MXPA97010391A - Powder coatings with double, thermal and ultraviol curing - Google Patents

Abstract

Thick film or opaque pigmented powder coatings for heat-sensitive substrates, such as wood, wood composites, for example medium density fiber board, and plastics, which can be cured, especially near the substrate, by incorporating a double cure system in the powder, comprising a thermal initiator, such as a peroxide, together with a UV initiator. The UV initiator cures the surface while the thermal initiator cures the inner part of the substrate. Surprisingly, virtually no gel preform occurs during the step of melting and flow under the action of heat prior to UV curing. Consequently, the hardened film finish formed on the surface shows an exceptional regularity that is comparable to the regularity of traditional powders curable with UV radiation. The hardened film finish is also fully cured and shows exceptional adhesion to the substrate, which can not be achieved with traditional powders curable with UV radiation that has been pigmented. Even though the dual cure system includes a thermal aspect, these powder coatings are especially suitable for application on heat sensitive substrates. Dual-curing, thermal and UV-curable powders cure at significantly lower temperatures and at significantly higher speeds than traditional thermal curing powders, making them safe to coat lime-sensitive substrates

Description

POWDER COATINGS WITH DOUBLE, THERMAL AND THERMAL HEAT ETA FIELD OF THE INVENTION the present invention refers to coating% dust. and 5 more pariiculanf.er.Le to coating. of powder curable by radium iolet iolet iolet (UV) in thick or pigmented films of opaque matrix which can - = > It is possible to obtain a total cure even in the presence of opaque pigments or gaseous films that normally prevent penetration. 3a- = .radiation ions in the coating and, consequently, inhibit healing under the surface, which is achieved by the use of a tangent in the 5-ions. powder coatings curable with ultraviolet ion ions along with the usual UV initiator Surprisingly, the presence of a thermal initiator does not affect the exceptional uniformity of the finishes of the hardened films.The dust reverses < " &dt; doubly thermally and radiation curable LtV of the present invention are especially suitable for coating substrates sensitive to heat e.g., for example, wood and plastic, since these undercuts are cured at higher speeds. Minor emperatures, reducing 5 so the thermal load pol.en L? 1 harmful mind on the r * - your time. BACKGROUND OF THE INVENTION Reversing dust, which are solid, free flowing, finely divided, dry materials. At room temperature, the bar has reached considerable popularity in recent years compared to the liquid pressures for several rabbones. One of these ? It is the fact that dust coatings are materials that affect the user and the environment less because they are virtually exempt from harmful fugitive organic solvent vehicles normally found in liquid coatings. Consequently, the powder coatings emit few volatile materials to the atmosphere, atmosphere or even volatile material. This eliminates the problems of emissions related to liquid ressources such as, for example, the cori nanation of health and health hazards for workers employed in reverse operations. The polyester lining is also clean and suitable for use. They are applied cleanly on the substrate since they are in solid, dry form. The powders are easily removed in the event of a spill and do not require special additives to clean or contain spills, as is the case with coatings. liquids. Therefore hygiene is also improved in the work. No liquids are used that adhere to the clothes of the workers and the coating equipment, which causes an increased downtime for the machines and cleaning costs. 5 Dust coatings are essentially 100% recyclable. The powder sprayed in excess can be fully recovered and recombined with it. powder fed. This * - provides very high coating effi ciencies and also substantially reduces the amount of waste generated. The recycling of liquid coatings is done during the application, which causes increased waste and costs for the removal of small waste, despite its many advantages, the powder coatings. usually do not know; They are used on heat-sensitive substrates, such as wood and plastic. Heat-sensitive substrates require lower cure temperatures, preferably below 121.1 ° C to avoid significant degradation and / or deformation of the substrate. Tempera tures of more curing is not possible with traditional thermally curable powders. Attempts were made that failed to coat heat-sensitive substrates with traditional powders. For example, when wood composites, for example tables of particles, fiber boards and other substrates that contain a significant amount of wood are heated to the high cure temperatures required for traditional powders, the residual moisture and resinous binders present in the wood composites for the integrity of the substrate are emitted invar i bleme te of the substrate. The removal of volatile curing substances results in significant bubbles, craters, orifices, and other surface defects in the hardened film finish. In addition, overheating causes wood compounds to become brittle, friable, burned, and worsened in another way in relation to their physical and chemical properties. This is unacceptable from a perspective of the quality of the film as well as from a perspec tive to a product quality. Curable powders UV at low temperatures have been recently proposed for reverse * i. substrates sensitive to heat. UV curable powders still require an exposure to heat that is higher than the glass transition temperature < Tg) or melting temperature (Tm), to melt su iciently and cause the powders to flow in a melted, soft, continuous film on the substrate arttes of radiation healing. However, the thermal load on the substrate is minimally reduced, since the UV curable polymers are formulated to melt and flow at temperatures that are much lower than those of the UV.

Traditional powdered inverts, typically from or at about 93.33ßC. Therefore, UV-curable polymers require only their low-temperature setting required for the powder to flow in a smooth melted film. the curing or curing of UV curable pores is achieved by exposing the melted film to lu z from a UV source, such as a UV mercury lamp, which cures the film quickly. Since the crosslinking reactions are triggered with UV radiation in e.7 of the heat1, this procedure allows the coatings to be ---. They can be cured more quickly and at much lower temperatures than thermally curable curable powders. 15 Another advantage sigr f? > _ to 11 v. of the curable powders with V-rays is that the heated flow passage separated from the curing step with UV rays. This allows UV-cured polyesters to completely remove olfactory particles from the substrate during flow and produce films.

Exceptionally, join together before the start of any healing reaction. Therefore, it is known that the film finishes created by curable dust »with lightning. UV have an extra ordinary softness. One drawback is that the opaque pint of the powders curable with UV rays is a problem. Opaque pigments and ^ they inherently absorb, reflect or otherwise interfere with the transmission of UV light through the invented reverse and, consequently, prevent the penetration of UV light into the lower layers of the pigmented film during curing. Curable powders with pigmented UV rays, when cured, continue to provide exceptionally soft film finishes with good surface healing properties, including good solvent resistance. However, curable powders with pigmented UV can not be properly cured through the film to the underlying substrate. As a result, the pigmented UV curable powder coatings exhibit insufficient total cure properties, including a low pencil hardness, limited adherence, and limited flexibility. * - UV curable powder formulations that are applied as thicker films greater than about 0.0508 mm exhibit similar healing problems. Most of. the reverse dust UV curable products produced today are formulated as thin clear coatings for wood and non-pigmented metals. The published document No. EP 0 636 669 A2 of DSM, N.V, dated February 1, 1995 presents reversals The powder can be cured with UV rays or electron beams, which can be applied to heat sensitive substrates such as wood, for example medium density fiber broth, and plastic. The UV-curable powders of EP 636 669 A2 contain: a) an unsaturated resin of the amorphous unsaturated polyester group or. { semi) crystalline, unsaturated polyacrylates, and mixtures thereof, with unsaturated polyesters derived from maleic acid and fumaric acid with particular preference; b) a crosslinking agent selected from an oligomer or a polymer having vinyl ether, vinyl ester or acrylate functional groups, with functional oligomers of vinyl ether and especially preferred, for example urethanes; Functionalized of divinyl ether; and, c) a photoinitiator for curing with UV rays or electron beams, wherein the equivalent ratio of unsaturation of polymers to the unsaturation of crosslinkers is preferably 1: 1. However, the UV-curable powders of EP 0 636 669 A2 are practically limited to their formulation with non-pigmented, ie clear, coatings, as demonstrated in example 1. A UV-curable powder with a clear coating similar based on an unsaturated polyester, an allyl ether ester crosslinker and a hydroxylketone photoinitiator appears in Example 2 of International Publication No. WO 93/191.32 of DSM, NV dated September 30, 1993. K.M. Biller and B. MacFadden (Herberts Pawder Coatings), UV-Curable Powders; A Marriage of Compliant Coatings, (UV curable powders: A couple of reliable revelations) Industrial Paint Z > . Pawder, pages 22-25 (July 1996) and K.M. Bi 1.1er and B. MacFadden (Herberts Powder Coatings) UV-Curable Powder Coatings: The Perfect Marriage of Compliant Coatings, (UV curable powder coatings: The perfect pair of reliable coatings) Radtech Conference North America 1996, pages 437- 445 (April 28, May 2, 1996), suggest the incorporation of special solid initiators of UV radiation designed to be activated despite the presence of several pigments. Supposedly, these special initiators of UV radiation have some ability to absorb and UV light at wavelengths greater than the reflectance of the pigments. F.M. Wit and E.S. de Jong (DSM, N.V.), Powder Coati.ngs On Heat Sensitive Substrates, (Coating of powders on heat-sensitive substrates), presented at the seminar DSM, N.V. which took place in Amsterdam (27-2S March 1996), show that some successes have been achieved in the laboratory with powder coating formulations curable with pigmented UV radiation based on a binder comprising a mixture of: a) a resin of unsaturated polyester, for example, an unsaturated polyester derived from maleic acid; and, b) a polyurethane crosslinking agent with vinyl ether function. This binder is similar to the binder described in the aforementioned EP 0 636 669 A2. In these formulations, a special class of UV radiation fatoinitiators especially suitable for pigmented UV coatings is used, for example, bis acylphosphine oxides and a 75/25 mixture of a hydroxyketone (Irgacure 184) and bis acylphosphine oxide, now available as Irgacure 1800 at Ciba-Geigy Corporation. Pigmented formulations with various amounts of pigments between 5 and 20% by weight are electrostatically applied to a table of medium density fibers in a layer thickness of 100 microns. However, even when enough tapir is reached with pigment loads between 15 * / weight and 20 * 4 weight pigments, the pendulum hardness and, therefore, the total cure does not fully develop shortly after curing by UV radiation, which is undesirable. The state of the art of powder coating, therefore, is that powder coatings curable with UV radiation that is opaquely pigmented or thick film can not be fully cured with UV light. US Patent No. 4,753,81.7 to Meixner et al., Presents curable coatings with liquid UV radiation opaquely picjmented for application on wood or wood type materials and plastic films. Such curable paints with pigmented liquid UV radiation are made by incorporating thermal initiators of dropieróx gone along with photoinitiators of UV radiation in liquid resins * - ~ derived from air-dried inosaturated polyesters exempt from copal mor.meros imer i rab is. The inclusion of moisturized in the curable formulation, liquid UV radiation improves healing in the lower layers of the coating to which UV radiation can not access due to the opaque nature of the pigments. Liquid paints also contain other ingredients- » essential oils that are not found in powder coatings, including plasticized colloidal cotton, for example, nitrocellulose, desiccants to promote air drying, as well as volatile organic solvents to adjust the processing viscosity for liquid applications, for example.

For example, toluene, xylene, isopropanol and butyl acetate. These curable liquids with pigmented UV radiation are first applied to the substrate in liquid form, then a gel is formed in advance at temperatures of 48.8BßC to 79.44 * 0, and then hardens b jo the application of UV radiation. There is nothing in the document by Meixner et al. that it provides no indication that suitable solid composition could be prepared as powder coatings. In addition, the curable reversals with liquid UV radiation from Meixner et al., Present other indications. For example, liquids curable with UV radiation contain organic solvents which generates emissions of solvent harmful to the environment and to personnel during drying. As mentioned above, powder coatings are essentially solvent-free and non-contaminating substances. UV-curable liquids also have pot lives of only up to 5 hours, which is relatively common. This would not be a suitable system for a powder coating that should remain for several weeks at room temperature, it is descending in a recovery powder paint application booth. Likewise, curing in the case of the Meixner et al. System occurs at a temperature ca. between 48.88ßC and 79.44 * C. At such temperatures, a significant gel or even curing preform is observed during extrusion which results in a dust reversal. to its. once p > It can cause processing difficulties because dust could settle on the extruder, leading to excessive extruder downtime and high cleaning costs. The liquids curable with UV radiation are based on low molecular weight polyester resins, said resins are in a highly reactive liquid state at room temperature and are cured without a crosslinker. Reversals of typical polyester powder require resins with higher molecular weights or higher glass transition temperatures for the material to remain solid at room temperature, which tends to reduce the reactivity of the resin and requires a retreat. ic? lador. Likewise, liquids curable with UV radiation contain elements of lower molecular weights, which can be expected to be transported more easily in biological tissues. If handled improperly, liquids curable with highly reactive UV radiation could be transported through the skin of an individual and into physiological functions. The use of higher molecular weight substances in powder coatings reduces the handling problems and reduces the risk of invasion in biological tissues. In addition, liquid curable coatings with liquid UV radiation from Meixner et al., Do not require an initial melting step and flow to form a smooth film on the substrate, as is required in the case of powders curable with UV radiation, since that these reverses are liquid at room temperature and inherently flow A. in the form of regular movies when they are emptied. Accordingly, the incorporation of a thermally activated peroxide cure component in a curable coating with liquid UV radiation is not a problem from a film quality perspective. However, the inclusion of a thermal peroxide cure component in a powder coating curable with UV radiation could produce coatings with low flow behavior and, consequently, low film qualities. HE would think that the addition of a thermal curing component to a UV curable powder will cause gel pre-forming during the heated flow passage and will cause an undesirable surface irregularity, or for example ba or gloss or orange peel appearance , in the finish of the hardened film, which could negatively affect the quality of the film and the aesthetic appearance of the coating. One might also expect that bubbles, craters, holes and other surface defects are visually apparent on the surface of the film hardened. In addition, the important preform of gel in the trickle during the melt mixing of the powder ingredients could, when a thermal initiator is used, cause processing difficulties since the powder mixture could begin to cure and set in the extruder, which would cause a considerable dead time of the extruder and increased costs of 1 im. What he is referring to is a reverse composition of UV-curable powder that is opaquely pigmented and / or thick film that e =. Suitable for coating heat-sensitive substrates, especially wood, wood composites, and plastics, and which can be completely absorbed through the incorporation of a thermal initiator along with the usual initiator of UV radiation without affecting the Exceptional regularity of hardened film finish. SUMMARY OF THE INVENTION It is an object of the present invention therefore to provide opaquely pigmented or thick film powder coatings that can be fully cured upon exposure to UV radiation despite the presence of opaque pigments and / or films. Thicknesses, both habitual inhibitors of healing in the reverse, through the incorporation of a "double" healing system, that is, a combination of thermal initiator and UV radiation photoinitiator, in the powders, where the healing initiator with UV rays cure the surface while the thermal initiator cures the lower capias near the substrate, however without affecting the exceptional regularity of the hardened film finish that is obtained on the surface.

It is another object of this invention to provide powder coatings curable with UV and dual thermal radiation having exceptional regularity comparable to conventional UV curable powder coatings. It is another object of the present invention to provide UV curable and thermally curable powder coatings having improved overall curing properties, including improved adhesion to the substrate, as compared to traditional UV curable powder coatings. s. It is another object of this invention to provide dual thermal curing powder coatings and UV radiation having relatively low cure temperatures and / or fast cure rates for safe cure on heat sensitive substrates without damage or deterioration of the substrate. . The present inventors have discovered that the use of dual cure initiators, i.e., an initiator with UV radiation along with thermal initiator, in the powder coatings, not only provide excellent surface cure to the film finish, but also a complete superior cure in the film to the underlying substrate, while still obtaining exceptional regularity and a desired gloss in the surface finish. It is quite surprising that the cured powder coating of this invention remains so regular. It could be expected that the addition of a thermal curing component to UV curable powders will cause gel pre-forming during the melting step and outputs and, in turn, will cause on the surface an appearance of p > orange or a lower brightness. Surprisingly, the hardened film finishes produced from powder coatings of this invention are at least as ex- pendently regular as those produced from traditional powders curable with radi- ations. UV, while also presenting a total cure. The invention relates to a composition of powder coating which can be double cured thermally and with UV radiation, and a composition in form. solid particles which is a mixture of: a) an unsaturated ream selected from unsaturated poly esters, unsaturated polyacrylates, unsaturated polyetheric esters, and mixtures thereof; b) an optional second optional copolymer resin crosslinker having a functional group - 3 selected from vinyl ether, acrylate, methacrylate, allyl ester groups, and mixtures thereof; c) a photoinitiator selected from compounds that generate photolytically activated free radicals; d) a thermal initiator selected from thermally activated free radical generating compounds, such as peroxides, azo compounds, and mixtures thereof; e) an opacity agent selected from pigments, fillers, and mixtures thereof; and f) optional catalyst, wherein the composition can be completely cured, both on the surface and in its entirety, on a heat-sensitive substrate when exposed to a temperature sufficient for melting and flow of the powder in a regular melted film and to activate the thermal component of healing, followed by an exposure of the film melted at a sufficient UV irradiation to activate the ultraviolet component of the cure and to form a regular hardened, fully cured film. The various objects, features and advantages of this invention; ion will be more apparent from the following description and appended claims. , DETAILED DESCRIPTION OF THE PREFERRED MODALITIES OF THE INVENTION During this spec. i f icac: ion, all parts and percentages specified here are by weight unless indicated otherwise contrary. BASE RESINS The thermally curable double UV curable powder coatings of this invention are based primarily on polymer resins forming Unsaturated films, such as, for example, unsaturated polyester resins, polyacrylate resins or p > imetacr i lato unsaturated, and / or mixtures thereof. The unsaturated polyester resins useful herein are products of the ethylenically unsaturated condensation reaction of one or more aliphatic alcohols to difunctional or functional polycycloaliphatics, or mixtures thereof, and one or more carboxylic acids. i.1 aliphatic, cycloal ifatic or aromatic bi functional or polyfunctional, or mixtures thereof. The carboxylic acids can also be used in their corresponding anhydrous form. Corresponding lower alkanol esters are also useful for ester i. f icac ion. Small amounts of monofunctional alcohols and monofunctional carboxylic acids or esters thereof can be found for polyester chain termination purposes. Even though the unsaturation can be supplied by means of alcohol, typically the acid is unsaturated and the alcohol is saturated. Saturated acids can also be found to reduce the density of the ethylenic unsaturation in the polyester. Examples of suitable difunctional and polyfunctional carboxylic acids which are useful herein include maleic anhydride, fumaric acid, anhydride ci. traconic, itaconic acid, endo-cis-bicyclo acid < 2,2, 1) -5-hepten-2,3-di-carbohydrate, 1,4,5,6,7,7-hexachlorobicyclo (2,2, 1) -5-he in - 2, 3-dicarboxylic acid (clorenic acid), mesaconic acid, di-acid methacrylic acid, and met i lbi acid > -? clo (2,2, 1) ~ -hepten- 2,3 ~ dicarboxy 1 co. Especially preferred are maleic anhydride, fumaric acid and mixtures thereof. It should be understood that if lower alkanol acids, anhydrides or esters are listed herein, any of these forms are contemplated for use herein. Ejemp > those of suitable saturated diacids or polyacids which are useful herein in combination with a substantial proportion of an unsaturated diacid include tetrachloroph soot acid, tetrahydric acid, and phthalic anhydride, adipic acid, teraphonic acid, acid isophthalic, terephtolic acid, acid or trilet 1 j > ~ n, azeleic acid, sebar acid. ico, dimet. i 1 tetefta 1 ato, di met i 1 isofta lato, succinic acid, gone dodeca n i carboxí 1 i co, acid has ah rof tal ico, acid he '< aclorooctah idrom ta nonaf t l end icarbox í lico, malonic acid, glutaric acid, oxalic acid, piiic acid, suberic acid, and anhydride p > i romel í tico. Examples of suitable monoacids which can be used here to terminate the polyester chain include linoleic acid, linolenic acid, geranic acid, dehydrogermanic acid, sorbic acid, hept3 tri-1, 3,5-ene-t-carboxylic acid, 1, 3,5, 7-ene-l-ca rbo í 1 ico, and? **** 20 other fatty acids from vegetable oils, abietic acid, methacrylic acid, and, benzoic acid. Examples of suitable dioxes useful herein include ethylene glycol, dietary, glycerol, 1,2-5-propylene glycol, 1,3-glycol, 1,4-di-etho-cyclohex-1, 2-butyl. icol, 1, 3-bu.ti-tongue 1-icol, 1, 4-butyl-ilol, 1, 2-c iclopenta diol, 1, 3-cyclopentiol, 1,4-cyclopentane, 1, 2-c ic: lohexand i ol, 1, '3-c ic 1 ohexand iol, 1, 4-cyclohexandi sl, 1,4-cyclohexanedimethanol, 4,4' -me i len- 10 bis-cyclohexanol), 4,4 '-i opro i 1 iden-b i (c icloh anol), 1, 3-b is (h idrox imet i 1) cic: l ohexane, 1, 3-b is (h idrox iet i 3) cyclohexane, 1, 3- bis (hydroxypropyl 1) cyclohexane, 1,3- bi (hydroxyethyl) 1-cyclohexane, xylene glycol, bisphenol A, hydrogenated bisphenol A, bisphene 3 A / oxide adducts propylene, hydroquinone / propylene oxide adducts, hydroxyquinone / ethylene oxide adducts, neopentyl glycol, 1,6-hexanediol, 2,2,4-trimeti 1-1, 3-penta diol, 1, 3- isobutanediol, 1,2-isobutanediol, 2,3-butanediol, and 2-butanediol (1,4). 20 Axis > those of polyols having 3 or more hydroxy functional groups useful here in small amounts to form pol. Branched esters, including glycerol, trimethylolpropane, pentaerythritol, allyl ether polyoles, polyalkylene glycol ethers, 1,1-trimetheloletane, sorbitol, mannitol, digliceroi, and dipentaeri tr i. tol.

Instead of the alcohol or in addition to the alcohol, epoxy compounds such as, for example, ethylene oxide and propylene oxide can be used. The preparation of the unsaturated polyester can be carried out with standard techniques well known in the art. For example, a two-step process can be used. In the first step, saturated or unsaturated glycols and acids are heated in the presence of an esterification catalyst, such as a tasting! tin oxide, for example monobutyl oxide, stannous actuate, and butyl or bleach di laurate, or an acid catalyst, for example p-oluensulonic acid, methansulfonic acid, and sulfuric acid, at a temperature comprised between about 204.4 ßC to 248, S8 ° C for about 2 to 24 hours with nitrogen application and reacting to an acid number or hydroxyl number given while collecting the water formed by the esterification. The resultant esterified prepolymer is cooled to a temperature of about 160 ° C to 198.880C. The glycol loss is measured by the refractive index and, if the lost glycol is added, added. Then, in the second step, saturated or more saturated and acid glycols are charged to the reaction vessel, again with nitrogen application. The reaction mixture is heated to a temperature between about 176.66 ° C to 232.22 ° C for about 2 to 8 hours and reacts to an acid number, viscosity and amount of water, and is appropriate given. The resulting resin is inhibited by hydroquinone or another substituted phenolic derivative inhibitor. You can also p > repair unsaturated polyester resins in a single step by heating saturated and unsaturated polycarboxylic acids with polyols and esterification catalyst, such as, for example, stannous oxide, with application of nitrogen at a temperature between approximately 60 ° C. and 248.88ßC for approximately 1 to 24 years. The drinking water is collected to give me the re-tion. The loss of glycol is my other one. ' and the glycol is added, if necessary. The reaction is carried out to the appropriate acidity or hydroxyl number and viscosity. The unsaturated polyester resins can be crystalline, (semi) crystal i ñas, or amorphous. Crystalline and semi-crystalline unsaturated esters are usually preferred in comparison with amorphous unsaturated polyesters since stable psi coatings with lower melt viscosity and better flow can be easily prepared from them. It is known in the art that some monomers used in the =. Polycondensation reactions provide crystal inida to the polyesters ins tured. For example, dihydric alcohol monomers that promote crystallinity are known and such monomers include e i lengl i col, 1,4-butanediol, nenpsn i lgl i col and c i clohexandi ethanol. Five monomers of cycloalkyl acid that promote crystallization are known and such monomers include terephonic acid and cyclohexanedicarboxylic acid. The preferred unsaturated polyesters useful herein have a long shelf life without cold flow at temperatures. substantially for Jan; of the ambient temperature of up to approximately 48.88 ° C and have a glass transition temperature (Tj) or a melting temp (Tm), lower than the desired flow temperature required for the preservation of sensitive substrates to heat, preferably between apiro; imadamente 71.11ßC and approximately l? l.ll * p. The p > Preferred oliesters and synthetics have a molecular weight that is within a range of P > rax imadamente 400 and approximately 10, OOO, more typically from approximately 800 and approximately 6,800, and, of preference, between approximately 2,000 and approximately 4, 50. The unsaturated polyesters preferably have a degree of unsaturation between about 2 and approximately 20 * > . in weight of ins turation, and Preferably, between about 4 and about 10 * 4 by weight of insuration. Whether the palyester has a solid function of carboxylic acid or a hydroxyl functionality depends on the molar ratio -COOH / -OH of the monomer mixture. If the unsaturated polyester 5 has a hydroxyl functionality, then the hydroxyl number of the polyester is located hat > in approximately 5 and approximately 100 and, preferably, between approximately 9 and approximately 50. If the unsaturated polyester has an ad-functional functionality, then the acid of paliéster is generally between about 1 and about 80, and preferably between about 9 and about 50"Preferably, the pal ies er" = "s Unsaturated are solid resins at room temperature or at a temperature above the ambient temperature, so that they can be easily formulated in non-sintering powders. If the resins are liquid, they must be able to be converted into a powder form and, consequently, to be counted as solid by absorption in silica-type filler materials inerts, such as, for example, fumed silica, before use, as is well known in the art. Exemplary exemplary polyunsaturated formulations herein are further specified in the examples of tea. The resins of the acrylate and methacrylate unsaturated useful herein include polymers containing unreacted acrylate or methacrylate groups in the main chain or side chain. The unsaturated acrylate or methacrylate polymers are the products of the reaction of one or more solid functional polymers having functional groups reactive with one or more flake anomers! i i zatales having coreactive functional groups capable of reacting • ion functional groups of the polymer with at least one of the functional polymer or copolymerizable monomer which also contains an acrylate group or metacri lato available for ultimate cure of the resin. The polymer obtained unsaturated acrylate or methacrylate in the above reaction may be an acrylated epoxy resin, acrylated urethane resin., Acrylated polyether resin or acrylated polyester resin an L or its Correspond iénte methacrylates. Polymers containing unreacted acrylate or methacrylate groups in the side chains can be prepared by standard techniques well known in the art. For example, a two-step process can be employed. In the first step, a solid functional polymer is formed using standard polymerization techniques. For example, the polymer formed in step one may be acrylate or methacrylate polymer function. Suitable monomers commonly used to form the structure of such acrylate functionalized methacrylate polymers include methyl acrylate, methyl methacrylate, acrylated ethyl etacri lato, ethyl acrylate, n-butyl methacrylate, n-but i it, acri. Isobutyl lato, isobutyl methacrylate, 2-ethylhexyl acrylate. it, methacrylate of 2-et i 1 lhexi la, and the like. In addition, suitable amounts of functional monomers are co-polymerized during the polymerization to obtain the functionalized polymer. Acrylate or methacrylate with acid functionality can be formed from monomers with functionality up to, for example, acrylic acid and methacrylic acid. Imeros Copal acrylate or methacrylate with hydroxyl functionality can be formed from hydroxy-functional monomers, such as methacrylate ci 2-hydroxyeth i what methacrylate, 2-hydroxypropy as methacrylate, 3-hydro IPROP i what methacrylate, 3 4-dihydroxybutyl lo. Acrylate or methacrylate polymers can be formed with epaxi functionality at p >The following are epoxy-functional monomers, such as glycidyl methacrylate, 2,3-epo-ibu-ti-methacrylate, 3,4-epoxy-ibu-ti-methacrylate, 2,3-epoxy-cyclohexyl methacrylate, and 10, 11-epoxyl methacrylate Isocyanate-functional polymers can also be formed from isocyanate-functional monomers, for example meta-isopropenyl 1-a 1fa, alpha-dimethyl-1-benzyl-1-isocyanate. : ianatate (TMI) The functional polymers formed in step one which react with bi-functional acrylate or methacrylate monomers may also be other types of solid resins, other than acrylates or ethacrylates, having acid, hydroxyl, epoxy or isocyanate, for example epidermal bisphenol A resins or acid-functional polyester resins, hydroxyl to isocyanate In the second step, a reaction is carried out between unreacted functional groups of the solid functional polymer formed n the step one with a copolymerizable monomer having both a coreactive functional group capable of reacting with the reactive functional groups of the functional polymer and an unsaturated acrylate or methacrylate group available for the final curing of the resin. Any of the acrylate or methacrylate functionalized monomers raised in the above list can serve as the copolymerizable monomer. The reaction is carried out by dissolving the solid functional polymer formed above in a suitable solvent for the polymer, such as for example butyl acetate, and then adding the imerizable and functional copal monomer which. it has unsaturated groups of acrylate or methacrylate pending, progressively, at elevated temperatures comprised, for example, between imimately 65.55 ° C and 148. ßC, until the reaction is subsequently completed. This reaction can also be carried out without solvent by capping the reagents above their melting points. For example, in the second step, an acrylic or acrylate methacrylate with acid functionality can react with a compound having an epoxy group, such as by an epoxy-containing acrylate or methacrylate anomer, for example, glyceidyl methacrylate, to form a polyester etacp lada. A polymer with isocyanate functionality, for example, TMI, can react in the same manner with an acrylate or ethacrylate monomer with hydroxy functionality, such as 2-h? Methacrylate. drox let- -. It can form an acrylated urethane. Resins that contain ace-plate or actable groups in the main chain can be prepared by the reaction of resins containing epaxy, carbomyl, hydroxyl or isocyanate with acrylate or methacrylate bi-fune ion monomers that can be used in the same way. that strap with the fun: canvas 11 dades before ences. For example, a polymer with a lipo epoxy function, such as polymethyl methacrylate or epoxidized bisphenol resin A, can react with a monomer that has an acid group, for example c? ds acrylic or methacrylic acid. In this reaction, the heat should be monitored closely to ensure that the acrylic acid does not polymerize. In addition, a polyester with acid function, such as a polyester prepared from neopenic acid, and glycol, adipic acid, and iso-tactic acid, can react with a non-functional acrylate or methacrylate compound epoxy, such as, for example, glycidyl methacrylate. Note also the reaction of acrylic or tartaric acid with a polyester of alcohol or hydroxyl function at elevated temperatures to form a polyester with actable functionality. The unsaturated group that remains in the polymer p > The final curing of the powder coating does not require that it be an acylate or methacrylate group, even though the unsaturated is preferably preferred with acrylate or unsaturated methacrylate. It is also possible to form other solid resins that have allyl functionalities, vinyl, vinyl ester, and styryl. For example, a polyester resin with hydroxyl functionality, as for example the resin made with neopent i. lglol, 1, 4-cyclohexand anal met, terephthalic acid and adipic acid, can react with TMI to form a resin with stipulated functionality. The acrylated polymer or unsaturated methacrylate 1 could be used as a polyester resin, <;"-- fifty unsaturated in this part of the formulation, the T, the molecular and the percentage range of unsaturation would be similar to those used for saturated polymers. The percentage of unsaturation in these cases will be governed by the amount of acrylate or methacrylate in the polymer. The percentage of unsaturation in the pejiester is governed by the maleic or fumaric acid content of the polyester. s * ~ Acrylate or acrylic polymer resins can be crosslinked without the addition of a crosslinking agent, even when referring agents with such formulations can be used. Preferably, the polyacrylate resins or unsaturated polyacrylate resins are found at room temperature or above room temperature, depending on the room temperature. such that they can be easily formulated into non-sintering powders. If the resins are liquid, they should be converted into a powder form and, therefore, should be sung with solids, by absorption in inert silica-type fillers, such as silica. smoked, before use as is well known in the art. Formulations of exemplary unsaturated acrylate or methacrylate polymers useful herein are further specified in the working examples. PETICULADOPES 25 Ptinolyester and unsaturated resins are useful here in combination with second polymerized resins having an ethy unsaturation. and that preferably have two sites of unsaturation per molecule. These second resins are used in the composition as crosslinkers for the base resin. Especially preferred is a predominance of monomers or prepolies which are solid at room temperature or above room temperature, so that they can be easily formulated into non-sintering powders. The second resins or copolymer copolymers useful here are preferably oligomers or polymers having vinyl ether, acrylate or methacrylate groups, or allyl ester, with oligomer or polymer having ether groups of vi them. 15 The second copolymer resins; having vinyl ether groups are preferably composed of urethanes with vinyl ether functionality, for example, a divinyl ester urethane based on the reaction product of a diisocyanate, such as, for example, hexamethylene diisocyanate. , and a vinyl ether with hydroxyl functionality such as vinyl hydroxybutyl ether. Other vinyl ethers with suitable hydroxyl functionality include hydroxyethyl vipyl ether and monovinyl 1-trimeric acid ether. Other suitable isocyanates include Isoform diisocyanate, methylene diisocyanate. met i lenbisc ic lohe i 1 isocyanate, diisocyanate of trheethexamethylbenzene, hexane diisocyanate, diisocyanate of hexa ethyl, hexacylamine diisocyanate, isocyanate cycloethylenebiscyclohexylo, toluene diisocyanate, 1, 2-diphenylenediane diisocyanate, 1,3-diphenylpropane diisocyanate, diisacyanate di dif or Imetans, dicyclohexynahexyl ohexyl 1, and other isocyanate and terpolymer prepolies. Functional prepolymers derived from these diisocyanates, such as, for example, urethane trimers, uretdiones, isocyanurates, and bi-rets can also be used. The functional vinyl ethers can be obtained in a conventional manner. For example, vinyl ether urethanes are prepared by the reaction of a vinyl ether with hydroxyl functionality with a monomer or polymer containing isocyanate or functional isocyanate in solvent, such as, for example, methyl chloride, ba or an atmosphere. of nitrogen, at temperatures between approximately the ambient temperature and l? 5ßC. Additional reference may be made to U.S. Patent No. 4,751,273 to Lßpin et al., For the preparation of vinyl ether functional urethanes, the disclosure of which is incorporated herein by reference in its entirety. Examples of v-nilcj ether urethanes are sold ba e? 1 the commercial names of resin s Urala. p > or DSM Resins and Olí gomeros Vecto er and Diluentes by «._ A11 ied Signa 1. Preferably, vinyl ether urethane prepolies are used which are in a non-crystalline state at room temperature or higher so that they can be easily formulated into non-sintering powders. i n. These non-crystalline solid materials can be obtained by reacting a non-crystalline diisocyanate monomer, as an example, with a polyol of crystallization or non-crystallization such as, for example, polyisocyanate. neopent and glycol, and by the reaction after the urethane adduct of the mixture obtained with a hydroxy vinyl ether, as an example of 4-hydrophilic vinyl ether, another way by the reaction of an aliphatic polyethiocyanate not cytostatic, ce- > ma p > or example isophorone diisocyanate trimer, a vinyl hydroxy ether, for example, 4-hydroxyl butyl ether. The reactions are typically carried out under a nitrogen atmosphere, in the presence of a tin catalyst, such as, for example, dibutyltin dilaurate, temperatures not higher than approximately 100-110ßC. Due to the polymeric nature of the vinyl ether urethanes p > repaired in this way, powder coatings based on the ismrj present a flexibility and adherence to the improved substrate after curing. A) Yes Also, such higher molecular weight materials are relatively safer to handle and have lower toxicities than traditional vinyl ether urethane curing agents. For a further description of such non-crystalline solid vinyl ether curing agents, reference may be made to the Na! Ial Patent application of Navin B. Shah and Andrew T. Daly entitled Salty Vinyl Ether Terminated Urethane C? Ring Agent, > ^ * (Urethane curing agent finished with solid vinyl ether), presented this very day, whose teachings were incorporate here by reference in its entirety. The second coprii imer i zata 1 resins are that they have acrylate or m ac il to groups. = e, preferably of urethanes with funeity on dimethacrylate, for example, based on d or i > inn or, as an example pnr, based on di isocianatr,, as worst example. hexand i i soci, and metacri the o with fune the hydroxyla lity, as for example methacrylate of hi drox íe i lo. Other isocyanates can also be used, for example, as above. In addition, other metabolic coughs with hydroxyl functionality Suitable hydroxypropyl methacrylate or other hydroxyalkyl methacrylates are suitable. This material can react in the same manner as the above vinyl ethers. The second copol imer i zabl resins are that they have groups ester of Ali lo = > e make up preferably of esteres e JD allyl with hydroxy functionality, for example, based on the reaction product of allyl alcohol and ethyl anhydride, which forms diallyl phthalate. Examples of oligomers functionalized thereon include dialkyl phthalate prepolymers, isopolylyl phthalate prepolymers, phthalate prepo ies > ie p-diallyl, diallyl maleate, cyanide-o-cycloalkyl, methacrylamide, 1-amide of chlorate monomer, lacyanurate citrate! i lo. If the second resin copol i er i? Ab? It is a sticky powder or a liquid and is used in sufficient quantities in such a way that the composition of the melted mixed powder coating does not flow freely in the proper manner, then this co-reactant can be absorbed in an inert filler, as example, if smoked, and can be counted as co or solid within the preferred scope of this invention. Except in the case of small r-antities of up to% by weight of the powder coating composition, these liquid elements are much less preferred than solid streams due to p >.; rob syllable slogans. The relative amounts of the polymer base resin and for the second unsaturated resin provided in the powder coating compositions > D of this invention depend in part on the choice of materials. For example, when the resin e =, a more saturated polyester and the second resin, a recycler, is a compound with vinyl ether function, the proportion equi lens between the polyester esteraturation and the inaturation of vinyl ether is between approximately 90; 10 and approve 10:90, and preferably around 50:50. When the resin is a polyester and laughter and the second resin, ret i > As a compound, it is a compound with ayl ester functionality, the equivalent ratio between the polyester unsaturation and the allylester ester ratio is between approximately 99: 1 and approximately 1:99, and preferably between approximately 70:30 and Appropriately 95: 5. When the resin is a polymer of acrylate or metal, it prefers to use a resin. Exemplary reticulation formulations other than here are specified .t »-iic? In the examples of the work, the UV photoinitiators that are incorporated in the powder coating compositions to provide low temperature, fast, powder actuation are well known in the art. Examples of suitable photo initiators that are known? as fatoinitiators of alpha dissociation free radicals include be zo ina and its derivatives, for example benzoin co or for example isobutyl ether pina v benc i lquet les, such as, for example, benzyl et i 1, 2-hydraxy -2- methyl-l-phenylepropane-1-one and ketone of 4 - (? ~ Hydroethoxy) f or 1-2-h? Drax? -2-propyl, others include acyl phosphines, coma for example 2, 4,6-trimethyl-ylbenzoyl ei-i-fem-1-phosphine oxide, aryl-cetanes can also be used, such as, for example, 1-hydroxy phenyl ketones, 2- benzyl, 1-2- di met i lamino-1- (4- or fal insf and 1) -buta-1-one, 2, 2-d im to i, 2-pheny1-acetophenone, mixture of benzophenone and phenol ketone of 1-hydroxycyclohex The diphenyl ether is described as per-1-on-one, and 2-met i 1-1- (4- (methytho-phenyl) -? - (4-morpholine)) - 1 -p opa on. Photoinitiators of free radical type can be used, abstraction of hydrogen in combination with the previous ones, either alone or for example. Michle's ketone (4,4 '-bi sd i met i laminobenzophenone), ethyl cione Michier (4,4' ethyl cretone -bi sdiet i lamí poben-afenon), benzophenone, thioxanthone, anthroquinone, d , 1-camforqu? N, d, 1-ethyl camphorquinone, ketocumapn, anthracene, or derivatives thereof, and the like. Cationic polymerization, especially with vinyol ether-containing reticulators, can be carried abo through cationic cure employing cationic inducers. The main classes of cationic photo- and standards are salts of diammonium and copper-like substances, such as, for example, hexafluorafasfate, of ij fem 1 i odium, -r ** '58 hexaf luoroarsi nato rie di bencí 1 i odonio y acetate de cobre- », salts of trian 1 sul fonio, such as hex f uorofosfto de ti feni lsul fanio, tertaf tri-feni 1 sulfonium luoroborate, salts of dialq? i Ifenaci 1 its ferium, ferroscenium salts, such as for example hexaf luorophosphate of cyclopentadienyl iron (II), cretonate of al-sulphonic acid, and benzylic silyl ethers can also be used. Preferably, the photoinitiators employed herein are solid. If preferred liquid initiators are used are absorbed in solid carriers, such as, for example, fumed silica, before their incorporation into the powder coating compositions of this invention. In general, the amount of photoinner employed in the powder coating composition of the present invention is located within > a range of about 0.1 to 10 parts per hundred resin (phr '), and preferably between about 1 and 5 pihr. Exemplary exemplary photoprint formulations herein are further illustrated in the example "workpiece" 20 Reference can also be made to EP 0 636 669 A2 to DSM, NV for additional examples of the aforementioned base resins, re fl ectors, and photoinitiators. mentioned above, whose embodiment is hereby incorporated by reference in its entirety THERMAL INITIATORS The thermal initiators useful in the coating compositions (ie powder of this invention are free radical generating compounds, preferably per-oxides and azo initiators. Suitable peroxide initiators include peroxide: dihydric idems, such as, for example, 2,4-dichlorobenzyl peroxide, di-isononanoyl peroxide, hydroperoxide peroxide, lauroyl peroxide, succinite acid peroxide, peroxide. of aeeti lo, benzoyl peroxide, diisobutyl peroxide, peroxides, cyan acetic acid, for example But the dicarbonates of di (np op i 1) dicarbonate but di, dicarbonate of di (ner ~ b? t 11) pera i, dicarbonate of acetyl cyclohex i lsn] foni lo, peroxi dicarbonates de dia. di (2-yihexyl 1 '/ peroxyl, di carbonate of Hi i? opropi lperon i, and dicarbonate of di c? »r 1 ohex i Iperox i, stere * - ci peraxi, as for example nepdecanoate of a 1 fa-mmi Iperoxi, pivalata of alpha-cu i lpero i, neodecanoata of t-amyl, neodecanoate ci t-ami lpera. i, T-butyl cyanoate, Iperoxy, pivalate of ta i Ipierax i, t-buty pivalate i Iperox i, 2,5-dimet i 1 -2,5-di (2-et i lhexanoi 1) hexar oo, hexanoate of ta i Iperox i-2-et i lo, hexanoate of t-but i Iperox i -2-et i la, and isobuty ato of t-but i Iperox i, zabis' alquilnitplo) perox i compounds, such as, for example, 2.2 '- a obis- 2, -d imet i Iva leron i trilo), azobi isobu i ron in 1 o, and 2,2' - ob - (2-me i lbut ironi tri lo ) 5 t-butyl i 1-but imalic acid, 1,1'-azobis- i 1 -cyclohexancarboni tp lo). Other thermal initiators include peroxy uet 1 is, as for example 1, 1- i (t ~ bu 111 perox i) -, 3,5- i met i lc ic 1 oh xano, esters of peroxy, co or for example carbonate of o, a'-t-5 buty 1-o-isopropy Imonop rox i, carbonate táe 2, - imet i 1-2,5- di (benzoi Iperoxy), carbonate o, o'-t-but i l-o- (2- ethexhex i 1) -monoperoxy, t-butyl acetate Iperoxy, benzoate of -> - t-but i Iperox, the ratio of tyl-t-but 11 di per ax i, and di-butyl phthalate I ipero i, i lqui 1 perox i do, for example ranged from die umi lo, 2, - i met i 1-2, -di t -but iperoxyxi) hexane, t-but peroxide 1 rum, di-t-bu peroxide what, and 2,5-im 11, 2,5-d? (t-but i 1 perox i) he? n-3, hydroperoxides, such as for example 2,5-dihi droperaxi-2,5-di met i hexano, hi drope o * -, i do de eumeno, hi drope or t-butyl ehi drop of t-amyl oxide, peroxides of ketones, as pilo axis n-bui 11 -4, 4-bi = - - t t-hut i 3 perox i) goes to lerata, cyclohexane of 1,1-dα (t-but i iperax i) -3,3,5-t í et ila, ciciohexane of 1, 1'-i-t-ami l-perox i, butane of 2,2-di (t-b? ti Iperox i), et i 1-3,3-di t-bui, i 1 perox i) but i ra to, and mixtures of the peroctoate 'i t ~ but it, and l, l -? -} i (t- but i I erox i) eiclohex na. Also included are carbons, or carbons, or carbons, such as, for example, carbonate of o-t-bu-t-1-o-1 soprop i 1 onop rox i, h i d a z a p, p Ox ibi s (benzenesul foni 1 o) and azo arbonamide accelerated.

Preferably, the thermal initiators employed herein are solid. If liquid initiators are used, however, they are preferably absorbed in solid carriers, such as, for example, fumed silica, before their incorporation into the coating compositions or powder of this invention. In general, the amount > The thermal inertia in the powder coating layer of the present invention is within a range of approximately 0.1 to about 10 pg; hr, and preferably within a range of from 1 to approximately 6 phr. Exemplary thermal initiator formulations useful herein are specified -title on] in the working examples. CATALYSTS It can be desired to include a catalyst in the powder coatings to increase the speed of crosslinking. As catalysts, metal compounds based on a fatty acid or oil can be incorporated into the pialvos. Examples of suitable metals are cobalt, manganese, lead, copper, and vanadium. Compounds containing cobalt, especially cobalt acids, such as, for example, cobalt esc toa, cobalt neodecanaate, cobalt naphthenate and cobalt octadecanoate or are preferred. Metal-containing compounds provide improved cure, especially in healing systems initiated by thermal peroxides. By means of a reduction oxide process, the metal catalysts tend to decompose the hydroxides created by inhibiting near-axis oxygen to the coating surface. They can also be used for example, for example, in the case of a catalytic device. Such compounds, if employed, are preferably used in amounts less than about 1o phr, and typically within > a range of approximately 0.1 and approximately .5 phr. OPTICITY AGENTFS the powder coating compositions of this invention may exhibit opacity or be dull without full healing properties. Examples of suitable examples here are black smoke, Shepard's No. 1 black, white of t? T ni > ~ > , chromium oxide green, zinc oxide, yellow, red, brown and black iron oxide, such as ferrite yellow, ferric oxides, raw siena and rhenized silica, lead chromate, phthalate blue of copper, blue and green of f ta Itric i aro na, blue ul ramar i rio, red of tol? idina, roj > -3 > paracels, reds and yellows of cadmium, blue and green of f ta loargana ina, iron blues, »organic rafés, and the like. Low-reflection pigments, such as the god of anatase, the sulfide of inc, and the mixed metal pigments, such as, for example, black of f n i ta d > ? Manganese, black green chromium hematite, cobalt aluminate blue spinel, black copper chromite spinel, and sulfo 1 ic or 5 sodium alumina are especially useful. With this technology you can also use metallic substances made with aluminum, mica or bronze. V "» - Reí lumberjacks can be useful to provide opacity or decrease the brightness of the coating of dust without diminish the properties of complete healing. Pile axes for woodcutters suitable for use here include silica, such as, for example, fumed silica, glass frit, flour, calcium carbonate, sulfate, barium, mica, ammonium chloride, b om "'ro de am»: >no, r. do b ric, tri x x antimony, smoked alumina, clays such as kaolin, china clay, talcum, lithopone, zinc sulphide, lead titanate, circejnio oxide, white lead, barium oxide, or calcium from calcium, oxide or manganese hydroxide, strip, asbestos, ceramic, glass hollow, my resin roesféras, essence of pieria, barite, diatoaceous earth, aluminum trih.drata, cyanix flour, calcium silicate, mixed silicates and the like. In general, the amount of pigments, refiners and opacifying agents used * - »in the composition of reverse imi nts of The powder of the present invention ranges from 0.1 to approximately 100 phr, and preferably from 1 to 6 phr. However, the charges may vary according to the degree of opacity desired of the dry skin. 5 OTHER INGREDIENTS In addition to the aforementioned components, the powder coating composition of the present invention can ^ "Contain also i i or powder coating convention ls romo for example control aids gloss, powder flow auxiliaries, leveling agents, dispersants, anti-cratering agents, stabilizers and standard materials dB other type. Gloss control agents with, for example, polyethylene waxes, polyethylene n-.; c}; .3 dice, pol i amides, t »f Ions, paliamide can be used in a formulation to adjust or obtain a lighter gloss coating. Preferred powder flow aids that can be employed in this invention are silicone or acrylic flow auxiliaries, resin compounds, whether acrylic or acrylic, respectively. Acrylic resins are generally liquids that have been converted to powder form by absorption in materials containing silica. An example of an acrylic flow aid is sold under the trade name Resiflow P67 in Fstron Chemical, and is a 2-25 acid compound of the ethyl ester polymer. Examples of suitable acrylic flow auxiliaries of another type are acrylic resins sold under the tradename BYK '352 and BYK 300 by BYK Chemie. When used, the auxiliary flow of the powder is generally provided in an amount comprised between 0.1 and approximately 0.1. about 6 phr, and, preferably, between about 0.7 and about 1.5 phr, in the thermosetting powder coating compositions of this invention. Dry flow additives, such as smoked silica or alumina oxide, are usually used to reduce the tendency to form cakes or blocks during transport or use. An example of fumed silica is sold under the trade name Cab-n-il by the Cabot Corporation Company. An example of aluminum oxide is aluminum oxide sold under the tradename Alumin ™ m Oxide X pair Degussa Corporation. When employed, the dry flow additive generally provides an amount of between about 0.05 to about 0.5 phr, and preferably between about 0.1 and about 0.1 phr. Auxiliary gas removal and crater formation can be used in these formulations to reduce or eliminate bubbles or gas trapped in the substrate or coating. Typical gas removal aids include benzoin (2-h? Drox? -1, 2-d? Fem-letanone) and its analogues, and plastics as well as low molecular weight phenoxy and phthalate substances. When employed, the gas removal aid is generally provided in an amount between approximately 0.1 and approximately 15 phr, and, preferably, between approximately 1 and approximately 5 phr. UV stabilizers are also used to improve weather resistance, for example, LIV absorbers and stabilizers similar to hindered amines or similar stabilizers -i phenol hindered. When used, UV stabilizers are usually provided in a range of about 0.1 to about phr, and, > the preference, between approximately 1 and approximately 3 phr. PREPARATION OF POL O The powder coatings of this invention are prepared by conventional techniques employs >; -Jas in the coating technique * on powder. Typically, the components of the powder coating formulation are thoroughly mixed together by means of a high intensity mixture until the mixture is homogeneous and dry, and then melt-blended, preferably in an extruder. Any ingredient that is in a liquid state at the mixing temperature can be absorbed locally into a dry substrate which can constitute one of the other ingredients of the mixture. The melt mixture is usually carried out within a temperature range between about 71.11 ° C and about 148.88 ° C, and preferably between about 82.22 ° C and about 121.11 ° C, with careful control of the temperature of the extruder to minimize eventual curing and gel formation in the extruder. Extrusion with a supercritical fluid such as, for example, supercrly CO 2, may be desirable with powders containing crystalline materials. the extruded composition, hab i. Usually in sheet form after cooling substantially at room temperature, it breaks, in flakes and then it is ground in a mill until it reaches a powder, while carefully controlling the temperature between -106.66 ° C (cryogenic) and approximately 32.22 ° C, and, preferably, between approximately -17.77 ° C and approximately 23.8 ° C, and then subsequently screened to achieve the desired particle size of powder, typically with an average particle size of about 30 microns. The powder coatings prepared by this invention have the following properties: long shelf life at temperatures preferably up to 7:. 2ß05 layer > : - ability to flow at relatively low temperatures preferably between about 71.ll.sup.C and about 121.11.sup.-2C; Relatively low flow viscosity; In the lower layers near the substrate, in spite of the presence of opaque pigments or in the case of thick films, it is possible to form exceptionally regular films having the desired gloss despite the presence of a thermal initiator; fast healing; together with other desirable properties, such as good fl exibility, adhesion, hardness, scratch resistance, etc. METHOD OF PURIFICATION First, the coatings > The powder of this invention is applied in the form of a solid powder > -3, free flowing, dry, on the surface to be coated. Preferably, the powders are sprayed onto the substrate by well known sputtering techniques such as crown discharge or tn in technique. Sprayed the trussed tribosphere. Then, the powders are exposed to a temperature only sufficient to melt, level and allow the flow of the powders in a continuous melted film having the necessary softness, and activates the thermal component of the cure. Fl 1 r can be provided in infrared oven (IR) or convection oven. ion, or a combination of both. The applied powders of the invention are "melted at sufficiently low temperatures and form smooth cells at very high temperatures so as not to damage a heat-sensitive substrate. The powder flow temperature is relatively low, preferably between approximately 100 ° C. and approximately 121.11 ° C., and it is preferably only between approximately 5 and approximately 1 second for the powder to flow properly. In a melted, uniform, continuous, regular film on the substrate, the viscosity of the flow is sufficiently low, for example, between approximately 1 O and 4,000 cones and plates, which allows e that the polymer has a good flux behavior during heating resulting in smooth reversals.A sufficient removal of the volatile gases from the substrate occurs simultaneously during the flow exit step to eliminate surface defects, such as, for example, The temperature curing of these powders also helps to eliminate the exit of gases, especially in metallic substrates with porous, co >.not for example in aluminum and zinc, and also in the case of heat-sensitive substrates, eg wood and plastic. While the powder coatings are melted, the films are exposed to a source of lur HV, as for example medium pressure mercury vapor lamps or gallium lamps such as H, D and / or V lamps. of fusion, to activate the ultraviolet component of the cure and to quickly cure the films in smooth hardened finishes. Radiation of electronic beams can also be used. When exposed to radiations I.IV, the melted films harden rapidly between approximately 1 ml and 1 sec. approximately 10 seconds, and preferably less than about 3 seconds. The dry hardened film finishes formed on the substrate preferably have a thickness between approximately 0.0127 m and approximately 0.635 m, and more preferably, between about 0.02 m and about 0.254 mm. Thicker films hardened with UV rays, for example, of more than 0.0508 mm, can be formed with a unique coating that has not been possible until the end. Thick films and pigmented films can be cured in an essentially total manner as well as thin and clear films using the dust reversals of this invention, which result from the presence of a thermal initiator in the reverse. In spite of the thermal initiator coating, the hardened film finishes produced from the powder coatings of this invention surprisingly present the same exceptional regularity as the regularity of the powder coatings. UV rays standard. The finish of the powder coating film rovides the appearance of a plastic or laminate coating. The surprising discovery is that the thermal initiator, as for example peroxide, improves the complete cure and adhesion on the substrate without affecting the flow behavior without losing the regularity and the desired gloss of the cured film. The powder coatings of the present invention are especially O il when applied to heat-sensitive substrates, such as wood, wood composites, plastics, due to the fast cure characteristics and low temperatures of these coatings. By using the aforementioned curing techniques with application of heat and UV radiation, it is possible to limit the thermal load on the substrate to acceptable levels for heat sensitive substrates, in order not to cause brittleness, loss of integrity, deformation : ion, and other *, damage to the physical / chemical properties of heat-sensitive substrates. However, it will be understood that the invention is not limited to heat-sensitive substrates, and that the powder coatings of this invention can form the same regular hardened film coatings on heat-resistant substrates, as for example met l. Exemplary substrates that can be coated with the powder coatings of this invention appear below. SUBSTRATES SENSITIVE TO HEAT Examples of suitable heat sensitive substrates useful a > They include wood, such as hardwood, hardboards, laminated bamboo, wood composites, such as particle board, the table of particles, the conductive, fiber board, medium density fiber board, Masonite board, Laminated bamboo, and other substrates that contain a meaningful > i wood. Any of these wood-based substrates can be replenished or they can be applied to materials such as UV fluids, powder initiators, or solvents or coatings carried in water to increase regularity and reduce the accumulation of the movie. Wood substrates are typically used for the production of kitchen furniture, units > storage and shelves, furniture piara home and office, furniture for equi &> of t or fucking, etc. Other heat-sensitive substrates are plastics with, for example, ABS, PPO, SMC, polyolefins, afri cos, nylons, and other copolymers which usually buckle and emit gases when coated and heated with traditional thermal curing powders. Plastics are typically used in automotive parts. Other heat sensitive substrates include paper, cardboard, and compounds and components with a heat sensitive appearance, and the like. HEAT RESISTANT SUBSTRATES Examples of suitable heat-resistant substrates include metals, such as steel and other alloys typically used in construction panels, bars, duct lines, coil springs, and steel shafts. Other heat-resistant substrates include glass, ceramics and ceramic, carbon and graphite mosaics, the invention will be explained more clearly by way of the following speci fi c examples the purpose of which is merely to exemplify the invention. EXAMPLE 1. . Coating preparation »of palmate powder / pigment vinyl ether with thermal curing and by accretion of double UV rays The ingredients presented in the following list of Table 1A were mixed in accordance with what was described to form a reverse. of pigmented powder of this invention which has a double, thermal and UV-curing appearance.

COMPARATIVE EXAMPLE 1. Preparation of powder coatings of paliester / vinyl ether pigmented with cure by UV action only. The ingredients listed below in Table IA were mixed in accordance with what was described to form a coating of piped powders that have only one curing aspect with UV radiation. TABLE Ingredients Phr Example. 1 Comparison Example 1 MIXING DRY UNTIL HOMOGENEITY Unsaturated paliéster XP 31.25 (1) 80 80 Vinyl ester ZW 3307 (2) 20 20 Photoinitiator Lucarin TPO (3) 2 2 Photoinitiator Irgacure 184 (4) 1. 1 Acrylic Flow Auxiliary 1.5 1.5 Re i lot-i P87 (5) Peroxide Lupersol 230XL (6) 2 0 Titanium dioxide TIPure R-902 (7) 25 .25 Total '131.5 129.5 LOADING THE EXTRUDER AND EXTRUDING IN LEAVES FUSING TEMPERATURE = 93.33 ° C COOLING WITH AIR AND RUPTURE IN LASCAS LOADING TO THE MILL AND MOI EP TO OBTAIN HIGH SPEED DUST SCREEN WITH A MESH 140 i t) XP 3125 unsaturated palester, is a semicrystalline polyester resin ina, with solid acid function, which is c > ^ e is derived from f? m-jpco acid, terephthalic acid and 1,8-hexandioi, and commercially available in DSM Resins. (2) ZW 3307, vinyl ether, is a urethane crosslinking resin with divinyl ether func tion which is derived from diisocyanate d & hemethyl wood and vinyl ether of 4-hydroxybutyl, and q? ^ is commercially available from DSM Resins. (3) Photoinitiator Lucen n TPO is a phosphine oxide > of 2,4,6-trimet and Ibenzoi ldi feni leí cially available in BASF. (4) Irgacute 184, photo-cycler, is a trie aryl ketone, phenyl ketone of 1-hydroxyl or hexyl, 1-available commercially available in Ciba Adcliti es. "(5) Pesiflom P87, acrylic flow aid , is a polyacrylate, which is a 2-propenoic acid ethyl ester polymer available at Estron Chemical. (b) L? pers n 230XL, peroxide, is a but 1, 1, lbisft-but i 1 peroxy) 3,, 5-tr i et i] c i > -]? _ > he? ano in a 1 inertator with 4 < V / "of commercial active ingredient available in Elf Atochem. (7) TiP? Re P-902 e? S a dioxide pigment »white titanium will be available in Du Pont. RESULTS The polymer coating compositions appearing in the list in Table IA were electrostatically sprayed > -. > - > n a tribe gun approximately 0.0762 mm to 0.1 4 mm in respective particle boards and 1.27 c, l. The tables were heated with quartz IR lamps for approximately 30 seconds at a temperature of approximately 121.11 ° C as the object of forming a reticle fi lm, then the tables were 1 cam > -Jas immedi- ately through a source of UV rays and curing by exposure to ra »i? a» in 1! V, first with a lamp V and then> np a lamp H, at a speed of approximately 30 ft / m. One second, the cured powder coatings were then subjected to performance tests with the results of the test, appearing in the same way as Table ID Table IB.

Proof Test 1 Adhesion Cross Match 3B 4B O / IB Appearance orange peel skin orange moderate orange mode Gas output none 1 Resistance to solvents, no effect, no effec < 50 double rubs) Hardness of L ^ iz Mar 3H EXAMPLE I 0 2 Prep rar: in coating of poly ester powder / ester of pigmented allyl with thermal curing and with double UV rays The ingredients listed below in Table 2A were zcla or conformed to read It is necessary to form a reversal of the pigmented powder of this invention which, in turn, is an essential element of the invention. 11 double radiation, thermal and with 15 UV radiation. COMPARATIVE EXAMPLE 2 Powder coating preparation of pigmented alester polyester ester with peroxide cure only The ingredients listed below in Table 2A were combined in accordance with that described to create a pigmented powder coating having only one aspect of peroxide thermal cure. Table 2A Go? Gred i entes Phr E jemp io. 2 E jemp 1o > to Compare. ón 2 MIXING IN SFCO UNTIL HOMOGENEITY Pioyester 275 polyester irisa turado ft) 8 8 Isoftalato de i l i lo < 2) 20 Resifloi-i PR7, au "i 1 r of f 1 u 1.5 1.5 acril i co Benrcuna <3) 0.8 0.8 Lupers »r > l 231 Peroxide (4) 3 Bencí lijimet i Iq? et a l, fotoini »í ador í5) 2 TiPure R-902, Dioxide de i Hamo? twenty Total 127.3 125.3 CARRIER TO THE EXTRUDER AND FXTPUIR IN HOTAS TF? GERATURA DF FUSION - B2.2 ßC COOLING WITH ATRE AND BREAKAGE IN THE SGAS LOADING TO THE MOI INO AND M01 FP UP TO OBTAIN A DUST AT HIGH VEl OC I AD SCRAMBLED WITH A MESH 140 fl) Piester 275, polyester matured is a ream of unsalted solid serrated polyester, with acid function, greetings, dB anhydride derivative with 7% saturation, and an acid index of 35 rc just available in Plastics »(2) ISO, fttlalo > 1e dial i lo e u agent > crosslink it with li d ester function »1e alilo co eré la 1 mind available in GCA Chemic l. (3) Ben? Aina is a trie removal agent > rle iz and against crater formation eat ''? al mente 'available at Estron Chemical. (4) Lupersol 231, peroxide is a but iquetal, 1,1-b? Sft-but i 1 perox i) 3,3,5-t i met i 3 > ~ \ > z lohexa no, e merc a 3 available in F3 f Atochem. • 5) Fotoi ni ': iador de quetal e hallullo, quetal de di tilo is a healing initiator with rays > IV of what I read and eat * - 1 1 m t c i i i l i i i i i i i i i i i i i i i i i i i i i i i i i l i i i i i i i i i l i i i i i i i i l i i i i i l i i i i i i l i i i i i i l i i i i i l i i i i i i l i i i i i l i i i i i i l i i i i i l i i l i i i i l l l PESUI TADOS The powder coating compositions listed in the 2A list were the e »r. rost t i r a n > With a pistol in a few density fiber plates? 'ed i. of 1.27 cm prec 1 packed with infrared lamps at a temperature of up to approx. 3.33ßC to 121. ItT. the boards were then added to the pole with IR lamps for up to 2 minutes at a temperature of 148.88ßC p > For the peroxide muostra only for the purpose of melting and curing the dust and? i? Approximately ím-u-Jameut 3? seconds to a. Approx temperature: - > At the same time, the double-curing sample has the object of initiating thermal curing and forming a melted particle. From the outlet of the flow, the double cure sample was immediately cured by exposure to U radiation, first with a B lamp and then with an H lamp, approximately 9.144 meters / minute, for approximately 1 second. Cured powder coatings were subjected to performance tests and the results of the tests appear in Table 2B. Table 2B Test Result Example 2 Example of < cimpa ra ». ion 2 Adhesion Cross Ma ch 6B Apari ncia pi l of orange skin of moderate n.ríftja • moderate Resistance MEl '5 no effect 3 detachment 5050 double frames) moderate Dure-ra de 1 apir Mar H H EXAMPLE 3 Preparation of pigmented acrylate epoxy powder coating with double thermal curing and UV radiation The ingredients that appear in the same list n l Table 3A were prepared in accordance with what was described to form a pigmented powder coating of this invention, which has a dual healing aspect, r v z r x? N b i thermal and healing radiation UV radiation. COMPARATIVE EIEMPI 3 Preparation of pigmented epyoxy fioiovo coating with peroxide cure only the ingredients listed below in Table 3A were consistent with that described to form a pigmented powder coating having only one aspect of thermal cure with peroxide. Tabl 3A Ingredients Phr E je lo. 3 E jemp 1 e e Comparison 3 MIXING IN SFCO UNTIL HOMORFNFTDAD Pro 1723 irisa turado poliacplato < 1) 1 OR 1 0 Lupersol 231 XL Pecó .; gone 5.0 5.0 TiP? Re P-9 0 Titanium dioxide 20 20 Resiflaut P87 < "5) Flow auxiliary 1.4 1.4 to ri 1 ico Benzoin 0.8 0.8 Photoinitiator of benz i id Id i me- 2.0 0 tilo Total 129.2 127.2 LOADING TO THE EXTRUDER AND EXTPUIP AT H0TAS TEMPERATURE DF FUSION = 82.22 * 0 ENFPTAMTFNTO WITH AIR AND RUPTURE FN l ASCAS LOADING TO THE MILL AND MOLER UNTIL OBTENFP DUST AT HIGH VEIOC IDAD SIZE WITH A MESH 140 < 1) Pro 1723, pol i -ter i 1 ato a solid epioxy acrylate resin available in Séromer C > r > mpany RESULTS The polystyrene coating and spinning tops that appear on list 3A were sprayed on the ct rostáti r ament with a tribo gun in fiber blink of density of med i 3 > of 1.27 cm respectively, p rer a lentoci using infrared lamps at a temperature of aprcix i mad. r -n e 93"33ßC to 121.11'C. the heated boards were subsequently heated with IP lamps > .ie cuarre »for up to 2 minutes at a temperature of approximately 148.88 ° C for the sample > of perox? d »: > only for the purpose of melting and curing the powder and for approximately 30 seconds at approximately 1 8.8 ß for the double healing sample with the object to initiate thermal healing and to form > ma melted film. After the discharge of the flow, the double curing sample was then cured immediately by exposure to radic acid. UV, first »-) with a lamp V and then with a 1 amp r-H to 9,144 met rm t» i for approx. 1 second. The cured powder coatings were then subjected to performance tests and the rebuffs of the tests appear on the list in Table 3B. Tab 3B Test Result E j m 1 or 3 E jemp lo d cumpa rae i n 3 Adhesion Cross Hatch 4B 3B Appearance orange peel orange peel 1 i gera 1 i ra Resistance ME ^ 6 no effect 2 detachment (50 double rubrics) important Last a > ie laμ-r Mar 'H B E TEMPLE 4 Preparation of the urethane reticulator with ether functionality of v i ni 1 n s l i o 222 grams 2.0 eq.) Of isophorone diisocyanate were weighed in a 0.5 liter vessel equipped with an acrylator and a nitrogen axis sprayer. Heating and stirring were carried out with a flow »ie nitrogen» of 3 < "> ml / ip in the presence of i-tin-1-dilaurate catalyst. Ociating the temperature to 75 ° C, 52 grams of neopent (i) (1.0 e.) was added for several hours. The exotherm was maintained at 100 ° C. The product has a free isocyanate content of 15.6 * / (theoretical 15.3 * 4.) At this point, 116 grams of oil were added. .) of vinyl ether and hydroxy bu i 1, giving the isotherm not to exceed 1 ° C. After finishing the addition, stir the mixture until the free isocyanate content is below of 0.3V .. The product of 1 = reaction, an amorphous, non-crystallizing solid was then discharged, cooled, and molluscumulated. ETFMPI.0 5 Preparation and removal of urethane with ether functionality Not even the solid were charged 116 yrs (1.0 eri.) of ether vi or 1 ilo of hi bibutil ith a 0.5 liter reation tank, equipped with an agitator and a sprayer. nitrogen, 116 grams (1.0 e. ) of diisocyanate trimer > from isoiorone to rec i bridge under gentle agitation. After the addition, the agitation proceeded with moderate application > heat (the maximum temperature did not exceed 60 ° C) until the dissolution of tocio the tríro of > i? isophorone isocyanate. The temperature was then raised slowly to 100 ° C and the re-metering was allowed to continue for 2-3 hours. At this point, the temperature was lowered to "0-75> 0 and a temperature sensor was added." • To control the exotherm due to or to 10 ° C. The percentage of free IMCO was 0.5% by age 4. Finally, the product of the reaction was discarded, cooled, ground, and then packed, a non-cystating amorphous solid. EXAMPLE 6 Preparation of polyurethane / vinyl ester coated pigment coating with cure »- double ion, thermal and with UV radiation The ingredients listed below in Table 6A were combined in accordance with what was described to form a pigmented powder coating of this invention which has a double curing, thermal and radiant aspect is UV. Table Ingre tients Phr F. jemp1 or 6 DRY ME7CI IN UNTIL HOMOGENEITY Polyester unsaturated XP 3125 80 Reti uladar de < * »I saw you neither (Example 4) 20 Photoinitiator I. ue rin TPO 2.0 Fotoinic i-stor I gscure 104 l.O Peroxide Lupersol 2 1 I. 2.0 Pe iflotu P - 87, acrylic flow aid 2.0 Dió of titanium Ti Pure P-902 25 CHARGE TO THE EXTRUSOPA AND EXTPUIP IN LEAVES FUSION TEMPERATURE = 82.22ßC COOLING WITH AIR AND BREAKING IN IASCAS CAROAR TO THE MILL AND MOI EP UNTIL OPTFNFP POI VO A ALTA VELOCI AD TAMIZAP WITH A MAltA 140 RESULTS The powder coating listed in Table 6A was sprayed electrostatic with a tribo gun on a medium density fiberboard of 1.27 > rm pre-heated or infrared lamps at a temperature between i > gives between apirox imadamente t? 3"33 ° C and 121.11 * 0. The coated board was subsequently heated between lamps of quartz IR to a:? temperature = _p > When the object formed a molten film, the melted film was then removed by exposure to UV radiation, first with a lamp V and then with a lamp H at 6.096. meter / min for approximately one second. The cured powder coating was subjected to performance tests and the results of the tests are based on the list in Table 6B. Due to polymeric a &z > the virulether urethane reticulators, this reverse of powder has a greater flexibility which resulted in an improved adhesion on the substrate after the ion cure. Table 6B Test Properties MF.i rubs (50 double rubs) no effect Adheren ia Cross Hatch 3B Hardness eie Pencil Sea HB Brightness 20 ° / 80 * 38/86 EXAMPLE 7 Preparation of crystal pigment powder coating and pigmented virolous ether with double curing, thermal and with UV radiation The ingredients presented in the following list of Table 7A were combined in accordance with that described to form a pigmented pigmented coating of this invention having a healing aspect d > z "ble, thermal and with U-radiation. Table 7A Ingredients Phr Example 7 MIXING DRY UNTIL HOMOGENEITY Pioester 313 unsaturated polyester (1) SO 7W-3307P (2) 20 L iucarin TPO 2.0 Photoconductor Photoinitiator Irgac? Re 184 1.5 Peroxide initiator »by lupersol 231XL 2.0 Resiflai-i P87 Auxiliary of f 1CIJO ac rí 1 ico 1.4 DIAGNOSIS of titanium T i Pure P-902 2C » LOAD TO THE FXTPUSORA AND EXTRUDE IN LEAVES FUSION TEMPERATURE = 82.22 * C COOL WITH AIRF AND BREAK IN LASCAS LOAD TO THE MILL AND MOLER UP TO OBTAIN POWDER TO HIGH VEI OCI AD TAMI7AR WITH A MALL 140 (1) Pioester 313, unsaturated polyester, is a solid crystalline unsaturated pal ester resin which is derived from ethylene glycol and fumaric acid, and is commercially available from Pioneer Plastics. (2) ZW-3307P, vinyl ether reagent, is a urethane reticule with a crystalline, solid, ether-derived ether functionality derived from vinyl ether? of 4-hydroxybutyl and 1,6-hexamethane di-isocyaninate, will be available in DSM Resms. RESULTS The powder coating listed in Table 7A was electrostatically sprayed with a tribo gun on a steel panel and heated with quartz IR lamps at a temperature of approximately 204.44 * C for approximately 5 seconds with the object qu * 3 the powder flows in a melted poly-ul = t. With crystalline materials, the flow tends to improve that which promotes more regular reversals. After the exit of the melted film, the panels were placed under an I IV V / H lamp of 600 mats at 6.096 meters / min. for about 1 second to finish the project. The coated powder coating was then subjected to performance tests and the results of the test are listed below in Table 7B. Table 7B Prophylactic tests ME rubs no effect (50 double rubs) Adherene: ia Cross H ch IB Tile hardness ?, Sea 5H Abrasion Taher, loss (mgs.) 23.9 Api r iene: ia moderate orange skin Gloss, 20ß / 80ß 55 / 86 the invention has been presented in the above modalities and examples and others; embodiments of the invention will be apparent to those skilled in the art. The invention is not intended to be limited to the exemplary embodiments, which are considered to be illustrative only. Therefore, the appended claims should be referred to evaluate the spirit and true scope of the invention, on which exclusive rights are claimed.

Claims (22)

1. CLAIMS 1. A double-curing, thermal and ultraviolet hot-melt coating composition, which is a solid particle form composition comprising a mixture of a) a base resin forming a film; b) a copal resin impregnable with said base resin; c) a photoinitiator; and d) a thermal initiator, wherein said composition is curable, both on the surface and in its entirety, when it is exposed to a sufficient thermal action and despires to UV radiation.
2. 2. The composition of claim 1, further comprising: e) an agent > of > opacity selected among pigments, fillers and mixtures »of them.
3. 3. The composition of the indication 1, which further comprises: f) a catalytic agent;
4. 4. A composition > of double-curing powder coating, thermal and ultraviolet, which is a film-forming composition in the form of solid particles which comprises a mixture: a) an unsaturated resin selected from unsaturated polymers, pallet 1 unsaturated atos », pol imet .cp 1 to unsaturated coughs, and mixtures > ie the same; b) a second copolymerizable resin having a functional group selected from vinyl ether, acrylate, methacrylate, and ethyl ester groups, and mixtures of the same; c) a photographer; and d) a thermal initiator.
5. 5. The composition > No. 4, which further comprises: e) an opacity agent selected from among pigments, reagents and mixtures thereof.
6. 6. The composition of the rei indication 4, further comprising: f) a catalyst selected from a metal compound based on a fatty acid or oil.
7. 7. The composition > of claim 6, wherein: said catalyst is a cobalt compound selected from cobalt octoate, neodecanoate and erobalt, crobalt naphthenate, and cobalt octadecanoate.
8. 8. The composition of claim 13, wherein; said unsaturated resin is a more saturated polyester resin derived from malignant or fumate acid, or else anhydride.
9. 9. The composition of claim 8, wherein: said unsaturated ream is a non-crystalline, semi-crystalline, or crystalline solid.
10. 10. The composition of claim 8, wherein: said second copolymerizable resin is a urethane polymer prepoly with vinyl ether functionality.
11. 11. The composition of claim 10, wherein; This second copolymerizable resin is a non-crystalline solid derived from the diisocyanate of 1-ophorone, neopentyl glycol, and vinyl ether of 4-hydroxybutyrate. 1 .
12. The composition of the reagent 10, in which: said second copal resin i mer i rabí e is a non-crystalline solid derived from isophorone diisocyte trimer and vinyl ether of 4-h idrox i but i 1 o.
13. 13. The composition of the rei indication 4, wherein: said thermal initiator is selected from compounds of peroxide and a or.
14. 14. The composition of claim 4, wherein: said composition is curable, both over the supe- ficity and in whole, upon exposure to sufficient heat to melt and cause the flow of said powder composition to obtain a regular melted film and to activate the thermal component of the cure, followed by exposure of the melted film to sufficient UV radiation to activate the ultraviolet component of the cure and form a fully cured hardened film.
15. 15. A dual, thermal and ultraviolet curing powder coating composition, which is a solid particulate film forming composition. which comprises a mixture of: a) an unsaturated resin selected from unsaturated polyacylates, polyether-unsaturated polysaccharides, and mixtures thereof; b) a starting photo; and c) a thermal initiator, wherein said > or position is curable, both on the surface and in its entirety, when exposed to a sufficient thermal application and then to UV radiation,
16. 16. The composition of 13 reivi ndi falls 15, which further comprises: d) an opacity agent selected from pigments, fillers, and the ace of the same.
17. 17. A method for the production of a fully cured film with a coating of curable powder or radiation on a substrate, comprising: a) the electrostatic application of a coating composition > of a curable substance with radiation on a substrate, said composition is in the form of solid particles, comprising a mixture of: i) a film-forming base resin; ii) a second optional copolymer resin impregnated with said base-axis resin, iii) a photo-nic; iv) a thermal initiator; and v) an optional opacifying agent selected from pigments and renderers; b) applying a sufficient amount of heat to said powder coating to melt and flow said coating into a regular melt film and to activate the thermal component of the cure; and > r) applies a sufficient ultraviolet radiation to said melted film to activate the ultraviolet component of the cure and form a hardened, fully cured film finish, both on the surface and in its entirety.
18. 18. The method of claim 17, wherein; said substrate is a substrate sensitive to heat.
19. 19. The method < The indication 18, in which: said heat-sensitive substrate is selected from wood and plastic materials;
20. 20. A substrate having the powder coating composition of any of the reations 1 to 16 coated and cured therein.
21. 21. The coated substrate of claim 20, wherein: said substrate is a heat sensitive substrate.
22. 22. The coated substrate > of claim 21. In cu 1: said heat sensitive substrate is selected from wood and plastic materials. 10 15 20 -.-- i) SUMMARY OF THE INVENTION Coarse film or opaque pigmented powder coatings for heat-sensitive substrates, such as wood, wood composites, for example medium density fibreboard, and plastics, which can be cured, especially c &rca of the substrate, by incorporating a double curing system in the powder, comprising a thermal initiator, such as a peroxide, join with a UV initiator. The UV initiator cures the surface while the thermal initiator cures the inner surface of the substrate. Surprisingly, virtually no gel pyreformation occurs during the step of melting and flow under the action > of the heat before curing with UV. Therefore, the hardened film finish formed on the surface shows an exceptional regularity that is comparable to the regularity of traditional powders curable with UV radiation. The hardened film finish is also fully cured and shows exceptional adhesion to the substrate, which can not be achieved with traditional powders curable with UV radiation that has been pigmented. Although the dual cure system includes a thermal aspect, these powder coatings are especially suitable for application to heat sensitive substrates. Dual curing, thermal and UV-curable powders cure at significantly lower temperatures and at significantly higher speeds than traditional thermal curing powders, whereby they are safe to coat heat-sensitive substrates.