MX2008006881A - Prepregs and cured in place solid surfaces prepared therefrom - Google Patents

Abstract

A prepreg which is capable of being cured-in-place into a solid surface by irradiation, heating or a combination of the two is prepared. The cured-in-place solid surfaces can be used as veneer cladding for rigid substrates such as floor and wall tiles, kitchen and bath counter tops, sinks, cabinet door veneers, bath surrounds, architectural surfaces such as columns and roofs and the like.

Description

PREIMPREGNATED LEAVES AND SOLID SURFACES CURED IN THE RIGHT PLACE PREPARED FROM THEMSELF Technical Field The description is directed to compositions capable of providing solid surfaces cured in the right place, solid surface cured in the appropriate place prepared from the pre-impregnated sheets, methods for make the pre-impregnated sheets and methods for preparing the solid surface articles. More particularly the description relates to veneers or solid surface coatings applied to a substrate wherein the solid surfaces are prepared from the pre-impregnated sheets of filler, a curable resin with radiation, an initiator, optionally curing speed additives, prepoly groupers or additives for increased maturation / thickening and optionally shelf-life enhancers. The cured solid surfaces in the proper place (Ci. PS) of .'1 to present description can be used as wood veneers for rigid substrates such as floor and wall tiles, kitchen and bathroom top covers, sinks, veneers Cabinet door, bathroom contours, architectural surfaces such as columns and ceilings and the like. Background The surface of kitchen cover surface of much more effective cost is the composite construction of the decorative laminate. This material offers a wide range of performance advantages in terms of wear resistance, hardness / durability and ease of installation. The material] is based on a coating of particleboard bound to urea formaldehyde (UF) with a laminated sheet (60-100 mils) of a laminate composed of Kraft Paper (c'l decorative laminate). At least two types of resin systems are used in composite construction. The volume of the compound is formed by saturating the paper with a phenolic enolase solution diluted with aqueous or polar solvent using a continuous process in which the water and / or the solvent are removed in a drying oven, allowing the advance (stage B) ) of the resin impregnated to a degree of advance such that a stack 5 (20-30 sheets) of the papers of the pre-impregnated sheets can be pressed into molded piles. This process is achieved at 1000 psi and 1.3? -176 ° C (2 / 0-3500) for 5-30 minutes to give a highly cross-linked compound that offers a wide range of environmental resistance. The surface performance in decorative laminates is achieved by covering the composite with 2-4 sheets of a pre-coated kraft sheet of resin "amine (melamine formaldehyde (MF) or urea formaldehyde (EU)) prepared similarly to the phenolic version. The top sheet of preimpregnated sheet with amine resin was Huecograba with the design and color scheme of choice. Many decorative laminates are engraved with a pattern of wood grain and other designs using decorated rollers. The joining of the decorative laminate to the particleboard is achieved by using a contact adhesive. The de-lamination of the sheet of the support particle board is a major problem in these constructions. The swelling of the board with moisture pick-up is a major source of performance failure. The surface appearance of decorative laminates is their primary deficiency. With use and aging, they degenerate into an outdated, very unpleasant appearance. Another type of surface, synthetic materials with a solid surface, are highly-filled, polymer-bonded compounds that offer a rock-like appearance and feel (heavy / solid). Its density and modulus present a "high" ring when glass or ceramic ware is handled over the uncoated surface.The first leader in this area was the Corian® product line from DuPont.This product is 70% aluminum trihydrate ( ATH) and a reactive polymer derived by dissolving a molecular weight polymethyl methacrylate in methylmethacrylate It is believed that the reactive mixture is cured by a free radical mechanism using a maleic acid ester ester having a high molecular weight component.

Tertiary alkyl ester (much more commonly used is butylpermaleic acid monoterria). Cocatalysts used in conjunction with this initiator are water-soluble Group II metal salts that allow commercially acceptable cure rates in a range of filler systems. The filled composite is formed into cast-cured blocks that are cut into white sheets for further adaptation by installers. Corian © storage sheets are easily machined and finished in a variety of design options. repair and refinishing are possible due to the material nature of the material. The filler system is uniform throughout the compound, allowing refinishing without changing the appearance of the article. The next generation of this product line is a system composed of 93% crushed quartz sold under the trademark Zodiac © by DuPont. BRIEF SUMMARY OF THE DESCRIPTION In contrast to the foregoing, the present disclosure provides pre-impregnated sheets cured in the proper place, preferably in the form of flexible sheets having a uniform thickness that are free from embossing or substantially free from embossing, and capable of being placed on and attached to flat, contoured, or irregular substrates to create a pre-impregnated sheet veneer without bonding. The resulting compound can be cured using ambient light sources, pressure, heat, incident radiation, or combinations thereof to give a solid surface plating having the abrasion resistance and durability required for applications such as kitchen top covers. The present disclosure relates to a prepreg sheet comprising the reaction product of a curable composition comprising: A. a polymerizable component comprising a monomer, oligomer and / or polymerizable polymer and a chemically reactive organic thickening chemical; B. a catalyst for the chemically reactive organic thickening chemical; C. a filler; and D. a photoinitiator; peroxide or both, and wherein the pre-impregnated sheet is flexible, free of tack and free of stamping or stamping-free substance. The prepreg sheets of the present disclosure may be formed into a sheet, or ot a form suitable for subsequent processing into a desired final product. The pre-impregnated sheets are preferably stamped-free, i.e. the cross-linking density of the preprinted pre-impregnated sheet is believed to be imparte recoverable elasticity to the fully mature pre-impregnated sheet; or its essentially stamped-free, i.e., it is believed that they lack sufficient cross-linking density to allow full recoverable elasticity but still allow joint preparation without joint. The pre-impregnated sheets can be prepared with flexible, tack-free sheets that exhibit a shelf life in their uncured state of greater than 100 hours at 60 ° C or greater than 30 days at room temperature. The mature prepreg sheets of this disclosure can be used to prepare solid surface coatings with the advantage that they can be cured to relatively thick sections using visible low energy light sources in reasonable curing times. In pre-impregnated sheet formulations containing high optical density reagents or pigments a combination of photo and infrared (IR) curing of the environment at about 70 ° C can be used to form a cured article in the proper place. In the sheet form, the prepreg composite of this disclosure comprises a mature prepreg sheet paste generally enclosed between two films designated as the carrier and release film sheets. The preimpregnated sheet compound works to allow the. transport of the sheet of pasta matures to the substrate surface after removal of a release sheet. The radiation-resistant carrier sheet serves as an oxygen barrier that allows rapid radiant curing of the mature pulp. For complex materials, the carrier sheet can be removed and replaced with a film coating prepared from a reactive liquid inert to the prepreg, such as an aqueous emulsion of polyvinyl acetate. The mature prepreg sheet of this disclosure may be provided in sheet form or otherwise as necessary for a specific application. In the case of surface coating applications it is necessary to have a mature pre-impregnated sheet of uniform thickness and with a flexibilthat allows for the coverage of small radius bends. It is equally important that the handling of the pre-impregnated sheets can be achieved without the deformations of the pattern that will modify the flat uniformof the desired surface. One aspect of the present disclosure relates to a radiation-curable prepreg sheet capable of providing cured solid surfaces in the proper place comprising a thermosetting polymer; polymerizable material; a reactive thickener, photo-initiator and / or peroxide; and a filler. Another aspect of the present description is relates to a solid surface cured in the appropriate place prepared from the prepreg sheet disclosed in the above. A further aspect of the present disclosure relates to an impregnated sheet composite comprising a mature prepreg sheet as disclosed herein which is located between a carrier sheet and a release film sheet. A still further aspect of the present disclosure relates to a method for making the pre-embossed sheet disclosed in the foregoing. Still another aspect of the present disclosure relates to a method for preparing solid surface articles. Still other objects and advantages of the present disclosure will become readily apparent to those skilled in the art from the following detailed description, where it is shown and described only in the preferred embodiments, simply by way of illustration in the best manner . As will be understood, the description is capable of other and different modalities, and its various details are capable of modifications in several obvious aspects, without departing from the spirit of the description. Therefore, the description will be considered in nature as illustrative and not as restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic representation of an apparatus used to prepare thermoplastic prepreg sheets having a top and bottom film. Figure 2 is a schematic representation of a process of an empilable prepreg sheet. Figure 3 is a schematic representation of a continuous pourable pre-impregnated sheet process that includes the features: 1. Filler 2. Prepolymer 3. Additives (With Partial Catalyst) 4. Partially Advanced Pre-paste 5. Vacuum Void Removal Through the Gas Removal 6. Final Catalyst Loading 7. Vibratory Mixer 8. Continuous Mixer: Development of Stage B Final Pre-impregnated Leaf Paste 9. Agitator (Screw, Or Other Similar Design) 10. Transfer of Preimpregnated Leaf Paste Stage B Early Carrier Film (Slot Mold, Scraper Box or Other) 11. Carrier Film 1 '. Early Stage 13 Preimpregnated Leaf Paste Coated over the Carrier Film. 13. Rotation Direction of the Coating Roller 14. Coating Line Heating Section 15. Coating Line Cooling Section 16. Release Film Placement 17. Thin Stage B Paste with Immature Paste to Prevent Overshoot Preview 18. Press Rollers to Refine The Uniformof Thickness of the Preimpregnated Sheet 19. Pre-impregnated Finished Sheet: Roll, Or Cut and Stacking for Final Maturation to the Leaf Preprint Free Prepreg Figure 4 is a diagram of a pre-impregnated sheet curing station using a halogen light source. Figure 5 is a graph showing curing temperature profile data for pre-impregnated pigmented and non-pigmented sheets. Figure 6 is a graph showing curing data for pigmented and non-pigmented pre-impregnated sheets. Best and Various Ways to Carry Out the Description Pre-impregnated leaves cured in the right place (CIPS) are prepared from resins or prepolymers termoendu.recibl.es, polymerizable materials low in volatile (for example monomers, oligomers and / or polymers) photoinitiators and / or peroxides, optionally additives that increase the speed, optionally shelf-life promoters, maturation / thickening chemicals or additives and fillers, and optionally thermoplastic polymer not reactive The thermosetting resins useful in the thermoenduded preimpregnated sheet versions receive from The present disclosure include standard commercial versions of unsaturated polyester resins having number average molecular weight (Mn) values in the range of 500-10,000 amu, such as resins of vinyl ester, unsaturated polyester, polyurethane functionalized such as acrylic polyurethane resins, and epoxy polymers. The reactive thermoplastic olimers include poly (meth) acrylic resins and thermoplastic polyurethane elastomers and the like which are capable of chain extension. The necessary resins are not fotocurabl.es by themselves but must be able to react with the reactive monomers to form a fofocubabie composition. Methods for preparing the resins are known in the art. By way of example, unsaturated polyester resins are prepared by polyesterifying an organic acid or its corresponding anhydride with a glycol, the organic acids used are typically mixtures of acids carbo i 1 J saturated unsaturated or anhydrides having at least two carboxyl groups. The thermoset resins are recycled using a reactive material, for example, one-atom, one-size and / or one-half polymer. Any reactive monomer known to be useful in the crosslinking of the thermosetting resins of the present invention can be used. Examples of these types of reactive monomers are styrene, a-methyl styrene, vinyoluene, and diviml benzene and the like. However, it is preferable to use materials considered to be non-ionic, low volatiles (hazardous aromatic Cotoreactive solvents), monomers, polymers and / or polymers when compared to additional reactive monomers such as styrene. Non-limiting examples of such low-volume monomers include compounds containing multiple acroplate functional groups such as tp met i ol propanotp acr i 1 allo (TMPT?), Compounds containing multiple acrylic functional groups where at least One of the acrylic groups has been modified to contain secondary radicals, some of which are derived from reactions of groups capable of forming secondary acrylic radicals. These can be derived from acrylic acid, or other po I i acrj 1 a fos capable of adding other functional groups of acplate or directly to reams, acrylic vinyl esters, condensed acids such as the products of Michael Addition of acryl acetoacetate to Liquids described in U.S. Patent Nos. 5,945,489; 6,025,410 and 6,706,414, the contents of which are expressly incorporated herein by reference or mixtures thereof. Exemplary acrylate monomers and / or oligomers include, but are not limited to monoacids, di-acrylates, trialates, acrylates, pol3, unc10nal., Acylates, cpoxy, aromatic urethane acrylates.acrylates, polyether acrylates, polyester ester acrylates, elamma acrylates and any combination thereof and the like. More specifically, exemplary monomers and / or oligomers of Acr 1. Lato include, but are not limited to, methyl acrylate, vinylacetate, n-butyl acrylate, t-butyl acrylate, acrylate ethyl, 2-ethylhexyl acrylate, isobornyl acrylate, hydroxyl acrylate 1 et. it, phenoxy acrylate (PEA), ctoxy acrylate cloxy et 1 I, (EOEOE?), acid acrylate (IDA), octiidecyl acrylate, phenol acrylate, ethoxylated, monoacrylate of formatic cyclic tpmethylpropane (CTFA), Versa tic 10® vinyl ester (a synthetic C-10 monocarboxylic acid having a structure to a well branched). Examples of oligomers and / or polymers are diaccolate of diethylene glycol, bisphenol A diacrylate ethoxylate (MW = 42), 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 1,3-propanediol diacrylate, 2-methyl-1, 3-propanediol diacrylate, polyethylene glycol diacrylate (MW = 302, 508), neopen-tylglycol propoxylate diacrylate (MW = 328) (PONPGDA or NPGPODA). Tetraethylene glycol diacrylate (MW = 302), methylene glycol diacrylate (MW = 258), tripropylene glycol diacrylate (DPGD?) (MW = 300), dipropylene glycol diacrylate, diacrylated epoxy bisphenol-A; pentaerythritol diacrylate, propoxylated glycerol triacrylate, trimethylolpropane triacrylate (TMPTA), trimethylolpropane triethoxylated triacylate (EOTMPTA or 'L'MPEOTA) (MW-428), propoxylated glycerol triacrylate (GPTA) (MW - = 428), tetraacrylate pentaerythritol (PETA), tris (2-hydroxyethyl) isocyanurate triacrylate (ME = 423), melamine triacide, polyacrylated versions of melamine and its partially ethoxylated systems; pentaerythritol tetraacrylate (PETA), pentaacrylate dipenitrite (DPPA), di ponte diitite hydroxypenalacrylate, tetraacrylate di-trimethylolpropane (di-TMPT?), And alkoxylated pentaerythritol tetraacrylate (PPTT?). The selection criteria placed on the members of the high molecular weight resin classes are those typically in combination that achieve the viscosity needed to generate a sheet sheet paste. pregnada prelnada useful in combination with the fillers of this description. For on-site facilities using the pre-impregnated sheet of this description with low volatility reactive monomers such as solvents that lower the potential for flammable ignitions during installation, as well as providing the installer and consumer with a safe environment during installation, with acceptable levels of hazardous volatile organic materials released or otherwise objectionable. For the method of emptying the prepreg sheet preparation, prepolymer resin compositions containing resin-reactive monomer combinations having low initial viscosities are advantageously used. This method allows a low viscosity slurry that can be more easily desalinated and cast in the prepreg sheet or other shapes that have the ability to latent thicken. These polymers require additional components (such as reactive thickener resins) capable of undergoing a "thickened" reaction of step A to form a pre-blended photoreactl.va stage B (mature) sheet slurry. The reactive thickener resins of this description operate using chemical substances that allow the retention of a sufficient level of photoreactive constituents that in the mature prepreg leaf paste to preserve the targets of performance of curing of preimpregnated sheet objective during the installation of curing in the right place. Photoinitiators are a kind of initiator used in pre-impregnated leaves cured in the right place (CIPS). The most useful photoinitiators are those activated in the range of visible light in the spectrum. An example of this class of photoinitiator is bis (2,4,4-trimethylbenzoyl) phenyl fos oxide available from Ciba-Geigy as Irgacure® 819 photoinitiator. This is a member of the acylphosphine oxide class of photoinitiators. These are described in US 4,265,723, and are distinguished by their high reactivity in irradiation with long wavelength radiation in the range of 300-500 nm, a portion of which falls in the visible spectrum, 400-800 n . This class is described by the following general formula, where R1 is straight or branched chain alkyl of 1 to 6 carbon atoms, cyclohexyl, cyclopenyl, aryl which is unsubstituted or substituted by halogen, alkyl or alkoxy, five or six membered heterocyclic radical containing S or contains N. R2 has one of the meanings of 10 (R1 and R2 can be identical or different), or is a alkoxy of 1 to 6 carbon atoms, aryloxy or aralkoxy, or R1 and R2 together form a ring. R3 is straight or branched chain alkyl of 2 to 18 carbon atoms, a cycloaliphatic radical of 3 to 10 carbon atoms, phenyl, naphthyl or five-membered heterocyclic radical or six members containing S-, O- or N and can contain replace additional tees in the group where R1 and R2 have the above meanings and X is phenyl or an aliphatic divalent radical or aliphatic cycle of 2 to 6 carbon atoms, and one or more of the radicals R1 to R2 can be unsaturated. A second class of photoinitiators consists of the cyanine borates developed as part of the Mead Imaging, Cycolor Process®. These photoinitiators are derived as organic soluble salts of cationic and tetraalkyl cyanine dyes, and / or functional aryl borate anions. These initiators release the alkyl constituents of borate, and / or aryl radicals as free radicals initiators of active olefin polymerization when subjected to the visible radiation associated with the max of the cationic cyanine ink component. These Photo and lights are dyes that impart color when used to initiate curing in a compound matrix, but they quickly fade to darkness by exposure to normal ambient light. These photoimagers can be designed to be active by visible radiation throughout the visible spectrum depending on the degree of conjugation extended in the dye component, and offer a unique mcdLO for curing C1PS composite systems containing a range of pigments. Examples of peroxides useful in the description include organic peroxides. Organic peroxides useful in this disclosure include: perox esters that include, but are not limited to, tert-but ilperox L-2-et.? Lhexi 1 carbonate, tert-amylperox.? - 2-et? Lhexanoa to, tert-but i 1 perox i -2-et lhexanoa to-98%, 50% in pl ast L fi ante 50% in organic mineral essences (WHO); terc-ami 1 perox i -2-et i 1 exanoa to-98%, -70% in plasticizer, -75% in (WHO), 2, -d i cti 1-2, bd (2-ethexanoxane) ? lperox?) hexane-90%, tert-butylperoxyphenone-75% in WHO, tert-but i 1 perox i -3, 5, 4-tr.?met? lhexanoate, tert-bu ti Iperox and isopropy 1 carbonate, tert-ami 1 perox? Benzoate-80% in amyl alcohol (??), tert-butyl perox? -2-met-benzoate-75% in WHO. The peroxy ketal is that they include but are not limited to, analogs of the following: 1, 1-d? (tert-Buty Iperoxy) -3, 3, 5- 1rime ti lc? clohexane-75% in pl asti f.? sing, -75% in isododecane. Po 1.1 ca rbona They include, but are not limited to di (tert-butylcyclohexyl) peroxycarbonate. Peroxides derived from ketones and hydrogen peroxides, such as MEK peroxide, containing a portion of hydroperoxide functionality, are not preferred for this application since it has been shown that hydroperoxides decrease in the shelf life of the prepreg sheet. Similarly, eumeno hydroperoxide is not preferred for applications requiring shelf life, of long prepreg. The hydroperoxides are also not preferred, especially since they tend to reduce the shelf life of the pre-impregnated leaves stored unusable. These materials have applications in those processes in which the methods defined herein are applied to a manufacturing process in which the pre-impregnated sheets of this description are used to make solid surface products with no storage interval. Contrary to standard peroxide curing systems which effect a cure when heat is added, the pre-impregnated sheets of the present disclosure are stable at 60 ° C, but are capable of increasing the photocuring performance at room temperature with the combination of photoinitiator and organic peroxide. They provide an auxiliary curing mechanism under conditions where the foam is insufficient to achieve complete cure depth. In In the case of reactive thickened polymers, peroxide additives can provide supplemental curing routes that allow the mechanical performance of the optimum prepreg sheet and hardness. It has been shown that the selected additives can lower the initiation temperature of the peroxide component to allow it to supplement the curing at ambient temperatures at the decomposition temperatures of the peroxide half-life. For systems of pre-impregnated things thickened with Michael Addition in certain embodiments, the curing speed seems to be greatly accelerated by having peroxide additives present during the maturation stage. This is achieved due to a combination of factors that include one or more of the following: (1) the presence of the heterogenous aluminum trihydrate, (2) advancement of the prepolymer to the top B of the prepreg sheet stage in which the polymers Higher molecular weight are created having high acrylic pending group functionality, and (3) pH modification system that has a positive effect on curing speed. Other additives can be used to further increase the hardness and cure rate performance of the photoinitiator-or peroxide peroxide system. The addition of low levels of active oxygen peroxide of the kind described above in combination with the additives curing speed boosters and a photoinitiator to the resin mixture increases the depth of curing in the cured compounds at the proper place in the description. These systems also have the ability to give through curing in the thick sections. In highly optical dense systems the curing speed enhancing additives are capable of reacting to provide thermal initiation. These curing speed enhancing additives include, but are not limited to, the following: mercaptans (aliphatic, aromatic, heterocyclic and as polyester components) such as trimethylolpropanotritiopropi onate or dodecyl mercaptan; disulfides (aromatic, aromatic heterocycles, aliphatic and combinations thereof as mixed disulfides); polysulphides such as thiurams (oxidically coupled adducts of dialkylamines and carbon disulfide) and benzothiazole polysulfide accelerators; phosphines (aromatic, aliphatic and polymers containing the phosphine group, phosphine oxides (aromatic, aliphatic, and mixed), phosphite esters such as triphenylphosphite, vinyl triazines, branched alkylaryl amines, sulfinamines, sulfinamides, and their derivatives, thioureas of alkyl and aryl or mixtures thereof When used in conjunction with photoinitiators and peroxides the resin formulations of the present disclosure have Curing speeds of increased surfaces and through. cured. In order to have the potential to generate solid surface compound, filler, resin, and a curing medium are required. For fotocurabl.es systems, a photoinitiator coupled with a radiation source provides the radical source. For highly-filled pre-impregnated sheets that require a fast curing speed, to achieve cure performance goals, a light source, photoinitiator, oxidant and propagating co-reactants should be employed. Generally, pastes for the CIPS prepreg can be made using the pre-written filling, prepolymers, initiator (s) and peroxide components indicated by this disclosure. The pastes can be prepared and stored closed (anaerobic), or open (aerobic) for substantial periods of time. Stability towards premature reaction of the prepolymer is provided by conventional stabilizers found in the monomers used and adequate levels of atmospheric oxygen dissolved in the prepreg. However, formulations containing some desired propagation co-reactants needed for light curing of the impregnated or light-cured sheet exhibited decreased pulp volume storage shelf life. These materials containing co-reactive propagation they seem to participate in continuous reactions that deplete the stabilizer-free oxygen content of the sample, resulting in curing of the prepolymer. The latter systems can be used commercially if the pulps can be kept in pre-impregnated sheets of mature pulp of thin oxygenated section. The volatile prepreg sheets that are formed by reactive thickening offer additional stability performance based on reduced reactive group mobility resulting from the thickening reaction process. The prepreg sheets of this disclosure can be maintained in the aerobic (oxygen stabilized) state by the use of oxygen permeable release films, this method is necessary to allow the use of thiol propagating co-reactants. The compositions of. Pre-impregnated sheet of this description are highly filled. In general, the fillers increase the hardness, stiffness and strength of the final article relative to the pure polymer. In this description it is shown that the filler can provide attributes to the formed prepreg sheet as it develops unique and desirable mechanical properties in the pre-impregnated sheet and in its solid surface composite formed by the substrate, the bonding adhesive, and the surface coating solid that results from ripened cured pasta. The primary reactive filler of this description is ATH. Its attributes are particularly suitable for this application, in particular a low optical density which allows the curing of the resins at significant depths at high filler levels. Its refined forms have high whiteness in the compound coupled with translucency that allows the definition of decorative auxiliary graters added. The surface chemistry of ATH is particularly treatable to the promotion of desirable thickening chemicals particularly with the thickness associated with the Michael reaction described herein as reactive thickness. In this case it is believed that the acidic (amphoteric) base nature of the ATH surface allows the use of caustic as a catalyst that allows the thickening of the paste in suitable proportions for processing the continuous prepreg. Other fillers that include other aluminum-based fillers can be used which offer additional options in the formation of pre-impregnated sheets and cured composites of this description. These include: alumina, alumina monohydrate, aluminum hydroxide, aluminum oxide, aluminum sulfate, aluminum phosphate, aluminum silicate, borosilicate, calcium sulfate, calcium phosphate, calcium carbonate, and calcium hydroxide, magnesium and all forms of crystalline and amorphous silica. Minerals containing Group II metals in combination with aluminum oxides and silica can also be used. Combinations of fillers can, of course, be used as desired. Thickener Reactions: 1. Carbodiimides Carbodiimides and polycarbodiimides react with pending monomer and prepolymer active hydrogens to create suitable crosslinking systems for this application. Oligomers and monomers containing carboxyl, hydroxyl, thiol, amine, reactive methylene and the like are reactive in this thickening system. Reactive thickening agents of this CIPS prepreg thickening option include carbodiimide-based and functional carbodiimide-based monomers in combination with monomers and oligomers reactive with the functionality of the carbodiimide. Carbodiimides and the polyfunctional carbodiimides exhibit suitable reactivity for the low temperature curing capacity with monomers and polycarboxy functional oligomers. N-acylurea groups are formed between the carboxylic sites. Other polyfunctional monomers useful in the formation of carbodiimide bonds include hydrazidyl, amino and / thiol groups. Poly-functional carbodiimides can be obtained from polyisocyanates using phospholine oxide as a catalyst as described, for example, in U.S. Patent No. 2,941,966. Other oligomers of Valid carbodi can be prepared by forming polyols and carbohydrates containing isocyanate groups, by reacting the reactants in the presence of 0.01 to 3% by weight, based on the reaction mixture, of a tin catalyst as taught. in U.S. Patent No. 4, 321,394. Urelane products can be produced at temperatures as low as 25-150 ° C, using such catalysts as tin acetate (11) or dibutyltin diacetate. Exemplary polyalcopolyols include, for example, polyesters, polyesters, polyesters, polypropylene. Examples of suitable carbodide compounds useful in the present invention are N, N'-d: cyclohexylcarbodi: my day, l-et? L-3- (3'-d? Et? Lam? Nopropi 1) carbodi imida, N-et? l-N '- (3-dLmet? lam? noprop? l) -ca rbod iii da, N' -di and sopropil-carbodi muda, N 'N' -ditere-bul i icarbodi Lmi gives 1-CJ c] o-hex 11-3- (4-d LeLil ammoc icl ohex LI) ca rbodi i mi da, 1,3-d? - (4-d? Et? L am ociclo-hexyl) carbodp mida, lc? clo ex? l-3- (di eti I ai noet? l) carbod pmida, 1-c? clohex? 1-1-c? Clohex? 1-3- (2-morpholm i 1- (4) -ethyl) carbodjimide, 1 -CJ clohexi I -3- (4-di et I-ni nocí cl ohex l) carbodi irruda and the like. There is a variety of soluble carbodi imds with commercially available solvents. COMPUTERS OF CARBIDE are available from Union Carbide Corp., USA under the UCARLNK® designation.

Thickening pastes for this invention contain: (1) carbodiimide-reactive oligomers such as carboxyl-functional polyurethane oligomers including, for example, those prepared from combinations of diols, dimethylolpropionic acid, and a diisocyanate; or carboxyl-functional unsaturated polyesters; (2) a carbodiimide or functional polycarbodiimide oligomer to provide crosslinking with the carbodiimide reactive oligomers; (3) A curable free radical resin component consisting of monomers and oligomers containing reactive olefin (4) a filler such as aluminum trihydrate; Y (5) an additive package containing a paste ripening catalyst, wetting / defoaming agents and a free radical curing initiator system. On a weight basis, the polymeric binder composition of this invention comprises between about 1 and 30% by weight of carbodiimide crosslinker per 100 by weight of the total polymerizable component (thickening plus reactive olefin component). On a weight percent basis, the total polymerizable component comprises between 1% and 30% carbodiimide crosslinker, between 9% and 90% of the free radical curable resin component, and between 9% and 90% polymer or high molecular carboxyl functional oligomer, or optionally another oligomer or polymer containing carbodiimide reactive functionality. The thermos composition Preferred hardenable contains at least 1% carbodiimide crosslinker. The carbodiimide crosslinker is typically mixed into the CIPS paste precisely prior to use. For a typical pasta composition, a test sample of 3.0 g of dicarbodiimide of the kinds described above is added to 70 g of a paste formulation as described above. After stirring to initiate maturation, the paste can be emptied into a rectangular structure having a thickness of 0.125 inches. The paste cures a manageable prepreg in periods of maturation that vary from 5.0 minutes to 24 hours when maintained at temperatures ranging from 25-60 ° C. The catalysis can be used to further refine the pulp processing for desired process adaptations, for carboxyl coupling. Lewis acids such as alkyl tin cations are useful. 2. Epoxy Reactions: The reactive epoxy thickener compositions for the applications of pre-impregnated sheets of disposable CIPS can be prepared from a resin composition comprising: (a) a polyisocyanate compound, (b) a polyepoxide, (c) a compound radically free polymerizable, (d) an oxazolidone-forming catalyst, (e) filler, and (f) a thermo or photo initiator. The compounds reactive thickeners and supplemental catalyst, provide maturation of the low temperature prepreg sheet paste to create a pre-impregnated sheet resistant to flexible stamping independent, latent free radical cure layers. Useful prepreg foil pastes can be prepared by mixing the components of (a) to (f) and vacuum degassing. Oxazolidone-forming catalysts such as dialkylbenzyl phenolic amines (such as those produced from phenol, formaldehyde and dialkyldiamines using the Mannich Reaction) are added to the pulp to facilitate ripening to produce flexible, pre-preg sheets that are useful for veneer production. solid surface. Epoxy reactive thickener compositions for volatile CIPS prepreg sheet applications can be prepared from a resin composition comprising (a) a polyalkylamine compound, (b) a polyepoxide, (c) a radically free polymerizable compound, (d) filler, and (e) a thermo and / or photo-initiator. The reactive thickener compounds provide maturation of the sheet slurry, preimpregnated at low temperature to create a pre-impregnated sheet resistant to flexible stamping independent free radical cure layers, to the latent. Polyalkylamine such as diethylenetriamine react with epoxies and reactive olefins such as acrylates. Useful prepreg sheets can be prepared first by creating an epoxy-amine polymer having reduced levels of the more reactive primary amines. The further addition of polyfunctional reactive olefin results in the crosslinking and grafting of adduct in the prepolymer. The addition of Michael competitive to the reactive olefin component by the amine component of the prepolyme.ro can be reduced by the replacement of a portion of the acrylic functionality with methacrylate analogues. Epoxy reactive thickener compositions for volatile CIPS prepreg sheet applications can be prepared from resin compositions comprising (a) a functional compound of polythiol, (b) a polyepoxide, (c) a radical polymerizable compound, (d) ) a catalyst to promote the tlol-epoxy (e) filler reaction, and (f) a thermo- and / or photoinitiator. The active thickener compounds provide maturation of the low temperature prepreg sheet paste to create a pre-impregnated sheet resistant to flexible stamping of independent, latent free radical curing. The Tiol-functional prepolymers can be prepared by the pro-reaction of politi.ol.es such as tetra (3-mercaptopropionate) pentaerythritol with a diisocyanate or diol terminated in diisocyanate. These prepolymers are reactive with the polyepoxy under base catalysis to induce reactive thickening. The addition of Michael competitive to the reactive olefin component by the polythiol prepolymer can be reduced by the replacement of a portion of the acrylic functionality with methacrylate analogues. Epoxy reactive thickener compositions for volatile CIPS prepreg sheet applications can be prepared from a resin composition comprising (a) a methylene-diketo-reactive compound, (b) a polyepoxide, (c) a radical polymerizable compound, (d) a catalyst layers to promote the reaction of methylene-reactive epoxy (e) filler, and (f) ) a thermo- and / or photo-initiator. The reactive thickener compounds provide maturation of the low temperature prepreg sheet stock to create a prepreg sheet resistant to flexible stamping layers of the independent latent free radical cure. Isocyanate Reactions: A type of reactive thickener comprises the use of the reaction of reactive resin chemicals including: urethane, urea, or thiocarbamate bonds or derivatives by reaction of isocyanate reactive prepolymer functionality with hydroxyl pendant or hydroxyl activated with amine, amine, or thiol functionality. These functionalities may have placement on an existing polymer, or monomer components of the prepolymer of the prepreg sheet. Also included are reactions between the isocyanates and the methylene carbanions derived from the base-activated methylenes including, but not limited to, acetoacetic esters. Similarly, reactions between the isocyanate functionalities and functional epoxy polymers that are catalyzed by the Mannich bases and other similar ones are included. Variations in these systems include aliphatic polyisocyanates, which have increased resistance to reactivity with water, an adverse reaction leading to the generation of carbon dioxide during the maturation process of the prepreg sheet. Class of reagents that are important are the products formed by the reaction of oxasolidines with activated aldehydes, and other systems that have isocyanate binding potential. The oxasolidine products perform as water scrubbers in the resin-filler paste system. Reactive polyurethane thickener networks useful for producing CIPS prepregs involve polyurethane-based prepolymers that contain hydroxyl and isocyanate functionalities. The required prepolymers are prepared using a range of compositions, and provide thickened networks capable of meeting the objectives of the CIPS prepreg. established. Provides the option of reactive olefin functionality and hardening of the final hardened webs to meet the mechanical and shrinkage requirements in solid surface plating final products. Polyisocyanates useful in this disclosure include: aliphatic isocyanates such as isophorone diisocyanate (IPDI), hydrogenated methylenedianiline disocyanate, hexamethylene diisocyanate (HMDI), HMDI trimer; and aromatic isocyanates such as diphenylmethane diisocyanate (MDI) and toluenediisocyanate (TDI). Polyisocyanate terminated polyurethanes extended in the chain useful in this disclosure can be prepared by the following methods: Polyisocyanate-terminated polyisocyanate diols of polyether diols: which include in this group are those diols derived from: ethylene oxide, propylene oxide, tetrahydrofuran, or extension of diol monomers such as ethylene glycol, polyester diols, including polycaprolactone diols. All diols can be converted to isocyanate-terminated polyurethanes by controlling the stoichiometry of the diol and the diisocyanate to produce isocyanate-terminated polyurethanes. Combinations of the above diols are included to produce polyurethanes terminated in mixed isocyanates.

The chain-terminated hydroxyl-terminated polyurethanes useful in this disclosure can be prepared by the following methods: The hydroxyl-terminated polyurethanes can be produced from the reaction of diols (ethylene oxide open ring polymerization polyether diol derivatives) , propylene oxide, tetrahydrofuran, or analogs thereof with simple diols such as ethylene glycol; polyesters; open-ring polyesterifications of diols using lactones such as? -caprolactone) with diisocyanates by controlling reactive stoichiometry to produce hydroxyl termination. Combinations of the above diols are also included to produce hydroxyl-terminated or mixed polyurethanes. Hydrocarbon terminated polyurethane terminated and hydroxyl-terminated polyurethane combinations are then used in combination with esters and polyesters functionalized with mono- and / or poly-activated olefins (this class includes acrylate and methacrylate functionalities), fillers, and initiators of polymerization to form CIPS prepreg sheet slurry compositions to be thickened to provide maturation of slurry with urethane catalysts such as dibutyltin dilaurate (DBTDL). Polyurethanes finished in diol extended in the Useful chains in this disclosure are prepared using the following methods: The polyisocyanate extended in the functional poly thiol terminated chain can be formed from the reaction of isocyanate-terminated polyurethane diols with thiol-containing monomers such as tris (3-mercaptopropionate) trimethylolpropane using stoichiometry designed to produce thiol-terminated polyurethanes. Reactions of the above thiol-terminated polyurethanes with isocyanate-terminated oligomers can be used in leaf pastes' impregnated with CIPS to produce thickened networks extended in the chain, which form thiocarbamate bonds during the maturation of the CIPS paste. Thiocarbamate thickening can be achieved under appropriate catalysts, such as the use of DBTDL. Michael's addition of competitive thiolate anion to the components of the activated olefin paste can be controlled by appropriate selection of acrylate / ethacrylate combinations. The slower speed of the addition of tolate anion to the methacrylate functionality prevents excessive cross-linking in the maturation stage of the pulp which retains those reactive olefin constituents for the free radical curing step of the plating facility. the pre-impregnated sheet of CIPS attached to the substrate.

Polyisocyanate reactions or polyisocyanate terminated oligomers with polyamines or methylolated polyamides are useful in that exclusion to provide networks extended in the chain and further crosslinked by maturation of the CIPS paste. These can be prepared using the following methods: Reactive functionalities in this disclosure include oligomers having amylolated amine or amide hydroxyls derived from formylated amines, melamine, urea and amides. These hydroxyls are reactive with isocyanate functionalities to form N-methane urethane bonds suitable for chain extension and cross-linking in the CIPS paste chain. Precursors for this oligomer class include dysfunctional or higher oligomers having amine or terminal amide functionality or slope suitable for methylation to generate hydroxyls. Examples include anionic polymerized polyether systems having suitable acrylamide terms for methylation to provide diols. Also included are examples of facially butylated methylated melamines having hydroxyl functionality > 2. Oligomer members of this class are corrective with the terminally functional isocyanate oligomers described above in this section. Enlac.es produced are highly polar, and have utility in creating crystal linked hydrogen domains in the pre-impregnated leaf of mature CIPS, which is venereal for handling and curing performance. The polyisocyanate-terminated polyisocyanates or oligomers react with amine-assisted polyols to provide a reactive thickener system useful for this disclosure. Examples of amine-assisted polyols include hydroxyethylated or hydroxypropylated amines to provide amine-assisted polyols. Such activated amines are much more useful when the amine component is converted to a tertiary amine incapable of generating urea linkage in the reaction with isocyanate functionalities. Examples of amine-assisted polyols include the reaction product of ethylene diamine and ethylene oxide to produce tetraethanol ethylene diamine. A second example class of amine-assisted polyol are the Mannich Reaction adducts of formaldehyde and diethanolamine with phenol to produce phenolites functionalized with dietanolbenzylamine. The reaction of the phenolic hydroxyl of this system with ethylene carbonate produces a polyol suitable for use in the thickening of stage B in resins which require maintenance of free radical curing processes in their use. The polyols of these classes are useful in combination with the polyisocyanates and polyols terminated in isocyanate identified as useful in thickening the paste of the CIPS prepreg to provide crosslinking network formation. Thickening paste formulations containing these materials must also contain oxazolidine or alkylorthoformate water scavengers to prevent the formation of carbon dioxide in mature prepreg sheet compositions. Adducts of mono- and polyfunctional B-dicarbonyl reactive methylene functionalities with polyisocyanates, or oligomers terminated in isocyanates are useful in this disclosure. This reaction forms suitable mono or dicarbamide adduct bonds for extension in the resin chain and crosslinking. Examples include the reaction of aliplacetoacetate esters or polyfunctional acetoacetates with polyisocyanates or oligomers terminated in polyisocyanate to produce mono or dicarbamide linkages. For CIPS paste systems that anticipate the use of a final free radical cure it is desirable to employ levels of methacrylate monomers or their polyfunctional oligomers. These materials are capable of undergoing thermo or photo-curing of free radicals, but are less reactive in the methylene coupling of competitive Michael Addition reagent. CIPS pre-impregnated sheets produced using this concept can use water scrubbers such as oxasolidine or alkyl orthoformate to prevent the formation of carbon dioxide induced in their mature compositions. Adducts of functional epoxy monomers or polymers with polp socianates or oligomers terminated in poly. I socyanate can form suitable oxasol linkage for chain extension and cross-linking of the resin. These systems have utility in this description as CIPS paste thickening agents. Polusocyanates useful in this disclosure include aliphatic isocyanates such as: isophorone d isocyanate (1 PD1), methylated endianyl hydrogenated dusocyanate, hexamethien dusocyanate (HMDT), trimer (HMDJ); and aromatic compounds such as diphenylmethane di socianate (MD1) and toluenensencyanate (TD]). Isocyanate terminated oligomers useful in this disclosure include those previously listed as reactive CIPS thickening agents. Di- and superior-functional epoxies useful in this disclosure include aromatic phenol-based epoxies such as EPON ™ 828 and its extended versions of bLS phenol A produced by the imidasol catalysis. Epoxy d and alphatic functional superiors provide advantages in their stability of increased UV use, their ream color performance in use and increased compatibility with other reams Free radical process reagents used in the curing step of the CIPS prepreg sheet. This class includes glycidylated versions of diols such as hydrogenated bisphenol A, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2'-dimethyl-1,3-propanediol, triols such as 1,1,1 -trimethylolpropane. An effective catalyst for the facilitation of the isocyanate-epoxy reaction to form oxyzolidone bonds is derived by the Mannich Reaction of a dialkylamine, formaldehyde, and phenol to produce a dialkyl benzyl amine functionalized phenolite. If necessary, these catalysts can be modified by acetylation or alkoxylation to terminate the phenolic functionality to cover their inhibition of free radical process so that they can be used in the maturation of the CIPS paste without affecting the curing of final free radicals of the pre-impregnated sheet. Urethane catalysts include Lewis Base catalysts such as tertiary amines including 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.3.0] undec-7-ene (DBU), dimethylpipracine, pentamethyl dipropylenetriamine , and bis (dimethylaminoethyl) ether, and Lewis acid catalysts such as DBTDL, dibutylbis (laurylthio) stannate, dibutyltinbis (isooctyl mercapto acetate) and dibutyltinbis (isooctylmaleate).

Other Thickeners Reactive and functional methylene compounds such as bisphenol A diacetoacetate can react with polyethoxide compounds to give prepolymers having residual crosslinking reactivity. This ability results from residual reactive methylene protons capable of being catalytically extracted to generate nucleophiles, which can react with residual olefins. Thus, reactive epoxides and methylene compounds can be reacted to produce extended structures in the chain. These structures can then be added to the reactive olefin component to induce thickening by an "Addition of Michael process." Useful catalysts for promoting the addition of reactive methylene to epoxies include tetraalkylammonium halides and their combinations with alkyl or arylphosphines. Thickening of Michael Addition Another type of reactive thickener comprises the use of the reaction between esters and / or functional β-dicarbonyl polyesters such as those based on acetoacetates with activated olefins such as those based on acrylic functional polyesters. of β-dicarbonyl of this disclosure contain reactive methylene groups convertible to reactive anionic species by selected catalysts, and then referred to herein as reactive methylene thickening agents. Pastes containing these thickening agents generate reactive pre-impregnated thickened sheets which can achieve low deformability, desired flexibilities, and high photo-reactivity (by virtue of the polymer structure of the mature pulp and the presence extracted from reactive methylene protons) which are key objectives of this description. This thickening technology is based on the polymer compositions which achieve chain extension development and rapid crosslinking in a continuous process time structure to create pre-impregnated sheet of solid surface plating to coat the existing decorative laminate or composite assemblies. Particle board adapted to create solid surface top covers that meet established business performance objectives. This thickening chemistry is based on variations of the Michael Addition reaction in which a portion of the reactive monomer of the paste and the unsaturated reactant polymer components are reacted with the reactive methylene thickening agent. These adducts are new and unique prepolymer compositions capable of providing desired maturation of the desired prepreg sheet and through-curing performance. This technology can provide leaves pregnadas of mature pastas or a continuous base. The thickening functionalities of the reactive methylene may be present in the reactive thickener oligomer as part of a chain, or its side chain or terminal pendant groups. While not wishing to be related by theory, the thickening of the prepolymer is believed to proceed through the formation of adducts which are initially comb structures, star, or extended in the chain depending on the structure of the thickening prepolymer. The mechanical and photo-curing performance of the final pre-impregnated sheet can be adjusted by varying the tyand ratio of the thickener polymer components. In this description the term Michael Addition reaction refers broadly to the reaction between a reactive methylene functionality (Michael Donor) and an activated olefin double bond (Michael acceptor) resulting in an individual bond formation between the reactants and the loss of the double link of the acceptor. Such bonds are additionally reactive since the second methylene hydrogen methylene reactive link forming agent can also be removed to create a new micron donor donor layer reacting with a second Michael acceptor. Thus, methylenes are dysfunctional with respect to the capacity of carbanion formation of Michael's Donor. A difference exists between the proportions of reaction of the first and second methylene hydrogen reacted. Generally, the reaction of the first hydrogen occurs at a higher rate than the reaction of the second hydrogen due to the spherical obstacle and to other factors. This property allows dysfunctional acetoacetates to react with di and higher functionality acrylates to create extended prepolymers in the chain that are capable of forming hard, flexible CIPS prepregs. Specific to this description are monomers, oligomers, or polymers having constituents containing activated methylene groups capable of conversion to nucleophiles of Michael donor carbanion with suitable base catalysts. Non-limiting examples of Donors and Donors of Michael are listed in U.S. Patent No. 5,945,489, the complete contents of which are incorporated herein by reference. Examples of Michael Donors of that description may include functional ß-dicarbonyl esters and polyesters containing malonic and / or acetoacetic functionalities among others. Michael Monomeric Reactive Thickening Agents based on the functionality of the ketoacetate can contain a single group of acetoacetate, as illustrated by their methyl, ethyl, n-butyl, and t-butyl esters. These systems contain two reactive methylene hydrogens are thus able to bind the acceptor molecules Michael . Suitable β-dicarbonyl compounds, including β-diketones, β-keto esters and malonates, which are useful for the preparation of the oligomers and polymers used as Michael reactive thickeners are for example pentane-2,4-dione, hexane-2 , 4-dione, heptane-2,4-dione, l-methoxy-2,4-pentanedione, 1-phenyl-1,3-bunedione, 1,3-diphenyl-1,3-propanedione, methyl ester of acid benzoylacetic acid, benzoylacetate ethyl ester, benzoylacetic acid butyl ester, propionylacetic acid ethyl ester, propionylacetic acid butyl ester, butrylylacetic acid methyl ester, acetoacetic acid methyl ester, acetoacetic acid ethyl ester, acetoacetic acid isopropyl ester , acetoacetic acid butyl ester, acetoacetic acid t-butyl ester, acetoacetic acid (2-methoxyethyl) ester, acetoacetic acid (2-ethylhexyl) ester, lauryl acetoacetic acid ester Ethical, 2-acetoacetoacetohexyl acrylate, 2-acetoacetoxyethyl methacrylate, acetoacetic acid benzyl ester, 1,4-butanediol diacetoacete, 1,6-hexanediol diacetoacetate, neopentyl glycol diacetoacetate, 2-ethyl-2-butyl diacetoacetate -l, 3-propanediol, cyclohexanedimethanol diacetoacetate, ethoxylated bisphenol A diacetoacetate, trimethylolpropane triacetoacetate, glycerol triacetoacetate, pentaerythritol triacetoacetate, pentaerythritol tetraacetoacetate, ditrimethylolpropane tetraacetoacetate, dipentaerythritol hexaacetoacetate, acetoacetate group-containing oligomers and polymers obtained by the transesterification of acetoacetic acid ethyl or t-butyl esters with oligomeric or polymeric polyols, and oligomers containing acetoacetate group and polymers obtained by the copolymerization of 2-acetoacetoxyethyl methacrylate, malonic acid dimethyl ester, malonic acid diethyl ester, malonic acid dipropyl ester, malonic acid diisopropyl ester, malonic acid dibutyl ester, di (2-) ethylhexyl ester), malonic acid, dilauryl ester of malonic acid, oligomers and polymers obtained by malonates and dialkyl diols. Particularly suitable are polymeric diacetoacetates which have been produced by the transesterification of unsaturated polyester diols with ethyl or t-butyl acetoacetate. These include: 1. Functional oligomers of diacetoacetates or di (ethylmalonate) produced by transesterification between acetoaceta Lo, or malonate esters with: a. Polyester diols produced from the polyesterification of aromatic or aliphatic diacids with diols, ether diols or diols of pol ether b. Polyester diols c. Crystalline diols such as bisphenol A hydrogenated. d. Insalurated polyester diols terminated in cyclopentadi ene. and. Bisphenol A diols alkoxy sides. F. Diols of pol i caprol actona. 2. Polyacetates work The higher or polyester-based Lonatos produced from tri and higher functional polyols of the classes described in the foregoing. 3. Esters of polyimal onate produced by the t ransestep f fall of d i eli 1 ma 1 ona Lo with diols. For this description, two types of oligomeric Michael thickening agents have been identified as much more typical. Michael Type J Donor thickener polyesters contain functional medium-chain ß-dicarboml functional esters that are methylene groups Activated Michael donors capable of subjecting Michael Ad-on reactions with multi-functional Michael acceptor molecules to achieve thickening of the pasta. Typical example gummers of this kind are given below: 1. 1878-1: res to MichaeL thickener Type I formed at React 5 moles of diethyl malonate with 2 moles of diethylene glycol and 2 moles of dipropylene glycol by ester exchange. 2. 1878-3: Michael Type I thickener resin formed by reacting 3 moles of diethylmalonate and one mole of fumaric acid with 3 moles of diethylene glycol. These Type 1 materials provide rapid thickening under catalysis bases in the presence of polyfunctional acceptors such as TMPTA and unsaturated polyesters. Type I thickening polyesters can be prepared with fumarate groups (example 1878-3 above). These resins are self-reactive and exhibit rapid thickening speeds. Type II Michael Donor Thickening Polymers are based on polyester diols or polyols that are terminated with acetoacetate functionalities. By way of example, the acetoacetate end groups of the polyester initially react with the polyacrylate monomer to create pendant acrylate end groups. As the thickening proceeds, some of the linked acrylate functionalities are attacked by acetoacetate moieties attached to other acetoacetate bearing chains. This process links two chains together leading to the extension in the viscosity building chain. In a parallel process, the remaining active interchain hydrogens present in the bonds in the extended prepolymer in the chain becomes activated and reacts with accessible Michael donors to facilitate cross-linking or side-chain joining of functional polyacrylate monomer at the same time. It is believed that polymers developed in this way have high levels of chain extension and high levels of side group acupuncture functionalities that can provide crosslinking during the curing of the prepregged sheet. It is believed that this last process is the key to achieving the need for module construction for the development of high surface hardness (Barcol hardness) in the curing compound in the resulting proper place. The components of the T Lpo 1 systems tend to carry desired crosslinking to provide mature preimpregnated sheets with dimensional stability L, including stamping resistance and small diameter bending capacity, while the Type L system components provide hardness due to its extension capabilities in the chain. Additional Type II Michael Donor thickener oligomers having terminal β-dicarboxylic functionalities greater than two include: Propane-1,1,1-triyltrimeti i tris (acetoacetate (AATMP) from Lonza, Inc. Donor Thickener Polymers Michael include Additional free radical polymers are believed to have pendant side chain β-dicarbonyl functionality. Such systems provide. Cure impregnated leaf impregnation, flexibility, and crack interception capability that allow the bonding of the veneers of the pre-impregnated sheets onto the low radius radius curvatures. An example of this type of functionalized acrylate is the experimental resin, 7401-172: The resin was produced by the free radical polymerization of a mixture of 2-ethylhexyl acrylate, 2-acetoacetoxyethyl methacrylate formulated in a 95 weight percent ratio /5. The resulting polymer was diluted by the addition of 20 percent 1,6-hexanediol diacrylate. This thickening agent resin was used much more effectively when extended in the chain by reaction with other acceptors and flexible Michael Donors before mixing and the region with the remainder of the CIPS prepreg. Subclasses of Michael Type II thickening agents have been identified which create objective performance of the desired CIPS prepreg properties. These include: Type II Cristalline Thickeners: This class is exemplified by hydrogenated bisphenol A diacetoacetate. Thickening reactions of the paste containing this agent They can produce pre-impregnated sheets that have desired stiffness for processing during installation, but sufficient flexibility to allow flexing shapes! on the curvatures of the substrate. Pre-impregnated sheets containing this agent can also produce high surface quality installations that require minimal finishing. Also, pre-impregnated sheet systems containing this agent exhibit minimal shrinkage upon curing. as a result of the polymer microstructure of the mature pulp and the fast curing at the high Barcol Hardness values. These performance benefits appear to be derived from the structure and conformational purity of the structural component of hydrogenated bisphenol A of this thickener. In mature pulp, the polar and unbound interactions between the constituents of hydrogenated bisphenol A provides moduli to provide rigidity, but the weakness of the interaction allows performance with minimal force. The desirable shrinkage and curing speed effects also tend to be based on the microstructure of the near final structure of the prepreg sheet. Other crystalline diols useful in this procedure include: 1, -dimethylolbenzene, neopentyl glycol, and 1,4-cyclohexanediol. A second class of Michael Type II Donor thickeners serves as bending agents to increase the formability and hardness of the bending of the pre-impregnated sheet Examples of these can be based on polyester, polyether, and polyurethane diols and other extended systems in the chain. Type II flexing agents include: Flexible Type Polyester Type II Michael Donor Thickening Agents: This class is exemplified by the following oligomer compositions: 1. 1848-10: Michael Thickening Resin is formed by the reaction of 4 moles of diethylene glycol with 3 moles of phthalic anhydride to produce a polyester diol which is then reacted with 2 moles of ethylacetoacetate by ester exchange. 2. 1878-12: It is formed by reacting 1.5 mol per diol of propoxylated hydroxyl bisphenol A with 2 moles of ethylacetoacetate by ester exchange. 3. 1878-14: It was formed by reacting 4 moles of diethylene glycol with 3 moles of maleic anhydride to produce a polyester diol. Reacting the diol with cyclopentadiene to produce nadic polyester, and reacting the polyester with 2 moles of ethylacetoacetate by ester exchange. 4. 7418-12: It is formed by reacting diol of polycaprolactone (1000 Mw Tone 2221 (Dow)) with two moles of t-butylacetoacetate by ester exchange. Michael Type II Flexible Polyester Donor Thickening Agents: This class is exemplified by the following oligomer compositions: 1. 7418-1: It is formed by reacting the polypropylene oxide ether diol (1000 Mw Poly G 55-112 (Arch Chemicals)) with two moles of t-butylacetoacetate. 2. 7418-121: It is formed by reacting diol of polypropylene glycol (425 Mw Arcol Polyol PPG 425) with two moles of t-butylacetoacetate. Michael Type Flexible Donor Type II Thickening Agents: This class uses the diverse range of polyurethane diols that can be prepared by forming polyisocyanates and available diols. Preferred are polyurethane diols prepared from aliphatic diisocyanates, such as isophorone diisocyanate (IPDI) and hydrogenated diphenylmethane diiocyanate (HMDI).

Aromatic diisocyanates are an option for use in flexible urethane thickening agents for pre-impregnated sheets based on colored yellow or carbon fillers. Useful diols in the preparation of donors of Type II include: polyester diols based on diacid-diol condensations as well as polyester diols based on diol extensions using caprolactone, polyester diols (polyalkylene oxide dioles based on diol extensions using propylene oxide, ethylene oxide) and its mixed systems; polyether polyols based on diol extensions using open ring polymerization of tetrahydrofuran; crystalline diols of the type described in the foregoing. The urethane diols described above can be reacted with t-butylacetate to produce the objective Type II Michael Donor systems. It should be noted that all free diisocyanate groups must be extended prior to the exchange of acetoacetate ester since the residual dibutyl tin dilaurate catalyst of the diisocyanate groups will result in product thickening and gelling through the isocilanate reaction of the Donor of Michael. Monofunctional Michael acceptors-included in this group are alkyl acrylates having methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, f-butyl, ethylhexyl, isobornyl groups, and the like. These materials can be added at any point in the formation of the paste, or ripening periods and as reactive diluents to aid processing and as mobile reagents for to facilitate the maturation process of the reactive pre-impregnated leaf paste or the conversion of the final free radical prepreg sheet to the plating of the solid surface. This class of Michael Acceptor also moderates cross-linking and chain extension processes in the paste thickening process by acting as terminating agents. Monofunctional and polyfunctional methacrylate esters having the same constituents as the established acrylates of this disclosure are subjected to the addition of Michael at slower speeds and may have higher speed of survival in the thickening stage of the pulp, but maintain the benefits established to the final curing stage. A second class of monomeric Michael Acceptor is alkyl fumarates. These can be simple alkyl esters, or they can be disubstituted analogs of unsaturated carboxylic acids, such as fumaric acid, which utilize diethylmalonate or diacetoacetate. Michael Polifunctional acceptors - based on oligomeric di- or higher functional acrylates: of course, these oligomers and polymers can be discussed as serving as the reactive material in the polymerizable component. Contents in that class are: Difunctional alkyl acrylates: this group includes functional diacrylates derived from primary, secondary and tertiary aliphatic diol combinations of C-1 through C-15. Members of this class include: 1,6-hexanediol diacylate, 2-methyl-1, 3-propane diacrylate, 2,2'-dimethyl-1,3-propane diacrylate, and the like. Crystal diacrylates: This group includes diacrylates derived from crystalline diols. This class is simplified by the hydrogenated bisphenol A diacrylate. Paste thickener reactions containing this agent can produce pre-impregnated sheets having desired stiffness to process during installation, but sufficient flexibility to allow conformal flexure over the curvatures of the substrate. Pre-impregnated sheets containing this agent can also be produced for high surface quality installations that require minimal finishing. Also, systems containing this agent exhibit minimal shrinkage upon curing as a result of the mature pulp polymer microstructure and fast curing for Barcol Hardness values. These performance benefits seem to be derived from the structure and conformational purity of the hydrogenated bisphenol A structure component of this thickener. In mature pasta, polar and unbound interactions between the constituents of bisphenol A provide modules to provide rigidity, but weak interactions intermolecular allow performance with minimal force. The desirable shrinkage and curing speed effects are also based on the microstructure of the final near structure of the prepreg sheet. Other crystalline diols useful in this process include: extensions of hydrogenated bisphenol A caprolactone, hydrogenated alkyl functional derivatives of bisphenol A such as those produced from substitutions of styrene and alkylstyrene, hydrogenated 2,6-naphthalenediol, 1,4-dimethylolbenzene, neopentyl glycol , 1-cyclohexane diol and diols derived from dicyclopentadiene, alkoxylated bisphenol A, vinyl acrylic esters, diisocyanate adducts with 2-hydroxyethyl acrylate (stoichiometry 1: 2) and diisocyanate adducts with 2-hydroxyethyl acrylate (stoichiometry 1: 1) further reacted with crystalline diols. Flexible diacrylates: This group includes urethane dichlorides, polyester diacrylates and polyether diacrylates. Flexible urethane diacrylates: This class uses the diverse range of polyurethane precursors including polyisocyanates, diols, and functional monohydroxy acrylates. Polyurethanes useful for the preparation of flexible urethane diacrylates include aliphatic diisocyanates such as isophorone diisocyanate (IPDI) and hydrogenated diphenyl methane diisocyanate (HMDI).

Aromatic diisocyanates are an option for use in flexible urethane thickening agents for pre-impregnated sheets based on a filler capable of covering, supplementing the slight yellowness observed with the use of aromatic diisocyanate. Diols useful for the preparation of flexible urethane diacrylates include polyether diols based on diacid diol condensations as well as polyester diols based on diol extensions using caprolactone, polyether diols including polyalkylene oxide diols based on diol extensions. prepared using propylene dioxide, ethylene oxide, and their mixed systems; polyether polyols based on diol extensions using open ring polymerization of tetrahydrofuran; crystalline diols of the type described in the foregoing. These diols can be reacted with diisocyanates in compensated stoichiometries to provide either diisocyanate or hydroxyl terminal polyurethanes. The hydroxyl terminal polyurethane systems can be acrylated using direct acrylic acid esterification, by transesterification with acrylic monoesters, including t-butyl acrylate, or acrylic anhydride. Isocyanate terminal polyurethane can be reacted with monofunctional acrylates (2-hydroxyethyl acrylate) in a post-reaction stage to achieve acrylic termination.

Flexible polyether diacrylates: This class is based on diols prepared from diacid-diol condensations or by transesterification of diester-diol as well as polyester diols based on diol extensions using caprolactone. These systems can be replaced with acrylates by reacting their hydroxyl groups with acrylic anhydride, by transesterification using activated acrylates such as t-butyl acrylate or by reaction with acryloyl chloride. Diacrylates of this type can be used to form hard, flexible CIPS pre-impregnated sheets. Flexible polyether diacrylates: This class is based on polyether diols prepared by the diol extensions using alkylene oxides or polytetrahydrofuran diols. These can be substituted with acrylate by direct esterification using acrylic acid, acryloyl chloride, or acrylic anhydride, or by transesterification of ester is methyl-, ethyl- or t-butyl acrylics. One member of this class is SR610, polyethylene glycol diacrylate, produced by Sartomer Company, Inc. Functional tri- and higher acrylates: This class is based on star polyols such as trimethylolpropane, pentaerythritol, and linear triols such as glycerin. These acrylates are the key to maintaining a high reactive olefin concentration in the mature pre-impregnated sheet, which is the key to the rate of free radical cure and hardness and strength based on final composite cross-linking density upon curing. Crystal functional tri- and higher acrylates: This class of Michael Donors is based on crystalline monomers that produce modules built into the mature CIPS pre-impregnated sheets, but provide latent flexibility over the failure-free resistance. Members of this class include Sartomer 368, tris (2-hydroxyethyl) isocyanurate triacrylate from Sartomer Company, Inc. and polyfunctional methylolmelamine acrylates. Unsaturated polyesters: This kind of Acceptor of Michael relies on unsaturated polyesters derived from combinations of unsaturated diacids or their anhydrides (such as fumaric acid or maleic anhydride), and aliphatic or aromatic acids or their anhydrides, and a range of diols including ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol. , 2-methyl-1,3-propanediol, 1,3-propanediol, and other diols. The unsaturated polyesters useful in this disclosure are designed by controlling stoichiometry to produce polyesters with low carboxyl numbers. This is necessary in order to minimize the use of high levels of basic catalyst, which may adversely affect final compound properties. Content The residual carboxyl can be further controlled by the use of reagents such as dialkyl or diarylcarbodiimides or by other carboxyl reactive agents. The reactivity of the unsaturated polyesters can be modulated by the partial reduction of unsaturation levels by reaction of the polyester with cyclopentadiene. Michael's Catalyst Systems. Catalysts for the Michael Reaction include those capable of converting reactive methylenes to nucleophiles capable of binding the formation with activated olefins. This group includes a combination of several: 1. Metal of Group I and II: (1) hydroxides, (2) hydrides, (3) carbonates, (4) alkoxides or phenoxides, (5) amides, such as those produced by the reaction of metal with ammonia, amines or amides, (6) salts containing anions of reactive methylene compounds such as those derived from methylenes aa electron extraction groups (including: nitrile, sulfonate, sulfoxide sulfate sulfone, nitro, carboxyl , (tri-, di-, and mono-) halocarbon, carbonyl, etc. 2. Resistant organic bases: (1) amines, (2) amidines and their salts (such as DBU and formed 1,8-diazabicyclo-octanoate [ 5.4.0] undec-7-ene), (3) guanidines, (4) ammonium, alkylammonium, arylammonium or alkylarylammonium hydroxide, (5) ammonium, alkylammonium, arylammonium or alkylarylammonium fluorides, (6) ammonium, alkylammonium, arylammonium or alkylarylammonium alkoxides, (7) ammonium, alkylammonium, arylammonium or alkylarylammonium phenoxides, ( 8) t-phosphines substituted with alkyl-, aryl-, or alkylaryl. 3. catalyst system comprised of quaternary salt and epoxy portion (such as glycidyl methacrylate, trimethylolpropane triglycidyl ether, diglycidyl ether of bisphenol A and the like). Quaternary salts include: (1) alkylammonium or alkylarylammonium halides, (2) phosphonium halides, (3) phosphonium acetates, (4) ammonium, phosphonium or suphonium fluorborate. The catalysis of Michael's reaction in the CIPS paste applications is different than in the unfilled reactions. Catalysts such as aqueous sodium hydroxide in some cases fail to initiate the reaction. In contrast, the same resins show fast reaction rates in the presence of fillers such as ATH. While it is not desired to be related by theory, it can be speculated that the aqueous catalyst becomes encapsulated in a second phase and incapable of participating in the catalysis of the desired reaction. When an appropriate filler is used, it serves co or a catalyst dispersant and transfer agent that allows the formation of Michael Donor anions in reagents of the components containing reactive methylene in the mixture. This phenomenon returns the pure, aqueous and alcoholic solutions of highly polar salts to become effective in the desired paste thickening reaction. The systems of pre-impregnated sheets cured in the proper place left by themselves to efficient modification with other additives capable of imparting desired decorative patterns that stimulate granite and other naturally occurring decorative solid surface materials. These additives offer domain variations based on size, shape, color, translucency and orientation. Additive materials can be plate structures, crystalline, mica-like, amorphous minerals such as glass flake, or any range of ground minerals that include granite, or quartz. Synthetic and natural minerals and glasses are available in various colors imparted by very small amounts of impurities or by thin surface depositions and color or reflectance producing agents. Similarly, polymeric flake materials are available with dye or pigment modification to achieve desired color effects and / or reflectivity of metal deposition and Similar. These additives can also be produced from polymer-bound fillers that can be variations on the mineral-based and polymer-based additives described above. In addition to the components listed in the above, the photocurable and thermosetting compositions used herein may contain components normally used in thermosetting resins including fibers, biocides, hardeners, plasticizers, pigments, wetting agents and the like. Composition to form the prepreg sheet comprising; 1. a thermosetting resin or prepolymer, 2. a reactive material, 3. a photoinitiator activated in visible light, a peroxide or mixtures thereof, 4. a filler, 5. a curing rate increaser, 6. a reactive thickener , optionally a shelf life extender. Typically the amounts of the various components in the compositions of which the prepregs are obtained are as follows wherein the ranges are given in percent by weight of the total composition: A. The polymerizable component is typically from about 15 to about 55 percent and more typically from about 25 to about 45 percent; B. The filler component is typically from about 45 to about 85 percent, and more typically from about 50 to about 75 percent; and C. The active component is typically about 0.2 to 3 percent, and more typically about 0.3 to about 2 percent. For the crosslinked CIPS prepreg sheet containing a reactive thickener, the polymerizable component A comprises the following components and amounts: 1. a reactive material typically in amounts of about 30 to about 90 more typically about 40 to about 85 percent; and 2. a reactive thickening agent typically in amounts of about 10 to about 70 percent, and more typically about 15 to about 60 percent. Please note that in some embodiments a component, for example one containing an active olefin component, can act as both a thickening agent participating in the thickening step as agents of curing in the curing stage of final crosslinking. Also, please keep in mind that thermoplastics such as polymethylmethacrylate do not participate in the final crosslinking curing stage but can be employed in the compositions. The most typical ranges of the components in the polymerizable component may differ depending on the particular type of the reactive thickening agent. For example, for a CIPS prepreg containing a reactive Michael thickener and optionally a reactive thermoplastic polymer, the polymerizable component comprises the following components and amounts: 1. A thermoplastic resin component reactive optional typically in amounts of 0 to about 70 and more typically from 0 to about 60 percent. 2. a reactive material typically in amounts of about 20 to about 90 and more typically about 30 to about 80 percent; and 3. a reactive thickener typically in amounts of about 5 to about 70 and more typically about 5 to about 60 percent. A typical example is shown in the Table below: All the components defined later in the present. Component 1 is the reactive thickener (15.4% of the total resin). Component 2 is the reactive material (46.1% of the total resin). Components 5 and 10 are unsaturated reactive thermoplastic reams (38% of the total resin). SR 610 is a polyether diacrylate, 914 VE is an acrylic vinyl ester made from a diepoxy (E 828) and acrylic acid. For CIPS prepreg containing a reactive urethane thickener and optionally a reactive thermoplastic polymer, component A polimepzable comprises the following components and amounts: 1. A thermoplastic resin component reactive optional typically in amounts of 0 to about 60 and more typically from 0 to about 30 percent; a reactive material typically in amounts of about 20 to about 90 and more typically about 30 to about 80 percent; and a reactive thickener typically in amounts of about 5 to about 70 and more typically from about 5 to about 60 percent. A typical example is shown in the Table below: 7428-47 No. Component gm. % 23.20 Description Monomer TMPTA 6.00 2.00 7.73 Reagent D N330A Polnsocianato Vorinol 800 1.00 3.87 Po ol Activated Zolidine MS 0.50 1.93 Water Scrubber 1-819 0.18 Photoinitiator 0.70 0.18 0.70 T-12 Urethane Catalyst 16.00 61.87 GE 241 25.86 Total 100.00 Filler ees All the components are defined later in the present. Component 1 is the reactive material (66.6% total resin) Components 2 and 3 are the reactive thickener (33.3% total resin) Component 3 is a tetra-ol monomer derived from ethylenediamine and ethylene oxide. For the pre-impregnated sheet of thermoplastic CIPS containing a thickener of reactive epoxy CIPS and optionally a reactive thermoplastic polymer, the polymerizable component A pol comprises the following components and amounts: 1. an optional reactive thermoplastic resin component typically in amounts of 0 to about 60 and more typically of 0 to about 30 hundred; 2. a reactive material typically in amounts of about 20 to about 90 and more typically about 30 to about 80 percent; and 3. a reactive thickener typically in amounts of about 5 to about 70 and more typically about 5 to about 60 percent. A typical example is shown in the Table below: For a volatile prepreg sheet paste the polymerizable component A comprises the following components and amounts based on the total composition: a. a thermosetting resin or prepolymer typically in amounts of from about 3 to about 20 percent and more typically from about 3 to about 15 percent; b. a reactive material typically in amounts of from about 5 to about 30 and more typically from about 10 to about 20 percent; c. a reactive thickening agent of the group that includes: i. a Michael Addition reactive thickener comprised of a methylene Michael donor reactive of β-dicarbonyl in amounts of about 3 to about 25 percent and more typically about 5 to about 20 percent; and an activated functional olefin Michael acceptor in amounts of from about 4 to about 25 and more typically from about 6 to about 20 hundred; or ii. an epoxy reactive thickener comprised of an epoxy functional monomer, or oligomer typically in amounts of about 3 to about 25 percent, and more typically about 5 to about 20 percent; and an epoxy reactive monomer or oligomer typically in amounts of about 1.5 to about 20 percent and more typically about 2 to about 15 percent; or iii. an isocyanate functional reactive thickener comprised of a polyisocyanate or polyisocyanate-terminated oligomer typically in amounts of from about 2.5 to about 25 percent and more typically from about 5 to about 20 percent and an isocyanate or oligomer reactive monomer typically in amounts of about 2.5 to about 25 percent; and more typically from about 5 to about 20 percent. The additive component C of the compositions of which prepreg sheets are obtained typically comprises the following components and amounts: a. an initiating component that comprises based on the total composition: i. a photoinitiator typically in amounts of from about 0.001 to about 0.2 and more typically from about 0.002 to about 0.15 percent; and typically it is activated with visible light, or ii. a peroxide typically in amounts of about 0.05 to about 1 and more typically about 0.05 to about 0.5 percent; or iii photoinitiator-peroxide mixtures typically in amounts from about 0.001 to about 0.2, and more typically from about 0.002 to about 0.14 percent and even more typically from about 0.009 to about 0.1 percent; b. a specific reactive thickener catalyst a, i. a Michael Addition Reactive Thickener typically in amounts of about 0.025 to about 0.25 and more typically from about 0.05 to about 0.15 percent; or ii. an epoxy reactive thickener catalyst typically in amounts of from about 0.1 to about 2 percent and more typically from about 0.1 to about 1.5 percent; or iii. an isocyanate functional reactive thickener catalyst typically in amounts of 0.1 to about 2 and more typically from about 0.2 to about 1.5 percent; c. optionally an air release agent / humectant component and when employed is typically in amounts of from about 0.5 to about 1.5 and more typically from about 0.1 to about 1 percent; d. optionally a stabilizing component and when employed is typically in amounts of about 10 to about 600 ppm and more typically about 20 ppm to about 400 ppm based on the reactive monomer component; Y and. optionally a bending component and when such is employed is typically in amounts of from-about 2. to about 25 and more typically from about 2.5 to about 20 percent. Wetting agents are typically highly polar species capable of decreasing interfacial surface film interactions that interfere with bubble coalescence and growth, and the ultimate aggression of the CIPS paste by degassing processes. Examples include materials such as BMC 806 described herein. Typically these additives contain a polar surface active carrier solvent such as an aliphatic ketone (ie methylethyl ketone) and minor amounts of a secondary surface tension lowering agent such as an alkoxysiloxane. The prepregs can be prepared by a number of different methods. In the direct mixing method a thermoplastic paste is prepared using typical molding preparation techniques. A high viscosity thermosetting resin and a low volatility reactive monomer, such as TMPTA, are combined using high touch mixing at room temperature. The remaining ingredients are added and mixed until They combine and no visible trapped air bubbles remain. The release of trapped air can be facilitated by the use of vacuum. A prepreg sheet is then formed between the two layers of film. Because oxygen in many cases inhibits the crosslinking reaction of the thermosetting prepreg sheet, one of the films must be permeable to oxygen to help increase the shelf life of the prepreg sheet. However, there are pre-impregnated leaf systems according to the present disclosure that exhibit a degree of natural oxygen barrier performance on the face of the pre-impregnated sheet formed on the Mylar carrier sheet. These systems heal quickly under sunlight. It is believed that the impermeability of the surface of the prepreg and its composition are factors. Example 7B (attached) is a rigid flexible class of pre-impregnated sheet of CIPS that easily cures under sunlight to a Barcol number. 50 in a curing period of < 30 minutes without the benefit of an oxygen barrier film. An example of an apparatus for forming the plastic pre-impregnated sheet sheet between two layers of film is shown in Figure 1. In Figure 1 the batch mixer or screw extruder can be modified to allow the application of a vacuum during the mixed Another method for preparing a prepreg sheet, The emptying method involves the use of a volatile polymer mixture containing a low viscosity, reactive monomer. The addition of subsequent components can be simultaneous or sequential. An example of a sequential addition would be as follows. The filler such as ATH is added to the prepolymer mixture with mixing. A wetting agent is then added to the mixture to aid in the release of trapped air. The release of trapped air is facilitated by the use of vacuum and vibration. Photoinitiators, peroxide, additives of reaction enhancers and other additives can be added at this point with mixing and degassing. The maturation prepolymers / thickeners or associative thickeners are then added, and then the mixture is stripped. The degassed paste can then be mixed at room temperature, or at a slightly elevated temperature (for example 25-45 ° C) to allow the ripening of the pulp to the voidable stage. This stage is the point in the ripening process in the pulp in which the pulp will then be emptied, proceeding to a preimpregnated sheet that can be used with this characteristic that is defined by the hardening time required to be manageable, as well as the mechanics of the sheet. prepreg, flexibility, and other desirable prepreg sheet performance requirements. The maturation stage of the pasta can facilitate achieving desirable properties in the pre-impregnated sheet. For example, the examples included in the application demonstrate the pre-reaction of Michael's donors and Donors extended them in the chain leading to increased flexibility, hardness, and resistance to irregular cracking all of which are desirable for installation and ultimate performance of the solid surface compounds of CIPS plating. The mixture can then be emptied onto a film using conventional motion doctor blade / band methods, and covered with a second film. Typically, the cast sheet is formed to a desired thickness, cut and allowed to mature into a dimensionally stable preimpregnated sheet. In one option the stock is allowed to thicken prior to the addition of a release film. The process can be carried out in a batch or continuous process. A schematic representation of the process of the voidable prepreg sheet is shown in Figure 2. A continuous process for making the sheet pre-impregnated depends on stopping a rapid thickening reaction capable of generating the sheet pre-impregnated sheet having desired properties in a short period of time . It has been found that concentrated sodium hydroxide is capable of catalyzing the resins of this disclosure at rates leading to a commercially desirable continuous process. While others catalysts such as potassium hydroxide, and organic bases such as DBU do not achieve the thickening ratios of the prepreg leaf paste observed using the caustic system at ambient temperatures. It is believed that the ATH acts as a co-catalyst in combination with the caustic to cause the polymers not to be easily achieved by other methods. An auxiliary catalyst useful in the continuous process is prepared by reacting diethylmalonate with sodium hydroxide. This catalyst is the sodium salt of the Michael Addition monomer. It appears to provide a mobile catalyst component that mitigates the need for agitation during advancement of the prepreg sheet stock. The pre-impregnated sheet pastes prepared without the auxiliary catalyst component must be vigorously stirred as they are thickened. By using the auxiliary catalyst, the pastes can be emptied at lower levels of advancement since it is believed that the mobile catalyst allows the generation of anion at new sites at a faster rate. In some cases, without the auxiliary catalyst, the loss of mobility in the polymer system resulting from molecular weight accumulation stops or decreases the reaction at normal ambient temperatures. This is undesirable in a continuous process in this case, the ripening paste in the casting can be made capable of accelerated maturation by heating in order to meet the objectives of the continuous process manufacturing ratio. The auxiliary catalyst fulfills another function in the development of the pre-impregnated sheet. Type II thickening resins are typically polyesters terminated in acetoacetate. These materials are subjected to the Michael Addition thickening via extensions in the polyacrylate chain in which two or more different Type II resin chains are subjected to the addition of Michael with the same polyfunctional acrylate. Under the high pH required for this reaction the acetoacetate termination groups are subjected to the color-body formation reactions (aldol condensations and the like). It is believed that the coloration is released in the presence of metal impurities produced in the polyfunctional acetoacetate derivatives during processing at elevated temperatures in high alloy metal reactor systems. For example, good sustained color performance is achieved in the pre-impregnated sheets produced with the Michael Donors produced in the glass, or at low temperatures. It is believed that the malonic color enhancement effect may come from its ability to preferentially complex with the metal ions responsible for the catalysis of the color forming reactions (aldol condensations and the like). Accordingly, the use of auxiliary catalyst decreases the potential for the formation of colored by-product. A schematic representation of the continuous casting process is shown in Figure 3. The continuous casting process for producing the prepreg sheet involves rapid thickening (step B) of the prepreg pre-polymer component. It is believed to involve a selective Michael Addition reaction involving Michael's Donor polyesters and Michael's acceptor components of the prepolymer resin system. This process is facilitated by using selected basic catalyst combinations that provide a desired combination of reaction rate and stage B polymer morphology. The resulting stage B prepolymer provides a prepreg sheet structure having aesthetic, handling and curing properties latent which include: tear strength, hardness, compressive strength, low color levels, dimensional stability, and performance of the cured pre-impregnated sheet (mechanical strength, hardness, color stability, high curing speed and curing depth) . The thickening or process of stage B proceeds at a speed conducive to the commercial process time to produce a sheet product capable of being supplied in the form of sheet or roll. The continuous casting process involves the mixing filler and pre-polymer system composed of Michael Thickening (donor) and the activated vinyl Michael (acceptor) plus the additive package with a portion of the catalyst component of Michael Addition. Immature pulp has a low viscosity that allows vacuum degassing, vibration, settling or a combination of these methods. The degassed pulp is catalyzed in a maturing reactor at a point where the viscosity is allowed to accumulate to a level required for the emptying of the pulp. Mixing during this process is achieved using ultrasonic or mechanical mixing designed to minimize hole generation. The coating viscosity of the target pulp film is maintained in the ripening reactor by using a continuous addition of middle maturity pulp to stabilize the viscosity buildup. The paste in the coating viscosity of the film is transferred to a suitably designed container to allow fluid coating on the carrier film by a number of possible process configurations including roll transfer, scraper box, etc. The coating line is designed to allow heating of the coated film to accelerate the viscosity accumulation of the paste. The use of other mobile catalysts such as DBU with the auxiliary catalyst provides increased thermal advance of the pulp over the ripening line which is necessary for the high process yield without adversely affecting the stability of the coating paste of the film at room temperature. The use of other mobile catalysts such as DBU with the auxiliary catalyst provides increased thermal advance of the paste over the ripening line which is desirable for high process performance without adversely affecting the stability of the film coating paste at room temperature . The combination of refined catalyst provides advancement of the prepreg sheet to a highly desirable crosslink density (necessary for dimensional stability) and the flexibility of coated stock (necessary for installation surface conformability). The mature film-paste composite passes through a cooling section and the deliberation film is added. The product can be rolled, or cut laterally to stack it into uniform sheet lengths. In a variation of the above methods, pre-impregnated sheet pastes that are thickened to the consistency of pre-impregnated thermoplastic sheets, which are almost stamping free, can be prepared using Michael's Additions of the sheet method emptied prepreg In Example 8 a prepreg sheet formulation of casting method was modified by raising its filler load. The advance of the system to form a plastic paste was achieved by the incremental addition of caustic material followed by kneading. The plastic paste that is heavy could be formed into a ball and comprised of a sheet of 100 mil thick. The description provides methods for preparing cured articles in the appropriate place of solid surface useful in commercial applications such as floor and wall tiles, top covers, cabinet contours of tub contours, sinks and baths of the aforementioned pre-impregnated sheets. in the above. According to the description, the pre-impregnated sheets are cured to a desired hardness and strength using a radiation curing process. The radiation source can be ambient light or an increased visible light source such as a halogen lamp and / or IR irradiation with the contribution of IR (heat) which is a critical component necessary for achieving the desired cure depth and crosslink density. The latter method also provides ease of curing to more pre-impregnated optically dense sheet systems. A key element of this system is the increase in curing speed that results from the IR heating of the compound. This effect can be supplemented additionally when heating the compound at the speed of the exotherm development once the radiation source is applied. The CIPS curing system of white light at room temperature can be improved by using a 500 watt halogen light cure. When halogen light is used, the resistance performance of the coupons produced is significantly higher. When the optical density is very large for the appreciable photoinitiation, the peroxide-based initiation, supplemented by the additives of increase in curing speed, is responsible. Thermal curing / combined curing is desirable to achieve the maximum curing potential in the system, although very rapid heating may result in a rigid product as a result of internal stress developed as a result of differential curing rates. In pre-impregnated sheet systems such as the unsaturated polyester-acrylic system which is inhibited by the presence of oxygen, the oxygen impermeable sheet material such as Mylar® can be used as the carrier membrane in the production of the prepreg sheet. A prepreg coated in this way cures quickly on exposure to irradiation since the photoinitiator system of the prepreg sheet generates radicals that deplete the inhibiting oxygen, and the film prevents the infusion of fresh oxygen. In cases where the sheet Prepreg has a complete configuration, a liquid-based film-forming solution or non-reactive emulsion with the pre-impregnated sheet can be applied to an exposed surface. The coating is then allowed to cure to an impermeable coating of oxygen. An example of such material includes aqueous polyethylene vinyl acetate (EVA) emulsions. These EVA emulsions are readily commercially available as wood glues. The emulsions can be applied by spray, brush application, etc. The pre-impregnated sheets can be formulated to look like marble, tile, granite, cultivated marble, other types of pieties etc. when it heals. The pre-impregnated sheets can be used as a veneer of wood for any rigid substrate. The thickness of the solid surface coating is typically 90 to 160 mils. Alternatively it can be from 100 to 150 mils. The mature, uncured prepreg can be bonded to a substrate and cured in the proper place or cut to fit, cured and then adhered to a substrate. The cured prepreg can be attached to a substrate by any appropriate means. Examples of media include adhesives in general, which include adhesives based on epoxy and urethane; double-sided adhesive tapes on both sheets and strips; partially cured rubber tapes such as brand tape PLIOSEAL®, commercially available from Ashland Inc., or mortar. Having thus described the description, the following examples are provided for purposes of illustration and should not be considered as limiting the scope of the description. Definition of AATMP compounds: LONZAMON® AATMP, tris (propan-1, 1, 1-triyltrimethyl acetoacetate from Lonza, Inc. Aerosil® 100: Degussa smoked silica Aerosil® 200: Degussa smoked silica Auxiliary catalyst: ready to make reacting diethylmalonate with 50% NaOH Pigment blue: Phthalo blue RS of Polytrend Industrial Colorants BMC 806: Release of air BMC 806, mixture of 2,6-dimethyl-4-heptanono and 4,6-dimethyl-2-heptanone from Bergen Materials Corp. CN968: Urethane acrylate Sartomer CN968, urethane hexaacrylate oligomer based on aliphatic polyester from Sartomer Company, Inc. DBU: 1,8-diazabicyclo [5.4.0] undec-7-ene DETA: diethylenetriamine DMAEMA: 2- dimethylaminoethyl methacrylate D N330A: Desmodur® N330A: Aliphatic polyisocyanate (HDI trimer) from Bayer Material Science. CN 120: E828 Epoxy Diacrylate: EPON ™ 828 from The Dow Chemical Company. EAA: ethyl acetate acetoacetate GE 241: Granite Elite 241 from J.M. Huber Corporation, Huber Engineered Materials H2BisA: Diacetoacetal of hydrogenated bisphenol A HDDA: hexanediol diacrylate Irgacure® 819: bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide of Ciba Specialty Chemicals 1-819: Irgacure® 819 12% SR285 Lupersol 256: 2, 5-dimethyl-2, 5-di- (2-ethylhexanoylperoxy) hexane from Atofina Chemicals, Inc. -256: Lupersol 256 Mod M: Magnesium dioxide thickening agent provided by Plasticolors, Inc. OE 431: Onyx Elite® 431: JM alumina trihydrate filler Huber Corporation, Huber Engineered Materials PDO: Luperox® 26M50, 50% p-butyl peroxy-2-hexanoate in pyroclastic minerlase essences PI-2: Darocure 1173 / Genocure TPO (80/20%) PMMA poly (methyl methacrylate) ELVACITE ® 2044 produced by: Lucite International, Inc. Q6585: unsaturated polyester of a mixture of diols and maleic anhydride from Ashland Performance Materials Thiourea: l-acetyl-2-thiourea T-12: dibutyltin dilaurate TMPDE: ethertrimethylolpropane diallyl 80. 2,2-bis (allyloxymethyl) -butan-1-ol Perstorp Specialty Chemicals AB. TMPTA: trimethylolpropane triacrylate, Sartomer 351, from Sartomer Company, Inc. TS: trimethylolpropane tris (3-thiopropionate) 914 VE: Vinyl ester formed from EPON ™ 828 and acrylic acid. Vorinol ™ 800: aliphatic amine initiated polyol from The Dow Chemical Company. ZOLIDINE® MS-PLUS: Oxazolidine moisture scavenger (3-ethyl-2-methyl-2- (3-methylbutyl) -1, 3-oxazolidine) from ANGUS Chemical Company. SR247: Sartomer 247, neopentyl glycol diacrylate from Sartomer Company, Inc. SR285: Sartomer 285, tetrahydrofurfuryl acrylate from Sartomer Company, Inc. SR349: Sartomer 349, ethoxylated bisphenol A diacrylate (3) from Sartomer Company, Inc. SR368: Sartomer 368, tris (2-hydroxy ethyl) isocyanurate triacrylate from Sartomer Company, Inc. SR415: Sartomer 415, ethoxylated rimethylolpropane triacrylate (20) from Sartomer Company, Inc.

SR506: Sartomer 506, isobornyl acrylate from Sartomer Company, Inc. SR610: Sartomer 610, polyethylene glycol (600) diacrylate, from Sartomer Company, Inc. SR9035: Sartomer 9035, ethoxylated trimethylolpropane triacrylate (15) from Sartomer Company, Inc. TMPTA / AROPOL ™ 7221 (30% / 70%): TMPTA at 30 / AROPOL ™ at 7221 at 70% Plástic 7221: AROPOLTm 7221 Plástic. 1878-1: The polymalonate formed of 5 moles of diethylmalonate, 2 moles of diethylene glycol and 2 moles of dipropylene glycol. 1878-4: Diacetoacetate formed by the transesterification of hydrogenated bisphenol A with 2 moles of t-butylacetoacetate. 1848-10: Micael Type II thickener resin formed by reacting 4 moles of DEG with 3 moles of phthalic anhydride, and finishing the polymer with 2 moles of acetoacetate derivative by exchange of ethyl acetoacetate ester. 1878-12: Propaxylated Bisphenol A Diacetoacetate 1878-14: Diacetoacetate formed by the transesterification of a polyester diol (formed by condensing 4 moles of diethylene glycol and 3 moles of maleic anhydride followed by the reaction with cyclopentadiene for the conversion of unsaturated main chain esters to nadic functionalities) with 2 moles of ethylacetoacetate. 1878-15: Diacetoacetate formed by the transesterification of a polyester diol formed by condensing 4 moles of diethylene glycol and 3 moles of phthalic anhydride with 2 moles of ethylacetoacetate. 7401-172: polymerization of free radicals of a mixture of 2-ethylhexyl acrylate, 2-acetoacetoxyethyl methacrylate formulated in a 95/5 weight percent ratio containing 20% HDDA. Definitions of CIPS. Reagent Thickener: A resin component, prepolymer, or a combination thereof, which is capable of forming a polymer network within the preimpregnated leaf resin component of CIPS during the period of maturation of the paste to provide sheet thickening prepreg increased Organic Reactive Thickening Chemistry: The polymer bond reaction chemistry used in a CIPS paste thickening chemistry examples of which are: a. Michael Thickening: Reactive thickening chemistry based on Michael's Addition reaction. b. Thickened Urethane: Chemistry of reactive thickening based on the isocyanate-alcohol reaction. c. Thickening of Epoxy :. Reactive thickening chemistry based on the reaction of an epoxy group with any co-reactive functionality. Pre-impregnated CIPS Flexible Sheet Plastically deformable (Reticulated): These are pre-impregnated CIPS sheet systems composed of combinations of crystalline extended chain thickener components in combination with prepreg Flexible CIPS The pre-impregnated sheets of this type are rigid, but can be bent to small radii without cracking or cracking. CIPS Resin Prepolymer: A resin that has the ability to undergo a combination of independent processes. One which is the ability to undergo maturation to an intermediate form (stage B) maintained in the pre-impregnated sheet. A second one is the ability to cure to a thermosetting stage by an appropriate secondary process. Maturation of CIPS Paste: A process by which a CIPS paste is catalyzed to allow a thickening reaction to take place to a sufficient degree to allow the emptying of the paste or extrusion into a sheet preimpregnated uniform thick film. This pre-impregnated sheet is capable of undergoing additional thickening, or cross-linking to allow the development of objective properties. Continuous Process of the CIPS Drained Preimpregnated Sheet: A method by which a pre-impregnated sheet of CIPS paste is matured by a continuous process to a stage in which the cast on a carrier film, or a coated band, will give as a result a finished sheet product in a commercially feasible time structure. Continuous Process of CIPS Extruded Pre-Primed Sheet: A method by which a pre-impregnated CIPS sheet slurry is processed in a continuous mixer (such as a Reedco Mixer) under vacuum to provide a thick, low void content paste suitable for extrusion to form a sheet product, with the product optionally having the ability to undergo further maturation subsequent to a finished product. Catalyst or Reagent CIPS Thickener: A component added to the CIPS pre-impregnated leaf slurry that initiates, or promotes, the paste thickening process. Highly Reacted Thickening Network of CIPS: A network formed in the process of maturation of CIPS created by extension in the extensive chain, or another process of cross-linking. Such networks require little additional crosslinking to achieve final curing. Systems of this type are characterized by shrinkage and low flatness maintenance on curing. Comparison Example 1 - Laboratory Preparation of the Prepreg For prepregs, the resin and the reactive monomer (70/30/7221 / TMPTA and TMPTA) were added to a Tripour® vessel and ATH (GE 241) was weighed on top of the resin. The system is mixed with a spatula and transferred to a clean section of the table top. The kneading by hand is used to form the resin filler in a thick paste. Next, an empty glass is used to weigh 1.5 grams of thickener / silica filler (Aerosil® 100). The additives (photoinitiator, peroxide, mercaptan, and amine methacrylate) are weighed on the silica and mixed. The silica-additive mixture is kneaded in the main raisin to create a slightly sticky, high-viscosity paste that has been thoroughly mixed. The paste is then placed between two sheets of the film and rolled into a sheet of uniform thickness. The recommended thickness for the solid surface coating is 100-150 mils. A carrier sheet is Mylar® which remains coupled with the prepreg sheet through an installation process, the second sheet is an easily removed film sheet such as Glad Cling rap. The components of the formulation are given in Table I. Table I Example 2-Development of a Gap-Free Paste (Free of Organic Thickening Chemistry) The pre-impregnated sheet composition described in Table II is produced by an associative thickening process that allows the use of low viscosity resin components to prepare pastes of completely degassed low voids that produced pre-impregnated leaves with low voids on the thickening. Table II The sheet preimpregnated in Example 1 is completely plastic with thickness that is provided by the filler system. In Example 2, the thickening comes from a combination of filler and associative thickening. In the latter case, Mod M is a product that contains magnesium oxide. This component is capable of forming complexes with the free carboxyl groups on the Q6585 polyester chain terminals. Over time the viscosity of the paste grows to convert the pre-impregnated sheet into a hard / flexible consistency. The system described in Example 2 has the advantage over Example 1 since lower viscosity pastes can be used. This example merely demonstrates that the use of low viscosity pastes can achieve degassing to provide low void levels that would be desirable in a CIPS product. Example 3-Formulation and Procedure for a CIPS Preimpregnated Sheet System Free of CIPS Volatile Preparation of the paste: An amount of 40 grams of Q-6585 (65% solids in styrene), 10 grams of styrene and 50 grams of OE 431 are mixed in a centrifuge mixer (FVZ speed mixing) for 1.0 minutes at 2200 rpm. The mixture is degassed for 10 minutes using a vacuum oven at 28.8 inches vacuum. The paste is verified by bubbles by spreading a 1 mil film of a raisin on a glass plate and observing under a microscope at 400X magnification. The system shows a high gap level (bubble). Additional paste components are added including 1.87 grams of BMC 806, 0.80 grams of 1-819, 0.70 grams of Lupersol® 256 and 2.5 grams of Mod M. The resulting composition is mixed for 1.0 minutes at 2200 rpm. The mixture is verified by holes. Very few gaps are noticed. The mixture is then degassed in a vacuum oven at maximum vacuum for 30 seconds. An additional verification for gaps reveals that the mixture is free of gaps.

The mixture is emptied onto a sheet of Mylar® in a pre-impregnated sheet thickness of 60 mils and allowed to thicken for 48 hours. After thickening, a canvas is placed on the exposed face of the pre-impregnated sheet. A nylon release film is placed on the canvas face and the pre-impregnated sheet is placed between two glass plates and compressed to create two parallel and flat surfaces. At this time the prepreg composite is found to be free of distortion and capable of being handled. At this point, the pre-impregnated sheet is suitable for indefinite storage. The canvas used is a fiberglass screen covered with vinyl plastisol that is easily separated from the prepreg sheet leaving a uniform grid pattern. A 2x2 inch square of a top cover material based on the particle board coated with decorative laminate is covered in 2 mils with a 2 part epoxy adhesive on the decorative laminated face. A 2x2-inch piece of the pre-impregnated sheet is prepared by removing the canvas backing. The rear side face of the prepreg sheet is placed in contact with the adhesive treated substrate and pressure is applied to consolidate the interface of the adhesive. After the epoxy is allowed to settle for 5 minutes, the face covered with Mylar® pre-impregnated sheet is exposed to a 500 Watt Halogen Lamp at a distance of 8.5 inches from the glass cover of the lamp for a period of 10 minutes. After curing, the Mylar® is removed. The pre-impregnated sheet cured in the right place has a high gloss surface with a Barcol hardness greater than 50. Results of the Mature Pre-Primed Sheet A sample of the above prepreg is aged at room temperature for a period of 24 days. During that time, the pass thickens beyond the measurement capabilities to > 200 MM cps. The Paste system is not completely cured and remains flexible enough to bend over a mandrel having a radius of 0.125 inches without cracking. The pre-impregnated sheet can be handled without stamping under normal handling. A 2x3-inch rectangle of the pre-impregnated sheet is cut and placed on the surface of a decorative laminate coupon. An acute angle inspection of the pre-impregnated sheet Mylar® film shows no detectable distortion. The reflection of the complex images by the film showed good reproducibility without distortion as well as indicating surface flatness. The support screen-screen is removed from the specimen backing of the pre-impregnated sheet that leaves a uniform grid pattern that covers the backing of the pre-impregnated sheet. A coating of 1-2 thousand of a 5 minute cure, apply 2-part epoxy adhesive to the decorative laminate coupon. The prepreg is placed over the adhesive and light pressure is applied to the surface of the prepreg using a flat surface roller. The pressure is maintained for 5 minutes. Next, the pre-impregnated sheet is cured for a period of 10 minutes under a 500 Watt halogen lamp at a distance of 8.5 inches from the glass filter cover of the lamp. At the end of the curing period, the sample is removed from the lamp and left to stand under ambient light for 10 minutes. The cover film Mylar © is removed to reveal a high gloss finish. An inspection for flatness identical to the initial inspection described above shows retention of flatness. Flatness before and after curing is estimated by observing an objective reflection consisting of a series of parallel lines. The flatness estimation is based on the maintenance of line linearity for reflections through the total sample. The flatness of the pre-impregnated sheet prior to curing was based on the reflection of the Mylar® carrier sheet, while the flatness after curing is estimated by reflection of the cured compound. For the appropriately formed pre-impregnated sheet (top and bottom parallelism of the mature pulp sheet of the pre-impregnated sheet) this "flatness" test indicates the retention of flatness after the composite curing. Example 4- Pre-impregnated Thickened Sheet with the Addition of Michael The following, Table III is a typical paste formulation using the Michael Thickening resin described in the definition of the compounds. Table III The resulting solution contains a mobile Michael anion catalyst. The paste formed from the composition described above is made by the following procedure: the prepolymer resin components (1848-10, TMPTA and 1878-1) are weighed into a Tripour © 50 ml vessel and mixed using a vibratory mixer the filler component is added, mixed with stirrer followed by vibratory mixing. The peroxide and the photoinitiating components are added. He Auxiliary catalyst component is then added by mixing. The 50% caustic component is added followed by mixing, and occasional vibratory mixing. The mixing is continued until the paste thickens. The pour point of the pre-impregnated sheet is reached when the consistency of the pulp was transitioned to a viscosity of stage B that forms a strand, as determined by removal of the mixing spatula from the mature dough. At the observed emptying point, the reaction mixture is emptied onto a sheet of Mylar®. A second sheet of the release film is placed on the emptied slurry which is then flattened between the rolls to a desired prepreg thickness. The release film is removed once the prepreg has achieved sufficient viscosity to allow separation of the release film. This time depends on the crosslinking speed in the prepreg sheet. The resulting pre-impregnated sheet is resistant to embossing and flexible. Example 5-Flexible Prepreg Sheet Prepared Using a Pre-Pipe Sheet Method Example 5 A-Preparation of the Pre-Pipe Sheet Flexible 9000 Gram Prepreg Sheet Preparation Process: A pre-impregnated sheet process of flexible CIPSit develops consisting of two stages. In the first stage, a serving of Donors and Donors of Michael are reacted to produce an extended prepolymer composition in the chain. In the second step, a trifunctional Michael acceptor facilitates the cross-linking of the extended system in the chain to originate a pre-impregnated sheet free of flexible stamping. In the process, the pastes of parts A and B are prepared by weighing the resin components in paper baskets of a double thickness gallon and by adding the respective filler loads. The thickener catalyst (50% NaOH) is added to part A (stage and extension in the chain) and the system is allowed to thicken. Subsequently, the Part B paste (crosslinking component) is added in stages to the thickened part A, with final mixing being conducted in a polypropylene basket together with additional catalysis immediately before casting. The thickened paste is emptied onto a preimpregnated sheet vibration casting table and stretched to thickness using a 0.125 inch gauge down bar. The pasta sheet is vibrated to remove the trapped gases. The ripening process is allowed to proceed to the final cross-linking stage, generating a flexible, manageable pre-impregnated sheet. The compositions of the pastes of part A and B are given in Table IV. The 9000 gram batch produced a pre-impregnated 3x5 foot sheet, which It is long enough to cover the typical top deck assemblies. Table IV Formulation in Batches of the Pre-impregnated Leaf Paste of 9000 grams Procedure in Lots of the Dough of the Hole to Preimpregnated of CIPS of 9000 grams: 1. (Part A) In a double paper bucket of 1 gallon, parts A-1 to A-9 are weighed and mixed. A-10 is added, mixed, and the resulting paste is decanted under vacuum. 2. (Part B) In a double gallon paper bin, parts B-ll and B-12 are weighed and mixed. Then, B-13 is added, mixed and the resulting paste is degassed under vacuum. 3. Next, 4.87 g of 50% NaOH is added to Part A and mixed. The mixture is left to exotherm and is increased in viscosity from 5500 to > 11000 cps. After the target temperature and viscosity are reached stage 4 starts. 4. The content of Part B is added in Part A in two stages. In the first stage the mixing is continued until the viscosity and the temperature prior to the addition are achieved. In this stand the remaining Part B components are added to the Part A / Part B mixture, and mixed until the viscosity and temperature observed prior to mixing are achieved. 5. Next, 3.65 g of 50% NaOH are added and mixed for 2 minutes before pouring the advanced paste onto a film of Mylar® on a pre-impregnated sheet casting table. 6. The sample is then leveled using a pull bar down, and degassed by vibration. 7. The emptying system gels in 6-7 minutes after emptying. The pre-impregnated sheet The resultant shows a high degree of flexibility and could be repeatedly bent at 180 ° angles and cracking or cracking. The finished pre-impregnated sheet is formed into a film with a nylon cover sheet for stacking and storage. In use, the cover sheet is removed to expose the surface of the prepreg to be folded to the substrate. The cover sheet of Mylar® can be retained during the curing to provide an oxygen barrier. Alternatively, the Mylar® sheet can be removed and replaced with a cast-in-film coating film (based on various brush-applied or polyvinyl acetate solutions) that serves as a conformal oxygen barrier film. The processing of these pre-impregnated sheet veneers has shown that the casting film provides a unique and unexpected advantage to the CIPS process. It seems that the films in if you impart a flatness to the surface of pre-impregnated cured sheet. These flatness films appear to form a coherent plate surface on the curing compound that is retained after the curing process. After the removal, a flat surface is achieved over the hard compound which requires minimum sanding to achieve the target surface performance. Films of this type mitigate effects such as "orange peel" seen on a Z directional shrinkage result under poorly bonded films such as Mylar®. Example-5B-Effect of the Composition of the Paste on the Processing of the Pre-impregnated Sheet The formulations presented in Table V are used to prepare pre-impregnated sheets in sheets that are bonded to decorative laminate substrates of particle board using a two-part epoxy adhesive. parts. The constructions are then cured using a halogen lamp of 500 Watts for 12 minutes at a distance of 8.5 inches from the glass protection of the lamp face. Table V WBSm 7277-176-1 7277-176-2 7277-176-3 7277-176-4 Component £ =% g. % _g. % gm. % 1848-10 2.02 13.63 2.11 14.15 3.93 13.30 3.93 14.27 TMPTA 4.00 26.98 4.00 26.82 8.00 27.08 7.50 27.23 1878-1 0.50 3.37 0.50 3.35 1.00 3.39 0.50 1.82 OE431 8.00 53.97 8.00 53.64 16.00 54.16 15.00 54.47 -819 0.06 0.37 0.06 0.37 0.11 0.37 0.11 0.40 L-256 0.07 0.47 0.07 0.46 0.14 0.47 0.14 0.51 Cat. Aux. 0.11 0.74 0.11 0.74 0.22 0.74 0.22 0.80 50% NaOH 0.07 0.47 0.07 0.47 0.14 0.47 0.14 0.51 Total 14.82 100.00 14.91 100.00 29.54 100.00 27.54 100.00 The following procedure is used to prepare pre-impregnated CIPS sheet samples using the formulations in Table V which are then used to prepare solid-surface veneers. The prepolymer components are weighed in a glass Tripour © and mixed using a vibrating mixer. The OE 431 is added and mixed. The peroxy ester components and photoinitiators are added and mixed as above. The reaction mixture is catalyzed using the established combination of the auxiliary catalyst * and 50% sodium hydroxide. ^ Auxiliary catalyst - (Aux Cat) is produced by adding 0.60 grams of diethylmalonate to a cup of 5 drachmas, then adding 0.7 grams of 50% NaOH, finally adding 0.060 grams of water and mixing it. The reaction mixture is subjected to continuous mixing during time in which thickening was observed. At a point of progress near the "gel point" of the paste, the thickened paste is discharged onto a sheet of Mylar®. A second film (nylon release film) is placed over the top of the discharged paste and the dough is rolled into a desired sheet thickness. For experimental formulations, the end point for the thickening is determined empirically and is varied with the composition of the formulation and the catalyst system of stage B. The "mixing time" of the paste is dependent on the amount and type of the catalyst used and the speed of agitation. The key feature associated with the use of the auxiliary catalyst system is the ability of the prepreg sheet to be emptied to continue the advance even after being "emptied" during the formation of the prepreg sheet. The cast pre-impregnated sheet sheet continues to advance (step B) to a point at which the release sheet can be neatly separated from the prepreg sheet. The point is known as the release time, which may vary in duration as a function of the rate of advancement of the prepreg sheet after casting and its initial proximity to the point of gelling the dough. Composite Preparation A 2 x 2 inch section of the prepreg 7277-176-4 having a thickness of 110 mils is attached to a prepared substrate using a 6 x 6 inch section of decorative laminate composite of standard particle board. To achieve bonding, the release film is removed from a 2x2 inch piece of the prepreg sheet. A sample of 2-minute 5-minute epoxy hardening adhesive is premixed and applied to the composite surface of the decorative laminate in a thickness of about 1.0 mil. The opposite face of the pre-impregnated sheet is placed on the adhesive coating pressure is applied to achieve intimate contact of the adherents. The compound is allowed to cure for a period of 15 minutes. Next, the sample is irradiated at 8.5 inches from the cover glass of a 500 halogen lamp for a period of 12 minutes. The sample is cooled and aged or normal fluorescent lighting for 24 hours. The Barcol hardness is > 50. The sample is tested for adhn to the substrate or exhibits excellent adhn. The effect of the advance of the paste on the emptying time on the flexibility of the prepreg sheet and the time of release are estimated during the prepreg preparation of the formulations of Table V. These data are summarized in Table VI. Table VI The time to release time is a measure of time to achieve the point where the tack of the pre-impregnated sheet is sufficiently reduced to allow removal of the release sheet. Example 6- Sample of Pigmented Pre-impregnated Sheet A typical formula for blue pigmented CIPS paste is presented in Table VII. The non-pigmented control formulation is identical except that it does not contain a pigment. Table VII Components gm-% Description Q6585 / TMPTA (50% / 50%) 21.15 22.95 R PDO 0.33 0.36 Ester of peroxy TS 0.60 0.65 Mercaptan 1-819 0.48 0.52 Photoinitiator Thiourea 0.07 0.08 Acylthiourea TMPDE 1.82 1.97 Dialyl ether Pigment Blue 0.10 0.11 Pigment OE 431 65.00 70.52 Filler Aerosir 100 2.62 2.84 Total Thickener 92.17 100.00 In order to simulate a current top-coated installation, the sample sections of a decorative particle board laminate is used as a substrate with a 0.1000-inch layer of the CIPS pre-impregnated sheet bonded to the substrate using 5-minute epoxy adhe. 2 parts. Samples of the pigmented and non-pigmented paste are prepared using the formula presented in the formula presented in Table VII and the lll procedure used in Example 1. This is cured using the apparatus presented in Figure 4. The pre-impregnated sheets having a thickness of 100 mil are prepared using a rolling process. To achieve this, a 5.0 gram sample of the prepreg prepared from the mixture of Table VII is formed into a ball. The ball is placed between two sheets of a separable nylon film and laminated to a circular pre-impregnated sheet using a rolling roller. The ded thickness is achieved by using spacers of 2-100 thousand. The prepreg formed thus is flat, faced parallel and circular in shape having a diameter of approximately 1.5 inches. A sample block of 1.5 X 1.5 inches is cut from a piece of particle board facing commercial deco-laminate. The block is used as a substrate to provide a current substrate simulation dned for a commercial process cured in the right place. A layer of a 5-minute epoxy of 2 parts ready-mixed is applied to the decorative laminate surface of the coupon in a thickness of 2-3 mils. One side of the pre-impregnated sheet has the film removed and the pre-impregnated sheet placed over the previously applied epoxy adhe, while the retaining face is separated from its film and covered with a Mylar® film, which is maintained on the surface of the pre-impregnated sheet. The sample during curing. The film Mylar © acts as an oxygen barrier. The bond of prototype adhe is allowed to cure for 5 minutes. The sample is then placed at a distance of 8.5 inches from the face of a 500-watt halogen lamp and irradiated. In the experiment described in this example, multiple samples are irradiated simultaneously. With this method, samples are removed during the course of irradiation at prescribed intervals. These samples are cut in cross section and the degree of curing is measured directly. In addition, a thermocouple wall is formed between the prepreg and the substrate surface of one of the set of samples allowing placement of a thermocouple to estimate the interface temperature of the prepreg / substrate during the course of irradiation. A) Yes, a curing temperature and depth profile is estimated simultaneously. In an initial experiment, a comparison was made between the halogen-light cure of non-pigmented and pigmented samples cured in the proper place. Figure 5 presents the observed temperature profiles for a pre-impregnated non-pigmented sheet at a distance of 8.5 inches from the face of the lamp for the duration of 10 minutes. Two samples of pigmented pre-impregnated sheets that run for 10 and 20 minute durations are also shown. Finally, a temperature profile curve is prepared for the pigmented sample cured at a distance of 5 inches from the face of the lamp. The Figure 6 shows the conversion data for the four samples. Example 7 Flexible Rigid Prepreg Sheet Methods designed to produce flexible CIPS pre-impregnated sheets generally produce systems that are very flexible. Manufacturers want pre-impregnated CIPS sheets that are formable but maintain a level of rigidity that approximates that of the decorative laminate. The following uses crystalline diacetoacetates to impart unique performance attributes to CIPS pre-impregnated sheet systems. The performance of the CIPS Michael Addition Thickener polymer networks can be improved through the use of extended thickener components in the crystal chain. These monomeric or oligomeric components that can be added to the pre-impregnated leaf paste resin systems to increase unlinked interchain interactions in their polymerized state. Generally, these materials are derived from crystalline components of high melting point that can be derivatized to achieve activities and compatibility in the thickening process. For this example, the spreader component in the chain is the diacetoacetate of hydrogenated bisphenes A. Similar derivatives of 1,4-cyclohexanediol, 1,4- dimethylolcyclohexane, norbornanthiols, and the like can provide similar beneficial effects. By 'themselves, the crystalline thickener additives produce pre-impregnated sheets of thickened CIPS that could maintain the improvement with respect to stiffness and flexibility. This property can be directed by adding a component of reactive flexibility. These materials are reactive with the thickener chemistry to form more flexible bonds, which allow for the achievement of smaller bending radii if the failure of the CIPS pre-impregnated sheet during installation. For this example the reactive thickener component is SR 610. CIPS pre-impregnated sheets produced with the above combination of thickener additive components produce systems that are both deformable without breaking, as well as having high retained stiffness. In addition, the casting of these pre-impregnated sheet pastes on a flat / smooth surface produces a prepreg sheet capable of maintaining flatness on the curing of their CIPS bonded pre-impregnated sheet veneers. These pre-impregnated sheets also show the ability to be surface finished to increase the adhesion of the posterior lateral bond and the flatness of the final product. Example 7A: Preparation of Rigid Pre-impregnated 3x3 Foot Sheet: General Preimpregnated Sheet Process: Part A and B Pastes are prepared by weighing the resin components identified in Table VIII in appropriate containers and by adding the respective filler loads. The thickener catalyst (40% NaOH) is added to Part A and the system is advanced to target viscosity and temperature. Subsequently, the paste from Part B is added to the paste from Advanced Part A and the reaction is allowed to proceed at the prescribed pouring temperature. The paste is emptied on a vibration table and stretched to thickness using a pull down bar, 0.125 inches of space. The pasta sheet is vibrated to remove the trapped gases. The ripening process proceeds to the final cross-linking stage, which generates a flexible, manageable pre-impregnated sheet. The example of batches of 5000 grams described later in Table VIII produces a large enough pre-impregnated sheet to coat an upper cover surface area of 4-6 square feet. Table VIII Procedures in Lots of CIPS Prepigmented Leaf Paste of 5000 gm: 1. In a double gallon paper cube (Part A), parts A-1 to A-4 were weighed and mixed. Part A-5 is added, mixed and degassed under vacuum. 2. In a 400 ml Tripour® glass (Part B) part B-7 is weighed and degassed under vacuum. 3. Part A-6 is added to Part A with mixing and the paste is left to exotherm at 33 ° C. After the target temperature is reached, proceed to stage 4.. The contents of Part B are added to the mixture of Part A. 5. The combination is mixed at a paste temperature of 42 ° C, emptied on the firing table down to a paste thickness of 100 mils, and Then it is vibrated to remove the trapped gas from the paste film. The cast sheet is hardened to a flexible reticulated prepreg sheet in 4-6 minutes. The finished prepreg sheet is free of tackiness and is storable without back side film formation. The Mylar® cover sheet can be retained during the curing to provide an oxygen barrier.

Alternatively, the Mylar® sheet can be removed and replaced with an emptied coating film in itself that serves as a conformal oxygen barrier film! as described herein in the foregoing. Installation: the substrate is a 2x2 foot x 0.75 inch particle board panel that has been reinforced on its perimeter in an additional standard particle board structure of 4.00 x 0.75 inches. The prepreg produced in this example is used to form a solid surface veneer on the substrate. This is achieved first by applying a uniform 2-minute 5 minute epoxy adhesive coating to the substrate surface using a trowel. The applied adhesive is allowed to solidify the tack prior to the application of the plating to the substrate. In this example the face of Mylar® is retained on the surface of the veneer to act as an oxygen barrier during curing. The pre-impregnated sheet is applied by contacting an edge of the pre-impregnated sheet with the substrate and by laminating the contacted surface with a 1-inch diameter lamination roll to extend the contact area. This procedure prevents the formation of unattached regions caused by air pockets. After the initial joining stage, the surface is laminated with a 3-inch diameter, 50-pound steel roller to ensure good adhesive contact and penetration. The compound is allowed to settle for one hour to achieve curing of the adhesive. Next, the context is placed in outside light. If the day is cloudy, then a curing of surface to hardness Barcol of 45-50 is achieved in 1 hour. Prior to the installation of the pre-impregnated sheet, the flatness of the substrate deviation form is noted by measuring the out-of-plane deviations at the corners of a flat surface. After curing, only one corner shows a measurable deviation (1 mm) from the pre-cure flatness measurements. This result confirms an early observation that the contraction in the rigid / flexible preimpregnated sheet system is minimal. Example 7B: Estimation of Shrinkage on Curing on the Rigid-Flexible Pre-impregnated Sheet The formulation in Table IX is used? to produce a pre-impregnated sheet system from CIPS. Table IX Procedure in Lots of the 100 grams CIPS-Rigid Flexible Prepreg Leaf Paste (based on 7239-094): 1. In a 100 ml Tripour® glass, add components A-1 to A-4 with mixing. 2. The A-5 is added with mixing and the paste is degassed under vacuum. 3. The A-6 is added and the paste is mixed. The temperature and time measurements start. 4. At 33 ° C, B-7 is added with continuous mixing. 5. At 42 ° C the paste is discharged. The previous paste is emptied into an aluminum structure with an internal dimension of 6x6 inches covered with 100 mils thick tape on a sheet of Mylar® film mounted with tape on a glass plate. The paste is leveled using vibration to produce a pre-impregnated sheet of uniform thickness sheet that assumes the interior dimensions of the aluminum structure after the completion of stage B of the paste. Next, the exposed surface of the pre-impregnated sheet is covered with an additional Mylar® sheet and a second glass plate. The pre-impregnated sheet thus formed matures to a flexible pre-impregnated sheet that takes the form of the structure. The sample is cured by placing the direct sunlight assembly for a period of 15 minutes for each side of the sheet prepreg After curing the assembly is cooled and the pre-impregnated sheet is marked with reference points on the structure before being removed from the structure. The structure and corresponding points on the cured pre-impregnated sheet are measured using a digital caliper instrument. The dimensions of the structure and the prepreg are compared to determine the shrinkage in the plane of the prepreg during the curing process. The shrinkage is 0.83 mils / inches. The Barcol hardness of the prepreg is determined to be 45. Example 8: Pre-Embossed Sheets of Stamped CIPS Example 8A This procedure to produce a pre-impregnated sheet of almost stamping free CIPS uses the development of Michael's reaction for the pre-impregnated leaf method emptied of CIPS. In an initial verification experiment, a pre-impregnated sheet paste formulation of the normal "emptying" method is modified by raising its filler load from 50% to 70%. In the 50% filler loading, thickening is ensured with the addition of 0.10 gm of 50% sodium hydroxide per 100 gm. From the paste of the prepreg leaf followed by mixing. The 50% filler paste composition was thickened to a stamping-free composition. In the modification used in this example, Michael's resin, a monomer from polyacrylate, and filler are combined to make a paste that is further modified by the addition of addictive photoinitiator. The advance of the system is achieved by incremental caustic addition followed by kneading the paste to promote the thickening reaction. The paste formulation used is given in Table X. Table X Prior to the addition of caustic, 0.220 gm. of 1-819 and 0.280 gm of L-256 are added to the paste with kneading. A total of 0.10 gm of 50% NaOH is added dropwise. The paste is kneaded for a period of 15 minutes during which time the system is transformed into a plastic paste, thickened. The paste is then formed into a ball and compressed to a thickness of 100 mils between two sheets of nylon film using flat plates and stopped. In overnight settlement, the pre-impregnated foil sheet increases in stamping resistance, but maintains the ability to be plastically deformed. The thickening speed of the advanced pre-impregnated sheet it is leveled at the end of 3 days providing in this way a pre-impregnated sheet of plastic CIPS that has the desired handling capacity. The prepreg can be bonded to a substrate and cured by irradiation to a solid surface veneer. Example 8B: Method for producing the prepreg sheet almost free from low shrinkage printing. Table XI Procedure: 1. To a Tripour® vessel components 1 and 2 are added with mixing. 2. Component 3 is added and mixed for 1-2 minutes to start the exotherm. 3. Component 4 is added and mixing continues until the reaction mixture reaches -28 ° C. At that point, component 5 is added with mixing until the reaction temperature of 28 ° C is restored. 4. Components 6, 7, and 8 are added consecutively with mixing. 5. The paste is mixed by kneading due to its high viscosity. Component 10 is slowly added and kneaded until the dough thickens to a mass-like consistency, (note: at this point, the dough exhibits an exothermic reaction, which raises the temperature of the dough to> 30 ° C) . 6. The thickened paste is rolled into a ball and spread flat to a thickness of 100 thousand uniforms between the two plastic films. The pre-impregnated sheet continues to thicken to an almost stamping-free consistency, achieving a ball penetrometer reading > 90 in 3-5 days. The above prepreg sheet is easily cured at a Barcol hardness of > 50 in 10-15 minutes under a 500 watt halogen light source when coated with an appropriate oxygen barrier film. This example describes CIPS prepreg sheet pastes that are thickened to thermoplastic prepreg sheets that are almost stamped free using the Addition of Michael and other thickening chemicals. In this example, Michael's Donor systems are added to the prepared resin pastes and reactive fillers. This can be prepared by abrading low viscosity blends to produce low void pulps. Then they can be formed into pre-impregnated sheets flexible sheet plastic, which thickens latently to provide almost stamping-free systems. Example 8C This example demonstrates a method for producing Michael's CIPS pastes that can be further reactively thickened to produce CIPS plastic pre-impregnated sheet systems. this example involves the preparation of pre-impregnated CIPS sheet paste components which can also be used to thicken conventional CIPS prepreg sheets. Example 8C1 Paste: A Typical Michael's Thickening Paste Table XII Procedure for the preparation of the paste 8C-1: 1. Components 1-6 are mixed. 2. Component 9 is added to complete the initial thickening. 3. The mixing of the dough is continued until a thick mass consistency is achieved. At this point, all thickening is a result of the addition of the filler; the reactive thickening only ensures the addition of the catalyst to the pulp system. 4. Catalyst components 7 and 8 are added with mixing immediately prior to mixing the combination paste described in the following procedure to make the prepreg CIPS sheet almost free of stamping. Michael's thickening paste 8C-1 is mixed with amounts of the traditional CIPS plastic paste mass described in 8C-2. Example 8C-2 Paste: Traditional CIPS Plastic Paste: A typical formulation of the traditional plastic mass is presented in Table XIII. Table XIII Procedure for 8C-2: 1. Components 1-4 are loaded into a ribbon mixer and mixed. 2. Component 5 is added slowly with mixing. 3. Component 6 is added with mixing to complete the plastic paste after mixing until it becomes homogeneous. 4. The paste is unloaded and spread flat in sheets, it is stored under refrigeration (0 ° C). Example 8C-3: reactive paste additive To a Tripour® beaker is added 20 grams of TMPTA and 10 grams of EAA. The reaction is initiated through the addition of a depleted 20% NaOH. The reaction has a long induction period, but it became very exothermic. The temperature is kept below 60 ° C by cooling the ice bath (with removal of the periodic sample to sustain the exotherm). The resulting product is a highly viscous liquid with no gel component. Optionally, the resin mixture can be extended with the OE 431 filler (30-50% by weight) for ease of handling. PROCESS FOR MAKING THE REPLICALLY THREADED, REPLICALLY THREADED CIP THERMOPLASTIC PROPRIETARY SHEET PRESSURE-FREE: This procedure is achieved by the reactive mixing of components 8C-1, 8C-2, and 8C-3 using the following procedure: 1. 60 grams of 7239-033 (paste 8C-2) is modified by adding 4 grams of 1848-10 and 10 grams of OE 431 to the paste. This is achieved by kneading the dough by hand. Designated paste A. 2. 7355-41 (paste 8C-1) designated as paste B. 3. A drop of 50% NaOH is added to 30 grams of paste A and kneaded for 5 minutes (exotherm system). 4. A drop of 50% NaOH is added to 30 grams of paste B with kneading (exotherm system). 5. Add half of paste A (modified in step 3) to 30 grams of paste B 1 drop of 50% NaOH, and then mix. 6. The remainder of paste A is added to the mixture with an additional drop of 50% NaOH with continuous mixing. 7. 10 grams of the reactive mixture of TMPTA / EAA (paste 8C-3) is added to the paste combination described in step 6, and two more drops of 50% NaOH are added with mixing until the paste is hot on contact. 8. The paste is separated into 5 balls of equal size, and placed on a nylon film mounted on a plate in an arrangement equivalent to 5-sites on a mold. A second film is placed on top of the arrangement and the paste is compressed between the two plates. The paste is compressed to a thickness of 0.125 inches using arrests of bar. At this point the release film can be separated and replaced to create a smooth top and the bottom face of the prepreg sheet. The pre-impregnated thickened sheet at rest provides a pre-impregnated sheet resistant to rigid stamping that is plastically deformed and capable of achieving small radius curvatures. A ball penetrometer (sold under the name of No. 473 Green Hardness Tester (B) Scale by Dietert Foundry Testing Equipment Inc.) shows the stamping strength of the prepreg that rises from a reading of 40 to > 98 on the dial scale of the penetrometer after resting at room temperature for 3 days. The mature pre-impregnated sheet is to be joined using a thermosetting adhesive to a rigid substrate prior to curing, and could be thermally or photolytically cured. The thermoplastic pre-impregnated sheet thus described is fused layers by applying pressure in the uncured state prior to curing to achieve a solid surface bond with no joints in the state. Pre-impregnated sheets of CIPS almost free of plastic stamps have the following key advantages. : 1. Being made of plastic, the pre-impregnated sheets can be fused in the installation to give joints without joints for installations. 2. Very high filler levels are possible, decreasing the cost of the pre-impregnated sheet. 3. High viscosity preimpregnated sheets of this type, with low resin volumes, have low shrinkage potential. 4. Adding a filler portion to the resin produces a fluid paste that can be degassed. The thickening of the pulp can provide sufficient pulp viscosity to withstand the pickup of additional air. The rest of the filler can be added to the paste followed by degassing under shear and vacuum to produce a low-void paste. 5. Mixing systems such as the Reedco Mixer, which is capable of generating high air-to-air interfacial areas during the pulp mixing cycle, can provide low void content pulps suitable for making pre-impregnated sheets of solid surface CIPS. Example 9: CIPS Preimpregnated Sheets Produced Using Reactive Urethane Thickening. Example 9A This example shows a method for producing a CIPS paste using the polyurethane generation thickening process which produces a plastic or thermoset pre-impregnated sheet of CIPS reactively thickened. A paste formulation that uses the thickening of urethane provides a level of thickening necessary for the handling of the prepreg sheet presented in Table XIV.

Procedure of Example 9A: 1. Components 1, 3, 4 and 5 are charged to a Tripour® vessel and mixed. 2. Component 7 is added with mixing. 3. Components 2 and 6 are then added with the mixing. The measurement of reaction time and temperature are started at this point. 4. After approximately 17 minutes at a paste temperature 36-38 ° C. The part is emptied onto a Mylar® film, and compressed to a target thickness (100 mils) using a second film, of bar tensions and a flat plate. 5. The formed prepreg sheet gels within 10 minutes, then time at which the films can be separated to reveal a pre-impregnated flexible low tack sheet suitable for use as a solid surface veneer.

In order to produce a cured compound, the example is held between the Mylar® sheets and cured in sunlight for 1 hour. A CIPS solid surface panel thus produced has a Barcol hardness averaging 35. EXAMPLE 10: CIPS Preimpregnated Sheets Using Example 10A of Epoxy Reactive Thickening. This example provides a method for producing a pre-impregnated sheet of CIPS using reactive thickening with epoxy. In this method a diepoxy monomer (EPON ™ 828) is pre-reacted with an amine having both primary and secondary amine functionality (DETA). The extended product in the resulting chain has secondary amine functionality of the secondary amines in the polyamine and those formed by the reaction of the primary amine groups contained with the epoxide groups of the epoxy monomer. In a subsequent step in the maturing process of the paste, a photoreactive polyacrylate monomer is added to the reaction mixture. The acrylic functionalities are reacted with any of the remaining primary amine groups through the addition of Michael to provide additional thickening of the pulp. A latent addition of the epoxy monomer results in the formation of a final crosslink network through the reaction of the secondary amine groups with the epoxide groups of diepoxy. The reaction sequence mentioned in the foregoing provides for the formation of a crosslinked polymer network that provides a flexible CIPS prepreg sheet. A paste formulation utilizing epoxy reactive thickening is presented in Table XV.

Table XV 7428-66 No. Component gm. % Description E828 5.00 9.21 Epoxy Monomer SR610 2.00 3.68 GE 241 Polyeteracplate 14.00 25.78 DETA Filler 0.50 0.92 Polyamipate TMPTA 5.00 9.21 Polyacrylic Monomer DETA 0.50 0.92 Polyamine GE 241 10.00 18.42 Filler TMPTA 5.00 9.21 Monomer Poliacplico GE 241 10.00 18.42 Filler 10 E828 2.00 3.68 Epoxy Mopomer 11 1-819 0.30 0.55 Photoinitiator Total 54.30 100.00 sffl K Filler 34.00 62.62 MM £ $ M? Procedure of Example 10A: 1. Components 1,2, and 3 are loaded into a beaker Tripour® and mix. 2. Component 4 is added with mixing allowing the system to progress through the incorporation of amine and acrylate in the prepolymer. The extension reaction in the chain is indicated by the solidification of viscosity and yarn formation. 3. Components 5 and 6 are added allowing the incorporation of acrylate and amine in the prepolymer using the end point defined in step 2. 4. Components 7, 8, and 9 are added consecutively to advance and thicken the paste. 5. The component 10 is added to provide the advance of the pulp to the step of emptying the prepreg sheet. 6. Component 11 is added during the advance period described in step 4. 7. The paste (when high viscosity and yarn formation is achieved) is emptied onto a uniform sheet formed between two Mylar® sheets using spacers. The emptying is allowed to remain interrupted until a gelled network is formed. 8. The pre-impregnated sheet is melted 60 minutes after casting, at which time the films can be separated to reveal a pre-impregnated sheet of flexible low tack suitable for the curing of a solid surface plating using visible radiation. 9. In this example, the prepreg formed in step 8 is removed from the carrier film, coated on both sides with an oxygen barrier casting film and cured under a 500 watt halogen lamp during minutes to provide a flat cured solid surface compound (indicative of low shrinkage) exhibiting a Barcol hardness of > 35. This is an example of a pre-impregnated sheet of CIPS formed using epoxy thickening chemistry. It shows that pre-impregnated sheets free of flexible stamping can be produced capable of being radiatively cured to pre-impregnated sheets of solid surface amenable. The specific intermediate prepolymer resin produced in this example consists of an epoxy amine reacted with polyacrylic monomers through the Michael addition of amine. Example 11: Pre-impregnated sheets of CIPS Produced by Incorporating Poly (meth) acrylate thickening. Example HA This example demonstrates a method for producing a CIPS paste incorporating high molecular weight thickening polymers that are capable of maturation to pre-impregnated sheets of rigid / thermoplastic CIPS / flexible that exhibit improved hardness in their cured state. A paste formulation incorporating PMMA as a curing agent is presented in Table XVI. Table XVI 7428-72 No. Component gm. % Description PMMA 4.70 4.77 Polymethylmethacrylate 1878-4 9.50 9.63 Donor Michael TMPTA-1 14.00 14.20 Acceptor Michael OE 431-1 28.00 28.40 Filler 20% NaOH 0.25 0.25 Catalyst Michael TMPTA-2 14.00 14.20 Acceptor Michael OE 431-2 28.00 28.40 Filler 8 -819 0.15 0.15 Photoinitiator ifjgffc Total 98.60 100.00 m Filler 56.00 56.80 i§aaBiai Procedure of Example 6A: 1. Component 1 is weighed in a glass or 50 ml vessel and heated to fusion. 2. Component 2 is added with heat and mixing to achieve a homogeneous molten material. 3. Component 3 is added with mixing and then component 4 is added to achieve a pre-impregnated sheet of CIPS. 4. Component 5 is added and mixed until it is thickened to a paste of high viscosity. 5. Components 6, 7, and 8 are added consecutively and mixed until the viscosity of the emptying is achieved. 6. The paste is emptied between two sheets of Mylar® and are left to mature to a manageable pre-impregnated leaf.

Example 12: Effect of the Composition of the Preimpregnated Sheet of CIPS and Additives on the Contraction in Plano during the Curing. Example 12A. The low shrinkage system is achieved by the addition of additive and oligomer. Table XVII shows two low shrinkage formulations containing E828, and which differ in the type of oligomer additive used: Table XVII 7239-090 «S Part A # 1 # 2 $? mk! »imk & No. Component gm. gm. Description 1848-10 1.80 1.92 1.80 1.91 Donor Michael 1878-1 1.50 1.60 1.50 1.59 Donor Michael 1878-4 1.50 1.60 1.50 1.59 Donor Michael E828 2.00 2.13 2.00 2.12 2.12 Epoxy Monomer SR415 1.00 1.07 1.00 1.06 Acrylic Monomer HDDA 1.50 1.60 1.50 1.59 Acp monomer BMC 806 0.23 0.24 0.24 0.23 0.24 Defoaming agent / Moisturizer 1-819 0.37 0.39 0.37 0.39 Photoinitiator L-256 0.30 0.32 0.30 0.32 Ester of Peroxi 10 GE 241 28.00 29.82 28.00 29.73 Filler 1 1 50% NaOH 0.08 0.09 0.08 0.08 Catalyst by Michael Mm Part B? JI SÜI O 12 TMPTA 4.63 4.93 0.00 0.00 Michael Acceptor 13 CN968 8.75 9 32 0.00 0.00 Acrylic Urethane 14 SR9035 0.00 0.00 13.68 14.52 Acrylic Monomer 15 BMC 806 0.23 0.24 0.23 0.24 Defoaming / Moisturizing Agent 16 GE 241 42.00 14.73 42.00 44.59"um" Total 93.89 100.00 94.19 100.00 The following procedure is used to prepare the above pre-impregnated sheets: 1. All the components in part A, except component 11, are Mix in a Tripour® glass. 2. All the components in part B are mixed in a second vessel. 3. Both parts A and B are degassed under vacuum. 4. A drop (80 mg) of 50% NaOH (component 11) is added to part A and with mixing. 5 .. Part A is mixed until a temperature of 29 ° C is achieved. 6. One half of the mixture of part B is added to the beaker containing A and mixed until a temperature of 31.0-31.5 ° C is achieved. 7. The remainder of part B is added to the A / B mixture. 8. The temperature of the mixture is allowed to rise to 31.5-31.9 ° C, and it is emptied. The Contraction and Barcol data for 7239-090-1 and -2 are presented in Table XVIII. Table XVIII.

The E828 and CN968 appear to be two key factors in achieving low shrinkage. Urethane allows the system to achieve good Barcol development along with low shrinkage. Example 12B: Low Shrinkage System achieved by the addition of E828. Table XIX shows two leaf formulations preimpregnated CIPS, one of which contains E828 and the other without E828. Table XIX Barcol development and hardness are presented in Table XX. Procedure to prepare the pre-impregnated sheets 7239-092-1 and -2: 1. all the components in part A, except component 9, are added to a Tripour® vessel with mixing. 2. All the components in part B are added to a second vessel with mixing. 3. Both parts A and B are degassed under vacuum. 4. A drop (60 mg) of 30% NaOH is added to part A with mixing.

. Part A is mixed until a temperature of 28.0 to 28.5 ° C is achieved. 6. One half of part B is added to part A by mixing until a temperature of 29.0-29.2 ° C is achieved. 7. The rest of part B is added and mixed until a temperature of 31.5-31.9 ° C is achieved and then emptied for the duration of maturation. Table XX Conclusion: The addition of E828 decreases the shrinkage of X-Y during light curing in the pre-impregnated sheet systems of previous CIPS. Example 12C: High Pre-Reaction Degree of the CIPS Preimpregnated Sheet These prepreg sheet systems are formed with a high level crosslinking in the stage of stage B of the prepreg sheet such that the contribution of the shrinkage addition step step High is minimized. The formulation in Table XXI is used to produce a pre-impregnated sheet system of CIPS. Table XXI 7239-094 Procedure for preparing pre-impregnated sheets 7239-094: 1. All components in part A except component 6, are added to a Tp? Our ° vessel with mixing. 2. All the components in part B are added to a second vessel with mixing. 3. Both parts A and B are degassed under vacuum. 4. One drop (50 mg) 40% NaOH is added to part A. 5. Part A is mixed until a temperature of 32.5-33.5 ° C is achieved. 6. Everything from part B is added to part A and mixed until a temperature of 40-42 ° C is achieved. 7. The product is then emptied. The dough is emptied in an aluminum structure to provide a sample for the measurement of contraction. The pre-impregnated product is cured using the prescribed shrinkage determination method. The cured pre-impregnated sheet gives shrinkage of 0.83 mils / inch, and a Barcol hardness of 45. Example 12D: High Pre-Reaction Grade of the CIPS Pre-impregnated Sheet-Second example. A second sample that has a high-level cross-linking in the stage of stage B of the pre-impregnated sheet is prepared and tested for contraction performance. The formulation in Table XXII is used to produce a CIPS prepreg sheet system. Table XXII Procedure to prepare the pre-impregnated sheets 7239-094: 1. Add the components 1-4 to a Tppour® vessel and degas under vacuum. 2. Components 5 and 6 are added to the vessel and mixed. 3. A drop (50 mg) of 40% NaOH is added to the mixture. 4. The paste is mixed until a temperature of 32.5-33.5 ° C is achieved and the formation of the pasta yarn is observed indicating extension in the high chain. The dough is emptied into an aluminum structure of 6x6 inches to provide a sample for shrinkage measurement. The pre-impregnated sheet is cured using the prescribed shrinkage determination method. The cured pre-impregnated sheet gives shrinkage of 0.96 mils / inch, and a Barcol hardness of 40. Example 13: Flexible CIPS Pre-impregnated Sheet Formed Using the Stages Process and Bonding Agents Donor of Michael Monomerico Example 13A: This example uses a variation of the pre-impregnated sheet process of CIPS. In this example, a Michael Addition polymer extended in the chain is prepared in a paste reaction of step A between a diacrylate monomer and a Michael donor layers of bonding two acrylic groups. In the second stage, a stage B paste containing a functional polyacrylate monomer it is added to the reactive A-paste with mixing. The resulting paste is allowed to mature at its pouring viscosity, whereby the prepreg sheet paste is emptied into a sheet advancing to a stamping-free state, providing a pre-impregnated sheet of CIPS suitable for handling. Table XXIII describes the composition of the formulation for this example.

Table XXIII 7355-121 Part A No. Component IBgm.i Vo «sa that * Decription 1 HDDA 3.00 7.09 Acceptor of Michael EAA 3.00 7.09 Donor of Michael GE 241 15.00 35.43 Filler -819 0.12 0.28 Photoinitiator L-256 0.12 0.28 Ester of Peroxi BMC 806 0.50 1.18 Defoamer / Moisturizing Agent 50% NaOH 0.10 0.24 Michael i M Catalyst Part B uf 8 TMPTA 5.00 1 m1.81a Michael Acceptor BMC 806 0.50 1.18 Defoaming / Moisturizing Agent 10 GE 241 15.00 35.43 Filler iH Total 42.34 100.00 maa Procedure: 1. The first six components of part A are charged to a Tripour® vessel with mixing. 2. All components to part B are charged to a second vessel. 3. The contents of each beaker are mixed and degassed under vacuum. 4. The seven components of part A are added to vessel A. 5. Part A is mixed until a temperature of 35 ° C is achieved. The reaction of EAA and HDDA generates a high level of extension in the chain. 6. Half of the contents of cup B are added to cup A and mixed until a temperature of 35 ° C is achieved. 7. The contents of a vessel A are added to the remaining contents of vessel B and mixed until the system achieves the desired pouring viscosity, as indicated by the formation of pulp yarn. 8. The contents are then emptied into an aluminum structure, and vibrated to remove the voids. The system gels after resting overnight to form a flexible prepreg sheet. The pre-impregnated sheet could be folded around a 1-inch mandrel and kept in that configuration overnight without cracking or cracking. In a control experiment, the above procedure was conducted with all the components that are added to a single vessel followed by mixing. After the addition of the caustic the contents are advanced to the emptying viscosity they are emptied into a aluminum structure. The control experiment, the flexibility of preimpregnated sheet to composite failure is very low as indicated by the immediate breaking of the compound in the bending around the 1 inch mandrel. This experiment indicates that the 2-step process produces a pre-impregnated ho a much stronger than as a result of the reaction of the extension in the chain of the initial stage A. Example 13B: In this variation of Example 13 A, a portion of EAA is replaced with a polyester polymer from Michael Donor based on diethylmalonate and diol ethers (1878-1). The revised formulation is shown in 1 to Table XXIV.

Table XXIV The procedure of example 13A is used on the composition of example 13B with 1878-1 which is added to stage A of the process. The system gels in less 30 minutes after emptying. The prepreg has equivalent flexibility to the prepreg sheet in Example 13A. Summary of Results: 1. Flexible pre-impregnated sheets can be produced at high levels (70% solids) of granular fillers using monomeric Michael Donors and poly functional acrylates. 2. The resulting pre-impregnated sheets contain highly advanced oligomers with outstanding acrylic functionality. Systems of this type - require only light additional polymerization to achieve objective hardness, and thus are low shrinkage systems. Example 14: Process Verification of the Continuously Emptied CIPS Prepreg Sheet; Processing Window of the Pasta A-B: To verify this capacity, a batch of pasta 9000 grams is prepared as described for the paste AB in example 5. In the preparation of the paste all of the paste B is added to the paste A at the end of the cycle of the paste A. The sample is mixed well and 100 -200 gm of samples are taken from the resulting paste in intervals of 4-5 minutes.

The viscosities of the samples of the pastes are measured, and the caustic is added to provide the advance of the paste necessary to form a pre-impregnated gelled sheet. The samples of the catalyzed paste are then emptied into a 6x6-inch structure, vibrated for hole removal and cured. A total of 14 samples are taken during a period of 90 minutes. Samples of initial 2-3 pulps are cured to low quality pre-impregnated sheets. This result indicates that the components of the paste A- and B-co-reaction desirably for a minimum period of time before the second addition of the caustic in order to produce pre-impregnated sheets of good quality. All other samples are cured to form pre-impregnated leaves of good quality showing desired flexibility and photo-cure performance. The most advanced samples are mixed for a shorter time prior to emptying. The use of less caustic material in the second caustic addition results in a prolonged processing window for these more advanced samples. The cooling of the mixture of the paste A-B- also prolongs the processing window after the second addition of the caustic. Conclusion: There is a window of ample period of time during which the paste A-B- can be processed (using secondary caustic addition) to a flexible prepreg sheet suitable for the preparation of plating solid surface. It can be catalyzed at the target curing rates necessary for a continuous CIPS pourable pre-impregnated sheet process. Field Experiment to Verify the Process of the Continuously Emptied CIPS Preimpregnated Sheet: The continuous continuously emptied CIPS prepreg sheet processing concept is further tested on a pilot continuous processing line under a quantity arrangement. In this experiment, a continuous process is used to make a pre-impregnated sheet of 0.125 inches of flexible thickness. The batch formulation of 9000 gm described in Example 5 above is used to prepare a suitable paste to be emptied onto a stainless steel strip designed for continuous emptying of the polymer sheets. Procedure for the Preparation of the Paste: 1. Part A and Part B are mixed separately. 2. Both Parts A and B are degassed under vacuum for 10 inches. 3. The first addition of NaOH is made to Part A with mixing. The temperature and viscosity of Part A is monitored. When a viscosity change of 4000 to 6000 cps is achieved, Part B is added to Part A in two stages. 4. Mixing time, temperature, and viscosity they are monitored. 5. The target endpoint values of the temperature and viscosity for the addition step of component B are determined empirically from results in previous batches. Normally, the reaction between Parts A and B takes 10 to 15 minutes. 6. A second amount of NaOH was added to the mixture. The combination is thoroughly mixed for a period of 2 to 3 minutes before emptying the mature pasta. 7. The paste is emptied on a continuous mobile stainless steel strip. Procedure for emptying the prepreg: 1. A liquid polyvinyl acetate film-forming solution is applied to the web by brush application, spraying, or dipping to create a release / cover film on the web to receive the preimpregnated sheet emptied. 2. The liquid film is dried using hot water, oil, or a steel band heated with hot air. 3. When the emptied release film coating reaches the emptying location of the paste of the continuous casting apparatus the film is completely dried so that the paste could be emptied over it. Note: in an alternative mode, a preformed polymer film can be spread directly over the band. 4. The paste is emptied onto the polymer film (either liquid formed film or laminated film). The paste gels at a certain distance from the location of the emptying. 5. A top release film is applied to sandwich the pre-impregnated sheet. 6. At the end of the band, the pre-impregnated sheet is rolled. Example 14: Additional Versions of the CIPS Preimpregnated Sheet System Based on Michael Addition Example 14A: Effect of monomeric acrylates on the rate of development of Barcol Polyfunctional acrylates can be crosslinked using polyfunctional acetoacetates. The addition of monofunctional acrylates to pastes containing these materials can increase the speed of development of Barcol hardness. The data in Table XXV illustrate this point.

Table XXV Comments: the resin components are added to a glass and mixed thoroughly. Then, the filler is added with the additional mixing. The catalyst is then added with the mixture monitoring the temperature. The paste is thickened and emptied onto a piece of Mylar at a short point of gelation. The paste is then sandwiched between the carrier sheet and a second sheet of Mylar and the thickening reaction is allowed to complete. Example 14B: Effect of the flexible diacrylate monomer on the curing speed of the prepreg and the flexibility. SR-368 is a crystalline polyacrylate monomer effective in producing pre-impregnated sheets of CTPS resistant to high stamping. The addition of a flexible acrylate (isocyanurate tris (2-hydroxy ethyl) t-acrylate) increases the flexibility of the resulting pre-impregnated sheet, and the rate of development of the Barcol hardness on the light curing The data presented in Table XXVI illustrate this point, Table XXVI Comments: The resin components are added to a Tripour © vessel and mixed thoroughly. Then, the filler is added with additional mixing. The catalyst is added with the mixing with the temperature monitoring. The paste is thickened and emptied onto a piece of Mylar® at a short gelling point. The paste is sandwiched between the carrier sheet and a second Mylar® sheet and the thickening reaction is allowed to complete. Example 14C: Effect of rigid diacrylates on the hardness development of the CIPS prepreg on curing: It has been shown that AATMP easily thickens the TMPTA pastes under caustic catalysis. Example 14A shows that the addition of monofunctional acrylate easily facilitates the rate of development of Barcol hardness upon curing for this system. In contrast, the addition of Rigid diacrylates appear to greatly inhibit the development of hardness upon curing of the prepreg. The data presented in Table XXVII illustrate this point. Table XXVII Comments: The resin components are added to a Tripour © vessel and mixed thoroughly. Then, the relinker is added with additional mixing. The catalyst is added with the mixing with the temperature monitoring. The paste is thickened and emptied onto a piece of Mylar® at a short point of gelation. The paste is sandwiched between the carrier sheet and a second Mylar® sheet and the thickening reaction is allowed to complete. Example 15 The CIPS pre-impregnated sheet for the installation of solid surface plating typically has a thickness of at least about 0.125 inches. It is desirable that such pre-impregnated sheets be capable of forming 1.0 diameter bends through bending 180 °. They are also typically desired to exhibit rigidity for ease of handling and installation. The pre-impregnated leaf curvature forming capacity is estimated by flexing and clamping pre-impregnated leaf samples of 3.0 inches by 0.5 inches 180 ° around 1.0-inch and 1.5-inch diameter mandrels with time determination at failure demonstrated by separation based on irregular cracking. The stiffness of the pre-impregnated sheet is estimated by a buckling test in which a pre-impregnated sheet sample of 1.0 inch x 5.0 inch x .125 inch is secured at one end in a horizontal position by a fastener. The degree of buckling of the horizontal sample is measured by a 4.0-inch conveyor that has its base in a horizontal position and origin at the point of the joint fastener sample, so the buckling of the horizontal sample can be measured in degrees on the conveyor. The degree of flatness measurement is defined as the buckling angle of the pre-impregnated sheet. For ease of processing the pre-impregnated sheet, buckling angles of less than 20 ° are desirable. The flexible rigid prepreg sheet formulation presented in Example 7B is used to prepare enough paste to form a pre-impregnated sheet sample 3.5 inches x 7.0 inches x 0.125 inches.

The sample is allowed to age for 3 days at which time the samples are cut to perform the buckling and curvature tests described in the above. The buckling test gives a derivation of < 10 ° for the pre-impregnated sheet in a failure time of less than 1 minute on the 1.0-inch mandrel curvature test. The following example provides a method for modifying the procedure of Example 7B to achieve a pre-impregnated sheet system of CIPS having the desired prior stiffness levels, while sufficient flexibility meets the curvature installation objectives of the prepreg sheet. In the following example of the formulation used in Example 7B is modified as follows. An experimental resin 7401-172 replaces a portion of polyether diacrylate flexing agent, SR610. The replacement resin is a polyacrylate containing pendant acetoacetate side groups. The crystalline diacetate (1878-4), SR610, and 7401-172 are pre-reacted under sodium hydroxide catalysis to create an extended prepolymer component in the chain that is advanced additively in a second step through the reaction with TMPTA. The resulting prepreg exhibits a good degree of rigidity in the buckling test (<20 °), but is distorted with minimum force at the desired level of curvature. The pre-impregnated sheets Prepared in the following example are tested in the curvature forming capacity test. The 180 ° bending test on a 1.0 inch diameter mandrel gives a failure time of > 2 hr. The experimental resin, 7401-172, used in the formulation 7428-138 below, is formed by the free radical polymerization of a mixture of 2-ethylhexyl acrylate, 2-acetoacetoxyethyl methacrylate formulated in a 95/5 weight percent ratio followed by dilution at a concentration of 80 weight percent with hexanediol of diacrylate after removal of the free radical initiator. Table XXVIII Procedure to prepare the prepreg 7428-138-3 sheet: 8. Components 1-5 are added in Part A in a Tripour © vessel with the mixer. 9. Components 7-11 in Part B are added to a second vessel with mixing. 10. Both Parts A and B are degassed under vacuum. 11. Component 6 is added to Part A and the system is advanced at a temperature of 35 ° to 36 ° C. 12. Next, the contents of the second beaker are added to the advanced paste A together with the component 12. 13. The resulting paste is to be advanced at a temperature of 40 ° to 41 ° C. 14. In achieving emptying temperature, the dough is emptied into a rectangular structure of 7.0 x 3.5 which has a thickness of 0.125 inches. The paste is left to mature for 16 hr. Before the initial evaluations. The ability of the pre-impregnated sheet of CIPS to form small bending curves with irregular cracking failure for long periods sufficient to allow the union of 1 to prepreg. Example 16 The pre-impregnated CIPS for the installation of solid surface veneering needs to have a thickness in the range of 0.125 inches. Such pre-impregnated sheets must also be capable of forming 1.0-in-diameter bends through a 180 ° bending. They should also exhibit rigidity for ease of handling and installation. The pre-impregnated leaf curvature forming capacity is estimated by flexing and clamping pre-impregnated sheet samples of 3.0 inches by 0.5 inches 180 ° around mandrels 1.0 inches and 1.5 inches in diameter with time determination for sample failure by separation based on irregular deterioration. The stiffness of the pre-impregnated sheet is estimated by a buckling test in which a pre-impregnated sheet sample of 1.0 inch by 5.0 inch x 0.125 inch is secured at one end in a horizontal position by a fastener. The degree of buckling of the horizontal sample is measured by a 4.0-inch radius conveyor which has its base in a horizontal position and origin at the point of the sample of the joint fastener. A) Yes, the buckling of the horizontal sample can be measured in degrees on the conveyor. The measurement of the degree of flatness is defined as the buckling angle of the preimpregnated sheet. For ease of processing of the pre-impregnated sheet, the buckling angles of less than 20 ° are desirable The formulation of the flexible rigid prepreg sheet presented in Example 7B is used to prepare enough paste to form a 3.5 inch x 7.0 inch x 0.125 inch prepreg sheet sample. Samples are allowed to age for 3 days at which time the samples are cut to perform the buckling and curvature capability tests described above. The buckling test gives a deviation of < 10 ° for the pre-impregnated sheet and a failure time of less than 1 minute on the mandrel curvature test of 1'0 inches. The following example (7466-33) provides a method for modifying the procedure of Example 7B to achieve a pre-impregnated sheet system of CIPS having desired levels of rigidity, while sufficient flexibility meets the curvature installation objectives of the prepreg sheet. In the following example the formulation used in Example 7B is modified as follows. A portion of the TMPTA is replaced with a crystalline triazintriacrilate, SR368, and the bending agent SR 610 is removed. The crystalline diacetoacetate, 1878-4, SR 368, and a portion of the TMPT? They are weighed in a Tripour® vessel (Vessel A) and heated to 46 ° C. At this point, the filler compound is added. The viscosity of the sample from vessel A is sufficiently low at this point to allow vacuum degassing. In a second vessel (Vessel B) additives, the remaining TMPTA, and the filler are added. After mixing, the vessel systems are degassed under vacuum. After degassing, the temperature of the contents of vessel A is 44 ° C. Next: Michael's Addition catalyst, 50 percent sodium hydroxide, was added to Vessel A and the paste matured for a period of 8 minutes at 45 ° C. Next, the contents of Vessel B are added to vessel A (mixing temperature is 39.5 ° C) and the system matures with mixing at a temperature of 41 ° C. At this point the dough is emptied into a rectangular mold of 7.0 x 3.5 inches x 0.125 inches thick and vibrated to remove gas bubbles to create a pre-impregnated sheet of low voids. The sample is allowed to mature for 16 hours at which time the resulting prepreg sheet exhibits excellent stiffness in the (<5 ° buckling test), but is distorted with minimal force at the desired level of curvature. The 180 ° flexion test on a 1.0 inch diameter mandrel gives a failure time of > 24 hr. The sample is cured under a halogen lamp to a Barcol of > 50. The sample is cured without distortion of flatness indicating low contraction.

Table XXIX Procedure for preparing prepreg 7428-138-3: 15. Components 1-4 in Part A are added to a Tripour® vessel with mixing. 16. Components 7-10 in Part B are added to a second Vessel B with mixing. 17. The glass A is heated in an oven at 60 ° C to a temperature of 4 ° C. 18. Component 5 is added to a Vessel? and the temperature drops to 44.0 ° C. The viscosity is sufficiently lowered to allow the samples 19 to be dewatered. Both Parts A and B are degassed under vacuum. 20. Component 6 is added to Part A and the system advances at a temperature of 45 ° C for a period of 7.5 minutes. 21. Next, the contents of cup B are added to the paste of the advanced cup A. In addition, the temperature The mixture of the combined sample is reduced to 39.5 ° C. 22. The resulting paste is allowed to advance with mixing at a temperature of 41 ° C for an additional 3.0 minute period. 23. At this point, the dough is emptied into a rectangular 7.0 x 3.5 inch structure that has a thickness of 0.125 inches and is vibrated to remove the gas bubbles. 24. The paste is allowed to mature for 16 hr. before the initial evaluations. The term "comprising" (and its grammatical variations) as used herein is used in the inclusive sense of "having" or "including" and not in the exclusive sense of "consisting only of". The terms "a" and "the" as used herein are meant to encompass the plural as well as the singular. The above description illustrates and describes the present description. Additionally, the description shows and describes only the preferred embodiments of the description, but, as mentioned in the foregoing, it is to be understood that it is capable of changes or modifications within the scope of the concept as expressed herein, in proportion to the previous teachings and / or skill or knowledge of the relevant technique. What is described in the above in this it is further proposed to explain the best known ways to 'practice the invention and to enable others skilled in the art to use the description in such, or other embodiments and with the various modifications required by the particular applications or uses disclosed herein. . Accordingly, the description is not intended to limit the invention to the form disclosed herein. It is also proposed that the appended claims be considered as including alternative modalities. All publications, patents and patent applications cited in this specification are incorporated herein by reference, and for any and all purposes, as if each publication, patent or individual patent application was specific or individually indicated that is incorporated by reference. . In this case of inconsistencies, the present description will prevail.

Claims (51)

1. CLAIMS 1. A prepreg sheet, characterized in that it comprises the reaction product of a curable composition comprising: A. a polymerizable component comprising a polymerizable material and a chemically reactive organic thickening chemical; B. an additive component comprising a catalyst for the chemically reactive organic thickening chemical and a photoinitiator; or peroxide or both, and C. a filler.
2. 2. The pre-impregnated sheet according to claim 1, characterized in that the amount of the polymerizable component is from about 15 to about 55 weight percent; the amount of the filler component is from about 45 to about 85 weight percent, and the amount of the additive component is from about 0.2 to 3 weight percent.
3. 3. The pre-impregnated sheet according to claim 1, characterized in that the amount of the polymerizable component is from about 25 to about 45 weight percent; the amount of the filler component is approximately 50 to about 75 weight percent, and the amount of the additive component is from about 0.3 to 2 weight percent.
4. 4. The pre-impregnated sheet according to claim 1, characterized in that it also comprises a non-reactive thermoplastic resin.
5. 5. The pre-impregnated sheet according to claim 1, characterized in that it is a crosslinked CIPS prepreg sheet wherein the polymerizable component A comprises a reactive material in amounts of about 30 to about 90 weight percent; and a reactive thickening agent in amounts of about 10 to about 70 weight percent.
6. 6. The pre-impregnated sheet according to claim 1, characterized in that it is a CIPS prepreg and contains a reactive Michael thickener, wherein the polymerizable component A optionally comprises a reactive thermoplastic resin component in amounts of about 70 percent by weight. weight; a reactive material in amounts of about 20 to about 90 weight percent; and a reactive thickening agent in amounts of about 5 to about 70 weight percent.
7. 7. The pre-impregnated sheet according to claim 1, characterized in that it is a sheet CIPS prepreg containing a reactive urethane thickener and wherein the polymerizable component A optionally comprises a reactive thermoplastic resin component in amounts of 0 about 60 weight percent; a reactive material in amounts of about 20 to about 90 weight percent; and a reactive thickener in amounts of about 25 to about 70 weight percent.
8. 8. The pre-impregnated sheet according to claim 1, characterized in that it is a CIPS prepreg sheet which contains a reactive epoxy thickener and wherein the polymerizable component? optionally comprises a reactive thermoplastic resin component in amounts of 0 to about 60 weight percent; a reactive material in amounts of about 20 to about 90 weight percent; and a reactive thickener in amounts of about 5 to about 70 weight percent.
9. 9. The pre-impregnated sheet according to claim 1, characterized in that it is a volatile stock wherein the polymerizable component A comprises at least one member selected from the group consisting of a thermosetting resin and a prepolymer in amounts of about 3 to about 20 percent by weight; a reactive material in amounts of approximately 5 to about 30 weight percent; and a reactive thickener selected from the group consisting of a Michael Addition reactive thickener comprised of a methylene Michael donor reactive of β-dicarbonyl in amounts of about 3 to about 25 weight percent; and an activated functional olefin Michael acceptor in amounts of about 4 to about 25 weight percent; an epoxy reactive thickener comprised of an epoxy functional monomer, or ol.igome.ro in amounts of about 3 to about 25 weight percent; and an epoxy or oligomer reactive monomer in amounts of about 1.5 to about 20 weight percent; and an isocyanate functional reactive thickener comprised of a polyisocyanate or polyisocyanate-terminated oligomer in amounts of about 2.5 to about 25 weight percent and an isocyanate reactive monomer or oligomer in amounts of about 0.025 to about 0.25 weight percent.
10. The pre-impregnated sheet according to claim 1, characterized in that the additive component comprises a member selected from the group consisting of a photoinitiator in amounts of about 0.001 to about 0.2 weight percent; and / or a peroxide in amounts of about 0.05 to about 1 weight percent; and mixtures thereof in amounts of about 0.06 to about 1.2 weight percent.
11. 11. The prepreg according to claim 1, characterized in that it comprises a reactive thickening catalyst of Michael addition in amounts of about 0.025 to about 0.25 weight percent.
12. The prepreg according to claim 1, characterized in that it comprises an epoxy reactive thickener catalyst in amounts of about 0.1 to about 2 weight percent.
13. The prepreg according to claim 1, characterized in that it comprises an isocyanate functional reactive thickener catalyst in amounts of about 0.1 to about 2 weight percent.
14. The pre-impregnated sheet according to claim 1, characterized in that it further comprises an air release agent / humectant component and in amounts of about 0.5 to about 1.5 weight percent.
15. 15. The pre-impregnated sheet according to claim 1, characterized in that it further comprises a stabilizing component in amounts of about 10 ppm to about 600 ppm on the reactive monomer.
16. 16. The prepreg sheet according to claim 1, characterized in that it further comprises a flexural component and in amounts of about 2 to about 25 weight percent.
17. 17. The pre-impregnated sheet according to claim 1, characterized in that it has a shelf life in its uncured state of greater than 100 hours at 60 ° C or greater than 30 days at room temperature.
18. 18. The prepreg according to claim 1, characterized in that the reactive thickener is at least one member selected from the group consisting of carbodiimides, polycarbodiimides, epoxide, polyisocyanates, and a reaction product of the Michael addition.
19. 19. The prepreg according to claim 1, characterized in that the reactive thickening agent comprises a Michael addition product.
20. 20. The pre-impregnated sheet according to claim 19, characterized in that the Michael addition product comprises at least one member selected from the group consisting of diol.es or polyester polyols which are terminated with acetoacetate functionalities; polyesters containing functional esters of medium chain β-dicarbonyl and hydrogenated bisphenol A diacetoacetate.
21. 21. The pre-impregnated sheet according to claim 1, characterized in that it comprises a photoinitiator.
22. 22. The pre-impregnated sheet according to claim 21, characterized in that the photoinitiator comprises a photoinitiator activated with visible light.
23. 23. The prepreg according to claim 21, characterized in that the photoinitiator comprises at least one member selected from the group consisting of an acylphosphine oxide and a cyanine borate.
24. 24. The prepreg according to claim 23, characterized in that the acylphosphine oxide is bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
25. 25. The prepreg according to claim 23, characterized in that the cyanine borate is a soluble organic salt of a cationic and tetraalkyl cyanine dye, and / or an aryl functional borate anion.
26. 26. The pre-impregnated sheet according to claim 1, characterized in that it comprises a peroxide.
27. 27. The pre-impregnated sheet according to claim 1, characterized in that the filler is at least one member selected from the group consisting of alumina, alumina monohydrate, aluminum trihydrate, aluminum hydroxide, aluminum oxide, sulfate aluminum, aluminum phosphate, aluminum silicate, borosilicate, calcium sulfate, calcium phosphate, calcium carbonate, calcium hydroxide, magnesium sulfate, magnesium phosphate, magnesium carbonate, magnesium hydroxide and silica.
28. 28. The pre-impregnated sheet according to claim 27, characterized in that the filler comprises aluminum trihydrate.
29. 29. The pre-impregnated sheet according to claim 1, characterized in that the filler comprises a Group II metal in combination with aluminum oxide and / or silica.
30. 30. The pre-impregnated sheet according to claim 1, characterized in that it further comprises a curing speed increaser.
31. 31. The prepreg according to claim 30, characterized in that the cure rate enhancer is at least one member selected from the group consisting of mercaptan of (alkyl, aryl or heterocyclic), disulfide, polysulfide, phosphine, phosphine, vinyl triazine, branched alkyl aryl amine, sulfinamine and derivatives thereof, sulfinamide and derivatives thereof, and alkyl and aryl thiourea.
32. 32. A pre-impregnated sheet composite, characterized in that it comprises a pre-impregnated sheet of according to claim 1 located between a carrier sheet and a release film sheet.
33. 33. The pre-impregnated sheet composite according to claim 32, characterized in that the carrier film is a conformable conformable film.
34. 34. The method for preparing the compound according to claim 32, characterized in that it comprises emptying the prepreg on a carrier sheet, allowing the composition to be thickened to a mature prepreg, and then applying a sheet of release film.
35. 35. The compound according to claim 32, characterized in that at least one of the sheets is permeable to oxygen.
36. 36. The pre-impregnated sheet according to claim 19, characterized in that the Michael Addition reaction product comprises a member selected from the group containing poly (meth) acrylates having side chain acetoacetate groups.
37. 37. The pre-impregnated sheet according to claim 19, characterized in that the Michael Addition reaction product comprises a member selected from the group containing the reaction product of a crystalline diacetoacetate and a crystalline polyacrylate.
38. 38. The pre-impregnated sheet in accordance with Vindication 19, characterized in that the Michael Addition reaction product comprises a member selected from the group containing the extended chain products formed by a pre-reaction between a crystalline di acetoacetate and a crystalline polyacrylate then reacted in a polymer network of Addition of Michael reticulado.
39. 39. A method for making the pre-impregnated sheet according to claim 1, characterized in that it comprises obtaining the polyme i zab component 1 e? and then add and mix with the polymeric component A, a reactive thickener, photomizer or peroxide or both and a filler and remove entrained air bubbles.
40. 40. The method according to claim 39, characterized in that the release of the entrained air is facilitated by using a vacuum and / or vibration.
41. 41. The method for making the prepregged article according to claim 39, characterized in that it also comprises partially curing in order to obtain the prepreg sheet.
42. 42. The method according to claim 39, characterized in that the pre-impregnated partially cured sheet test sample has a degree of buckling from the horizontal of less than 20 degrees.
43. 43. The method of compliance with the re-indication 39, characterized in that the partially cured preimpregnated sheet test sample has a degree of buckling from the horizontal of less than 5 degrees.
44. 44. The method according to claim 39, characterized in that the prepreg sheet is formed between two layers of film.
45. 45. A method for preparing a solid surface article, characterized in that it comprises curing the prepreg sheet of claim 1.
46. 46. The method according to the claim 45, characterized in that the curing comprises irradiation.
47. 47. The method according to claim 46, characterized in that the radiation comprises ambient light.
48. 48. The method according to claim 45, characterized in that the curing comprises heating.
49. 49. The method according to claim 45, characterized in that the curing comprises a combination of radiation and heat.
50. 50. The method according to claim 44, characterized in that the cured prepreg has a linear shrinkage on curing of less than 1 mil / inch.
51. 51. A solid surface article, characterized in that it comprises the cured pre-impregnated sheet of claim 1 attached to a support substrate.