MXPA98009751A - Thermoformable multilayered polyester sheet - Google Patents

Abstract

A thermoplastic composite comprising an extruded thermoformable self-supporting sheet having an outer decorative chemically resistant and renewable filled polyester layer and an adjacent inner supporting thermoplastic layer for enhancing desirable mechanical properties of the composite.

Description

MULTI-COMPLEX THERMALLY COMFORTABLE LAYER FOLIESTER SHEET FIELD OF THE INVENTION This invention relates to a mixed sheet of polyester that can be thermally formed into a variety of articles such as sinks and bathtubs.

BACKGROUND OF THE INVENTION It is often difficult to form crystalline resin mixtures filled »in profiles or sheet. The crystalline resin has poor portion strength and high shrinkage immediately after cooling. This is difficult to see thick sections with good dimensional tolerances. Typically, the extruded crystalline resins may also exhibit a very rough surface. The 5,441,997 patent discloses polyester molding compositions having similar qualities to that of ceramics. They can be molded into relatively thin sections and have an impact resistance. The composition is directed to a polybutylene terephthalate and / or polyethylene terephthalate and aromatic polycarbonate with inorganic fillers selected from the group consisting of barium sulfate, strontium sulfate, zirconium oxide and zinc sulfate. If desired, a styrene rubber impact modifier is described which is added to the composition as well as fiberglass reinforcing filler. Although these compositions are suitable for many applications in which qualities similar to those of ceramics are desired, it is desirable to have even improved and cheaper molded structures. The patent of E.U.A. 5 »510» 398 of Clark »et al. Describes the use of non-dispersing pigments to impart a polyester thermoplastic composition to a" granulated or mottled "granite surface appearance on an extruded sheet that provides a" distinct color "visibly distinct and identifiable. in numerous places through the surface of the material wherever it is visible from the pigment material. Potential non-dispersing pigments that are useful "as long as the ratio of spectra is adequate" include titanium filaments and other natural fibers "as well as water-based thermoplastic thermoplastic rubber-crushed materials. With the signal of a filled polyester material, the resulting decorative polyester composition typically has chemically resistant properties. The Ghahary 5,304,592 patent relates to a simulated mineral article comprising the plastic in the form of particles of thermoplastic and thermosetting resin material within a thermoplastic matrix. It is desired to obtain more highlights for polyester materials »to chemically resistant polyesters, of the filling type» especially decorative »enhancements that include better thermal conformability in large parts» greater rigidity »better resistance to impacts and higher thermal resistance. Accordingly, it is desirable to provide polyester materials having enhanced structural properties without sacrificing decorative surface properties and chemical resistance. Additionally it is desirable to provide economically decorative and chemically resistant polyester materials that exhibit shrinkage and reduced shear shrinkage during molding operations. The patent of E.U.A. 4,737,414 of Hirt et al. Discloses a mixed multilayer material in which a layer comprising an aromatic polyetherimide is adjacent to a layer comprising an aromatic polyester. An adhesion layer of a carbonate copolyester is written.

BRIEF DESCRIPTION OF THE INVENTION The compositions of the present invention provide an inexpensive polyester material having enhanced portion strength and need without undesirably affecting the desirable decorative surface and chemical resistance properties. According to the present invention, a mixed thermoplastic material comprising an extruded, thermally conformable, self-supporting sheet having a layer of polyester is provided. exterior decorative filling »chemically resistant and renewable» and an adjacent indoor self-supporting thermoplastic layer to enhance the desirable mechanical properties of the mixed body. The outer decorative polyester layer comprises a dye »an inorganic filler» an effective amount of a stabilizer »a UV stabilizer and optionally polisarbonate» and / or an impact modifier. To enhance the mechanical properties of the overall mixed composite the adjacent inner thermoplastic layer comprises a thermally deformable layer having mechanical properties such as impact resistance and melt strength which desirably exceeds these properties possessed by the outer polyester layer. Also provided is a method for preparing a decorative article comprising extruding a multi-layer sheet "feeding at least two different resin compositions into an extruder" by extruding said two at least resin compositions into the multi-layer self-supporting co-extruded sheet and thermally forming at least a portion of said sheet extruded to an exhaust article in which at least one outer surface of the article comprises a resin and an adjacent layer comprises the other resin. One resin comprises the decorative layer and the other layer includes the support layer "as previously discussed.

DESCRIPTION OF THE PREFERRED MODALITIES The thermoplastic composite material comprising an extruded thermoplastic self-supporting sheet has a chemically-resistant exterior decorative filled polyester layer and an adjacent thermoplastic support layer for enhancing the desirable mechanical properties of the composite body. Both layers are formed from extrudable reein compositions. It is contemplated that a layer with baterizer or adherent intermediate to the decorative layer and the backing layer may be included. It is also contemplated that the backing layer may be a laminated or multi-layered structure including the regrind layer of unused resin material or waste that is desirable to be recirculated. It is also contemplated that another polyester layer adjacent to the backing layer may be used so that the inside of the sheet "both top and bottom are formed from a material of the polyester type. The layer immediately adjacent to the outer decorative sap is also contemplated to be another layer of filled polyester material. Preferably »this second polyester sheet is made of colored polyester material having a color that is in contrast to the outer decorative layer-Removing a portion of the outer sheet by mechanical or other means» the color of the layer will be revealed adyasente. Accordingly, a decorative design can be imparted to the sheet material using an adjacent layer that contrasts with the outer layer and removing the outer layer in a pattern. The following consideration related to the preparation of a mixed multi-layer body refers to the coextrusion of multiple layers using a plurality of extruders. Each layer is desirably formed from a single extruder with multiple layers formed using a number of extruders corresponding to the number of layers desired and an annealed mold assembly, in order to produce the appropriate number of layers. According to the co-extrusion process, a plurality of common extrusion machines can be used. Typically, the extruder has a housing having a central opening with an ericoloidal screw for rotation along an inner axis to a drum portion. A motor drives the screw through a gear reducer. At one end of the opening »a hopper is used to feed the material by extruding the back portion of the screw. The siloisoidal threads provided on the screw are soldered to move the material of the posterior portion of the screw to the anterior portion. As the material or feeding twill is carried along the screw, the feed twill is heated by the frictive phases, which are damaged by the screw rotation. It is also contemplated that an external heating source "such as electrically resistant heaters" can be provided to heat the feed load. To form a multi-layer extruded sheet, the feed charge in molten form of a respective extruder is fed to a mold assembly. Coextrusion systems for forming films or sheets of multiple layers of thermoplastic materials are generally known »as shown for example in DuBois and Pribble» "Plástic Mold Engineering Handbook" »Fifth Edition» 1994 pages 524 to 529. As described » Feeding several molten polymer bath beads of the respective extruders having a feed block for combining the upstream thermoplastic layers without finishing mold dispersion which is generally of the sucker type is also referred to as the "fish only" type. " From the point of combining the molten bath castings, the mold is used to form the molten bath streams combined in a needle in which the layers have been spread to make a multi-layered product. The thickness of each layer in the final sheet is proportional to the thickness of its particular feed block. Other structures provide a mold cavity for receiving the separate tubular system "so that the combination of the layers immediately after leaving the tubular system" takes place inside the mold itself and is as close as possible to the chamber entrance. expansion. The tubular system comprises a plurality of distribution behaviors of "slotted" layers opening to the expansion chamber »the conduits comprising mutually separated openings • with each other that are parallel to the opening of the uradas. The resultant multilayer extruded sheet can be transformed into a final article of desired configuration, by thermal forming methods known in the art. The thermal shaping comprises simultaneously heating and transforming the extruded sheet into the desired configuration. Once you have obtained the The desired configuration cools the article formed below • its thermoplastic temperature and it is removed from the mold. In vacuum molding, the extruded sheet is placed on a concave mold and is heated, for example, with an infrared heater. Vacuum is applied to extract the extruded sheet to the correct place against mold savity. The above can be modified by combining positive air pressure on the extruded sheet with vacuum from the lower side to increase the molding force. In machi brado or compression molding, molds or machimbrados male and female dies are used and the sheet is formed extruded between the mechanically compressed molds. The molds are typically made of a metal having high thermal connectivity such as aluminum. The methods and tools for thermal shaping are described in detail »in Dubois and Pribble» "Plástic Mold Engineering Handbook" » Fifth Edition »1995, pages 168 to 49S. The "chemically resistant" outdoor decorative filled sapa is a polyester material. The polyesters include those that have the measures of the following formula: O O 11 1! 0 * or s A1 c wherein is independently an aliphatic hydrocarbon, divalent aromatic alicyclic or polyoxyalkylene radical. or mixtures thereof and each A3- is independently an alicylisic or divalent aromatic aliphatic radical or mixtures thereof. Examples of suitable polyesters containing the structure of the above formula are poly (alkylenecarboxylates), liquid crystalline polyesters and polyester polymers. It is also possible to use a branched polyester in which a branching agent has been fed, for example, a glisol having three or more hydroxyl groups or a trifunctional or multifunctional sarboxyseous acid. In addition, it is sometimes desirable to have several acid sonsentrasions and hydroxyl end groups in the polyester, depending on the final end use of the composition. The radisal R can be, for example, an alkylene radical of Ca_aLO, a radisalis of Cß_ ss, an aromatic radical of Cß_ao or a radisal polyoxyalkylene in which the alkylene groups contain approximately 2-6 and very often 2 or 4 atoms. of carbon. A radical Ax in the above formula is 10 very often p- or m-phenylene »a cycloaliphatic or a mixture thereof. This class of polyester includes poly (alkylene terephthalates). Such polyesters are known in the art as illustrated in the following patents which are incorporated herein by referensia. 2 »465» 319 2,720,502 2 »727» S81 2 »S22» 34B 3,047 »539 3» 671 »4B7 3,953,394 4,128,526 Examples of aromatic dicarboxylic acids represented by the dicarboxylic residue AA are isophthalic or terephthalic acid» l »2-di ( p-carboxy nyl) tano »4,4'-dicarboxydiphenyl ether» 4'4 acid, bisbenzoic acid and mixtures thereof. Acids containing fused rings, such as 1,4-, 1,5- or 2,6-na-allenedicarboxylic acids may also be present. Preferred dicarboxylic acids are terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexanedicarboxylic acid or mixtures thereof. The most preferred polyesters are polyethylene terephthalate ("PET"), and poly (1,4-butylene terephthalate ("PBI"), polyethylene naphtanoate ("PEN"), polybutylene naphtanoate, ("PBN") and polypropylene terephthalate ("PPT"), and mixtures thereof The above polyesters are also contemplated herein with minor sanities "for example" of about 0.5 to about 5 weight percent "of units derived from aliphatic acid and / or aliphatic polyols to form copolyesters Aliphatic polyols include glycols »such as poly (ethylene glycol >); or poly (butylene glycol). Such polyesters can be made following the teachings "for example" of the U.S. Patents. Nos. 2,465, 319 and 3,047,539. The preferred poly (1,4-butylene terephthalate) resin used in this invention is one which is obtained by polymerizing a glycol component of at least 70% mol, preferably at least 80% mol, which consists of tetramethylene glycol , and an ester acid component of at least 7054 mol, preferably at least 80 mol%, which consists of terellic acid, and derivatives formed of polyesters therefor. The preferred polyesters used herein have an intrinsic viscosity of from about 0.4 to about 2.0 dl / g as measured in a mixture of phenol / tetrachloroethane at 60:40 or similar solvent at 23 ° -30 ° C.

Preferably, the intrinsic viscosity is from 1.1 to 1.4 dl / g. Preferably the polyester composition includes a decorative component. Typical decorative components include dyes in the form of dyes or fillers. One such decorative dye is described in the patent of E.U.A. 5,510,398 to Clark et al. A marbled surface is formed by means of a non-dispersing pigment as opposed to a filler "because the non-dispersing pigment does not mix appreciably with the base color of the resin. Instead "the non-dispersing pigment provides a separate color" visibly distinct and identifiable at numerous sites across the surface of the material wherever the pigment material is visible. In other words, the mottling is visible in the filled polymer matrix as a different region of contrasting solor. The preferred polyester composition is a combination with one of polysarbonate. The polysarbonate resins useful in the preparation of the combinations of the present invention are preferably aromatic polysarbonate resins. Typically these polycarbonates are prepared by re-targeting a dihydric phenol with a carbonate precursor, such as phosgene, a halogenoformate or a carbonate-ester. The carbonate polymers can be characterized as having recurring structural units of the formula or II O A or C wherein A is a divalent aromatic radical of the dihydric phenol used in the reaction to produce the polymer. The dihydric phenols which can be used to provide such aromatic carbonate polymers are mononuclear or polynuclear aromatic compounds which contain as functional groups two hydroxy radicals, each of which is directly bonded to a carbon atom of an aromatic nucleus. Typical dihydric phenols are: 2, 2-bis (4-hydrox-phenylpropane, hydroquinone, resorcinol, 2,2-bis (1-hydroxyphene D-pentane, 2, t- (dihydroxydiphenyl) methane, bis (2-hydroxyphene) ethane; bis (4-hydroxyphenyl) methane; l, l-bis (4-hydroxyphenyl) -3,3,5-rimethylcyclohexane; luorenonbis enol, 1-1-bis (4-hydroxyphenyl) ethane; 3,3-bis (4-hydroxyphenyl) Ipentane, 2,2-dihydrodiphenyl, 2,6-dihydroxin, tadalane, bis (4-hydroxyphenyl) sulfone, bis (3,5-diethyl-4-hydroxyphenyl) sulfone, 2,2-bis (3,5-diforomo-4) -hydroxy enyl Jpropane; 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 2,4-dihydroxydiphenylsulfone; 5 * -chloro-2,4'-hydroxydiisulin; bis- (4-hydroxyphenyl) diphenylsulfone; 4,4'-dihydroxydiphenyl ether, 4,1'-dihydroxy-3, 3-dichlorodiphenyl ester, 4,4-dihydroxy-2,5-ihydroxydiphenyl ether, and the like, other dihydric phenols are disclosed which are also suitable for use in the preparation of the above polycarbonates in US Patents Nos. 2,999.8 35; 3.038.365; 3.334; 154; and 4 »131.575. These aromatic polycarbonates can be prepared by known processes, such as, for example and as mentioned above, by reacting a hydrophobic phenol with a precursor of sarbonate, such somo-phosphorus according to the methods set forth in the aforementioned literature. in the US patent No. 4,123,436, or by transesterification methods, such as those disclosed in the US patent. No. 3,153.00B, as well as other methods known to those skilled in the art. It is also possible to employ two or more different dihydride phenols or a polyol of a dihydric phenol is a glycol with a polyester terminated with hydroxy or in acid or is a dibasic acid in case a sopolymer or interpolymer is desired instead of a "aarbonate" homopolymer for use in the preparation of the polysarbonate mixtures of the invention. It is also possible to use polyarylates or polyester resins of a carbonate or its biosiones. Branched polycarbonates are also useful, such as those described in U.S. Pat. No, 4,001,184. Also »you can use linear polycarbonate and a branched polysarbonate. further, combinations of any of the above materials may be employed in the practice of this invention to provide an aromatic polycarbonate. In any case, the preferred aromatic sarbonate for use in the practice of the present invention is a homopolymer, for example, a homopolymer derived from 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A) and phosgene, available commercially with the LEXAN factory designation, registered trademark of General Electric Company. The present polycarbonates are preferably high molecular weight sarbonate aromatics »polymers having an intrinsic visuosity» as determined in chloroform at 25 ° C, approximately O.3 to about 1.5 dl / g, preferably from about 0.45 to about 1.0 dl / g. These polycarbonates can be branched or unbranched and will generally have a weight average weight average weight of about 10,000 to about 200,000, preferably from about 20,000 to about 100,000, as measured by gel premeasuring chromatography. The branched polycarbonates can be prepared by adding a branching agent during the polymerization. These branching agents are well known and can comprise polyfunctional organic compounds containing at least three functional groups which can be hydroxyl »sarboxyl» carboxylic anhydride »halogenoformyl and mixtures thereof. Some specific examples include the strong trimethylism, trimethylisohydride, trimethyl trichloride, tris-p-hydroxyphenyl-ethane, isatin-bis-f-nol, tris-phenol, TC (1, 3, 5-tris (p-hydroxyphenyl) isopropyl) benzene). , ris-phenol PA (4 (4 (1 »1-bis (p-hydroxy-n-ethyl) -alpha), alpha-di-ethyl-benzyl) phenol)» 4-chloroformyl-phthalic anhydride, trimesic acid and benzophenoltetracarboxylic acid. the branching agent at a level of about 0.05-2.0 by weight .. Branching agents and methods for making branched polycarbonates are described in US dimension patents Nos. 3 »635» 985; 4t 001.184? and 4 »204.047 which are incorporated by reference. It is contemplated that all types of polycarbonate end groups are within the scope of the present invention.

It is further preferred to employ an inorganic filler of the thermoplastic resin to impart additional bene? Cial properties such as thermal stability, increased density and texture. Inorganic fillers provide a sensation similar to that of ceramics to articles formed thermally from a resin somposision. Preferred inorganic fillers that are used in the present thermosetting compositions include: zin oxide »barium sulfate, zirconium silicate» strontium sulfate »as well as mixtures of the above. The preferred form of barium sulfate will have a particle size of 0.1-20 mers. Barium sulfate can be obtained from a natural or synthetic source. The molding compositions may include 20-85% by weight, preferably 30-75% by weight and more preferably 30-45% by weight of the composition of an inorganic filler component. For certain applications where ceramic-like products are desired, more than 50% or more preferably 60-85% by weight of the total composition of the filler component should be used. The filler material is chosen to enhance the decorative properties and the renewable properties of the resin sheet. The sulfate salts of metals as well as hydrates are the preferred mineral fillers. Preferred salts of metal sulfates are the metal sulfates of group IA and the group of IIA, with barium, calcium and magnesium sulfates being preferred. Especially preferred is barium sulfate which is nontoxic and insoluble in lurid acids. The barium sulfate can be in the form of baritines present in nature or co or barium sulfate synthetically derived using well-known synthetic techniques. The particle size may vary from 0.5 to 50 microns, preferably from 1 to 15 microns and more preferably to 8 microns. The composition desirably contains impact modifiers such as a rubber impact modifier. Preferably, such impact modifiers are used in an amount of less than about 30 and preferably less than about 20%, more preferably less than about 15% by weight based on the total weight of the deposition. Preferred thermal forming additives for forming thermics have a linear or radial (branched) A-B-A block constraint. They include styrene-budiene-styrene (SBS) and styrene-isoprene-styrene (SIS). A diblock polymer of the styrene-ethylene-ethylene / propylene (SEP) type can also be included. The most preferred thermoforming additive is a block structure A-B-A of the styrene-ethylene / butylene styrene (S-EB-S) type. The filled polyester molding composition includes a polygon resin an inorganic filler material, a polycarbonate resin; and an effective amount of styrenic modifier which can include random random »block and radial block polymers. The particularly useful class of modifiers comprises AB (in diblock) and ABA (in triblock) polymers, »alkenylene aromatic compounds, especially those comprising styrene blocks. The conjugated diene blocks can be unsaturated »partially or entirely hydrogenated» whereby they can be represented as ethylene-propylene or other blocks and have properties similar to those of the olefin block copolymers. Examples of triblock copolymers of k10 are polystyrene-oligo-styrene-polystyrene (SBS) »polystyrene-polybutadiene-polystyrene (SEBS) hydrogenated polystyrene-polyisoprene-polystyrene (SIS), poly (a-methylstyrene) -obutadiene-poly (a) - ethylstyrene) and poly (α-ethylstyrene) - oliisoprene-oli (α-methylstyrene). The Particularly preferred triblock copolymers are commercially available as CARIFLEZ ---. Kraton D--, and KRATONGj-. of Shell. The impact modifiers typical of one or more selected onomers are derived from the group consisting of JO olefins, vinyl aromatic monomers, acrylic acids and alkylacrylics and their ester derivatives as well as co-occurring dienes. Impact modifiers include high molecular weight rubber materials including natural polymeric materials and synthetics that show elasticity at temperature The environment includes both homopolymers and copolymers "including random copolymers" in block "in radial block" of graft and ion layer "as well as combinations thereof. Suitable modifiers include core-shell polymers formed from a rubber-like core on the sual where one or more layers have been ingested. The core consists of substantially regulating an acrylate rubber or a butadiene rubber. One or more layers are usually grafted onto the core. The layer preferably comprises an aromatic vinyl composition and / or a vinyl bond and / or alkyl methacrylate. The nickname and / or layers often comprise motimo-functional compounds which can act as an entanglement agent and / or as a grafting agent. These polymers are usually repaired in several stages. Olefin-containing copolymers such as olefin acrylates olefin diene interpolymers can also be used as modifiers in the present compositions. An example of an olefin asprilate sopolymer impasto modifier is ethylene ethylacrylate.

Other higher olefin monomers can be used in the polymers are alkyl acrylates, for example, propylene and n-butyl acrylate. The olefin diene terpolymers are too many in the art and fall generally within the EPDM (ethylene-propylene-diene) family. Polyolefins »such as polyethylene» polyethylene copolymers by alpha-olefins »are also useful in those compositions. Polyolefin eopolytes with acrylates or glycidyl methacrylates are espe- cially effective at odorifing the impact of oxygen. combinations containing polyester. Styrene-containing polymers can also be used as impact modifiers. An example of such polymers acrylonitrile-butadiene-styrene (ABS), acrylonitrile-butadiene-alpha-ethylstyrene "styrene-butadiene" styrene, butadiene styrene (SBS) »styrene ethylene butylene styrene (SEBS), ethacrylate-butadiene-styrene (MBS) , and other polymers that contain high impact styrene. Impact modifiers are typically based on a high molecular weight styrene-diene rubber. A preferred class of rubber materials are copolymers "including block randomized copolymers" and grafting of vinyl aromatic compounds or dienes. Examples of these materials are hydrogenated, partially hydrogenated or non-hydrogenated block copolymers of the type ABA and AB, where A is polystyrene and B is a dienoelastomer, ie polybutadiene, polyisoprene, polystyrene between the styrene radial block and a polystyrene. dieno sonjugado in Y, styrene odifisado by resins aclisas-resins of utadieno and similars; and xarrage copolymers obtained by copolymerase from a monomer or mixtures of monomers containing a styrenic compound with the main substance to a rubber-like polymer. The rubber-like polymers used in the graft copolymer are already described herein, without the addition of polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer, copolymer-butylene, polyacrylate copolymer and the like. Styrenic compounds include styrene, methylstyrene, dimethylstyrene, isopropylstyrene, α-methylstyrene, ethylvinyltoluene, and the like. The processes for the preparation of these polymers are found in the patents of E.U.A. Nos. 4 »196» 116; 3 »299,174 and 3,333,024, all suals are insorporated by reference. An effective amount of a block copolymer of type A-B-A as an impact modifier can be used. In accordance with the principles of the present invention, the ingredient of the type A-B-A is present in an amount sufficient to enhance the thermal stability of the articles produced from the resin. A is a polymerized monoalkenyl aromatic hydrocarbon block and B is a polymerized conjugated diene hydrocarbon block. In the previous type, blocks A typically constitute 30-50% by weight of the copolymer and the unsaturation of block B has been reduced by hydrogenation. The filled polyester molding composition of the present invention comprises 5-40 parts by weight and preferably 10-30 parts by weight of the block copolymer. With respect to the hydrogenated block polymers of the type A-B-A, they have been obtained by means of silicates in the tansy and are obtainable commercially. These materials are described in the US patent.

No. 3,421,323 to Jones "which is incorporated herein by reference. Prior to hydrogenation, the terminal blocks of these copolymers comprise homopolymers or copolymers preferably prepared from aromatic alkenyl hydrocarbons and particularly aromatic vinyl hydrocarbons in which the aromatic moiety may be either oncyclic or polycyclic. The monomers include styrene. alpha-methylstyrene »vinylxylene» ethylvinylxylene »vinylnane and similar» or mixtures thereof. The central core can be derived, for example, from polyisoprene or polybutadiene. The ratio of the polymers and the average molecular weights can vary widely, although the molecular weight of the central block must be greater than the combined terminal blocks. Typically, the terminal blocks A have average molecular weights of 4, OOO-115, OOO and the sentral block B, for example a block of polybutadiene, are an average weight of 20,000-450,000. Even more preferably, the terminal blocks have average molecular weights of 8,000,000-60,000, while the polybutadiene polymer blocks have a weight of between 50,000 and 300,000. The terminal blocks may comprise 2-50% by weight or »more preferably» 5-30% by weight of the total block polymer. The preferred sopolymers will be those formed from a polypolytadiene block having a sentral block in which 35-55% or more preferably, 40-50% 40-50% of the butadiene carbon atoms are lateral loads of vinyl. Block sopolymers, such as Kraton G-GXT-0650, Kraton G-GXT-0772 and Kraton G-GXT-0782 are obtainable from Shell Chemical Company »Polymers Division. Block copolymers of type A-B-A can also be considered with respect to block copolymers A'- B'-A '. The relationship of the co-monomers can vary widely. Typically, the molecular weight of the central block is greater than that of the combined terminal blocks.

Preferably, with the above limitation, the molecular weight of one of the terminal blocks will vary from about 2000 to about 100,000"while in the central block it will vary from about 25,000 to about 1,000,000. The impact modifier is desirable present in an amount from 0 to 40 percent in peos, preferably from 4 to 15 per cent, and for deep imbedding sheets »refers to a higher level in the order of 20 to 40 percent . In thermoplastic compositions containing a polyester and a polycarbonate resin, it is preferable to use a stabilizing material. Typically, such stabilizers are used at a level of O.O.sup.-1% by weight and preferably at a level of 0.05-2 weight percent. Preferred stabilizers include an effective amount of an acid phosphate salt; an acid, mixed alkyl or aryl phosphite having at least one hydrogen or alkyl group; a metal phosphate salt of Group IB or Group IIB; a phosphorous oxo acid, an acid metal pyrophosphate or a mixture thereof. The suitability of a particular compound for use as a stabilizer and the determination of how much to be used as a stabilizer can be determined by preparing a mixture of the polyester component, the polycarbonate and the filler with the particular compound and without it, and determining the efesto. in the visuosity of the molten bath or the color stability or the interpolymer shaping. Acid phosphate salts include sodium acid phosphate, zinc monophosphate, potassium hydrogen phosphate, salty acid phosphate and the like. The phosphites can be of the formula: wherein Re »R" 7 and RT are independently selected from the group consisting of hydrogen, alkyl and aryl with the proviso that at least one of RG, "7 and Rβ is hydrogen or alkyl. The phosphate salts of a Group IB or Group IIB metal include zinc phosphate, envelope phosphate and the like. Phosphorous oxo acids include phosphorous acid »phosphoric acid» polyphosphoric acid or hypophosphorous acid. The polyacid pyrophosphates of the formula: Ms = H P O where M is a metal »x is a number that varies from 1 to 12 and y is a number that varies from 1 to 12, n is a number from 2 to 10» z is a number from 1 to 5 and the sum of ( xz) -fy is equal to n + 2. These compounds include aaHP ^ O ^ K ^ H ^ P ^ O ^; The particle size in the polyaside pyrophosphate should be less than 75 millimeters, preferably less than 50 millimeters and more preferably less than 20 microns. The preferred polyester layer comprises a decorative component, polycarbonate, an organic filler, a reinforcing material and a stabilizer. The polyester material preferably comprises Enduran ™ 7322 obtainable from GE Plastics component of General Electric Company is a preferred material of polyester resin for the outer layer. The preferred composition includes the following: polyester of about 10 to about 40 weight percent, with the polyester preferably comprising polybutylene terephthalate in an amount of about 7 to about 25 per cent and polyethylene terephthalate of about 3 to about 10 percent, aromatic polycarbonate from • about 10 to about 25 percent »stabilizer from about 0.01 to about 10 percent, impact modifier from 4 to about 15 percent» barium sulfate from about 30 to about 40 percent "the pigment or dyes being present in an amount effective to generate the desired effect on the surface and when combined with additional ingredients being present at a sanctity of less than about 5 percent. An adjacent thermoplastic support layer comprises a thermally deformable material having mechanical properties »such as impact strength and melt strength desirably exceeding such decorative polyester layer properties» in order to enhance the mechanical properties of the composite body. The thermoplastic organic polymers for the inner layer include acyl nitrilbutadienestyrene (ABS) »polycarbonate» combination of polycarbonate / ABS, a copolycarbonate-polyester, acrylic styrene-acrylonitrile (ASA), phenylene ether resins, polyphenylene ether / polyamide combinations (NORYL GTXR of General Electric Company), combinations of polycarbonate / polybutylene terephthalate and impact modifier (XENOY1 * by General Electric Company) »polycarbonate / PET / PBT binaaions, polyamides» phenylene sulfide resins »polyvinyl chloride (PVC)» polymethyl methacrylate (PMMA) »and high impact polystyrene (HIPS). A preferred embodiment for the support sap comprises a polymer of the type (ABS). In general, ABS type polymers contain two or more polymeric parts of different compositions that are chemically linked. The polymer is preferably prepared by polymerizing a conjugated diene, such as butadiene or a conjugated diene, with a monomer copolymerizable therewith, such as styrene, to provide a polymeric base structure. After formation of the base structure, at least one graft monomer is polymerized, and preferably two in the presence of the prepolymerized base structure to obtain graft polymer. These resins are prepared by methods well known in the art. The polymer of base structures, as mentioned, is preferably a conjugated diene polymer, such as polybutadiene, polyisoprene, or a polymer, such as butadiene-styrene, butadiene-acrylonitrile, or the like. Examples of dienes which can be used are butadiene, isoprene, 1,3-hepta-diene, methyl-1 -3-pentadiene, 2, 3-dimethyl-1,3-butadiene, 2-ethyl-1,3-pentadiene; 1,3- and 2 »-hexadienes» butadienes substituted in chlorine and bromine, such as diclobutadiene, bromobutadiene, dibromobutadiene »mixtures thereof and the like. A preferred play diene is butadiene. A monomer or group of monomers that can polymerized in the presence of the prepolymerized base structure are the monovinyl aromatide hydrocarbons. Some examples of monovinyl aromatics and substituted vinyl aromatic compounds are "cycloalkyl" aryl. alkaryl »aralkyl» alkoxy »aryloxy» and others include styrene, 3-methylstyrene; 3-5-Diethylstyrene »4-n-propylstyrene» alpha-methylstyrene, alpha-methyl vinyl toluene »alpha -solotostyrene» alpha -bothostyrene »dicorostyrene, dibro-es-irene» tetra-chlorostyrene, mixtures thereof »and the like. The preferred monovinyl aromatic aromatic hydrocarbons which are used are styrene and / or alpha-methylstyrene. A second group of monomers which can be polymerized in the presence of the prepolymerized base structure are acrylic monomers such as acrylonitrile, substituted acrylonitrile and / or esters of acrylic acids exemplified by acrylonitrile and alkyl acrylates such as methyl methacrylate. Examples of such monomers include acrylonitrile »ethacrylonitrile, methacrylonitrile, alpha-chloroacrylonitrile» beta-chloroasrylonitrile »alpha-bromoacyl-nitrile» and beta-borochrylonitrile, methyl acrylate »methyl methacrylate» ethyl acrylate »butyl acrylate» propyl acrylate »acrylate of isopropyl and mixture thereof. The preferred acrylic monomer is acrylonitrile and the preferred acrylic acid esters are methyl acrylate and methyl methacrylate. In the preparation of the graft polymer, the conjugated diolefin polymer or copolymer employed by the 1,3-butadiene polymer or copolymer comprises approximately 50% by weight. % by weight of the total graft polymer composition. The monomers polymerized in the presence of the base structure "exemplified by styrene and acrylonitrile" comprise from about 40 to about 95% by weight of the total composition of the graft polymer. The second group of graft monomer »exemplified by acrylonitrile» ethyl acrylate or methyl methacrylate »of the graft polymer composition» preferably comprises from about 10% to about 40% by weight of the total composition of the graft monomer. graft copolymer. The monovinyl aromatic hydrocarbon exemplified by styrene comprises from about 30 to about 70% by weight of the total composition of the graft polymer. In the preparation of the polymer, it is normal to combine a certain percentage of the polymerization monomers which are grafted to the base structure, some are other and a free copolymer is present. If styrene is used, one of the graft monomers and acrylonitrile is the second graft monomer which has been added to the composition and copolyzed as a styrene-acrylonitrile-free copolymer. In the case in which the alpha-methylstyrene (or other monomer) is substituted for the styrene of composition used in the preparation of the graft polymer, only a percentage of the composition can be an alpha-methylstyrene-asyronitrile copolymer. Also, there are occasions where a sopolymer, such as alpha-methylstyrene-asyronitrile, is added to the polymer biosynthesis and graft sopolymer. When referred to herein "co-graft or combination of polymer and copolymer" is optionally meant to include at least one copolymer combined with the graft polymer composition and which may contain up to 90% free copolymer. Optionally, the elastomeric base structure can be acrylate rubber, such as a base of N-butyl acrylate, ethylacrylate, 2-ethylhexylacrylate, and the like. Additionally, minor amounts of a diene may be copolymerized in the base structure of the acrylate rubber to produce an improved graft with the matrix polymer. The preferred ABS material for the support layer comprises resin of CYCOLAC1 * GPX3800 and CYCOLAC1 * LSA »obtainable from the GE Plastiss component of General Elestris Company. Additional material for the support layer includes polycarbonate and polycarbonate blends. The polysarbonate is as described above, with Lexan ** resin »obtainable from the CE Plastics component of the General Electric Company. Polycarbonate resin sombinasiones can also be used. Preferred polisarbonate resin blends include Xenoypl1731, a polycarbonate-poly (butylene terephthalate) co-bination, CicoloyRMC8002 and MC8100 combinations of polycarbonate and ABS. The typical polyethylene ether resin is a poly (2 »6-dimethyl-4-phenylene ether) reine having an intrinsic viscosity of about OS dl / g at about 0.60 dl / g in chloroform. the present are well known in the tea industry and can be prepared from a number of non-catalytic and non-catalytic processes from the corresponding phenols as well as reagents thereof. Examples of polyphenylene ethers and methods for their production are disclosed. US Patent No. 3 »306» 874; 3 »306, 875; 3,257,357 and 3,257,358 »all inaorporated in the present by referensia. The typical polyamides prepared for the present invention can be obtained by polymerizing a monosarboxylic acid or a lactam thereof having at least 2 carbon atoms between the amino group and the sarboxylia acid group; or polymerizing substantially equimolar propions of a diamine which contains at least 2 sarbono atoms between the amino groups and diaarboxylic acid; or by polymerizing a solid monoaminesarboxylic acid or a lastam thereof as defined above together with substantially equimolar proportions of a diamine and a dicarboxylic acid. The dicarboxylic acid can be used in the form of a functional derivative thereof, for example an ester.

The ENDURAN1 * 7322 resin multi-ply structures with other resins offer lower cost alternatives to the single layer ENDURAN1 * 7322 resin while maintaining the surface appearance of a resin layer ENDURAN11 7322ENDURAN »7322 replacing a portion of the resin layer ENDURAN3 * 7322 are resins to lower susto. The performance properties, such as thermal resistance stiffness »impact resistance and / or flammability in the structures, are improved by feeding materials that enhance these properties in relation to the performance of the single layer ENDURAN1 * 7322 resin. Treatment advantages in thermal shaping are also achieved by feeding materials with higher melt strength in the single layer structure of one of the larger parts can be thermally formed. The multi-layer structures of ENDURAN1 * 7322 can be combined with several other resins to produce systems with reduced cost and / or improved performance. These other resins include ABS (CYCOLAC resin * GPX3800 »CYCOLAC resin» LSA »PC / PBT blends (XENOYR), polycarbonate (LEXAN1 * resins), PC / ABS blends (CYCOLOY * MC8002 resins, CYCOLOY * MC8100 resin), base blends of resin PP0R (resin N0RYLR, polyvinyl chloride (PVC, and high impact polystyrene (HIPS).) These resins may also contain reinforcing fillers (such as glass fibers) that increase the rigidity of the structure. Struts by extrusion and may consist of one or more different materials in addition to the ENDURAN11 7322 layer. The sacks may include material of regrind The sheet produced by coextrusion can be thermically shaped later to manufacture parts The sheet with the manufactured parts maintain the qualities of surface (appearance, feel, etc.) and ENDURAN1 * 7322 single-layer products and can also be used with special color effects used with ENDUR's single-layer sheet AN1 * 7322. The thermal deformation of the sheet is carried out by collating the sheet on a conical mold and heated, for example, by an infrared window cleaner. It is vacuum-packed to extract the extruded sheet to the correct place against the mold cavity. Co-injections of ENDURAN1 * 7322 have been extruded are CYCOLAC3 * CGX3B00, CYCOLAC ** LSA and CYCOLOY1 * MC80O2 and formed thermally from a 30.48 cm by 30.4B cm tool with a depth of 2.54 cm. All the corabinasiones have produced leaves of good salience are adhesion and sompatibility of good materials. The thermically formed pieces retained the admission of the sapas and the saliency of the superfisie. Other combinations are being extruded and thermally forming. Multiple flutes can be used either as surface coating materials (top countertop surfaces or wall coverings) in the form of a struded sheet or any thermoforming embedding that involves the resin in ENDURAN ** 7322, such as sinks or tubs . The preferred thickness of the outer decorative layer is about 0.0508 mm to approximately 6.35 mm, with the preferred thicknesses of the thermoplastic reinforcing layer being about 1.27 mm to about 12.7 mm. Preferred multilayer structures include the following which are exposed to continuation: ENDURAN ™ resin / CYCOLAC1 * resin to thermally form scrubbers and other articles. A two-walled shell having a total thickness of 5.08 μm to 10.16 μm »preferably 7.62 μm, with the outer top layer being 15 to 40% of the total thickness. ENDURAN ^ / CYCOLAC1 * for surface coating applications such as users and walls. A two-layer structure having a total thickness of 2.92 to 3.18 μra, the outer top layer being 15 to 30% of the total thickness. ENDURAN ^ M / ENDURAN ™ for decorative applications of surface coating, in which a design is developed by removing a portion of the outer layer to expose a sapa adyasente. A two-layer shell having a total thickness of 2.92 to 3.18 μm, with the upper outer layer of the to 30% of the total thickness. A two-layer structure comprises resin ENDURAN ^ / r CYCOLAC1 * sine and regrix mix. The upper outer layer is approximately 33% of the total thickness. The total thickness is 2.92 μm. The resin CYCOLAC1 * and the mix • Trailer contains 50% by weight of trailer. A structure of three sapphires resists resin 5 ENDURAN ^ / resin CYCOLAC ** and mixture of trawl / resin CYCOLAC1 *. The outer top layer is approximately 33% of the total thickness. The total thickness is 2.92 μm. The CYCOLAC1 * resin and the trawl mix contain 50% by weight of trawl. The lower layer of CYCOLAC1 * resin is 33% of the total thickness. As referred to in these examples, the regrinding layer comprises polyester resin and acrylonitrile-butadiene-styrene resin which remain after treatment in the form of waste and excess material. The waste material is crushed and insorporated in the estrustura of multiple sapes separate somo sapa or part of an acrylonitrile-butadiene-styrene resin sap. A highly preferred two-layered structure comprises • a co-extruded layer of ENDURAN ™ 7322 »square 1» adjacent to a layer of CYCOLAC resin ** 29344A, square 2. The resin ENDURAN ™ and CYCOLAC1 * resin are available from GE Plastiss component of General Electric Co pany.

TABLE 1% in Weight of Endurant resin * "of the ingredient based on% in total weight.

TABLE 2% weight of resin Cicolac1 * of the ingredient based on the total weight 360 HRG-high rubber graft ABS 60 570 SAN-styrene-acrylonitrile 40 Pluronic F-88- 0.2 Anti-oxidant stabilizer Hingstay® L 0.15 Stabilizer Ultranox® 626- chemical products GE Specialty 0.2 Silicone Fluid 0.10 Santicizer 0.40 The desired thickness of the coextruded sheet is more dependent on the use of the sheet. Generally, the total thickness of 0.508 to 12.7 m is preferred, the thickness of the Enduran resin layer being from about 5 to about 85 percent of the total thickness. In some three they expose some of the preferred thicknesses for different types of uses.

TABLE 3 Coextruded resin thicknesses Enduran / Cicolac resin For a two-layer coextruded, it is highly desirable that the sheets be compatible so that the layers adhere. It is desirable to avoid ingredients in one layer that could react with the ingredients of the other layer. The above layers are compatible and are characterized by the absence of reactive materials, such as some oxides of metals such as magnesium oxide. To achieve adequate moisture it is contemplated that the foam layer may be adjacent to the support or interior layer. Typically »the foam layer has a density reduction of 10% to 50% for a lower cost» appropriate weight and moisture reduction. The foam can be foamed in place. See E.U.A. 5,486,407 from Noell et al. It is also contemplated that the inner support layer can be adhered to a cellulose-based material such as particle-cutting, fiber-cutting, felling of overlapping wood chips and wood. It is also contemplated that abrasive resistant coatings may be used, such as described in US Pat. No. 5,446,767, in connection with the present invention. Thermal forming methods can be used as set forth in the U.S. patent. 5,601,679 of Mulcahy et al. A so-extruded sheet can be confirmed under vacuum. Typically, the vacuum molder and the surrounding metal structure can be preheated to minimize cooling of the sheet. The sheet is placed on a sheet of sand and mounted on the bottom side of the moulder or pattern. The abrasive structures are designed to mechanically hold the blade in place. A suitable thermal protector, such as an aluminum foil, can be used to avoid heating the surface at selected locations such as a different portion of a sink. The sheet is then placed in the thermal blast furnaces. Upper and lower heaters are used. During the heating »the leaf starts to convave. Once the sheet reaches its proper forming temperature, the assembly is moved alternately to a vacuum forming box in the sink to conform to the vacuum in a box. The box has a plurality of openings in a mold to attract the sheet to the mold, during the shaping operation. After cooling »the resulting thermally formed sheet is removed. The following. Specific examples illustrate the present invention. The examples set forth in Table 4 are for comparison purposes »the formulations 4 and 6 illustrating the results employing the preferred clock modifiers of the present invention.

TABLE 4 Table 4 contains comparative studies of rheology modifiers in unfilled systems. Regardless of the modifier used, the elongation of molten bath of the resulting formulation is completely superior to 555%. Therefore, these systems do not differentiate between the used rheology modifiers. Table 5 is directed to the comparison of rheology modi icators in filled systems.

TABLE 5 Clearly »the elongation of molten bath decreases considerably when moving from unfilled systems to filled systems. The formulations 1 »2» 9 »10» 11 have the highest elongation of molten bath and all of them are modified are Kraton G1651. For those skilled in the art, the modification of the rheology of unfilled PC / PBT for enhanced blow molding and / or thermal shaping are achieved using core / layer modi? Ers in single phase or double phase modi? Cation. In the barium sulfate-filled formulations outlined above, formulations 3 to 8 have the lowest melt bath elongation, although the core / shell modifiers < I? E0M, MBS) are being used. Another important test result of this study is vertical wall thickness after thermal shaping. The vertical walls in the thermally formed part are the most susceptible to thinning. The thinning of the piece is an important measure of the distribution of material in a given piece. Again, formulations 3 to 8 have the highest thickness retention, while those with Kraton G1651 have the highest. Consequently »taking into account the elongation of molten bath and the vertical wall thickness, the formulations that are Kraton G1651 perform better than those containing HEOM and / or MBS. Table 5 shows the influence of the high molecular weight acrylic polymer. According to reference 11 »these additives improve the melting strength of unfilled PB / PBT mixtures, TABLE 6 The addition of the high molecular weight acrylic polymer clearly improves the elongation of the molten bath with the formulations 4 to 7 as compared to the formulation 3. However, if they have a detrimental effect on the retention of thickness; thus "they are detrimental to the thermal shaping and / or blow molding of the filled PC / PBT mixtures. Preferred compositions have a molten bath elasticity as% elongation of about 300.

TABLE 7 In table 7 it is shown that impact modifiers of type A-B-A desirably have a high molecular weight in order to provide high elasticity of molten bath. In addition »the type of the rubber block afflicts the pasture of the final produsto» which is also important in its function as an article are formed as a useful entity. Although those skilled in the art have relied on modified polymers (crystalline and / or amorphous) to improve thermal formability and blow moldability, that assertion is not universal in the filled systems we are evaluating. Formulations 1 and 2 contain branched polysarbonate; however, its elongation of molten bath is less than that of the formulation containing a linear polycarbonate, but of high molecular weight. Furthermore, the thickness retention of the vertical walls of the thermally shaped parts containing polysarbonate is not as good as that of the polycarbonate of high linear molecular weight. We would rather propose the double concept of high molecular weight and branched as beneficial for thermal conformation and / or blow molding.

Claims (2)

1. NOVELTY OF THE INVENTION CLAIMS 5 1.- A mixed thermogenic body qu & it comprises an extruded thermally conformable self-supporting sheet having a decorative outer layer »chemically resistant and renewable» and an inner support thermoplastic sheet for enhancing the desirable mechanical properties of the core.
2. 2. A thermoplastic composite body according to claim 1 further characterized in that the decorative outer polyester layer comprises a colorant »an inorganic filler» an effective amount of a stabilizer and Optionally polycarbonate and an impact modifier 3. A mixed thermoplastic body according to claim 2 is also characterized in that the inner thermoplastic sheet comprises a thermally deformable sheet having mechanical properties such as impact strength and resistance to deformation. the melt »that desirably exceed those properties possessed by the outer polyester layer. 4. A mixed thermoplastic body according to claim 3 »further characterized in that the layer 25 adjacent inner thermoplastic comprises a mixture of acrylonitrile-butadiene-styrene »polycarbonate» polycarbonate / acryl nor rile-butadiene-irene, copolycarbonate-polyester »acrylic-styrene-acrylonitrile» acrylonitrile- (ethylene-propylene-diamine modified) -styrene »resins of phenylene ether »polyphenylene ether / polyamide blends» polybutylene terephalt and modified polystyrene blends »polycarbonate / PET / PBT blends» polyamides »phenylene sulfide resins» polyvinyl chloride »polyethylene ethacrylate (PMMA) ) and high impact polystyrene. 5. A thermoplastic mixed body according to claim 4 »further characterized in that said outer polyester layer comprises an inert mineral filler. 6. A thermoplastic mixed body according to claim 5 »further characterized in that said outer polyester layer comprises an inert mineral filler comprising barium sulfate. 1. - A thermoplastic composite body according to claim 6 »further characterized in that said outer polyester layer comprises from about 10 to about 40 weight percent polybutylene terephthalate or polyethylene terephthalate» aromatic polycarbonate of about 10% by weight. to about 25 per cent "stabilizer" from about 0.01 to about 10 percent "impact modifier from about 4 to about 15 percent, barium sulfate from about 30 to about 40 percent, and additional ingredients including pigment or SO tinctures present in an effective amount of less than 5 percent. 8. A mixed thermoplastic body according to claim 7 »further characterized in that said outer polyester layer and said adjacent inner layer are extruded and have a total thickness of 0.508 mm to 12.7 mm» where the thickness of said polyester layer it is about 5 to about 85 percent of the total thickness. 9. A thermoplastic composite body according to claim 6, further characterized in that said outer polyester layer comprises a thermally formed material comprising a two-layer structure having a total thickness of 5.08 mm to 10.16 mm with an outer shell that It comprises polyester material and it is 15 to 40 percent of the total thickness. 10. A mixed thermoplastic body according to claim 6, further characterized in that a multi-layer material comprises a sheet having a two-layer structure having a total thickness of 2.27 mm to 3.18 mm wherein said outer polyester layer it appears about 15 to 30 per cent of the total thickness and said inner layer comprises an acrylonitrile-bi-adieno-styrene resin. 11. A mixed thermoplastic body according to claim 6 »comprising at least one outer layer of polyester of two layers to have a decorative surface having said inner layer different from that of said outer layer, said design being developed by removing a portion of the outer layer to expose said adjacent layer, said two-layer structure having a total thickness of 2.29 m to 3.18 mm where said outer layer is from 15 to 30 per cent of the total thickness and said inner layer it comprises an acrylonitrile-butadiene-styrene resin. 12. A mixed thermoplastic body according to claim 6 »comprising at least two layers, said outer layer comprises polyester and said inner layer comprises a mixture comprising an acrylonitrile-butadiene-styrene resin and a trawling mixture» said outer layer is approximately 33 percent of the total thickness. 13. A thermoplastic composite body according to claim 1 comprising a 3-layer structure comprising an outer polyester layer and adjacent layers comprising an acrylonitrile-butadiene-styrene resin and a trailing layer comprising said layer of regrind a mixture of polyester and an acrylonitrile-butadiene-styrene resin. 14. A process for preparing a decorative article comprising extruding a multi-layer sheet incorporating at least two different resin compositions to an extruder, extruding said at least two resin compositions to the multi-layer self-supporting co-extruded sheet and shaping thermally at least a portion of said coextruded sheet co or a decorative article wherein at least one outer surface of the article comprises a resin and an adjacent layer comprises the other resin, said resin forming said outer decorative surface comprising a layer of polyester chemically resistant filled and an adjacent inner support thermoplastic layer to enhance the desirable mechanical properties of the mixed body. 15. A method for preparing a decorative article according to claim 14, further characterized in that said decorative outer polyester layer comprises a colorant »an inorganic filler, an effective amount of a stabilizer and optionally polycarbonate» an impact modifier or a UV stabilizer and mixtures thereof. 16. A process for preparing a decorative article according to claim 14, further characterized in that the adjacent inner thermoplastic layer comprises a thermally deformable layer having mechanical properties, such as impact resistance and melt strength that desirably exceed these properties possessed by the outer polyester layer. 17. A process for preparing a decorative article according to claim 14 »characterized in that the thermoplastic layer comprises acrylonitrile-butadiene-styrene» polycarbonate »mixture of poly arbonate / acrylonitrile-butadiene-styrene» copolicarbo-n p lies er »acrylic-styrene-acrylonitrile» acrylonitrile- (modified ethylene-propylene-diamine) -styrene »phenylene ether resins» polyphenylene ether / polyamide mixtures »polybutylene terephthalate / polybutylene terephthalate mixtures and impact modifier» polycarbonate / PET / mixtures PBT »polyamides, phenylene sulfide resins» polyvinyl chloride and high impact polystyrene. 18. A method for preparing a non-destructive sonicity article with claim 14, further characterized in that said adjacent polyester is selected from the group consisting of polyethylene ter talate (.tPETrt) and poly (l »4-butylene) terephthalate ( "PBT") »polyethylene naphtanoate (" PEN "), polybutylene naphtanoate C BH") and polypropylene terephthalate ("PPT") and mixtures thereof.