MXPA00012593A - Thermoset volatile monomer molding compositions and method for molding - Google Patents

Abstract

A molding composition including reactive high-volatility monomeric groups, such as acrylics, at least one primary thermal initiator and at least one secondary thermal initiator is described. Molding process using molding compositions including reactive high-volatility monomeric groups are also described.

Description

COMPOSITIONS OF THERMOSTABLE VOLATILE MONOMER MOLDING AND METHOD FOR MOLDING SUCH COMPOSITIONS BACKGROUND OF THE INVENTION 1. FIELD OF THE INVENTION This invention relates to a composition that includes volatile monomers, which are useful for thermoforming molding and to methods for molding the compositions, * 2. DESCRIPTION OF THE RELATED TECHNIQUE The compositions for thermosetting molding, also known as bulk molding compounds (BMC), sheet molding compounds (SMC) or thick molding compound (TMC), are well known and widely used. The compositions can be formed: in forms by compression, transfer or injection molding. During the molding process polymerization or crosslinking reactions, or both, are initiated thermally, which results in the composition being polymerized or "cured" in the shape of the mold cavity. The resulting articles; show resistance to heat, tenacity, rigidity and precision Ref: 124972 dimensional. The types of resin that are typically used include unsaturated polyesters, allyls, amines, epoxy resins, phenolics and silicones. However, it has been shown that some of these compositions are useful for producing articles / materials that have the aesthetics and manufacturing capability required for use in applications of. decorative surface coating. Acrylics in general have not been widely used for thermosetting molding in solid surface coating applications due to the high volatility of acrylic monomers, particularly methyl methacrylate. When introduced into preheated molds, a portion of the monomer can be volatilized before the polymerization / crosslinking reactions are carried out, resulting in poorer physical properties and visual defects. In addition, conventional molding of such compounds often results in the formation of internal and external voids, also related to the high volatility of the acrylic monomers. Acrylic molding materials are known which include a single thermal initiator. For example, published Japanese applications H9-110496A, H9-110497A, H9-111084A, H9-111085A and H9-111086A describe compositions that include methyl methacrylate monomer, polymethyl methacrylate polymer and a resin polymer powder having a core-shell structure. The molding of the thermosetting molding compounds is generally carried out by means of three fundamental molding techniques: compression molding, transfer molding and injection molding. A description of these molding techniques can be found in: Wright, Ralph E. , Molded Thermosets: A Handbook for Plastics Enaineers, Molders. and Designers, Hanser Publishers, Oxford University Press, New York, 1991. The choice of molding technique is determined primarily by the design and functional requirements of the molded article and the need to produce the molded article economically. Although each of these methods has some similarity with the others, each has its own design and operational requirements. Factors to consider when choosing a molding technique to make an article include, for example, characteristics of the design of the article, a design of the mold, molding procedures, selection and operation of the press and tools and devices after molding. The compression molding generally uses a hydraulically operated vertical press which has two plates, one fixed and one mobile. The mold halves are fastened to the plates. The previously measured molded composite load is placed in the heated mold cavity, either manually or automatically. Automatic loading involves the use of process controls and allows a wider application of the molding process. The mold is then closed with application of the appropriate pressure and temperature. At the end of the molding cycle, the mold opens hydraulically and the molded part is removed. The compression molding design consists essentially of a cavity with a plunger. Depending on the design of the final part, the mold will have several slots, ejection pins or movable plates to aid in the operation of the mold and removal of the molded article. Mold vaporization separation and dimensional tolerances can be adjusted to accommodate composite characteristics and part requirements. Transfer molding is similar to compression molding except for the method in which the load is introduced into the mold cavity. This technique is typically applied to multiple cavity molds. In this method the load is introduced manually or automatically into a cylinder connected to the mold cavities via a sliding system. A screw can be used to introduce the material into the transfer cylinder. A secondary hydraulic unit is used to drive a plunger which drives the molding compound through slides within the mold cavities of the closed mold. Then a vertical hydraulic press is applied with the necessary pressure at the appropriate temperature for compression in the mold of the designed part. The transfer mold design is a bit more complicated compared to the compression molds due to the presence of the transfer cylinder in the slides and due to internal mold flow considerations, but the general attributes are similar. The use of a shuttle press can be used to allow the encapsulation of molded inserts. In general, injection molding is closely related to transfer molding except that the hydraulic press is generally oriented horizontally and the molded compound is screw-injected into the closed mold cavities by means of a casting tube bushing and a system of gates and sliding doors. Then pressure is applied at the appropriate temperature to cure apart. The mold is opened for part ejection and removal, and then the mold is closed, and the next load is injected per the screw. This thermosetting molding technique has a significant advantage in the time cycle compared to the other techniques sized before. As such, it is widely used in multiple precavities molding applications. The injection molding designs are even more complex and require special attention for the flow - + *? ^ '- ¿&&. ~. of internal mold of the molded compound. In an extended injection molding application, a vertically oriented shuttle press can be used to allow the encapsulation of molded insert parts. In summary, the compression molding technique is mainly a semiautomatic method which typically shows at least part of shrinkage and the highest part density, but has the longest cycle time, is limited by its ability to produce pieces of molded insertion and is limited in terms of mold design complexity, and requires the greatest amount of work to finish the molded product (vaporization removal). Transfer molding and injection molding are semi-automatic and automatic methods, respectively, with shorter method cycle times, excellent operability in the production of molded insert parts and less work in the finishing of molded parts. Both techniques typically show a lower part density and an increased shrinkage versus compression molding. Despite the process differences in c.e molding techniques, thermosetting molds have several common characteristics in their design and use. These molds often run isothermally; an optimum molding temperature is maintained throughout the molding cycle. For reasons of cycle time, the mold cycling temperature is not common in high productivity applications. The high productivity molds are designed with internal channels to circulate hot oil or with internal electric heating elements for a faster response of the heating of the mold. If needed, cooling channels (oil or water) can be included. The molds can also be heated and cooled by contact with heated / cooled plates; this is representative of low volume production and prolonged cycles. Finally, the thermoforming molding cycles involve the immediate application of the final molding pressure through the pressure profiles (gradual application of pressure to a selected final molding pressure later in the curing cycle) that are used in various situations .

BRIEF DESCRIPTION OF THE INVENTION This invention is directed to a molding composition which is suitable for thermosetting molding. This composition includes at least one volatile monomer reactive material. The composition also comprises at least one viscosity increaser and at least two thermal initiators having different activation temperatures. Unless stated otherwise, the value in percent , ..- < ? A? T «jéqS» m < _l! < Mat - - * «_. in proportioned weight is based on the total weight of the molding composition. Specifically, the composition comprises: (a) from about 10 to about 25% by weight of a liquid polymerizable material that includes; at least one volatile monomer reactive material; (b) at least one viscosity increaser; (c) at least one primary thermal initiator having a half-life temperature of ten hours of primary thermal initiator; and (d) at least one secondary thermal initiator having an average life temperature of ten hours of secondary thermal initiator of at least 5 ° C greater than the average life temperature of ten hours of primary thermal initiator; (e) optionally at least one crosslinked nc polymer; (f) optionally at least one filling material; wherein at least about 0.05% by weight are one or more crosslinking agents. The invention is further directed to methods for making an article from the molding composition described above. The method used generally depends on the viscosity of the composition and the geometry of the mold. The method also depends on the type of molded article that is - * s_.y .. > »- is to be processed, that is to say, a solid part or part in which a non-reactive insert is encapsulated or covered. or nucleus In a first embodiment of the method, the composition is molded at a single temperature and pressure. In general, the mold loading unit or units are heated in an enclosed mold at a temperature sufficient to cause the secondary thermal initiator to pass through 3-10 half-lives within about ten minutes or less, and is maintained; at a pressure sufficient to maintain the internal and surface integrity of the mold load, preferably of; about 3447-10342 kPa (500-1500 psi (35-105 kg / cm2)). This embodiment is particularly useful when satisfying one of two preferred conditions: (a) the mold has a vaporization separation tolerance of no greater than about 130 microns; or (b) the reactive composition has a spiral flow length not greater than 150 cm, preferably not greater than approximately 100 cm. In a second embodiment of the method, the composition is molded using a double temperature profile at a single pressure. In general, the mold loading unit or units are placed in a mold cavity of a mold having an initial mold temperature that is no more than about 10 ° C lower than the boiling point of the more volatile component. Preferably, the mold is ifcÜ. preheat to reduce cycle time. Most preferably, the mold is first heated to an initial temperature that is at least about 50 ° C. The mold is then closed and pressure is applied at a sufficient molding pressure to maintain the internal and surface integrity; of the mold load, preferably about 3447-10342 kPa (500-1500 psi (35-105 kg / cm2)). The mold temperature is then increased to a temperature sufficient to cause the secondary thermal initiator to pass through about 3-10 half-lives within about ten minutes or less. Then the mold is cooled to the original temperature before the removal of the molded article. For this embodiment also, the method is particularly useful when one of two preferred conditions is met: (a) the mold has a vaporization separation tolerance of no greater than about 130 microns; or (b) the reactive composition has a spiral flow length not greater than about 150 cm, preferably not greater than about 100 cm. In addition, this method is particularly useful for intricate mold patterns that require multiple loads of molding composition, for molded articles having at least one highly glossy surface and also for encapsulating non-reactive core materials. In addition, it can be useful for injection molding.

In a third embodiment of the method, the composition is molded at a constant temperature and with a double pressure profile. In general, the thermosetting molding composition is placed in the mold cavity of a mold that is preheated to a temperature sufficient to cause the secondary thermal initiator to pass through about 3-10 half-lives, preferably within about 10 minutes or less. An initial molding pressure sufficient to fill the mold with the mold load preferably of approximately 689-3447 kPa (100-500 psi) (21-35 kg / cm2)) is applied and maintained for a sufficient time to seal the vaporization separation, preferably for about 30-90 seconds. Then the pressure is increased to a selected molding pressure sufficient to maintain the internal and surface integrity; of the mold load, preferably about 3447-10342 kPa (500-1500 psi (35-105 kg / cm2)). The mold temperature and the final molding pressure is maintained for a sufficient time for the secondary thermal initiator to complete about 3-10 half-lives. In general, this; The method is useful for lower viscosity compositions where there is a need for flow in complex parts. In a fourth embodiment of the method, the composition is molded with a double temperature profile and a d6 'double pressure profile. In general, the molding composition is first placed in the mold, which has an initial mold temperature no greater than about 10 ° C lower than the boiling point of the more volatile component. The mold is preferably preheated to reduce the cycle time. More preferably, the mold is preheated to an initial mold temperature of at least about 50 ° C. Pressure is applied to fill the mold with the mold load, preferably at about 2068-3447 kPa (300-500 psi (21 to 35 kg / cm2)) and is maintained for a sufficient time to seal the mold. vaporization separation, preferably for about 30-90 seconds. Preferably, at the same time the mold is closed (again, to reduce the cycle time), and the mold is heated to a temperature sufficient to cause the secondary thermal initiator to cicle through from about 3 to about 10 half lives in the next approximately ten minutes or less. The pressure is then increased to a selected sufficient molding pressure to maintain the internal and surface integrity of the mold load, preferably at about 3447-10342 kPa (500-1500 psi (35-105 kg / cm2)). The mold temperature and a final molding pressure are; hold for a sufficient time for the secondary thermal initiator to complete approximately 3-10 half-lives. In addition, this method is particularly useful for patterns of; intricate molding that require multiple loads of; _. ^ S », ¿_. . » - ~ ^. -_. * fi- »j» < IIfrfe_fc-A * - molding composition, for molded articles having at least one very bright surface and also for encapsulating non-reactive core materials. In addition, it can be useful for injection molding. The invention is further directed to molded articles made from the composition described above. The invention itself, together with other additional objects and advantages, will be better understood with reference to the following detailed description.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES Molding composition The compositions of the invention are useful for forming polymeric articles by thermoforming molding process. The term "article" is intended to include both sheet materials and three-dimensional parts. The article may have a non-reactive core or insert that is encapsulated or coated by the thermosetting molding composition. By "non-reactive" it is meant that the material does not participate in the thermosetting reactions during the molding process, although some interactions may occur on or within the surface of the non-reactive insert (e.g., some of the components of the mold composition, or may permeate within the outer surface layer of the insert part and react during the mold process, or so that a gradient adhesive layer is formed with the outer insert part layer) . The article may also have a layered structure in which the molding composition is adjacent to a surface of the sheet or structure made from a different composition. The molding composition of the present invention is cured at least 95% when heated in a closed mold at a temperature from about 100 ° C to about 145 ° C for about 10 minutes or less. By "95% cured" is meant that less than 5% by weight of the monomer remains unreacted (based on the weight of the liquid polymerizable material).

Liquid polymerizable material The liquid polymerizable material is a liquid starting material. By "liquid" is meant that the material is fluid at room temperature. The Brookfield viscosity of the liquid can be as high as 20,000 cps, measured at 40 ° C. The liquid polymerizable material may include one or more of the following: (a) at least one volatile monomer reactive material; (b) at least one reactive non-volatile monomer material, and (c) at least one oligomeric reactive material. The present invention is particularly useful when the liquid polymerizable material includes at least one volatile monomer reactive material, and optionally (a) at least one non-volatile monomer reactive material, or (b) at least one non-volatile oligomeric reactive material , or both. It will be appreciated that the choice of liquid polymerizable material or materials will depend to some extent on the desired properties of the final molded article. For example, if addition to a hydrophilic substrate is desired, an acrylic material with acid or hydroxyl groups may be used. For flexibility, (Meth) acrylates with lower Tg, such as butyl acrylate, can be used. For thermal stability, it is preferred that the acrylates are used and; n combination with methacrylate. For improved hardness, it is preferred that functional oligomers of (meth) acrylates with high Tg are used. (a) Volatile monomeric reactive material By "volatile monomer reactive material" is meant a monomeric material with a low boiling point which includes at least one unsaturation site which is copolymerizable in an addition polymerization reaction _ ^ se_a initiated by radicals. In general, useful volatile monomer reactive materials have boiling points of less than the highest molding temperature, measured at atmospheric pressure (1 atm). The present invention is especially useful for molding compositions that include at least one volatile monomer reactive material having a boiling point less than about 110 ° C. Suitable volatile monomer reactive materials may include, for example, monomers having at least one acrylic group, monomers having at least one vinyl group, monomers having acrylic and vinyl groups, substituted butadienes or compositions thereof. Examples of volatile monomer reactive materials include at least one acrylic group including methyl (meth) acrylate and ethyl (meth) acrylate, wherein the term "(meth) acrylate" refers to acrylate, methacrylate and combinations thereof. same. Examples of volatile monomer reactive materials include at least one "vinyl group" that includes acrylonitrile, methacrylonitrile, and vinyl acetate. Other useful liquid polymerizable materials include those that polymerize under the same conditions as the volatile monomer reactive materials. In one embodiment, these other liquid polymerizable materials are preferably completely miscible with the volatile monomer reactive material. Examples of suitable liquid polymerizable materials include acrylics, allyl and other vinyl monomers, siloxanes and silanes. I also know; they can use combinations of liquid polymerizable materials. (b) Non-volatile monomeric reactive material The non-volatile monomer reactive materials can generally be used to adjust the physical or aesthetic properties, or both, of the molded article. A suitable non-volatile monomeric reactive material tip is an ester of an acrylic or methacrylic acid. The ester is generally derived from an alcohol having 3 to 20 carbon atoms. The alcohols can be aliphatic, cycloaliphatic or aromatic. The ester may also be substituted with groups including, but not limited to hydroxyl, halogen and nitro. Representative (meth) acrylate esters include butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (me) acrylate, cyclohexo (meth) acrylate, isobornyl (meth) acrylate, siloxane (meth) acrylate and the like. Acrylic and methacrylic acid can also be used. Other types of reactive acrylic materials include acrylic functionalized materials such as, for example, urethane (me t) acrylates formed by (meth) acrylic functionalization of urethane oligomers or by in situ reaction of oligomeric isocyanates with (meth) acrylic residues.; epoxy (meth) acrylates such as mono- and di- (meth) acrylates of epoxy resins of bisphenol A; (meth) acrylate functionalized with unsaturated polyester oligomers and resins. By "functionalized acrylic material" is meant any compound having at least one reactive (meth) acrylic group attached to the material. Combinations of reactive acrylic materials can also be used. (c) Oligomeric reactive material An oligomeric material is "reactive" when the material is physically associated or chemically reacts with any other component or components in the molding composition. The oligomeric reactive materials may include oligomers of any of the monomers (a) or (b), or both, described above, urethanes, unsaturated polyesters, epoxies, and combinations thereof. Preferably, the oligomeric reactive material is incorporated in the polymerized material constituting the molded article during the molding process. In thermosetting molding, the final molded article is often smaller than the mold cavity due to volume contraction during the polymerization process. The difference between the mold dimension and the dimension of the final molded article, usually measured along the longest edge, is referred to as shrinkage. In the molding industry, it is desirable to minimize and characterize the shrinkage in order to facilitate the design of the mold. mold and accurately predict and reproduce the dimensions of the parts. To minimize the total shrinkage in forming the molded article, it is preferred that the amount of the volatile monomer reactive material and the non-volatile monomeric reactive material, when used, be no more than about 25% by weight, preferably not more than about 18 by weight, based on the total weight of the molding composition. Preferably, a minimum amount of monomer reactive material or materials (volatile or non-volatile, or both) is present, to provide sufficient liquid viscosity to facilitate processability. More preferably, this minimum amount is about 5% by weight, more preferably about 10% by weight, based on the total weight of the molding composition. The oligomeric reactive materials are also used to replace the polymerizable monomer (ie, the non-volatile monomeric reactive material and the volatile monomeric reactive material) as a means to reduce the total shrinkage of the molded article.

The present invention is particularly useful for a molding composition wherein at least about 1% by weight of the liquid polymerizable material is a volatile monomer reactive material; more particularly useful when at least about 20% by weight of the liquid polymerizable material is a volatile monomer reactive material; more particularly useful when at least 50% by weight of the liquid polymerizable material is a volatile monomer reactive material. The total amount of liquid polymerizable material in the molding composition is generally present in an amount of about 10 to about 25% by weight, based on the total weight of the molding composition. Preferably, the liquid polymerizable material is from about 10 to about 20% by weight of the total molding composition.

Non-crosslinked resin polymer The molding composition of the present invention optionally includes at least one non-crosslinked resin polymer. The non-crosslinked resin polymers of the present invention can be reactive, non-reactive or a. combination of them. A non-crosslinked resin polymer is "reactive" when the polymer physically associates or reacts chemically with any other component or components in the molding composition. In a preferred embodiment, the resin polymers not crosslinked to reactants are also incorporated into the polymerized material constituting the molded article during the molding process. The term "non-crosslinked" as used herein, refers to polymers that are linear, branched, blocked or combinations thereof, such as an initial material prior to the introduction of the molding composition having lines with no bond between the chains. The non-crosslinked resin polymer contributes to the strength of other physical properties of the molded article and decreases the amount of liquid polymerizable material required. The non-crosslinked polymer may be soluble or insoluble in the liquid polymerizable material. The combination of the soluble non-crosslinked polymer dissolved in the liquid polymerizable material is generally referred to as a "syrup". Suitable polymers include, but are not limited to homopolymers and copolymers made from any of the monomers or oligomers included above as liquid polymerizable material. It is understood that any polymeric material can be used in the present invention as a non-crosslinked resin polymer, limited only by the desired property of the final molded articles.

Preferably, the polymer has an average molecular weight in the range of about 30,000 to about 200,000, more preferably about 60,000 to about 200,000. In one embodiment, the polymer can be added in the form of spheres having a median particle size (d50) in the range of about 100 to about 300 micrometers and mixed to dissolve. Spheres having a smaller particle size can also be used. The preferred non-crosslinked polymers are the homopolymers and copolymers of (meth) acrylate esters. The non-crosslinked polymer or polymers, when present, are generally present in an amount of about 1 to about 20% by weight, based on the total weight of the molding composition; preferably from about 2 to about 10% by weight.

Filling materials The molding composition of the present invention optionally includes at least one filler material. Suitable types of fillers useful in the present molding composition include, for example, mineral fillers, decorative fillers and functional fillers.

The mineral filler material increases the strength of the final molded article. It will be understood that in addition to the resistance, the mineral filler material can provide other attributes to the molded article. For example, it may provide other functional properties such as flame retardancy or it may function for decorative purposes and modify aesthetics. Any of the mineral fillers known in the field of solid acrylic surfaces can be used in the present molding composition. Some representative mineral fillers include alumina, alumina trihydrate (ATH), monohydrated alumina, Bayer hydrate, silica including sand or glass, glass sphere, magnesium hydroxide, calcium sulfate, calcium carbonate, barium sulfate and particles. ceramics You can also use combinations of mineral fillers. In addition, these mineral fillers may optionally be treated by coating with coupling agents such as silane (meth) acrylate such as Silane Methacrylate A-174 available from OSI Specialties (Friendly, WV) or ZelecMR MO available from E.l. du Pont de Nemours and Company (Wilmington, DE). The mineral filler material is generally present in the form of small particles, with an average particle size in the range of about 5-200 microns.

The nature of the particles of the mineral filler material, in particular the refractive index, will have a pronounced effect on the aesthetics of the final molded article. When the refractive index of the filler material closely matches that of the liquid polymerizable material after polymerization, the resulting molded article has a translucent appearance. Since the refractive index deviates from that of the polymer matrix after polymerization, the resulting appearance is more opaque. The refractive index of ATH is very close to that of polymethyl methacrylate (PMMA), and often ATH is the preferred filler material for PMMA systems. For other polymer systems and filler material, the refractive indexes can be adjusted to provide the desired appearance. When the mineral filler material is present, it is generally present in an amount of about 10 to about 75% by weight, based on the total weight of the molding composition; preferably from about 40 to about 70% by weight. Optionally, the molding composition may include decorative fillers. Such materials, although they may have a minor effect on physical properties, are present mainly for aesthetic reasons. Examples of suitable decorative filler materials include - f L ^ larger particles of reticulated or non-crosslinked polymeric material not filled or filled. Such materials; They generally have a particle size of approximately! 325 to approximately 200 mesh (0.04-10.3 mm in its largest average dimension) and may be, for example, pigmented PMMA particles filled with ATH. Alternatively, you can. use very large particle size filler materials. The particle sizes of decorative fillers can be larger than the mold cavity in the Z dimension so that they can be ground by applying pressure to provide an interesting fractured aesthetic. In addition, the significantly larger pieces of decorative fill material in the X, Y plane of the mold cavity (for example 2.54 to 15.2 cm (1 to 6 inches)), can be encapsulated leaving an exposed side to provide an interesting aesthetic. Since the particle size and the amount of the large polymeric particle filler material are increased, it is generally necessary to adjust the amount of viscosity increaser present to maintain a consistent viscosity of the molding composition. Other types of decorative fillers include: pigments and dyes; reflective flakes, - metal particles; rocks; colored glass; colored sand of various sizes, - wood products such as fibers, shavings and powders; and others. The decorative filler material may be present in an amount of O to about 80% by weight, based on the total weight of the molding composition; more typically from about 1 to about 25% by weight. The molding composition optionally may include functional filling materials. Such filler materials impart special additional properties for applications! specific. Examples of such functional filler materials include flame retardants, antibacterial agents. and others known in the art. Functional fillers, when used, are present in an amount sufficient to be effective, but generally not greater than about 25% by weight, based on the total weight of the molding composition. The total amount of filler materials present in the molding composition is generally about 1-80% by weight, and preferably about 40-70% by weight, based on the total weight of the composition.

Viscosity enhancers The molding composition of the invention includes at least one viscosity increaser. The functions of the viscosity increaser include rapidly and irreversibly achieving a preferably stable viscosity of the molding composition during the mixing process and stabilizing and maintaining the viscosity of the molding composition during the mixing process so as not to interfere with the reaction of polymerization during the molding process. The viscosity increaser further maintains the viscosity of the molding composition until the molding composition is used in the molding process. The viscosity builders useful in the present invention increase the viscosity of the molding composition through physical or chemical interactions, or both, with other components in the molding composition. The viscosity builders useful in the present invention include: (1) ionic crosslinkers, (2) chemical crosslinkers, (3) setting agents, (4) thickeners and combinations thereof; same. Of course, the suitable viscosity increaser is functional at the mixing temperature of the composition; molding (temperature which is preferably about 10-60 ° C, more preferably about: 20-40 ° C). Preferably, the total amount of viscosity increaser ranges from about 0.1% to 25% by weight. (1) Ionic crosslinkers Ionic cross-linkers generally facilitate the ionic interaction of a metal ion with, for example, acid or hydroxyl residues. Examples of useful ionic crosslinkers include magnesium hydroxide (MgOH) and various zinc salts. (2) Chemical crosslinkers Chemical crosslinkers generally facilitate lae; chemical condensation reactions such as, for example, condensation of polyisocyanates with hydroxyl residues. (3) Setting agents Setting agents generally facilitate the physical inhibition of liquid components in solid materials. The setting agent useful in the present invention may be: (a) an organic polymeric fiber, (b) a fine particulate polymeric material, (c) a polymer composite / filler material, or combinations thereof. Suitable setting agents are compatible with the liquid polymerizable material and result in a fast increased viscosity in the molding composition during mixing. By "fast increased viscosity" it is meant that the viscosity of the molding composition is increased in the following 5 hours or less, preferably in the next 1 hour or so, or less. In a preferred embodiment, the compatible setting agent satisfies one of two conditions: (1) the setting agent does not form a separate phase in the molding composition; (2) if the setting agent does not form a separate phase and has a refractive index sufficiently close to that of the liquid polymerizable material after the polymerization so that the separated phase is not visible in the molded article. In general, the setting agent is a polymeric material with very high Tg which absorbs or imbibes the components of liquid polymerizable material. Organic polymeric fibers that absorb suitable monomers (a) include, for example, polyester fibers that provide improved process latitude by absorbing the polymerizable monomer and subsequent sealing of the mold vaporization separation rapidly. The fine particle polymer materials are generally prepared directly either by suspension or by emulsion polymerization. Suspension polymerization is generally a practiced technique which generally provides polymer spheres having a size of; particle in the range of 80-130 micrometers. The particles; They are made of many polymer chains with molecular weights, generally not higher than 100,000. The polymer particles are solid and non-porous. Emulsion polymerization is a well-known practical technique which 't ^ j- typically provides a water-soluble dispersion of particles, generally referred to as primary particles, between 0.2 and 2 microns in diameter. The particles are generally made of only one polymer chain with an average weight of molecular weights exceeding 500,000 and generally greater than one million. Polymeric particles can be porous, depending on the drying technique. Suitable polymeric materials, setting agents (b) are generally manufactured by emulsion polymerization. Aqueous dispersions of polymers prepared by emulsion polymerization, typically referred to as latex, can be dried using a variety of techniques, such as freezing, drum drying and spray drying. Each technique has its own requirements regarding the temperature of operation and speed of water removal. As water is removed, the polymer particles tend to agglomerate. Since this is accompanied by increasing amounts of heat, the polymer particles will tend to coalesce, losing their individual identity and forming a larger particle with reduced surface area. Furthermore, if the drying method does not use severe temperatures, the level of coalescence can be minimized to greatly increase the available surface area morphology of the polymer particle. The resulting high surface area, the porous polymer particle with a size ranging from 2-150 micrometers offers the ability to embed more monomers quickly to rapidly increase the viscosity to a stable and reproducible level. It has been found that the latex particles dry with a median particle size (d50) of about 20 to about 150 microns to be the most effective. In addition, it is also preferred that the enumerade particles have morphologies that are friable, and therefore, they are easily separated into smaller particles and therefore provide a larger surface area for rapid liquid indivision. The polymerization of the emulsion is a well-known technique and has been described, for example, in Sanderson, U.S. Patent 3,032,521, Hochberg, U.S. Pat. 3,895,082 and Fryd et al., U.S. Patent. 4,980,410. The emulsion polymerization process can be controlled to produce polymer particles having a molecular weight (average weight) exceeding one million. In general, polymer particles having an average molecular weight in the range of about 500,000 to about 2,000,000 in the compositions of the invention are useful. For the compositions of the invention, the polymer setting agent can have a Tg greater than 50 ° C; preferably greater than 80 ° C; and more preferably greater than 90 ° C.

Examples of suitable polymers that can be used as setting agents include homopolymers and copolymers of: acrylic acid; methacrylic acid; esters ele (meth) acrylate of alcohols having 1-20 carbon atoms; vinyl ethers; vinyl esters; acrylonitrile; methacrylonitrile; acrylamide; methacrylamide; styrene which includes substituted styrenes; butadiene. Polymer combinations can also be used. A preferred type of setting agent is a meth) acrylic polymer or copolymer. The particles of setting agents can also serve as a core-shell structure in which the monomers polymerize to form the core of the particle and differ from the polymerized ones to form the shell. Such core-shell particles have been described, for example, in Fryd et al., U.S. Pat. 4,726,877. The cover can be crosslinkable, functioning as an additional crosslinking agent in the molding composition. Suitable polymeric particle setting agents for the compositions of the invention are commercially available as PARALOID (R) K-120N-D, 99-100 ?, from poly (methyl methacrylate / ethyl acrylate from Rohm and Haas (Philadelphia, PA); Kane Ace FM-25, 98% Poly (methyl methacrylate / acrylic) core-shell copolymer from Kaneka Texas Corp. (Pasadena, TX); Elvacite (R) 2896; -'f ^. «áA & .__ fa.- t Elvacite (R) 2041, both 99% polymethylmethacrylate from ICI Acrylics, Inc. (Wilmington, DE). Another type of setting agent is a polymer / filler composite material (c). One such; Compound setting agents are prepared by spray drying an aqueous latex dispersion with a mineral filler material such as ATH. The resulting dry powder is composed of a filler particle with a thin latex coating which has formed a coalescence. This structure provides a polymer of large surface area. It also provides the advantage that the polymer of the setting agent is dispersed in the mixture by its association with the surface of the filling material, with the help of the method design and helps to avoid inhomogeneities of material in the molding compound which results in incomplete mixing and wetting of the setting agent of the polymeric particle. Such composite materials have been described, for example in Sasaki et al., U.S. Pat. 4,678,819. A second composite setting agent is derived from the powder generated during grinding, sawing and sanding of filled solid polymer decorative surface materials. Such powder generally has particles with particle sizes in the range of about 5 to about 250 microns. It has been A median particle size of about 60 microns was found useful. Preferably, the molding composition includes from about 2% to about 20% by weight of the setting agents. (4) Thickeners Thickeners generally facilitate an increase in viscosity by accumulating structure between; Thickening and filling particles. The examples of; Suitable thickeners include silica and structured silica, as well as zeolites.

Primary thermal initiator The primary thermal initiator (primary initiator), when heated, generates free radicals which initiate polymerization reactions. The general function of the primary thermal initiator is to facilitate the polymerization reaction in the molding composition during the initial period, preferably in the first minute of the reaction. Factors that can be used to choose the type of initial and secondary thermal initiators include the proposed cycle time, the mold temperature and the maximum temperature of the volatile reactive monomer or monomers. By "maximum temperature" is meant the temperature at which the polymerization and depolymerization of the monomer or monomers reach equilibrium. further, in general, the lower the half-life temperature of the thermal initiator, the shorter the shelf life of the molding composition. Therefore, it is preferred that the primary thermal initiator has a half-life of ten hours in the range of about 40 to about 80 ° C. The "half-life temperature of ten hours" is a conventional measure of initiators which indicates the temperature at which half of the initiator will undergo decomposition to provide initiating radicals in the following die. hours . Thermal initiators are generally composed. peroxy or azo compounds. Illustrative compounds include t-butyl peroxinodecanoate which has a half-life of about 10 hours at about 48 ° C, commercially available as Lupersol ™ 10M75 from Elf Atochem, King of Prussia, PA); and t-butyl peroxypivalate, which has a half-life of ten hours of about 58 ° C (commercially available as LupersolMR II from Elf Atochem).

An azo initiator such as VazoMR 52 of E.l. is commercially available. du Pont de Nemours and Company (Wilmington, DE) which has an average life of ten hours of 52 ° C. The primary thermal initiator is generally present in an amount of from about 0.01 to about 5%, preferably from about 0.02 to about 1.0% by weight based on the total weight of the molding composition.

Secondary thermal initiator The general function of the secondary thermal initiator (secondary initiator) is to complete the reaction or polymerization reactions after the primary thermal initiator has essentially run out. The ten-hour half-life of secondary thermal initiator is preferably at least about 5CC, more preferably about 8-20 ° C higher than the 10-hour average lifetime of the primary thermal initiator. Preferably, the 10-hour half-life of the secondary initiator is in the range of about 60 to about 120 ° C, more preferably about 60-80 ° C. In most cases, the secondary thermal initiator is an azo compound. An illustrative compound is 2,2-azobis (methylbutyronitrile) which has a half-life of 10 hours from about 67 ° C, commercially available as VazoM 67 from E.I. du Pont: de Nemours and Company (Wilmington, DE). The secondary thermal initiator is generally present in an amount from about 0.001 to about 1%, preferably from about 0.005 to about 0.5% by weight, based on the total weight of the molding composition. The amount of primary and secondary thermal initiators used in the molding composition often depends on the desired cycle time and the completeness of the polymerization in the molding process. In addition, the typical molar ratio of the primary thermal initiator to the secondary thermal initiator ranges from about 3 to about 6, preferably from about 5 to about 6.

Crosslinking agents The composition of the invention includes an effective amount, preferably of at least about 0.05% by weight, based on the total weight of the composition of at least one crosslinking agent. The crosslinking agent is generally a multifunctional material having more than one reactive group that reacts with the liquid polymerizable material and other reactive materials (such as a reactive non-crosslinked resin polymer) at the molding temperature. The reactive group can be one which polymerizes with the liquid polymerizable material, such as an ethylenically unsaturated polymerizable group. The reactive group may also be one which reacts with a chain or side residue of the liquid polymerizable material after polymerization such as a hydroxyl, carboxyl, isocyanate or epoxy group. The reaction of the multifunctional reactive material forms a network crosslinked with the liquid polymerizable material. The crosslinking resins can be used as crosslinking agents such as epoxy resins, novolacs, amino resins and (meth) acrylated resins. The crosslinking agent may be a liquid polymerizable material, generally a multifunctional monomer or oligomer. A preferred class of crosslinking agent is the poly (meth) acrylate esters. Representative examples include ethylene glycol di (meth) acrylate, di (meth) acrylate hexanediol, tri (meth) acrylate dimethylolpropane, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate and the like . Other suitable types of crosslinking agents include divinyl compounds such as divinyl ethers, allyl (meth) acrylate, di- and poly- (meth) acrylates of urethane. The crosslinking agent may be a non-crosslinked polymer having multiple reactive groups. The reactive groups may be pending or in the polymer backbone. The crosslinking agent can be a setting agent having multiple reactive groups. The reactive groups may be present through the setting agent polymer or may only be present on the surface of the setting agent particle, for example, in the shell polymer or polymers of a core-shell microgel setting agent. It is understood that the crosslinking agent can also be a combination of the liquid polymerizable material described above, the non-crosslinked polymer and the setting agent or a material outside of these groups of materials described. It is further understood that a component useful in the present invention that functions as a crosslinking agent at the molding temperature may also function as a viscosity enhancer at the mixing temperature when the component has reactive groups with different reactivities (e.g. a group that reacts at the mixing temperature, although a separate group reacts at the molding temperature). For example, (1) a useful component can contain two isocyanate reactive groups in which an isocyanate group is blocked at the mixing temperature and unblocked at the molding temperature; (2) a useful component may contain isocyanate and epoxy reactive groups; and (3) a useful component may contain isocyanate and acrylic reactive groups. The amount of crosslinking agent present affects the physical properties of the polymerization curing time of the - *. » _ * Ajfr * & lil «Slr« - molded article. The increased levels of crosslinking agent improve the hot strength of the article, that is, the structural integrity of the article when it is removed from the mold while still hot. With lower levels of crosslinking agent, the molded article must be cooled before removing it from the mold because it is still too flexible and flowable when hot. Generally, increasing the level of crosslinking agent also increases the brittle condition of the molded article and can; decrease impact resistance and tenacity. The final level of crosslinking agent is determined by a balance between these and other desired properties. The nature of the crosslinking agent can have a significant impact on the physical properties of the molded article. The material combinations of the crosslinking agent can be optimized to provide the desired hot strength without severely impacting the physical properties. The amount of crosslinking agent depends on the equivalent weight of the crosslinking agent and the proposed use of the molded article. By "equivalent weight" is meant the molecular weight of the crosslinking agent divided by the number of reactive groups in the crosslinking agent. In general, the crosslinking agent is present in an amount of at least about 0.05% by weight, based on the total weight of the molding composition, preferably at least about 0.2% by weight, much more preferably so less about 1% by weight.

Other ingredients The molding composition may optionally include a fiber reinforcement for additional resistance to impact, bending and tension. Useful forms of fiber include free fibers, woven or non-woven fabrics, fabrics or veils and combinations thereof. The fibers can be polyester, polyaramide, sizing or unsized glass, carbon fibers or liquid crystal fibers. The fibers that absorb monomer such as those useful as setting agents are generally not visible in the molded article. The polyamide and carbon fibers provide toughness as well as a latitude of method, but are generally visible. The glass fibers provide a latitude of method and aesthetics, but also cause staining. The fibers may be pre-wetted with liquid polymerizable material before being added to the composition. The non-woven or woven fiber mats can also be embedded as a surface treatment on one or both sides of the molded article. Alternatively, the fiber mat can be encapsulated in the molded article. The fibers are generally present in an amount of up to about 50% by weight based on the total weight of the molding composition. In one embodiment, the fibers are present in an amount of about 5-10% by weight. The molding compositions may also contain coupling agents. The coupling agents generally have a double functionality: one end has a polymerizable group which can be copolymerized with the liquid polymerizable material; and the other end has a group which forms complexes with, or has affinity for, particular mineral fillers. Therefore, the coupling agents can be used as an auxiliary in the wetting of particulate filler material with the liquid polymerizable material. For coupling agents of (meth) acrylate / ATH systems which are particularly; useful as those having (met) acrylate functionality and a phosphate or silane group. The coupling agents are; They can add as a pretreatment to mineral fillers during the production method, as referenced in the previous sections describing the filler materials. Alternatively or additionally, these coupling agents can be added in situ to the molding composition. Examples of commercially available coupling agents include ZelecMR MO from E. I. du Pont de Nemours and Company (Wilmington, DE) and as A-174 from Osi Specialties, as a subsidiary of Witco (Friendly, WV). Er _ & ».. * auSJ? Jaca. Generally, up to about 0.5% by weight of the total molding composition can be coupling agents. Other additives which may be present in the molding composition include internal mold release agents such as zinc stearate, the sodium salt of dioctyl sulfosuccinate (such as Aerosol "" OT-S Surfactant (sodium salt in sodium 70% dioctyl sulfosuccinate in petroleum naphtha) available from Zytec Industries Incorporated, West Patterson, NJ), zinc octoate and silicone oils and siloxanes with (meth) acrylate functionality; wetting agents; surfactants, antioxidants; plasticizers and other known components; to be used in polymeric materials. For thermoforming molding, the compositions must have a consistency similar to a bread dough, or even thicker. It is difficult to measure the viscosity reliably for such thick materials. A better measure of this is the spiral flow length. The spiral flow length provided herein are values determined by the spiral flow length measurement technique described in the Examples. For thermosetting molding, the composition preferably has a spiral flow length less than about 102 cm (40 inches) for an isobaric process. A spiral flow length of more than about 102 cm (40 inches) is preferred for a process involving a pressure profile. Of course, the higher the viscosity, the shorter the spiral flow length.

Preparation of molding composition The molding compositions can be prepared, in general, simply by mixing the components at a high cutting rate. This is generally carried out in a device known as a kneader. For batch methods, a kneader / extruder or a dc extruder may be used; double screw or similar. For continuous methods, you can; Use a Buss or List kneader. Such mixers, as they are well known in the food industry and the compounding industry. In general, the components are mixed in the order of one of two sequences. In a sequence, all liquid components are first mixed together. To this are added the mineral filler materials (if present), the setting agent (s) (if present) and the thickener or thickeners (if present), which all must be premixed. Finally, all other components can be added. In a second sequence, the mineral filler material and the setting agent are first mixed together. To this, the liquid components are added individually. ~ * t? Finally, all the other components are added. The choice of mixing sequence depends on the nature of the process requirements. It is understood that other mixing commands can be used to prepare the molding composition. It is further understood that the mixing temperature must be maintained to prevent the initiation of polymerization. Preferably, the mixing temperature is maintained between about 10-60 ° C, more preferably between about 20-40 ° C. The composition, as formed, is suitable for immediate molding, although the viscosity may continue to increase slightly over time (e.g. in about 24 hours).

Treatment, packing and storage of a mixed compound later Once the molding compound is prepared by the appropriate combination or compound formation method, it can be packaged and delivered either in bulk form or as a preformed filler. The preform is generally made either by compression of a measured quantity of the molded compound in an unheated mold designed to provide a load in the proper form or by consolidating and extruding the molded compound through a specific profiling die and cutting of the molded compound. profile in measured lengths consistent with the weight of the necessary load of the design of the feeder by injection. The latter can be fed continuously from a continuous mixer, if so needed. The molded compound (bulk form or preformed charge) is then packaged in a waterproof plastic bag. The sealed bags are then packaged in rigid containers and stored or transported, preferably under refrigeration. In an extension of the above extruded profiling method, the molding compound can be continuously extruded through a slot die, between two sheets of polymer film and within a calendering system to produce a continuous SMC profile. The composite is laminated and sealed for storage or transport. The molded compound can be stored at refrigerated temperatures until it is used in order to preserve the activity of the thermal initiators which are part of the thermosetting formulation; The usefulness of this action depends on the nature of the thermal initiators involved. Typical storage temperatures vary from 5 ° C to room temperature. The shelf life of commercial molding compounds varies up to six months, depending on storage practices and conditions. - < &; **. & * In a production molding environment, the compound will be used as supplied or fed into a mechanical preformer which conforms the material to a specific form of known density for use in the proposed molding application . The preforming can also be carried out in a continuous manner as indicated in the above. The preformed race may then be preheated to a temperature below that necessary to carry out the polymerization, but at a temperature high enough to help the compound flow into the mold. It is preferred to carry out the preforming of the molding composition immediately after mixing. This is especially valid for conformation in an SMC format.

Molding process The molding composition of the present invention can be used in all conventional molding techniques: compression molding, transfer molding and injection molding. The temperature and pressure conditions in the molding process of the present invention depend on many factors. One factor is the rehology of the molding composition. Different thicknesses or viscosities may require different temperature or pressure profiles, or both, as a function of their curing containers. A second factor is the molding technique that is chosen. The geometry of the mold is also a factor. A critical feature of the mold is what is called "vaporization separation" or "vaporization tolerance". This term indicates an open space between the mold halves or the mold components, or both, after the mold is closed through which the uncured molding composition can be pushed by pressure. The vaporization operations must be filled by molding composition and partially cured compositions before the mold completely seals for application of the final molding pressure. Another consideration is the shape of the mold. More intricate designs of finished articles, such as, for example, molded holes, differential thicknesses, insects for screws, multiple extraction angles or moving components, may require multiple composition changes of; molding and a good internal mold flow before lei polymerization. This will affect the pressure and temperature profiles. The molding conditions also depend on the type of molded article to be made, i.e., a single solid part or a part in which a non-reactive core is encapsulated. As used herein, the term "mold loading" refers to a quantity of molding composition that is to be molded into a molded article. It is understood that, depending on the characteristics of the final molded article or the geometry of the mold cavity, or both, the load may be a single unit or a multiple unit charge (i.e., the mold charge may be constituted by a or more load * units). It is also understood that, when more than one load unit is used to make an article, the units of; loading may have different molding compositions. Various embodiments of the molding process of the present invention are described below: Process mode 1; Unique pressure profile, isothermal In this method, the temperature of the mold is maintained at essentially constant level throughout the molding cycle. The pressure is increased to the final molding pressure immediately after closing the mold and is maintained at that pressure. This method is especially useful when the vaporization separation of the mold is very small or if the mold composition is highly viscous. Therefore, in such applications it is preferred that one of the following two conditions be met: (a) the mold has a vaporization separation of no greater than about 130 microns; or (b) the molding composition has a spiral flow length no greater than about 150 cm, preferably not more than about 100 cm. Additionally, the molded composition must have sufficient hot strength to allow removal of the molded part while it is still hot, without bending or spilling. Therefore, the method generally may not be suitable for making encapsulated parts or parts with very intricate designs. The first step in the molding process is to provide the mold loading, preferably at ambient temperature. In some cases, the molding compositions are; prepare in advance and store at temperatures; refrigerated The compositions are generally not malleable enough at lower temperatures to be easily used. In addition, the temperature gradient in the curing part, especially for thick parts, can lead to internal voids. Therefore, if it is not found beforehand at room temperature, the composition can be heated to room temperature, which means a temperature of about 15-30 ° C. The second step is to place the molding composition at room temperature into the cavity of a preheated mold. The preheat temperature should be sufficient to cause the secondary thermal initiator to pass through 3-10 half-lives, preferably at about 4-6 half-lives, within about 10 minutes or less, preferably in the following about 4 minutes or less . The temperature must also not be so hot that it causes the depolymerization to degrade any of the properties of the molded article. In general, for the acrylic-based compositions of the invention, a temperature in the range of from about 100 ° C to about 145 ° C is useful. The third stage is to close the mold and secure it closed before pressurization. The mold preferably closes as soon as possible to avoid volatilization of a mold load. The fourth step is to increase the pressure to a selected final molding pressure. The final molding pressure is selected to maintain the internal geometric and surface integrity of the molded article. The term "molding pressure" refers to the force applied per unit area in cross section in the plane of the mold cavity (in units of pounds per square inch, psi, or kilogram per square centimeter (kg / cm2)) . By "maintaining the internal geometric integrity" it is meant that the pressure is chosen to minimize or avoid internal defects such as shrinkage marks and molded hollows in the articulation. By "maintaining the geometric surface activity" is meant that the pressure is chosen to produce essentially the same finish on the surface of the molded article as on the surface of the machined mold cavity. The exact pressure chosen will depend on the molding position used and the desired physical characteristics of the molded article. In general, pressures in the range of about 3.4 MPa to about 10.3 MPa (500-1500 psi (about 35 to about 105 kg / cm2)) are useful. This stage is preferably carried out as soon as the equipment allows it. Often, the third and fourth stages can be performed in one action. The fifth step is to maintain the temperature and pressure for a sufficient time to ensure that the secondary thermal initiator has passed through 3-10 half-lives, preferably about 4-6 half-lives. This amount of time is necessary within about 10 minutes or less, more preferably within about 4 minutes or less. The sixth stage is to reduce the pressure at atmospheric pressure. The seventh stage is to open the mold and remove the molded article. Generally, the molded article is removed without cooling. mold.

Process mode 2; Simple pressure profile. double temperature In this method, two different temperatures are used during the molding cycle: initially a lower temperature, which then increases to a higher temperature. The pressure is increased to a final molding pressure immediately after closing the mold and is maintained at that pressure. This method can often be used in very small vaporization separation or the molding composition is very rigid. Therefore, it is preferred that one of the following two conditions be met: (a) the mold has a vaporization spacing no greater than about 1300 micrometers; or (b) the molding composition has a spiral flow length not greater than about 150 cm, preferably not greater than about 100 cm. Due to the double temperature profile, the method can often be used to encapsulate non-reactive core components and to produce parts with intricate designs. At a lower temperature, the molding composition can flow to fill the appropriate spaces without fully polymerizing and without volatilization of the monomer or monomers and other volatile components. After this, at a higher temperature, the polymerization reactions are completed.

The first step in the method is the same as in the previous method: provide a mold load at room temperature. The second step is to place the molding composition at room temperature in the mold cavity. The initial temperature of the mold should be set as maximum approximately 10 ° C below the boiling point of the most volatile component. As used herein, the term "the most volatile component" refers to any component in the molding composition that has the lowest boiling point. The mold must be set at this initial mold temperature prior to the placement of the mold load in the mold cavity in order to avoid significant volatilization of the more volatile component prior to closure of the mold. The upper limit for the initial mold temperature is determined by the molding composition. It is preferred that the mold is preheated to an initial mold temperature of preferably at least about 50 ° C in order to reduce the cycle time. In general, an initial mold temperature in the range of from about 50 to about 90 ° C is useful. The third stage is to close the mold and secure it closed before pressurization. The mold is preferably closed as soon as possible.

The fourth stage is to increase the pressure at a mold pressure selected as in the fourth stage in the process mode 1. Often, the third and fourth stages are performed in one action. The fifth stage, which is carried out concurrently with the fourth stage, is to increase the temperature to a temperature which is sufficient to ensure that the secondary thermal initiator passes through 3-10 half-lives in the next approximately sixteen minutes or less, preferably in the next approximately four minutes or less. As discussed above, for acrylic-based compositions, a temperature in the range of from about 100 ° C to about 145 ° C is useful. The rate of temperature increase can be adjusted to obtain a desired method cycle time. The sixth step is to maintain the temperature and pressure for a sufficient time to ensure that the secondary thermal initiator has passed through about 3-10 half-lives, preferably about 4-6 half-lives. This step is to ensure that the polymerization is complete and that the secondary thermal initiator essentially lacks. Generally, this amount of time is preferably within about ten minutes or less, more preferably within about four minutes or less. The seventh step is to cool the temperature to the original preheated temperature of step (2). The eighth stage is to reduce the pressure to atmospheric pressure. Depending on the application, the seventh and eighth stages can be carried out concurrently. The ninth stage is to open the mold or remove the molded article.

Mode 3 of process: double pressure profile, isothermal In this method, the temperature of the mold is maintained at a constant level throughout the molding cycle. The pressure is increased to a first level and maintained for a period of time and then increased to a final molding pressure for the remainder of the molding cycle. This method is often suitable for molds with larger vaporization separations and for molding compositions with higher flux. The first stage of the molding process is to provide the charge at room temperature. The second stage is to place the mold load and room temperature in the cavity of a preheated mold.

The preheated mold temperature should be sufficient to cause the secondary thermal initiator to pass through 3-10 average cycles, preferably about 4-6 half cycles, in about ten minutes or less, preferably for about four minutes or less. it must be so hot as to cause depolymerization or to degrade any of the properties of the molded article. In general, for the acrylic-based compositions of the invention, a temperature in the range of about 100 to about 145 ° C is useful. The third stage is to close the mold and secure it closed before pressurization. The mold preferably; It closes as soon as possible. The fourth step is to increase the molding pressure to an initial level sufficient to fill the mold with the mold load. By filling the mold, it means that the. Mold loading is supplied to each volume of the mold cavity, including vaporization separation. In general, the preferred molding pressure is from about 0.7 MPa to about 3.4 MPa (100-500 psi (7235 kg / cm2)). The fifth stage is to maintain the pressure at this level for a sufficient amount of time to seal the vaporization separation. Generally, the preferred amount of time is from about 30 to about 90 seconds. By sealing the vaporization separation, it is meant to allow the polymerization of the mold charge to such an extent that the viscosity of the mold charge is sufficient to prevent the additional mold loading material from passing through the vaporization separation. . The sixth step is to increase the pressure at a selected molding pressure to maintain the internal geometric and surface integrity of the molded article. The selected molding pressure should preferably be at least about 1.4 MPa (200 psi (14 kg / cm2)) greater than the initial molding pressure. The seventh step is to maintain the mold at the mold temperature and at a final molding pressure for a sufficient time to ensure that the second initiate: has gone through about 3-10 half-lives, preferably about 4-6 half-lives . Generally, this will be within approximately 10 minutes; or less, more preferably within about; four minutes or less. This stage is done to ensure that! the polymerization is complete and that the secondary thermal initiator has been depleted. The final molding pressure may be the same as or different from the selected molding pressure. The eighth stage is to reduce the pressure to atmospheric pressure. The ninth stage is to open the mold and remove the molded article without cooling the mold.

Process mode 4: Double pressure profile - double temperature profile In this method two different temperatures are used during the molding cycle and two different pressures. The method is often suitable for molds with larger vaporization separations and for molding compositions with a larger flow. As with process mode 2, due to the double temperature profile, the method can be used to encapsulate non-reactive core components and to produce parts with intricate designs. The first step in the method is to provide the mold charge at room temperature. The second step is to place the mold charge at room temperature in the cavity of a mold having an initial mold temperature which is no greater than about 10 ° C lower than the boiling point of the most volatile component in the composition. Preferably, the mold is preheated. More preferably, the mold is preheated to an initial mold temperature of at least about 50 ° C. In general, a useful initial mold temperature is from about 50 ° C to about 90 ° C.

The third stage is to close the mold and secure it closed before pressurization. The mold is preferably closed as soon as possible. The fourth step is to increase the temperature to a temperature which is sufficient to ensure that the secondary thermal initiator passes through about 3-10 half-lives, preferably about 4-6 half-lives, within about ten minutes or less, ds most preferably about four minutes or less. Generally, a temperature range of about 100 ° C to about 145 ° C is used. The fifth step is to increase the pressure to an initial level sufficient to fill the mold with the mold load as in the fourth stage of the process mode 3. The sixth stage is to maintain the pressure at this level for a sufficient time to effectively seal the vaporization separation, as well as the fifth stage of the process mode 3. The seventh step is to increase the pressure at a selected molding pressure to maintain the internal geometric and surface integrity of the molded article. Preferably, the selected molding pressure is; Select is at least about 1.4 MPa (200 psi. (14 kg / cm2)) is greater than the initial molding pressure.

The eighth step is to maintain the mold at a mold temperature and a final molding pressure for a sufficient time to ensure that the secondary thermal initiator has passed through about 3-10 half-lives, preferably about 4-6 half-lives. The final molding pressure may be the same as or different from the molding pressure selected in the seventh stage. This amount of time is preferably within about 10 minutes or less, more preferably within about four minutes or less. This step is to ensure that the polymerization is complete and that the secondary thermal initiator is essentially suppressed. The ninth step is to cool the mold to the original preheated temperature of stage (2). The pressure during this cooling stage may be different or equal to the final molding pressure. The tenth stage is to reduce the pressure at atmospheric pressure. Depending on the application, the ninth and tenth stages can be carried out concurrently. The eleventh stage is to open the mold and remove the molded article. The molding process of the invention, the temperature and pressure control allows the formation of defect-free parts both on the surface and internal defects. It also allows for low cycle times with minimum parts shrinkage, which lowers manufacturing costs. The use of the refrigeration loading temperature (process modes 2 and 4) allows parts to be produced without lines (ie fabric material resulting from monomer volatility), and also allows easy production of parts free of surface defects. The use of double pressure profiles (process modes 3 and 4) allows the use of low viscosity compositions and minimization of part shrinkage. It is understood that those embodiments of the present invention that utilize a "double pressure profile" can utilize stages intermediate pressure also means "intermediate pressure" means a pressure during the molding process that is different from the initial and final molding pressures, similarly, it is understood that those embodiments of the present invention that use a "profile" of double temperature "can also use stages at intermediate temperatures." Intermediate temperature "means a temperature perature during the molding process that is different from the initial and final molding temperature.

Process Modes 5-8: Intricate Design Method The present invention also relates to a method for making an article having at least one intricate design detail. In a preferred embodiment, this method is performed using the general steps of any of the process modes 1 to 4. The general stages of process mode 3 or process mode 4 can beThey are especially useful for making items that have intricate design details using lower viscosity molding compounds such as mold loads. The double pressure profile of the process modes 3 and 4 can be useful not only to avoid vaporization of the molding compound outside the vaporization separation, but also to allow the application of increased pressures to follow the polymerization shrinkage and to avoid internal casting, shrinkage drilling areas, and other internal and external defects in the molded article. Regardless of which of the general stages of the process mode are used, the mold loading is preferably preformed first into a single unit charge or a multiple unit charge consistent with the dimensions of the mold cavity. The embodiment generally provides advantages such as the following: (1) minimizes the distance of material flow within the mold; (2) minimizes the amount of monomer exhaust gas from the mold compound as the mold closes and fills. As used herein, "exhaust gas" refers to the volatilization of the mold compound, resulting in the formation of dry spots in the finished article. After c.e. performing mold loading, it is placed in the mold cavity, preferably as fast as possible. Especially for making items that have multiple intricate design details, several different shapes of dimensions may be needed to sufficiently load the mold. Once the mold has been loaded, it must be closed without delay and the molding cycle is continued as described in any of the process modes 1 to 4. Particularly in compression molding, the compression conditions of the process mode 2 are preferred for making articles containing intricate designs because the lower loading temperature removes or reduces the level of monomer exhaust gas at the point of contact between the molding compound and the heated surface of the mold cavity. Particularly in the cases of transfer of injection molding, the preforming of the load is not critical. The non-shaped molded composition billet can be cut and introduced into the mold, which performs its own preforming via the transfer cylinders or injection screws. While a cooler "charged" temperature may or may not be useful in these methods, it may increase the cycle time.

Process modalities 9-12: Encapsulation method The compositions and methods of the invention are also suitable for the encapsulation of non-functional materials. By "non-functional materials" are meant materials which capture volume, can impart a desirable aesthetic appearance, but do not impart one. new functional capacity in the molded article. Examples of non-functional materials include sheet materials of wood products such as particle board, filled and unfilled polymers, decorative surface materials such as Corian ™ solid surface materials, recycled plastics; and others. Such materials can be encapsulated by the compositions of the invention to obtain the aesthetics of solid surface materials at a lower cost. Part features, such as screw insert parts, can be encapsulated by the molding composition, too, resulting in integral physical equipment in the parts. Such parts are also hermetically sealed and are resistant to environmental effects, such as humidity.

In addition, metallic and metal / plastic composite materials can be encapsulated to provide good heat transfer for surface materials. The; fiber mats or glass fabrics or organic polymers, such; as polyaramides, they can be encapsulated to provide structural reinforcement or flame retardancy, or both. Lae: Honeycomb structures can be encapsulated to produce small weight items. Such encapsulated articles are conveniently produced by injection molding, however, compression and transfer molding techniques can also be used. The compositions and processes of the invention are also useful for the encapsulation of functional inserts. By "functional insertion piece" is meant a material which imparts a new use or function of the article. Such new use may be heating or cooling, electrical equipment, plumbing, sound deadening, to provide a fire barrier, making an article resistant to penetration or penetration proof, among others. Examples of suitable functional insertion parts include electrical parts, light emitting materials, heated resistance wires, electronic wiring, plumbing units, heating and cooling coils and many others. Such encapsulated articles can also be conveniently produced by injection molding, however, compression and transfer molding techniques can also be used. The present invention is further related to a method for making an article that includes at least one encapsulated core. The encapsulation can be obtained using compression molding, preferably after the general steps of the above process modes 1 or 2, or using transfer or injection molding, preferably after the general stages of the previous process mode 3 or 4. When compression molding is used to encapsulate a core, the encapsulating core preferably; is interposed between at least two preformed loads of; Molding compound in a "composite material" filler. This. The load can be joined by secondary loads for complete loading of the mold as indicated in the above in any of the process modes 1 to 4. The encapsulant core can be held in place by physical elements inserted into (or as part of) the encapsulant, by bolts which are an integral part of the mold design, or by the thickness and homogeneity of the charges made equal in themselves. . The mold is closed and cycled with the same considerations to the above in the process mode 1 or 2. By encapsulating a core using transfer or injection molding, the core is preferably ^^^ "ss ^ ^ -áw = fe ^ a ^ w- enters the mold cavity and is held in place by either the design of the encapsulant itself or by mold design elements such as, for example, internal bolts or devices The mold loading can be introduced into the mold via injection where the molded compound is driven into the mold, and the inserted core is encapsulated The mold is closed and cycled according to the general steps described in Process Mode 3 or 4 The nature of the encapsulant, such as the impurities contained in the encapsulant, often affect the method chosen to carry out the molding.For example, a steel sheet encapsulant does not generally expand; The molding process Therefore, any of the process modes 1 to 4 described above may be suitable for making a molded article that encapsulates a sheet of steel. It can usually contain moisture that can be vaporized during the molding process. Therefore, the process modes 2 and 4 may be more suitable for making a molded article that encapsulates a particle board. It is understood that the present invention is further directed to a method for making an article having at least one core encapsulated therein and at least one intricate design on the surface of the article, which method preferably includes a combination of the steps Y. * »To generals described in any of the modes 5 to 8 of the process, with the general stages described in any of the 9 to 12 process modalities.

Finished The finish is related to molded products that are generally much smaller versus those found in the cast products. The finished surface of the molded part is mainly defined by the finish of the machining mold. The termination of the molded parts mainly involves the removal of vaporization or residual polymerized compound which accumulates as mold separations such as mold division lines, ejection bolts and slides. This is removed by sanding or milling to provide the finished part. In some cases, surface defects in the molded parts are observed due to mold design or mold finishes such defects should be removed if possible by sanding and polishing. The compositions and processes of the invention are also suitable for producing articles in which the molded material is on at least a part of one or more, but not all surfaces of a substrate. In such articles, the substrate is not completely encapsulated by the material]. • ^ - ^ »v * eSam» - - • «Nff-molding. The substrate can be a flat sheet with a sheet of molding composition superimposed on the whole part of one side. Such molded structures can have advantages in terms of adhesion and strength when compared to laminated structures which are bonded by adhesion. In some cases, the substrate will be pre-tensioned prior to molding to avoid distortion in the final moldaco article arising from the forces of time and / or shrinkage. Alternatively, the molding composition can be molded on two to four sides of a flat substrate, which leaves the sides or ends exposed. In addition, a three-dimensional shape can be molded onto a flat substrate, the flat sheet can be molded onto a three-dimensional substrate, and a three-dimensional shape can be molded onto a three-dimensional substrate. It will be evident that there are various molding options in which the molding composition is molded on all or part of a substrate. Examples of suitable substrates include wood, metal, woven and non-woven fiber mats, fabrics or fabrics and veils, transparent polymeric materials, filled polymeric materials, honeycomb structures and others. Combinations of substrates including composite substrates can also be used. An unfilled acrylic sheet is particularly suitable as a substrate either for a sheet molded material or for a shaped molded material.

Alternatively, a woven or non-woven fiber may be impregnated in the molded article for structural reinforcement and / or as a structural barrier. The compositions and methods of the invention are also suitable for producing articles in which the molding material is not the only surface of a substrate. Examples of suitable substrates include wood, metal, transparent polymer sheets, honeycomb structures and others. In some cases, the substrate will be pretensioned to avoid distortion in the final molded article that surges by time or shrinkage forces, or both. Alternatively, a non-woven or woven fiber mat may be impregnated into the molded article for structural reinforcement or as a structural barrier, or both. The molding process of the present invention produces molded articles that require fewer finishing steps when compared to articles made from casting processes. The molding process has low cycle times and results in products which are robust. The molding methods of the present invention are especially suitable for high volume production of parts subjected to high quality engineering. When using acrylic-based molding materials, the products made from the composition and methods of the invention have the aesthetic appearance of the filled acrylic materials. In addition, they have other advantages associated with filled acrylic materials, such as UV radiation stability. opacity, hardness, reparability, inconspicuous seams, resistance to stains and manufacturing capacity. The aspects of the present invention are shown by the following examples for purposes of illustration. These examples and modalities do not mean that they limit the invention in any way. Those skilled in the art will recognize that clarifications, additions and modifications can be made, all within the spirit and scope of the invention and the manner in which it relates to the production of new ones; functionalities and aesthetics for the surface industry; sold.

EXAMPLES Various components of the molding compositions used in Examples 1-22 are described below.

Acrylic syrup A reactive acrylic syrup constituted of 15-25% by weight of a non-crosslinked polymer resin dissolved in a monomer solution prepared either by: (1) partially polymerizing an acrylic monomer mixture, or (2) is prepared TO_ . O &Z - J * dissolve one or more acrylic resins in one or more acrylic monomers. In the first case (1), a syrup comprising 24% polymethyl methacrylate (Mn approximately 32,000) dissolved in methyl methacrylate is prepared by partial polymerization of methyl methacrylate using initiator 2,2'-azobis (isobutyronitrile) [ supplied by VAZO 64 of El du Pont de Nemours and Company] in a continuous reactor process. In the second case (2), such syrup is prepared by dissolving one or more of the following acrylic resins in MMA at 3-24% by weight solids: Acrylic resin V045 99.5% poly (methyl methacrylate / methyl acrylate), Mn > 60,000; supplied by ATOHAAS, Philadelphia, PA; ElvaciteMR 2014 Resin 98-100% pol i (methyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid), Mn > 70,000; supplied by ICI Acrylics Inc., Wilmington, DE The soluble poly- (meth) acrylic oligomeric species can also be included in the syrup formulations. Polymerization inhibitors such as methylhydroquinone (MEHQ) may be added as needed.

Initiators The examples used in one of the primary thermal initiators are included below: Lupersol 10M75 Peroxyne-3-tert-butyl oleate supplied as a 75% solution to WHO (Odorless Mineral Spirit) by Elf Atochem (King of Prussia, PA); with a half-life of 10 hours at 48 ° C; or Lupersol 11 T-butyl peroxypivalate provided as a 75% solution in WHO by Elf Atochem; average life temperature of ten hours at 58 ° C.

The secondary thermal initiator used is 2,2'-azobis (methylbutyronitrile) supplied as a 100% solid by DuPont (Wilmington, DE) under the trademark VAZO 67, cor. a half-life temperature of ten hours of 67 ° C.

Alumina Trihydrate (ATH) The ATH filler materials that are included in Table 1 below are used in the Examples: Table l. ATH filling materials Supplier Size Materials filled with ATH particle d50 (micrometers) * ATH not treated 36 ALCAN (Quebec, Canada Untreated ATH or 11 SOLEM (China) ATH treated with silane A174 ATH treated with 47 Nippon Light silane A174 Metals (Japan) * Particle sizes and particle size distributions are measured using a Leeds & Northrup Microtrac FRA.

Acrylic decorative filled particles (DFAP) The decorative filled acrylic particles are; prepare from PMMA filled with ATH by grinding by grinding, or both, to the desired degree. The composition of? material is characteristically 55-65% ATH by weight and contains pigments to obtain the desired color. The particle sizes are then separated by sieve into fractions. These fractions are combined in various ratios necessary to obtain the desired aesthetic pattern effect in the molded article. Mixed fractions of different colors are used to obtain the desired color effect in the molded article.

Setting agent The polymeric particles setting agents used in the examples are included in Table 2 below: Table 2: Setting agents for polymer particles Composition Agent Available particle setting size d50 (micrometers) * PARALO I D R 99-100% of 122 Rohm and Haas K- 120 N-D poly (Company methacrylate, methyl / Philadelphia acrylate, PA ethyl) Kane Ace FM- > 98% Copolymer 150-190 Kaneka, Texas 25 Core / Roof Corporation. of poly (methacrylate Pasadena, TX, methyl / acrylic) Kane Ace FM- > 98% Copolymer 150-190 Kaneka Texas 20 Core / Coated Corporation. of poly (methacrylate Pasadena, TX, methyl / acrylic) Elvacite "> 99% methacrylate 7-130 ICI Acrylics 2896 from polymethyl Inc., Wilmington, DE Elvacite "[> 99% methacrylate 150 ICI Acrylics 2041 polymethyl Inc.

* Particle sizes and particle size distributions are measured using a Leeds & Northrup Microtrac FRA.

The setting agents of composite polymer particles / fillers used in the examples are: filled acrylic particles generated from milling, sawing and sanding of acrylic polymer solid surface materials filled with ATH Corian ™; with a d50 of 60 micrometers. Particle sizes and particle size distributions are measured using a Leeds & Northrup Microtrac FRA. Unless stated otherwise, all mixing steps are carried out at room temperature. For those mixing steps, a mixing chamber cooled by water is used, the mixing temperature is between; about 10 ° C and about 15 ° C. The additional materials used in this work are common to those skilled in the art and are described below in the specific examples.

Spiral flow length measurement The spiral flow length is related to the. viscosity and is measured under molding conditions. In the examples a spiral flow method is used using the test mold manufactured by Atlantic Tool & Die Company (S. Plainfield, NJ). _________ É ___ til_i_ti _ ^ _ É ___ fl__ This spiral mold has the following dimensions: 190.5 cm (75 inches) long, - 0.95 cm (0.375 inches) wide, - 0.32 cm (0.125 inches) deep; with a piston diameter of 6.03 cm (2-3 / 8 inches). The lower half of the mold is graduated in increments of 0.635 cm (0.25 inches). The technique used for mold transfer in which the molding composition is driven out of the transfer cylinder and into a spiral slide under the conditions of pressure and temperature to be used in the molding application. A load of approximately 50-100 g of molding composition is placed in the mold transfer cylinder which is to be preheated to a temperature of about 125 ° C. The mold is then closed with a clamping pressure of approximately 3.4 MPa (500 psi (42.2 kg / cm2)). The mold opens after approximately 3 minutes and the part is ejected; molded The maximum flow distance is then measured by reading the scale printed on the bottom of the piece. _t_______ EXAMPLE 1 Preparation of molding compound A liquid mixture is prepared having the components that are included in table 3 below.

Table 3. Example 1, liquid mixture The liquid mixture is mixed to ensure homogeneity. The black pigment dispersion used is a ________________; -_: ... _afc__sái _._ ...;., ..- "_... dispersion of 5% solids of carbon black in epoxidized soy bean oil as provided by RBH Dispersions, Boundbrook, NJ. The solid materials included in table 4 below are fed into a 5.71 (1.5 gallon) double arm sigma blade mixer with constant rpm (Bakei-Perkins) and premixed for 1 minute: Table 4. Example 1 solid materials The liquid mixture is added and the molding compound is mixed for 8 minutes, at which point the material is transformed into a thick molding compound of uniform composition. The molding compound is removed from the mixer and packaged in bulk in an airtight plastic bag. The compound is then stored at 5-10 ° C.

Gfe & In the next 24 hours of mixing, the consistency of the molding compound and the operation are evaluated using a spiral flow molding at 125 ° C with an applied pressure of 3447 kPa (500 psi). Under these conditions, the flow length decreases between (78.7 cm (31") and 86.4 cm (34 ')).

EXAMPLE 2 Isobaric / isotropic molding process of the composition of example 1 The molding compound of Example 1 is evaluated by compression molding in a 25.4 cm x 25. i cm (10"x 10") test mold constructed of steel, and designed with a pond separation of 25 microns (0.001"). ) and which has internal electric heating units.The mold is preheated to 125 ° C and 1040 g loading of molding compound is placed in the cavity.The mold is closed and a pressure of 5516 kPa (800 psi (56.4 kg) is applied / cm2)) After 5 minutes the mold is opened and the resulting plate is removed.Although the resulting molded plate exhibits excellent surface reproduction and mold dimension, it also shows surface defects associated with boiling elimination of monomers before of the closure of the. mold. These defects are superficial in nature and manifest as blanched micro-void areas at the bottom of the part where the molding charge is in contact with the hot mold prior to closing the mold. The physical properties of the molded material are shown in Table 5 below in comparison with the typical values for an acrylic solid surface material filled by Corian ™ Genesis Pearl Gray continuous casting.

Table 5. Comparative physical properties EXAMPLE 3 Isobaric profile molding process / temperature of the composition of example 1 The molding of the compound of Example 1 is evaluated using a mold with a loading temperature of 80 ° C. A load of 1040 g is introduced into the mold cavity and the mold closed. Pressure is immediately applied and increased to 5516 kPa (800 psi (56.4 kg / cm2)) and the mold temperature is increased to 125 ° C. Three minutes after the mold temperature reaches 125 ° C, the mold is opened and the resulting plate is removed, the bleached surface defects observed in example 1 are not present.

EXAMPLE 4 __________? _ á ______ li_______i Use of a smaller particle size of ATH in the composition of Example 1 The molding compound of Example 1 is reproduced by replacing Solem ATH treated by silane by the NLM treated with ATH silane. The mixing character is identical to that of the molding capacity of the resulting molding compound. The resulting material shows improved physical properties and at the same time maintains an aesthetic appearance. The data physicists are included in table 6 below.

Table 6 fifteen _____________! __ _____k____ _ &_tt_H ___? EXAMPLE 5 Calcium carbonate filter substituted for ATH in the composition of example 1 The molding compound of example 1 is reproduced; substituting calcium carbonate (Polar Minerals, Mt. Vernon, IN) for ATH treated with NLM silane. In addition, a syrup (nominally 24% solids) prepared by partial polymerization on an industrial scale of MMA using 2, 2'-azobis (2-methylpropanonitrile) [sold as VAZO 64 by DuPont Company, Wilmington, DE] as a thermal initiator is used. . The mixing behavior of this formulation is somewhat more difficult, requiring more time to contain uniform mixing. The molding capacity of the resulting molded compound is similar to the foregoing. As expected, the molded plate shows a more opaque appearance compared to that of example 1. The physical data are included in table 7 below: -_______, _., ^. - -_.__.._. -. .... ^^ a., ^^,. ^^^. ^ -. ^. ^. ^,. ^^ ,.

Table 7 EXAMPLE 6 Fiber of Dacron R as a setting and reinforcement agent The molding compound of example 1 is reproduced; using the following mixture of solid components included in table 8 below: Table 8. Solid components In addition, a syrup (nominally 24% solids) prepared via partial polymerization on an industrial scale MMA using 2, 2'-azobis (2-methylpropanonitrile) [sold as VAZO 64 by DuPont Company, Wilmington, DE] as a thermal initiator was used . The liquid mixture is added to the above mixture after mixing for 1 minute. The molded compound is mixed for 7 minutes before it is removed from the mixer and packaged. Due to the absorptive nature of MMA of the Dacron® fiber, the material reached a similar viscosity. The molding compound was evaluated using a test mold of 25.4 cm x 25.4 cm (10"x 10") and the profile isothermal / isobaric pressing described Example 1. In the molding element, little vaporization is observed. It appears that the expanded polyester fiber helps seal the mold cavity in the initial stages of the molding process. Although the flexural properties remain unchanged, the presence of fiber reinforcement prevents catastrophic failure (fragmentation) in flexural and impact measurements.

S¡ »EXAMPLE 7 Formulation without non-reticulated polymer resin A liquid mixture is introduced into a 9.5 1 (2.5 gallon) double planetary mixer cooled with water (Charles Ross &Son Company; Hauppauge, NY). The liquid mixture contains the components that are included in table 9 below: Table 9. Liquid mixture ^ ^^^ A ^ ¡ñ "The liquid mixture is mixed to ensure homogeneity. The dispersion black pigment used is ur.a solids dispersion 5% carbon black bean oil, epoxidized soybean used as provided by RE.H Dispersions, Boundbrook, NJ To this mixture are added the components listed in Table 10 below, in the order indicated: Table 10 The zinc stearate is mixed with the liquids for 5 minutes. ATH is added and the mixture is combined for an additional 5 minutes to ensure uniform wetting. Then Rohm & Haas K120ND at high rpm of the mixer, forming a dry mix which coalesces into n rigid molded compound in the next 3 minutes. The compound is then mixed for an additional 20 minutes under _______M > ___ £ _____ t__í _____ Vacuum of 735 mm Hg (25"Hg) The molded compound is removed from the mixer and packaged in bulk in an air-tight bag The compound is then stored at 5-10 ° C. molding is evaluated using a 25.4 x 25.4 cm (10"x 10") test mold and the isothermal / isobaric pressing profile described in Example 1. The physical data are presented in Table 11 below.

Table 11 10 fifteen EXAMPLE 8 Formulation using decorative fillings A mature liquid containing the; components that are included in table 12. The liquid mixture is introduced in a double planetary mixer of 9.5 1 (2.? > - - ---- - «•» -'- «- '** * - ______________" • "" "- invffcMltrii ar ™ ** -" gallons "cooled with water (Charles Ross &Son Company; Hauppauge, NY): Table 12. Liquid mixture This liquid mixture is combined to ensure homogeneity. The following solid materials included in table 3 below were premixed and introduced together into the mixer: ________________ _________. _____ Ü __? ÍB_M__ .dMH _______ «_ ai __? ________ > -_, J __-_. _ _____ Table 13. Solid components The mixture is combined for 2 minutes at which point the material is transformed into a paste. A mix of; Acrylic decorative particles filled with ATH (DFAP's) within a range of 30 to 150 mesh size (approximately 100-560 micrometers) are added and mixed in: The mixture is mixed for 15-20 minutes under vacuum of 735 mm Hg (25"Hg) during which the material is transformed into a thick molded compound of uniform composition.The molded compound is removed from the mixer and packaged in a When the bulk is in an air-tight plastic bag, the compound is stored at 5-10 ° C. In the next 24 hours of mixing, the consistency of the molding compound is evaluated using a spiral Now it is molded at 125 ° C and a pressure of 3447 kPa (500 psi) is applied Under these conditions, the decreases in flow length are between 71.1 cm (28") and 81.3 cm (32").

EXAMPLE 9 Isobaric / isothermal molding process of the composition of example 8 The molding compound is also evaluated for compression molding in a 25.4 cm x 25.4 cm (10"x 10") test mold in example 1. The mold is preheated to 125 ° C and se; place a load of 530 g of molding compound in the cavity.

The mold is closed and applied at a pressure of 5516 kPa (800 psi (56.4 kg / cm2)). After 5 minutes, the mold is opened and the resulting plate is removed. Although the resulting molded plate exhibits excellent reproduction of the surface and dimensions of the mold, it also shows associated surface defects cor. Removal by boiling monomer before mold closure. These defects are superficial in nature and are; they manifest as blanched micro-hollow areas on the underside of the part where the molding charge is in contact with the hot mold before the closure of the mold. E._ molded article has a uniform appearance similar to granite that shows a translucent visual depth. The physical properties of the molded material are shown in Table 14 below in comparison with the typical values for a solid surface material filled by Corian ™ Sierra Dusk continuous casting.

Table 14. Comparative physical data By gas chromatography analysis, the total residual MMA of 0.62% by weight of the polymerized sample is measured. These are translated to 3.4% of the amount of monomers present in the original molding composition.

EXAMPLE 10 Isobaric profile molding process / temperature of the composition of example 8 The molding compound of Example 8 is evaluated using a mold loading temperature of 80 ° C. A load of 1040 g is introduced into the mold cavity and ss closes the mold. Immediately pressure is applied increasing to 5516 kPa (800 psi (56.4 kg / cm2)) and ss increases the melt temperature to 125 ° C. 3 minutes after the mold temperature reaches 125 ° C, the mold is opened and the resulting plate is removed. There are no - - "« - fc_fc-¿* .V bleached surface defects observed in example 8.

EXAMPLE 11 5 Effect of increasing the amounts of crosslinking agent in the composition of Example 8 The effect of the crosslinking agent on the heat strength of the molded article is evaluated by altering the crosslinking agent in the molded compound. Two compositions are prepared (A and B). The liquid mixtures of compositions A and B are included in Table 15 below. Each of the two liquid mixtures is introduced into a 9.5 1 (2.5 gallon) double planetary mixer cooled with separate water, (Charles Ross & Sen Company; Hauppauge, NY).

Table 15. Component of the liquid mixture 20 Component Composition A Composition B (Parts by weight) (Parts by weight) ___ = ______ ti_í_é? - _? ____ __ií __? _______? ^? ¿^^ _ __? _____ Each liquid mixture is combined to ensure homogeneity. The solid materials included in Table 16 below were premixed and introduced into the mixer for one of the two liquid mixtures: Table 16. Solid components for the compositions A v B Component Parts by weight ATH-NLM treated with silane 1436 Rohm & Haas K120ND 120 ________ _l_____________________ - - - * »- Zinc Stearate 4.5 The mixture is combined for 3 minutes, at which point the material is transformed into a paste. A decorative mixture of acrylic particles filled with ATH (DFAP's) is added to each composition within a range of 30 to 150 mesh size (about 100-560 microns) and is; they mix in: The mixture is mixed for 15-20 minutes under a vacuum of 735 mm Hg (25"Hg) during which the material is transformed into a thick molded compound of uniform composition.The molded compound is removed from the mixer and packaged in bulk in a air-tight plastic bag The compound is stored at 5-10 ° C. The molding compounds are evaluated versus the formulation of Example 8 using a 25.4 cm x 25.4 cm (10"x 10") mold described in the example. 1. The mold is preheated to 125 ° C and a load of; Molding compound sufficient to create a 0.64 cm (0.25") thick molded plate The mold is closed and a pressure of 5516 kPa (800 psi (56.4 kg / cm2)) is applied After 5 minutes the mold is opened and the resulting hot plate is removed using internal ejector bolts.After cooling, the molded plates are examined for deformation and bleaching at the contact areas with the ejector bolt.The plate prepared from the above formulation P shows deformation and significant bleaching, even on the upper surface of the plate The plate prepared from the formulation of Example 8 shows less deformation and light bleaching on the lower surface The plate prepared from the above formulation B does not show visible deformation or blanching.Therefore, the plate of Formulation B shows the highest hot resistance to the removal of the article from the mold.An analyzed instrument is used r impact, INSTRON DYNATUP model 8250 available from Instron, to measure the maximum impact energy of the samples from molded articles made from the formulations A, B and the composition of Example 8. The dimensions of the sample were 10 cm x 10 cm x 6 mm (4 x 4 x 0.25 inches). The instrumented impact data are shown in Table 17 below. ^ 4 «8 ^^^ Sj? ^ A ^ Table 17 EXAMPLE 12 Effect of the character of the crosslinking agent on strength to heat and physical properties The effect of the crosslinking character on the physical properties and the heat resistance of the molded article is demonstrated by the use of an oligomer of aliphatic urethane polymethacrylate. This material is supplied by Sartomer Company (Exton, PA) as CN1963, a 75% solution of trimethylolpropane t r ime t a r r e a r t a t ion. A liquid mixture is prepared. The components of the liquid mixture are included in Table 18 below. The liquid mixture is introduced in a 9.5 1 (2.5 gallon) double planetary mixer cooled with water (Charles Ross &Son Company, Hauppauge, NY): Table 18. Liquid mixture The liquid mixture is combined to ensure homogeneity. The solid materials included in table 19 below were pre-mixed and introduced into the mixer: Table 19. Solid components The mixture is combined for 3 minutes, point at which material is transformed into a paste. A mixture of acrylic particles filled with decorative ATH is added (DFAP's) within a mesh size range of 30 to 150 (approximately 100-560 micrometers) and mixed in: Component Parts by weight DFAP 's 690 The mixture is combined for 15-20 minutes under vacuum of 735 mm Hg (25"Hg) during which the material is transformed into a thick molded compound of uniform composition.The molded compound is removed from the mixer and packed into - • - "-: - - * - 1" -'- "8" - - • '- "* - - - bulk form in an airtight plastic bag The compound is stored at 5-10 C. The molding compound is evaluated using the 25.4 cm x 25.4 cm (10"x 10") mold described in Example 1. The mold is preheated to 125 ° C and a composite charge is placed in the cavity. enough molding to create a 0.64 cm (0.25") thick molded plate. The mold is closed and a pressure of 5516 kPa (800 psi (56.4 kg / cm2)) is applied. After 5 minutes the mold is opened and the resulting hot plate 10 is removed using the internal ejector bolts. It is found that the resulting molded article has excellent hot strength. The instrumented impact tests measure a maximum impact energy of 0.87 J (7.7 inches-1 fibers). 15 EXAMPLE 13 Use of FAP as setting agents A liquid mixture having the components included in Table 20 below is prepared. The liquid mixture is introduced into a 9.5 1 (2.5 gallon) double planetary mixer cooled with water (Charles Ross &Son Company, Hauppauge, NY): __________ ___ < ^ -_ .____. _ ______ ^ __ ^ _________ ^ __ ¿_ - »^^ .. ^^ > _ ^ - ^ -__ a1s ... t »f LA |». . ... - | r) * > ,. -. . ..t _ .., ....

Table 20. Liquid mixture This liquid mixture is combined to ensure homogeneity. The solid materials included in table 21 below were pre-mixed and introduced into the mixer: Table 21. Solid composition The mixture is combined for 3 minutes, at which point the material is transformed into a paste. A mixture of acrylic particles filled with decorative ATH is added (DFAP's) within a mesh size range of 30 to 150 (approximately 100-560 micrometers) and mixed in: The mixture is mixed for 20 minutes under a vacuum of 735 mm Hg (25"Hg), during which the material is transformed into a thick molded compound of uniform composition.The molded compound is removed from the mixer and packaged in bulk form an air-tight plastic bag The compound is stored at 5-10 ° C. The resulting molded composite is molded using a hand-tight steel mold with a 15.24 cm diameter (6") cavity, which molds a part 1.27 cm (0.5") thick.The mold cavity is preheated to approximately 80 ° C by placing the mold between press plates at 125 ° C. The mold is loaded and returned to the press and placed under 6895 kPa (1000 psi (70.45 cm / cm2)) for 6 minutes, during which time the outer mold temperature increases to 118 ° C for a period of at least 3 minutes.The plates are then cooled with water until the temperature External mold reaches approximately 80 ° C in which the mold is removed and opened. The molded plate shows excellent surface quality. The selected physical properties are shown in Table 22 below: Table 22 EXAMPLE 14 Composition of molding compound using a core / shell latex setting agent ^^^ ¡¡¡¡¡¡¡¡¡¡A liquid mixture is prepared having the components listed in Table 23 below. The liquid mixture is introduced in a 9.5 1 (2.5 gallon) double planetary mixer cooled with water (Charles Ross &Son Company, Hauppauge, NY): Table 23. Liquid mixture This liquid mixture is combined to ensure homogeneity.

The following solid materials included in Table 24 below were premixed and introduced into the mixer: Table 24. Solid components The mixture is combined for 3 minutes, at which point the material is transformed into a paste. A mixture of acrylic decorative particles filled with ATH (DFAP's) is added within a range of 30 to 150 mesh size (approximately 100-560 micrometers) and mixed in: The mixture is combined for 10 minutes under a vacuum of 735 mm Hg (25"Hg), during which time the material _! _____________ • | i-i l '? _? 1_íi'- |? _l_lÉ? It is transformed into a thick molded compound of uniform composition.The molded compound is removed from the mixer and packaged in bulk in an airtight plastic bag. Store at 5 -10 ° C.

EXAMPLE 15 Encapsulation of a particle board insert with the composition of Example 14 A particle board insert is prepared from a 16 mm (0.625") board with dimensions of 24.4 cm x 24.4 cm (9.625") x 9.625"). Screw inserts are placed on the particle board at each corner, separated 5.1 cm (2 inches) from each side. The holes in each insert are covered with a urethane foam material. Focus strips of Black Pearl CorianMr (DuPont Company, Wilmington, DE) with a cross sectional dimension of 6 mm x 6 mm (0.25"x 0.25") and fastened in loo edges of the particle board using commercial cyanoacrylate adhesive. Two loads of the above formulation, each weighing 603 g, are pre-pressed to a uniform thickness, with a circular load of approximately 22.9 cpi (9") in diameter The board insert Irr rr i - - iit 'rrt_ "r, Mm * - ^ - ^ - ^. ^^^^^? ^ ¿¡^? * l ^ a ^ ¡^^^^^^^^^^ particles are interposed between the charges to create a composite charge.The composite charge is placed in a 25.4 cm x 25.4 cm (10"x 10") aluminum frame at room temperature in a hand mold that has a vaporization separation of 127 micrometers (0.005"). The mold is closed and placed in a hydraulic press at a platen temperature of 140 ° C. Initially a pressure of 1724 kPa (250 psi (17. (5 kg / cm2)) is applied to fill the mold.The pressure is gradually increased to 3792 kPa (550 psi (38.7 kg / cm2)) for 3.5 minutes. pressure and heat for 8 minutes, during which time the external temperature of the mold reaches 115 ° C for a period of at least 2 minutes.The mold is then cooled in the plate under pressure until the external temperature of the mold reaches approximately 80 C. The pressure is then released and the mold is removed and opened.The molded article is removed from the mold and the urethane foam is removed from the screw insertion holes.The resulting molded article is therefore composed of a insert part of encapsulated particle board and has a molded band on the edge and molded screw insert parts, both the edge band, and the screw inserts integrally join; The molded article shows excellent; quality and represents a composite tray ready for use.

Upon evaluation, it was found that the polymerizable fraction of the molded compound permeates the insert material by a distance of up to approximately 0.63 cm (0.25") within the insert material, which was found to greatly improve the impact properties of the article versus the clamping of a welded surface material similar to a particle board using commercial adhesives.

EXAMPLE 16 Encapsulation of a thermoplastic sheet insert with the composition of Example 14 An insert with a thickness of 12.7 mm (0.5") of extruded recycled PVC material is prepared.Two charges of the formulation of Example 14, each weighing 603 g, are pre-pressed each in a uniform thickness with a circular load approximately 22.8 cm (9") in diameter.

The insert is interposed between the charges to create a composite charge. The composite charge is placed at room temperature in a 25.4 cm x 25.4 cm (10"x 10") aluminum frame mold having a vaporization spacing of 127 micrometers (0.005"). The mold is closed and placed in a hydraulic press at a plate temperature of 140 ° C. Initially a pressure of 1724 kPa (250 psi (17.6 kg / cm2)) is applied to fill the mold.The pressure is gradually increased to 4342 kPa (550 psi (38.7 kg / cm2)) at 3.5 minutes.The pressure and heat are maintained for 8 minutes, during which time the external temperature of the mold reached 115 ° C for at least 2 minutes.The mold is then cooled in the plate under pressure until the external temperature of the mold reaches approximately 80 ° C. Then the pressure is released and the mold is removed and opened The molded article is removed from the mold and is constituted by an insertion foot PVC encapsulated.The molded article shows excel entity and represents a ready-to-use composite part.

EXAMPLE 17 Encapsulation of a sheet of Nomex paper " A liquid mixture is prepared having the components that are included in Table 25. The liquid mixture is introduced into a 9.5 1 (2.5 gallon) double planetary mixer cooled with water (Charles Ross &Son Company; Hauppauge, NY): • j * M ^^^^^ j ^^^ ¡& fe¡i ^^^^^ 2g | t Table 25. Liquid mixture This liquid mixture is combined to ensure homogeneity. The solid materials included in table 26 below were pre-mixed and introduced into the mixer: Table 26. Solid components Component Parts by weight The mixture is combined for 3 minutes, at which point the material is transformed into a paste. A mixture of acrylic decorative particles filled with ATH (DFAP'e) is added within a range of 30 to 150 mesh size (approximately 100-560 micrometers) and mixed in: Component Parts by weight DFAP 's 630 The mixture is mixed for 20 minutes under a vacuum of 735 mm Hg (25"Hg), during which the material is transformed into a thick molded compound of uniform composition.The molded compound is removed from the mixer and packaged in bulk form an air-tight plastic bag The compound is stored at 5-10 ° C. A 0.01 mm (0.004") insert is prepared from accumulated N0MEXMR paper (DuPont Company, Wilmington, DE), with dimensions of 24 cm x 24 cm (9.5"x 9.5"). They are pressed | t. , _._ > ._____-_,. * ... ^ .. ^ - r. ^^ m * & * -. previously two loads of the previous formulation, each with a weight of 195 g, in a uniform thickness with a circular load of approximately 22.9 cm (9") in diameter The NOMEXMR insert is interposed between the loads to create a load The composite charge is placed in a 25.4 cm x 25.4 cm (10"x 10") aluminum frame portable mold at room temperature that has a vaporization spacing of 127 micrometers (0.005"). The mold is closed and placed in a hydraulic press at a plate temperature of 140 ° C. Initially a pressure of 3792 kPa (550 psi (38.7 kg / cm2)) is applied to fill the mold. The pressure increases gradually to 3792 kPa (550 psi (38.7 kg / cm2)). The pressure and heat are maintained for 6 minutes, during which the external temperature of the mold reaches 125 CC for at least 2 minutes. The mold is then cooled in plate to lower pressure until the external temperature of the mold reaches approximately 80 ° C. Then the pressure is released and the mold is removed and opened. The molded article is removed from the mold to provide a sheet approximately 0.32 cm (0.125") thick with an N0MEXMR paper encapsulant suspended on the article sensor.The adhesion of the encapsulant and the molded compound is excellent.

,. ... ^ ¿.,.,., ^ ... "J ... - _.," _ _ _ -_.__-, - tl ». LJ-fi fi I I I H ft ft ft ft ft ft EJ EJ EJ EJ EJ EJ EJ EJ EJ EJ EJ EJ EJ EJ EJ EJ EJ EJ Adhesion of acid functionality to the molding compound to promote adhesion A liquid mixture is prepared having the; components that are included in table 27 below. Lei liquid mixture is introduced in a double planetary mixer; of 9.5 1 (2.5 gallons) cooled with water (Charles Ross &Son Company; Hauppauge, NY): Table 27. Liquid mixture ._ai-4_a_-aab- Zelec MO 2.5 The liquid mixture is combined to ensure homogeneity. The solid materials included in table 28 below are entered in sequence: Table 28. Solid components The mixture is mixed for 20 minutes under a vacuum of 735 mm Hg (25"Hg), at which point the material is transformed into a thick molding compound of uniform composition.The molding compound is removed from the mixer and packaged in a in bulk in an airtight plastic bag The compound is stored at 5-10 ° C. 4 £ ^^^ 3 & ^ * ^^ p¡ ^ g * - EXAMPLE 19 Encapsulation of aluminum reinforcement with the composition of example 18 An insert is prepared from aluminum 0.32 cm (0.125") in sheet, with dimensions of 24.4 cm x 24.4 cm (9.625" x 9.625") .The sheet is cleaned with sandblasting and washed with isopropanol. before use, the insert weight is treated with ZelecMR MO 1% in isopropanol solution to improve adhesion Two loads of the composition of Example 18, each weighing 582 g, are pre-pressed to a uniform thickness , with a circular load of approximately 22.9 cn (9") in diameter The insert of aluminum foil is interposed in the loads to create a composite charge.The composite charge is placed at room temperature, in a portable mold of aluminum frame of 25.4 cm x 25. cm (10"x 10") a vaporization separation of 12E.micrometers (0.005") is obtained. The mold is closed and placed in unat cold hydraulic press and pressed at 1034 kPa (150 psi (10.5 kg / cm2)) for approximately 30 seconds to fill the mold. The mold is then inserted into a second hydraulic press with a plate temperature of 140 ° C. It is applied - 12.0 ^ - initially a pressure of 1034 kPa (150 psi (10.5 kg / cm2)). The pressure is gradually increased to 3792 kPa (550 psi (38.7 kg / cm2)) in the following 3.0 minutes. The pressure and heat are maintained for 7.5 minutes, during which time the external temperature of the mold reaches 115 ° C for at least 2 minutes. The mold is then cooled by plate under pressure until the external temperature of the mold reaches approximately 80 ° C. Then the pressure is released and the mold is removed and opened. The molded article is removed from the mold to provide a fully encapsulated aluminum sheet. When subjected to evaluation, it is found that the molded article dissipates applied heat very efficiently: a 5 minute contact with a hot steel block (at a sufficient temperature of 220 ° C) does not cause visible damage while the controls without a core of internal aluminum show irreversible heat damage.

EXAMPLE 20 Application on one side of the composition of Example 18 to an aluminum sheet. A molding compound having the composition of Example 18 is prepared using the same procedure, with the exception of the use of ALCAN not treated with ATH. An aluminum foil substrate is prepared to example slide 16. A single charge of molding compound weighing 420 g is pre-pressed in a circular container of uniform thickness approximately 9"in diameter. is placed on the upper side of the aluminum foil and the resulting composite load is placed in the mold used in example 19 at room temperature. The mold is closed and inserted into a cold hydraulic press and pressed at approximately 1379 kPa (200 psi (14 kg / cm2)) for 30 seconds. The mold is then inserted into a second hydraulic press gaining a plate temperature of 135 ° C. Initially a pressure of 1034 kPa (150 psi (10.5 kg / cm2)) is applied. The pressure e; e increases gradually to 3792 kPa (550 psi (38.7 kg / cm2)) in the following 3.0 minutes. The pressure and heat are maintained for 7 minutes, during which time the temperature external mold reaches 120 ° C for at least 2 minutes. The mold is then cooled in a plate under pressure until the external temperature of the mold reaches approximately 80 ° C. Then the pressure is released and the mold is removed and opened. The molded article is removed from the mold to provide a two-layer structure that have an application in only one _ _ The_ _, . - - ___ ____ ^ > _ «! -__. ^^ a _- ^ _ ...-__...., ...... _ .. .__ _-___, ___, _. _-___F__-___. _____, _ side of filled acrylic material. By letting it cool, e.e returns a part significantly. The adhesion of the molded material to the aluminum substrate is found to be excellent. The interface survives many repeated impacts. In addition, when the composite structure is folded, the molded material is fragmented, but does not lose adhesion, even when bent at 90 °.

EXAMPLE 21 Application on one side of the molding compound for a transparent acrylic sheet A liquid mixture is prepared containing the components that are included in Table 29 below. The liquid mixture is introduced in a 9.5 1 (2.5 gallon) double planetary mixer cooled with water (Charles Ross &Son Company; Hauppauge, NY): Table 29. Liquid mixture Component Parts by weight Acrylic syrup, 24% of 726 solids V045 in MMA __ ^ ______ ri ___ t? __? ___ ^ __ É ______________________ The mature liquid is mixed to ensure homogeneity. The following solid materials are introduced in sequence in Table 30: Table 30. Solid components The mixture is combined for 3 minutes at which point the material is transformed into a paste. A mixture of acrylic decorative particles filled with ATH (DFAP's) within a range of 30 to 150 mesh size (approximately 100-560 microns) are added and mixed in: The mixture is mixed for 30 minutes, during which time the material is formed as a thick molded compound of uniform composition. The molded compound is removed from the mixer and packaged in bulk in an airtight plastic bag. The compound is stored at 5-10 ° C. An insert sheet is prepared from a concentrated transparent acrylic sheet with a thickness of 0.64 cm (0.25") with dimensions of 17.8 cm x 17.8 cm (7" x 7") .A single load of the above molding compound weighing 425 g is pre-pressed to a uniform thickness with a circular load of approximately 15.2 cm (6") in diameter. The molded composite is placed on the upper side of the acrylic sheet substrate and the resulting composite filler is placed in a 17.8 cm x 17.8 cm / 7"x 7" cavity mold at room temperature similar to the mold used in Example 19. The mold is closed and inserted into a cold hydraulic press and pressed at approximately 1379 kPa (200 psi) (14 kg / cm2)) for 30 seconds. The mold is then inserted into a second hydraulic press with a plate temperature of 125 ° C. Initially a pressure of 3654 kPa (530 psi (37.4 kg / cm2)) is applied. The pressure is gradually increased to 7033 kPa (1020 psi (71.9 kg / cm2)) in the following 3.0 minutes. The pressure and heat are maintained for 7 minutes, during which time the external temperature of the mold reached 120 ° C for at least 3 minutes. The mold is then; It cools by plate under pressure until the outer temperature of the mold reaches approximately 80 ° C. The pressure is then; free and the mold is removed and opened. The molded article is removed from the mold to provide a structure of doe: layers having an application on only one side of filled acrylic material. When leaving to cool, the part shows unites. small amount of wrap. The resulting molded article is polished to provide a very deep aesthetic. The impactc tests of the acrylic sheet surface at a force of 0.68 J, 1.4 J, 2.0 J, 4.1 J and 9.0 J (6, 12, 18, 36, and 80 inch-pounds) show little or no damage. The impact tests of the control materials, a transparent acrylic sheet of a S ^ ^ - ^ - molded plate molding compound, resulting in obvious visual damage at a pressure of 1.4 J (12 inch-pounds) and catastrophic failure to 9.0 J (80 inch-pounds).

EXAMPLE 22 Encapsulation of a Corian ™ solid surface material by the composition of Example 8 A CorianR solid surface material, 0.64 cm (0.25") thick, is broken by impwith a hammer.The material notices vary from a dimension of 13 mm to 7. (5 cm (0.5-3.0") in dimension and placed in the heated mold described in example 8. a charge of 400 g of the compound molded described in example 8 is precompressed under vacuum in an isolated diameter of 20 cm (8.0") load then;. places in the heated mold, and the upper part of the broken Corian.The mold is closed and the molding cycle described in example 8 is followed. The resulting molded article is smooth to expose an interesting pattern in which the molded compound encapsulates Corian ™ pieces to produce a continuous material. __-- J- - * & __.! * & '._., .. .--. ^ _ £ ______ EXAMPLE 23 Use of a complex pressure profile in the molding of a three-dimensional article A liquid mixture consisting of the following is prepared, which is introduced into a 9.5 1 (2.5 gallon) double planetary mixer cooled with water (Charles Ross &Son Company, Hauppauge, NY): fifteen twenty This liquid mixture is mixed to ensure homogeneity. __ £ ______, ______- ___________ ua_f_? I __- ¡* & _________i_____? The following solid materials are introduced into the mixer: The mixture is combined for 2 minutes, at which point the material is transformed into a paste. a mixture of acrylic particles filled with ATH decorative (DFAP's) within the size range 30 to 150 mesh (about 100-560 micrometers) is added and mixed in: fifteen The mixture is mixed for 15 minutes under a vacuum of 735 mm Hg (25"Hg), during which the material is transformed into a thick molded compound of uniform composition.The molded compound is removed from the mixer and packaged in bulk form in an airtight plastic bag The compound is stored at 5-10 ° C. ____ i? _r r it- T ___ tÍf ______ Í ____-- S ^^^^ i ^ The above molded compound is evaluated in a mold heated to the aluminum plate coated with nickel, which molds a flower pot shape with a diameter of 15.2 cm ( 6 inches) that has a depth of 11.4 cm (4 5 inches). Is placed a load of toroidal shape that weighs 7? > 3 g in the mold at a mold temperature of 22 ° C. The mold is placed in a hydraulic press with plates heated to 185 CC and an initial pressure of 2.3 MPa (340 psi (24 kg / cm2)) is applied. After 4 minutes, the external molcle temperature has reached 100 ° C and the pressure is increased to 10.2 MPa (14 £ 0 psi (103 kg / cm2)). After 6.5 minutes, the pressure is reduced to 3.6 MPa (530 psi (37.4 kg / cm2)). At 10 minutes, the external temperature of the mold reached 128 ° C and the cooling cycle begins, and the pressure is reduced and maintained at 2.4 MPa (355 psi 25 kg / cm2)) until the demoulding at 75 ° C. The resulting molded article shows excellent reproduction of the dimensions of the mold cavity without bleaching defects by pressure in the areas which are perpendicular to the force applied during the molding cycle. Of course, it should be understood that a wide range of changes and modifications can be made to the preferred embodiment described above. Therefore, it is intended that the foregoing detailed description be considered as illustrative rather than limiting and that it should be understood that they are the following claims, including all equivalents;, which are intended to define the scope of this invention. It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention.

Claims (13)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. A molded article made of a molding composition of a molding composition comprising at least one liquid polymerizable material that includes at least one volatile monomer reactive material; at least one primary thermal initiator having an average life temperature of 10 hours of primary thermal initiator; and at least; a secondary thermal initiator, wherein the temperature of; Average life of 10 hours of the secondary thermal initiator is at most about 5 ° C higher than the average video temperature of 3 hours of primary thermal initiator.

2. A mold composition, comprising the mold composition described in accordance with. claim 1, characterized in that it further comprises: from about 10 to about 25% in weight of a liquid polymerizable material that includes at least one volatile monomer reactive material; and at least one viscosity increaser; wherein at least about 0.05% by weight is one or more crosslinking agents.

3. A molded article comprising a substrate having more than one surface and a component molded on at least part of a surface of the substrates, characterized in that the substrate and the molded component can independently be flat or shaped and the substrate is not completely encapsulated for the component; molded, and wherein the substrate and the molded component can independently be flat or shaped, and wherein; the molded component is made of the mold composition; described in accordance with claim 1.

4. A method for making the molded article, according to claim 1, characterized in that it comprises the steps of: (1) providing at least one mold loading unit having a mold composition comprising: (a) of about 10 to about 25% by weight of a liquid polymerizable material that includes at least one volatile monomer reactive material, (b) at least one primary thermal initiator having an average lifetime of 10 hours of primary thermal initiator, (c) ) at least one secondary thermal initiator having an average life temperature of 10 hours of secondary thermal initiator of at least about 5 ° C higher than the average life temperature of 10 hours of the primary thermal initiator, - (2) placing At least one mold loading unit in a mold cavity of a mold, the mold cavity has a preheated mold temperature sufficient to cause the thermal initiator to The secondary material passes through approximately 3 to approximately 10 half-lives in the next approximately 10 minutes or less, - (3) apply pressure to the mold at a sufficient molding pressure to maintain an internal geometrical integrity and a geometric surface integrity of the molded article , (4) maintaining the preheated mold temperature and molding pressure for a sufficient time to ensure that the secondary thermal initiator has passed through; from about 3 to about 10 half lives.

5. A method for making the molded article, according to claim 1, characterized in that it comprises the steps of: (l) providing at least one mold loading unit comprising: (a) a more volatile component, (b) by at least one primary thermal initiator having a primary thermal initiator of a half-life temperature of 10 hours, - £ ^^^^ ¿^^^ ^^ g ^ - ».« _. * ._ .. ~ .., ...-. and (c) at least one secondary thermal initiator, wherein the half-life temperature of 10 hours of the secondary thermal initiator is at most about 5 ° C higher than the average lifetime of 10 hours of the primary thermal initiator; (2) placing at least one mold loading unit in a mold cavity of a mold having an initial mold temperature that is at most about 10 ° C lower than the boiling point of the more volatile component; (3) apply pressure to the mold at a sufficient molding pressure to maintain an internal geometrical integrity and geometrical surface integrity of the molded article, - (4) heat the mold to a final mold temperature sufficient to cause the secondary thermal initiator Cycle through about 3 to about 10 half lives within about 10 minutes or less, - (5) Maintain the final mold temperature and molding pressure for a sufficient time to ensure that the secondary thermal initiator has passed through.; about 3 to about 10 half lives.

6. A method for making the molded article, according to claim 1, characterized in that it comprises the steps of: (1) providing at least one mold loading unit comprising (a) at least one primary thermal initiator having a average life temperature of 10 hours of primary thermal initiator; and (b) at least one secondary thermal initiator having a half-life temperature of 10 hours of secondary thermal initiator that is at least about 5 ° C higher than the average lifetime of 10 hours of primary thermal initiator; (2) placing at least one mold loading unit in a mold cavity of a mold, the mold having a vaporization separation and a preheated mold temperature sufficient to cause the secondary thermal initiator to cicle through about 3 to about 10 half lives within about 10 minutes or less, - (3) applying sufficient initial molding pressure to fill the mold with at least one mold loading unit; (4) maintaining the initial molding pressure for a sufficient time to seal the vaporization separation; (5) apply sufficient selected molding pressure to maintain an internal geometrical integrity and geometric surface integrity of the molded article, - and (6) maintaining the mold temperature and the final molding pressure for a sufficient time to ensure that the secondary thermal initiator has passed through about 3 to about 10 half-lives.

7. A method for making the molded article, according to claim 1, characterized in that it comprises the steps of: (1) providing at least one mold loading unit comprising: (a) a more volatile component, (b) by at least one primary thermal initiator having a tare half-life of 10 hours of primary thermal initiator; and (c) at least one secondary thermal initiator having an average life temperature of 10 hours of secondary thermal initiator that is at least 5 ° C greater than the average life temperature of 10 hours of primary thermal initiator, - (2) placing at least one mold loading unit in a mold cavity of a mold, the mold having a vaporization separation and an initial mold temperature which is, at most, about 10 ° C lower than the point of boiling the most volatile component; (3) apply an initial molding pressure sufficient to fill the mold with at least one loading unit (Mold, - (4) maintaining the initial molding pressure for a sufficient time to seal the vaporization separation, (5) heating to a final mold temperature sufficient to cause the secondary thermal initiator to cycle through about 3 to about 10 half lives for the next approximately 10 minutes or less; (6) cplirrating a selected molding pressure sufficient to maintain an internal geometrical integrity and geometric surface integrity of the molded article; and (7) maintaining the final mold temperature and a final molding pressure for a sufficient time to ensure that the secondary thermal initiator has passed through from about 3 to about 10 half-lives.

8. A method for making the molded article according to claim 1, characterized in that at least one design detail involved therein comprises the steps of: (1) providing at least one mold loading unit having a composition of mold comprising: (a) at least one primary thermal initiator having an average lifetime of 10 hours of thermal initiator . -. '^ * • __- primary, (b) at least one secondary thermal initiator having an average lifetime of 10 hours of secondary thermal initiator of at least about 5 ° C greater than the average life temperature of 10 hours of primary thermal initiator, (2) placing at least one mold loading unit in a mold cavity of a mold, the mold cavity having a preheated mold temperature sufficient to cause the secondary thermal initiator to pass through from about 3 to about 10 half lives within approximately 10 minutes or less, - (3) apply pressure to the mold at a sufficient molding pressure to maintain an internal geometrical integrity and geometric surface integrity of the molded article; (4) maintaining the preheated mold temperature and molding pressure for a sufficient time to ensure that the secondary thermal initiator has passed through about 3 to about 10 half lives.

9. A method for making the molded article, according to claim 1, including at least one core encapsulated therein, characterized in that it comprises the steps of: (1) providing at least two load units to form a shape that corresponds to a portion of the molded article, the preformed load units have an inner side and an opposite outer side, wherein the preformed load units 5 have a molded composition comprising: (a) at least one primary thermal initiator which has a primary thermal initiator with an average tartar temperature of 10 hours, (b) at least one secondary thermal initiator having an average life temperature of 10 hours 10 of secondary thermal initiator which is at least about 5 ° C. greater than the average life temperature of 10 hours of primary thermal initiator; (2) providing a composite load by placing at least one core adjacent to the inner side of the preformed load units 15; (3) placing the composite charge in a mold cavity of a mold, the mold cavity having a preheated mold temperature sufficient to cause the secondary thermal initiator to pass through about 3 to 20 about 10 half-lives within about 10 minutes or less; (4) applying pressure to the mold at a sufficient molding pressure to maintain an internal geometrical integrity and geometric surface integrity of the molded article, - __ «____ ^ __-, -___._» __-, »* _ .. > _..._.,. ".. .._ -__.-_ -_-_-._. ___ ^ ________ j__fe _ ^ _ a ____ s. ^ _ ^ -.-_ * • -. ».. .A ^ .. ^ ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ molding pressure for a sufficient time to ensure that the secondary thermal initiator has passed through about 3 to about 10 half lives.

10. A method for making the molded article, according to claim 1, including at least one core encapsulated therein, characterized by the steps of: (1) providing at least two preformed loading units that form a shape corresponding to a portion of the molded article, the preformed load units have an inner side and an opposite outer side, wherein the preformed load units have a molding composition comprising: (a) a more volatile component, (b) at least one primary thermal initiator which; it has an average life temperature of 10 hours of primary thermal initiation; and (c) at least one secondary thermal initiator having a half-life temperature of 10 hours; of secondary thermal initiator of at least 5 ° C greater than; the average life temperature of 10 hours of primary thermal initiator, - (2) providing a composite charge when placing chicken minus a core adjacent to the inner side of the preformed loading units1, - - '"°° - ^ - _ _....,. _- _ _, ___ s _ ^ _____ i__. __.. _ T. ^ - ^ .. ^^^^. ^ ^,., __ ^ ^ M ^^? ^ J, (3) placing the composite charge in a mold cavity of a mold, having an initial mold temperature which is at most about 10 ° C lower than the boiling point of the more volatile component; (4) apply pressure to the mold at a sufficient molding pressure to maintain an internal geometric integrity and geometric surface integrity of the molded article; (5) heat the mold to a mold temperature, sufficient to cause the secondary thermal initiator Cycle through from about 3 to about 10 half lives in the following, about 10 minutes or less, (6) maintain the final mold temperature and casting pressure for a sufficient time to ensure that the secondary thermal initiator has passed. through about 3 to about 10 half lives.

11. A method for making the molded article, in accordance with claim 1, which includes at least one core encapsulated therein, characterized in that it comprises the steps of: (l) providing at least one core in a mold cavity of a mold, the mold has a vaporization separation, - (2) providing at least one mold loading unit having a molding composition comprising: (a) at least one primary thermal initiator having an average life temperature of 10 hours of primary thermal initiator; and (b) at least one secondary thermal initiator wherein the half-life temperature of 10 hours of the secondary thermal initiator is at least 5 ° C higher than the average life temperature of 10 hours of the primary thermal initiator; (3) heating the mold to a mold temperature; sufficient to cause the secondary thermal initiator to cycle through about 3 to about 10 lives; means within about 10 minutes or less, - (4) placing at least one mold loading unit 'in the mold cavity, wherein at least one mold loading unit comprises at least one core in the mold. mold cavity, - (5) apply sufficient initial molding pressure to fill the mold with at least one mold loading unit, - (6) maintain the initial molding pressure for a sufficient time to seal the vaporization separation , - (7) applying a selected molding pressure sufficient to maintain an internal geometrical integrity and geometric surface integrity of the molded article; and (8) maintaining the mold temperature and the final molding pressure for a sufficient time to ensure that the secondary thermal initiator has passed through about 3 to about 10 half-lives.

12. A method for making the molded article, according to claim 1, including at least one core encapsulated therein, characterized in that it comprises the steps of: (1) providing at least one core in a mold cavity of a mold, the mold cavity has a vaporization separation and an initial mold temperature which is at most about 10 ° C lower than the point of; boiling of the most volatile component; (2) provide at least one loading unit of; mold in the mold cavity, wherein at least one mold loading unit comprises at least one core in the mold cavity, at least one mold loading unit has a molding composition comprising: (a) a volatile component, (b) at least one primary thermal initiator having an average lifetime of 10 hours of primary thermal initiator, - and (c) at least one secondary thermal initiator, having a half-life temperature 10 hours of the secondary thermal initiator of at least 5 ° C higher than the average life temperature of 10 hours of the primary thermal initiator; (3) applying a sufficient initial molding pressure to fill the mold with at least one mold loading unit, - (4) maintaining the initial molding pressure for a sufficient time to seal the vaporization separation; (5) heating to a final mold temperature sufficient to cause the secondary thermal initiator to cycle through about 3 to about 10 half-lives within about 10 minutes or less; (6) applying a selected molding pressure in order to maintain the internal geometrical integrity and geometric surface integrity of the molded article; and (7) maintaining the final mold temperature and leaving the final molding pressure for a sufficient time to ensure that the secondary thermal initiator cycled through about 3 to about 10 half-lives.

13. The molded article, according to claim 1, characterized in that it is made from a molding composition comprising: (a) from about 10 to about 25% by weight of a liquid polymerizable material that includes at least one reactive material volatile monomer, (b) at least one initiator ? __ primary thermal having a half-life temperature of 10 hours of primary thermal initiator, (c) at least one secondary thermal initiator having a half-life of 10 hours of secondary thermal initiator of at least about 5 ° C greater than the half-life temperature of 10 hours of primary thermal initiator, wherein at least about 0.05% to weight is UTO or more cross-linking agents.