or harm to the film.

Example 7

[0059] Nitrocellulose lacquer made from mixture of epoxy acrylate oligomer in 75% of the oligomer in 25%, tripropylene glycol diacrylate (TPGDA) difunctional photo- reactive monomer and hydroxy methyl phenyl propanone photo-initiator.

Components Percent by weight

• Epoxy acrylate oligomer 19.5%

• Low viscosity nitrocellulose 21.2%

• TPGDA photo-reactive monomer 54.1% • Photo-initiator 5.2%

[0060] The nitrocellulose was solubilized in the TPGDA photo-reactive monomer. After dissolution the epoxy acrylate oligomer and photo-initiator were added. The resulting varnish was applied on glass, plastic, metal and wood as substrates, and cured by mercury lamp under a mat. The cured film showed the following properties:

• Conversion rate: 98%

• Adhesion: Level 0 (high adhesion to substrate)

• Brightness at 60° (Glossmetrer): 63 ub (units of brightness)

• Pencil hardness (HB series): F

• Solvent Resistance: The film showed resistance to the main functional solvents, ketones, alcohols, aromatics and glycols. It did not showed staining, changes in brightness, blistering, adhesion loss, bloating or other adverse effect or harm to the film.

Example 8

[0061] Nitrocellulose varnish produced by mixture of urethane acrylate oligomer, trimethylolpropane triacrylate trifunctional photo-reactive monomer and hydroxy methyl phenyl propanone photo-initiator.

Components Percent by weight

• Aromatic acrylate urethane oligomer 14.7%

• Low viscosity nitrocellulose 21.2%

• TMPTA photo-reactive monomer 58.9%

• Photo-initiator 5.2%

[0062] The nitrocellulose was solubilized by stirring in monomers (TMPTA). After dissolution it was added to the aromatic urethane resin and photo-initiator. The resulting varnish was applied to glass and wood as a substrate, cured by mercury lamp under mat. The cured film performance was as follows:

• Conversion rate: 88%

• Adhesion: High adhesion to the substrate

• Brightness at 60° (Glossmeter): 67 ub (units of brightness)

• Pencil hardness (HB series): H

• Solvent Resistance: The film showed resistance to the main functional solvents, ketones, alcohols, aromatics and glycols. It did not showed staining, changes in brightness, blistering, adhesion loss, bloating or other adverse effect or harm to the film.

Example 9

[0063] Filler putty for wood on the base of nitrocellulose with epoxy acrylate oligomer, two photo-initiators, difunctional monomers (TPGDA) and trifunctional (TMPTA) and mineral filler.

Components Percent by weight

• Nitrocellulose 12.7%

• TMPTA photo-reactive monomer 7.2%

• TPGDA photo-reactive monomer 31.8%

• Benzophenone photo-initiator 1.5%

• Photo-initiator 3.4%

• Epoxy acrylate oligomer 32.7%

• Mineral filler 10.8%

[0064] Nitrocellulose was solubilized in monomers (TPGDA) and (TMPTA). After dissolving epoxy resin and photo-initiators were added. Stirring was carried out using a disperser to disperse the mineral filler in the solution. The resulting putty was applied to glass and wood as substrates, cured by mercury lamp under a mat. The cured putty showed the following performance:

• Excellent spreading

• High coating power and pores filling

• Excellent sandability

Example 10

[0065] Nitrocellulose based white paint for wood, metal, plastic, with two photo-initiators, difunctional (TPGDA) and trifunctional (TMPTA) monomers and white pigment (titanium dioxide dispersed in nitrocellulose and monomer).

Components Percent by weight

• Nitrocellulose 20.0%

• TMPTA photo-reactive monomer 11.0%

• TPGDA photo-reactive monomer 50.0%

• Benzophenone photo-initiator 3.0%

• Photo-initiator 5.0% • Titanium Dioxide 11.0%

[0066] Nitrocellulose was solubilized in TPGDA and TMPTA monomers. After dissolution the photo-initiators were added. The dispersion of titanium dioxide that was pre-dispersed/grinded in nitrocellulose/monomers was performed. The resulting paint was applied on glass, metal and wood as substrates, cured by mercury lamp under a mat. The cured putty showed the following performance:

• Excellent spreading

• High coating power

• Resistance to polar and non-polar organic solvents

• Adhesion to substrate: grade 0 (high adhesion)

• Brightness at 60° (Glossmeter): > 80%