EP0000223B1 - Production of articles from an unsaturated polyester resin, mineral fillers and glass fibres and articles thus obtained - Google Patents

Production of articles from an unsaturated polyester resin, mineral fillers and glass fibres and articles thus obtained Download PDF

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Publication number
EP0000223B1
EP0000223B1 EP78200045A EP78200045A EP0000223B1 EP 0000223 B1 EP0000223 B1 EP 0000223B1 EP 78200045 A EP78200045 A EP 78200045A EP 78200045 A EP78200045 A EP 78200045A EP 0000223 B1 EP0000223 B1 EP 0000223B1
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EP
European Patent Office
Prior art keywords
process according
mixture
polyester resin
unsaturated polyester
glass fibres
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78200045A
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German (de)
French (fr)
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EP0000223A1 (en
Inventor
René Leopold Eduard Van Gasse
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Stamicarbon BV
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Stamicarbon BV
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Publication date
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Publication of EP0000223A1 publication Critical patent/EP0000223A1/en
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Publication of EP0000223B1 publication Critical patent/EP0000223B1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
    • B29C67/242—Moulding mineral aggregates bonded with resin, e.g. resin concrete
    • B29C67/243—Moulding mineral aggregates bonded with resin, e.g. resin concrete for making articles of definite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/02—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising combinations of reinforcements, e.g. non-specified reinforcements, fibrous reinforcing inserts and fillers, e.g. particulate fillers, incorporated in matrix material, forming one or more layers and with or without non-reinforced or non-filled layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/02—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising combinations of reinforcements, e.g. non-specified reinforcements, fibrous reinforcing inserts and fillers, e.g. particulate fillers, incorporated in matrix material, forming one or more layers and with or without non-reinforced or non-filled layers
    • B29C70/021—Combinations of fibrous reinforcement and non-fibrous material
    • B29C70/025—Combinations of fibrous reinforcement and non-fibrous material with particular filler
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/06—Unsaturated polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • B29K2105/0854—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns in the form of a non-woven mat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2309/00—Use of inorganic materials not provided for in groups B29K2303/00 - B29K2307/00, as reinforcement
    • B29K2309/08—Glass

Definitions

  • the invention relates to a process for the production of moldings by mixing unsaturated polyester resin, inorganic fillers and magnesium oxide, thickening this mixture in the presence of glass fibers and pressing parts of the thickened mass at elevated temperature.
  • molded parts which contain unsaturated polyester resin, mineral fillers and glass fibers, have long been known in the trade as 'dough molding compound' (DMC). These masses contain relatively large amounts of resin and fairly long, bundled glass fibers. Such compositions are less suitable for the production of thin-walled, arbitrarily shaped and / or strongly curved molded parts.
  • the glass fibers orient themselves in certain directions during the pressing process, as a result of which the polymerisation shrinkage is not evenly absorbed, so that the reinforcement of the strength and elasticity is not homogeneous.
  • the glass fiber bundles lying on the surface of the molded part act like capillaries, which has an adverse effect on the quality of the product in a moist environment. Because a lot of air is trapped in the mass, it is difficult to process into thin-walled, arbitrarily shaped parts.
  • the high resin content makes the molded parts relatively expensive.
  • SMC 'sheet molding compound'
  • This mixture is allowed to thicken in the presence of a glass fiber layer between the polyethylene film. Then you fill a mold with the mass or with parts of it together with the glass fiber layer and the whole is pressed at elevated temperature. The processing of masses of this type is quite labor intensive. The required high glass fiber content and the resin also make the molded parts relatively expensive.
  • a third mass called the 'bulk molding compound' (BMC)
  • BMC 'bulk molding compound'
  • the object of the present invention is now to produce molded parts from a mixture of the composition mentioned at the outset, which is easier to process, is cheaper and has an equally good or even better modulus of elasticity than the mixtures mentioned.
  • the mixture comprises 80 to 95% by weight of inorganic fillers with a grain size mainly between 0 and 500 microns, 1 to 5% by weight of glass fibers , based on the entire mixture, of which at least 3/4 have a length of less than 15 mm and are mainly present as random threads and contains 0.5 to 5% by weight of magnesium oxide, based on the unsaturated polyester resin, which mixture is thickened until it is compact and almost air-free.
  • the invention is based on the knowledge that it is possible to produce a molding compound with a very high filler content, which can be pressed very well into thin-walled molded parts of any shape and good quality.
  • the prerequisite for this is that the glass fibers are available in a well-specified form and quantity.
  • the low content of resin and glass fibers makes the cost price of the molded parts to be lower than when using the known mixtures.
  • Another prerequisite for the method according to the invention is that the mass is compact and almost air-free before it is pressed.
  • glass fibers are necessary to catch the polymerization shrinkage. In order to be able to distribute this shrinkage well, the glass fibers must be randomly distributed as threads in the molding compound. In order to keep the arbitrary distribution of the fibers during pressing, it is still necessary that they be relatively short. It has also been found that the mixture is difficult to process before thickening if the glass fiber content is higher than stated above. Despite the small amount of glass fiber, the molded parts have a sufficiently high modulus of elasticity. A glass fiber content of not more than 1 to 2.5% by weight gives very good results. Because the fibers are absorbed in the form of threads, they do not act capillary, so that there is no exposure to moisture.
  • a suitable length of the glass fibers is predominantly 6 to 12 mm, the average length preferably being approximately 9 mm.
  • the fibers can be fed to the device in which the mass is mixed in a bundled manner, stirring being carried out so long that the glass fibers are finally randomly distributed as threads in the mixture.
  • the arbitrarily oriented glass fibers continue to ensure that the polymerisation shrinkage is well distributed even in strongly bent places and that the modulus of elasticity of the molded part is the same in all directions.
  • any inorganic, preferably mineral, filler is suitable as filler, such as calcium magnesium carbonate (domomite), calcium carbonate, quartz powder, talc, various types of clay and the like.
  • filler such as calcium magnesium carbonate (domomite), calcium carbonate, quartz powder, talc, various types of clay and the like.
  • a well compressible mass for not too thick-walled Shaped parts with a wall thickness of, for example, 5 to 10 mm are obtained when the grain size of the filler is mainly between 0 and 500 microns and preferably not more than 200 microns.
  • the unsaturated polyester resin can be any suitable reaction product of polyhydric alcohols and polyhydric and saturated acids or acid-forming anhydrides.
  • alcohols propylene glycol, ethylene glycol, pentanediol, butanediol, butylene glycol and dipropylene glycol can be mentioned.
  • acids are maleic anhydride, phthalic anhydride, isophthalic anhydride, adipic acid and the like. Like. Common.
  • the unsaturated polyester resin is usually cross-linked.
  • Unsaturated compounds such as styrene, methyl methacrylate, vinyl acetate and diallyl phthalate are suitable for this purpose.
  • the usual peroxides such as benzoyl peroxide or tertiary butyl perbenzoate can be used as a catalyst in this crosslinking.
  • a product such as hydrogenated bisphenol A plus catalyst, known commercially as 'Synolite 373', is also useful for this purpose.
  • the mixture of resin, fillers and glass fibers described above is viscous.
  • the mixture is poured into a container or the like and allowed to thicken to a compact, almost air-free molding compound in 1 to 48 hours.
  • a compact molding compound With a compact molding compound, a dense mass similar to window putty is indicated, which is so viscous that it almost does not lose a given shape and can be divided into parts by cutting.
  • This thickening is based on the effect of the magnesium oxide, which is also mixed in.
  • the required amount can be cut off from the thickened mass and placed in the press mold or die, after which the whole is pressed to the desired molded part at elevated temperature. It is of crucial importance that, in contrast to the known molding compounds, an air-free, compact molding compound is obtained.
  • Temperature and pressure are not critical when pressing the mass and are among other things due to the wall thickness of the desired molded part in relation to the optimal pressing time and the catalyst. Usual temperatures are 100 to 250 ° C, usual pressures are between 3 and 20 MPa.
  • the pressing time will normally be between t and 30 minutes and preferably about 1 t to 6 minutes.
  • Molded parts produced using the method described above can be provided with a hard and / or decorative surface layer during or shortly after pressing.
  • the molded part which is still hot and not yet fully cured, can be treated with a powdery resin, for example, shortly after pressing.
  • Epoxy resins containing free hydroxyl groups, such as methylol or phenol groups, or unsaturated polyester resins and mixtures of an epoxy and a polyester resin are suitable for this purpose.
  • the free hydroxyl groups of the not yet fully cured molded part can also bring about three-dimensional crosslinking in this way, as a result of which good adhesion between the surface layer and molded part is achieved.
  • the molded part according to the invention has a high heat content thanks to its high content of inorganic fillers.
  • Treatment with powdered resin can consist of spraying, electrostatic atomization, and dipping into a fluid bed of the powder. In general, 50 to 300 g of powder are applied per m 2 .
  • the modified epoxy resin does not have to be monochromatic, it is also possible to use systematic or arbitrary shades of color
  • Another method of applying a hard surface layer is to apply one or more pre-impregnated glass mat.
  • one or more glass fleece impregnated with an epoxy or polyester or a mixture of these two resins is placed in the mold or die before the molding compound is poured into the mold or die. If a transparent or partially transparent layer is desired, this corresponds to Refractive index of the resin after curing preferably about the refractive index of the glass fleece.
  • a decoration can be beautifully attached by placing it between two glass fleece. There are a number of possibilities for this decoration. You can e.g. Place finely divided inorganic or organic substances between the glass fleece. Examples are metal powder, colored minerals, polymer parts, etc.
  • One of the two glass nonwovens can also be printed with a motif beforehand, preferably using a colored or pigmented resin. Combinations of both methods are possible.
  • molded parts can also be provided with a decoration in the manner described in Dutch patent application 7305807.
  • the surface can be structured using a press mold with structured walls.
  • a glass fleece is preferably also applied to the other side of the molded part.
  • a mixture is produced which, based on the total mass, contains 85% by weight calcium magnesium carbonate with a particle size of 0-200 microns and 1.5% by weight glass fibers with a length mainly between 6 and 9 mm contains.
  • the viscous mixture was poured into a container. After 24 hours, the mixture has thickened to an almost air-free, compact and cuttable molding compound. A part cut from this mass is then pressed in a die 1 1 30 "at a temperature of 200 ° C and a pressure of 150 kg / cm 2 (15 MPa) to a plate with a thickness of about 8 mm.
  • the E -Module of this material is approximately 150,000 kg / cm 2 (15 GN / m 2 ) compared to 115,000 kg / cm 2 (11.5 GN / m 2 ) or 110,000 kg / cm 2 (11 GN / M 2 ) for the Compressed BMC or SMC compounds commercially available in the same way.
  • the same plate with an untreated surface is exposed to the weather conditions of a sea climate for a long time.
  • the surface shows no visible changes.
  • the same pressing test is carried out with 0.5 or 6% by weight of glass fibers.
  • the plate In the first case the plate is very brittle; in the second case, the mixture cannot be poured out and cannot be converted into an air-free, compact molding compound.
  • a molding compound as described above with the same weight ratios of the components, but with long glass fibers is less suitable for pressing into strongly curved, thin-walled molded parts than a molding compound with short, arbitrarily oriented glass fibers. In this case, it turns out that the strength at bent points is less good than when using short fibers. The risk of breakage on strongly curved stiffeners is too great to produce everyday objects from this mass.
  • the invention also relates to molded parts whose bodies, based on the total body weight, are 80 to 95% by weight of inorganic fillers with a grain size mainly between 0 and 500 microns, and a maximum of 5% by weight, based on the total Body weight, made of glass fibers, from which at least 3/4 have a length of less than 15 mm and are mainly available as threads in an arbitrary distribution, and consists of hardened polyester resin containing magnesium oxide.
  • the present invention is not only limited to relatively complicated molded parts, but also includes relatively simple molded parts such as tiles or wall panels.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Health & Medical Sciences (AREA)
  • Structural Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Reinforced Plastic Materials (AREA)
  • Moulding By Coating Moulds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Formteilen durch Vermischung von ungesättigem Polyesterharz, anorganischen Füllstoffen und Magnesiumoxid, Eindickung dieses Gemisches in Gegenwart von Glasfasern und Verpressung von Teilen der eingedickten Masse bei erhöhter Temperatur.The invention relates to a process for the production of moldings by mixing unsaturated polyester resin, inorganic fillers and magnesium oxide, thickening this mixture in the presence of glass fibers and pressing parts of the thickened mass at elevated temperature.

Häufig benutzte Pressmassen, welche ungesättigtes Polyesterharz, mineralische Füllstoffe und Glasfasern enthalten, sind im Handel bereits seit langer Zeit als 'dough moulding compound' (DMC) bekannt. Diese Massen enthalten relativ grosse Harzmengen und ziemlich lange, gebündelte Glasfasern. Für die Herstellung dünnwändiger, willkürlich geformter und/oder stark gebogener Formteile sind derartige Massen weniger gut geeignet. Die Glasfasern orientieren sich während des Pressvorgangs in bestimmten Richtungen, wodurch die Polymerisationsschwindung nicht gleichmässig abgefangen wird, so dass die Verteifung der Festigkeit und Elastizität nicht homogen ist. Weiterhin wirken die an der Oberfläche des Formteils liegenden Glasfaserbündel wie Kapillaren, was sich ungünstig auf die Qualität des Produktes in feuchter Umgebung auswirkt. Weil in der Masse viel Luft eingeschlossen wird, lässt sich diese schwer zu dünnwändigen beliebig geformten Teilen verarbeiten. Schliesslich macht der hohe Harzgehalt die Formteile relativ teuer.Frequently used molding compounds, which contain unsaturated polyester resin, mineral fillers and glass fibers, have long been known in the trade as 'dough molding compound' (DMC). These masses contain relatively large amounts of resin and fairly long, bundled glass fibers. Such compositions are less suitable for the production of thin-walled, arbitrarily shaped and / or strongly curved molded parts. The glass fibers orient themselves in certain directions during the pressing process, as a result of which the polymerisation shrinkage is not evenly absorbed, so that the reinforcement of the strength and elasticity is not homogeneous. Furthermore, the glass fiber bundles lying on the surface of the molded part act like capillaries, which has an adverse effect on the quality of the product in a moist environment. Because a lot of air is trapped in the mass, it is difficult to process into thin-walled, arbitrarily shaped parts. Finally, the high resin content makes the molded parts relatively expensive.

Eine andere Pressmasse ist unter der Bezeichnung 'sheet moulding compound' (SMC) bekannt. Diese enthält neben den vorgenannten Bestandteilen auch Magnesiumoxid. Dieses Gemisch lässt man in Gegenwart einer Glasfaserschicht zwischen Polyäthylenfolie eindicken. Anschliessend füllt man eine Form mit der Masse oder mit Teilen derselben zusammen mit der Glasfaserschicht und wird das Ganze bei erhöhter Temperatur verpresst. Die verarbeitung von Massen dieser Art ist ziemlich arbeitsintensiv. Der erforderliche hohe Glasfasergehalt und das Harz machen die Formteile ebenfalls relativ teuer.Another molding compound is known as 'sheet molding compound' (SMC). In addition to the aforementioned components, this also contains magnesium oxide. This mixture is allowed to thicken in the presence of a glass fiber layer between the polyethylene film. Then you fill a mold with the mass or with parts of it together with the glass fiber layer and the whole is pressed at elevated temperature. The processing of masses of this type is quite labor intensive. The required high glass fiber content and the resin also make the molded parts relatively expensive.

Eine dritte Masse, die als 'bulk moulding compound' (BMC) bezeichnet wird, hat die gleiche Zusammensetzung wie SMC, wird jedoch in einem Kneter hergestellt und hat wegen der darin enthaltenen grossen Glasfasermenge dieselben Nachteile wie DMC.A third mass, called the 'bulk molding compound' (BMC), has the same composition as SMC, but is produced in a kneader and has the same disadvantages as DMC because of the large amount of glass fibers it contains.

Aufgabe der vorliegenden Erfindung ist nunmehr die Herstellung von Formteilen aus einem Gemisch der eingangs erwähnten Zusammensetzung, das sich besser verarbeiten lässt, billiger ist und einen gleich guten oder sogar besseren E-Modul hat als die vergenannten Gemische.The object of the present invention is now to produce molded parts from a mixture of the composition mentioned at the outset, which is easier to process, is cheaper and has an equally good or even better modulus of elasticity than the mixtures mentioned.

Nach der vorliegenden Erfindung wird dies erreicht, wenn das Gemisch neben dem ungesättigten Polyesterharz, bezogen auf das gesamte Gemisch, 80 bis 95 Gew.-% anorganische Füllstoffe mit einer hauptsächlich zwischen 0 und 500 Mikron liegenden Korngrösse, 1 bis 5 Gew.-% Glasfasern, bezogen auf das gesamte Gemisch, von denen zumindest 3/4 eine Länge von weniger als 15 mm haben und hauptsächlich als willkürlich verteilte Einfäden vorhanden sind, und 0,5 bis 5 Gew.-% Magnesiumoxid, bezogen auf das ungesättigte Polyesterharz, enthält, welches Gemisch eingedickt wird, bis es kompakt und nahezu luftfrei ist.According to the present invention, this is achieved if, in addition to the unsaturated polyester resin, based on the entire mixture, the mixture comprises 80 to 95% by weight of inorganic fillers with a grain size mainly between 0 and 500 microns, 1 to 5% by weight of glass fibers , based on the entire mixture, of which at least 3/4 have a length of less than 15 mm and are mainly present as random threads and contains 0.5 to 5% by weight of magnesium oxide, based on the unsaturated polyester resin, which mixture is thickened until it is compact and almost air-free.

Die Erfindung beruht auf der Erkenntnis, dass es möglich ist, eine Pressmasse mit seht hohem Füllstoffgehalt herzustellen, die sich sehr gut zu dünwändigen Formteilen beliebiger Form und guter Qualität verpressen lässt. Voraussetzung dabei ist, dass die Glasfasern in gut spezifizierter Form und Menge vorhanden sind. Der geringe Gehalt an Harz und Glasfasern macht den Selbstkostenpreis der herzustellenden Formteile niedriger als bei Anwendung der bekannten Gemische. Eine weitere Voraussetzung für das erfundungsgemässe Verfahren ist, dass die Masse kompakt und nahezu luftfrei ist, bevor sie verpresst wird.The invention is based on the knowledge that it is possible to produce a molding compound with a very high filler content, which can be pressed very well into thin-walled molded parts of any shape and good quality. The prerequisite for this is that the glass fibers are available in a well-specified form and quantity. The low content of resin and glass fibers makes the cost price of the molded parts to be lower than when using the known mixtures. Another prerequisite for the method according to the invention is that the mass is compact and almost air-free before it is pressed.

Die Anwesenheit von Glasfasern ist erforderlich, um die Polymerisationsschwindung abzufangen. Um diese Schwindung gut verteilen zu können, müssen die Glasfasern willkürlich verteilt als Einfäden in der Pressmasse vorhanden sein. Um die Willkürliche Verteilung der Fasern beim Verpressen zu behalten, ist es weiterhin erforderlich, dass diese relativ kurz sind. Es hat sich auch herausgestellt, dass das Gemisch sich vor dem Eindicken schwer verarbeiten lässt, wenn der Glasfasergehalt höher ist, als oben angegeben wurde. Trotz der geringen Glasfasermenge haben die Formteile einen ausreichend hohen E-Modul. Sehr gute Resultate gibt ein Glasfasergehalt von nicht mehr als 1 bis 2,5 Gew.-%. Weil die Fasern in Form von Einfäden aufgenommen werden, wirken sie nich kapillar, so dass keine Einwirkung von Feuchtigkeit auftritt.The presence of glass fibers is necessary to catch the polymerization shrinkage. In order to be able to distribute this shrinkage well, the glass fibers must be randomly distributed as threads in the molding compound. In order to keep the arbitrary distribution of the fibers during pressing, it is still necessary that they be relatively short. It has also been found that the mixture is difficult to process before thickening if the glass fiber content is higher than stated above. Despite the small amount of glass fiber, the molded parts have a sufficiently high modulus of elasticity. A glass fiber content of not more than 1 to 2.5% by weight gives very good results. Because the fibers are absorbed in the form of threads, they do not act capillary, so that there is no exposure to moisture.

Eine geeignete Länge der Glasfasern ist vorwiegend 6 bis 12 mm, wobei die mittlere Länge vorzugsweise ca. 9 mm beträgt. Die Fasern können der Vorrichtung, in der die Masse gemischt wird, auf Wunsch gebundelt zugeführt werden, wobei so lange gerührt werden muss, dass sich die Glasfasern schliesslich willkürlich verteilt als Einfäden im Gemisch befinden. Die willkürlich orientierten Glasfasern tragen weiterhin dafür Sorge, dass die Polymerisationsschwindung auch an stark gebogenen Stellen gut verteilt wird und der E-Modul des Formteils in allen Richtungen gleich ist.A suitable length of the glass fibers is predominantly 6 to 12 mm, the average length preferably being approximately 9 mm. If desired, the fibers can be fed to the device in which the mass is mixed in a bundled manner, stirring being carried out so long that the glass fibers are finally randomly distributed as threads in the mixture. The arbitrarily oriented glass fibers continue to ensure that the polymerisation shrinkage is well distributed even in strongly bent places and that the modulus of elasticity of the molded part is the same in all directions.

Als Füllstoff ist jeder anorganische, vorzugsweise mineralische, Füllstoff geeignet, wie Calciummagnesiumcarbonat (Domomit), Calciumcarbonat, Quarzmehl, Talk, verschiedene Tonsorten u. dgl. Eine gut verpressbare Masse für nicht allzu dickwändige Formteile mit einer Wandstärke von z.B. 5 bis 10 mm wird erhalten, wenn die Korngrösse des Füllstoffes hauptsächlich zwischen 0 und 500 Mikron und vorzugsweise nicht mehr als 200 Mikron beträgt.Any inorganic, preferably mineral, filler is suitable as filler, such as calcium magnesium carbonate (domomite), calcium carbonate, quartz powder, talc, various types of clay and the like. Like. A well compressible mass for not too thick-walled Shaped parts with a wall thickness of, for example, 5 to 10 mm are obtained when the grain size of the filler is mainly between 0 and 500 microns and preferably not more than 200 microns.

Das ungesättigte Polyesterharz kann jedes geeignete Reaktionsprodukt von mehrwertigen Alkoholen und mehrwertigen undgesättigten Säuren oder säurebildenden Anhydriden sein. Von den Alkoholen können Propylenglycol, Äthylenglycol, Pentandiol, Butandiol, Butylenglycol und Dipropylenglycol genannt werden. Von den Säuren sind Maleinsäureanhydrid, Phthalsäureanhydrid, Isophthalsäureanhydriet, Adipinsäure u. dgl. gebräuchlich.The unsaturated polyester resin can be any suitable reaction product of polyhydric alcohols and polyhydric and saturated acids or acid-forming anhydrides. Of the alcohols, propylene glycol, ethylene glycol, pentanediol, butanediol, butylene glycol and dipropylene glycol can be mentioned. Of the acids are maleic anhydride, phthalic anhydride, isophthalic anhydride, adipic acid and the like. Like. Common.

Das ungesättigte Polyesterharz wird normalerweise vernetzt. Zu diesem Zweck sind ungesättigte Verbindungen wie Styrol, Methylmetacrylat, Vinylacetat und Diallylphthalat geeignet. Als Katalysator bei dieser Vernetzung kann man die üblichen Peroxide wie Benzoylperoxid oder tertiäres Butylperbenzoat verwenden. Ein produkt wie hydriertes Bisphenol A plus Katalysator, im Handel als 'Synolite 373' bekannt, ist egenfalls zu diesem Zweck brauchbar.The unsaturated polyester resin is usually cross-linked. Unsaturated compounds such as styrene, methyl methacrylate, vinyl acetate and diallyl phthalate are suitable for this purpose. The usual peroxides such as benzoyl peroxide or tertiary butyl perbenzoate can be used as a catalyst in this crosslinking. A product such as hydrogenated bisphenol A plus catalyst, known commercially as 'Synolite 373', is also useful for this purpose.

Das obenbeschriebene, aus Harz, Füllstoffen und Glasfasern bestehende Gemisch ist dickflüssig. Nach einer Ausführungsform der vorliegenden Erfindung giesst man das Gemisch in einen Behälter o. dgl. und lässt man esin 1 bis 48 Stunden zu einer kompakten, nahezu luftfreien Pressmasse eindicken. Mit einer kompakten Pressmasse wird hier eine dichte, Fensterkitt ähnliche Masse angedeutet die derart viskös ist dass sie eine gegebene Form nahezu nich verliert und durch schneiden in Teilen unterteilt werden kann. Dieses Eindicken beruht auf der Wirkung des ebenfalls eingemischten Magnesiumoxids. Von der eingedickten Masse kann man jeweils die benötigte Menge abschneiden und in die Pressform oder Matrize geben, wonach das Ganze unter erhöhter Temperatur zum erwüschten Formteil gepresst wird. Von entscheidender Bedeutung dabei ist, dass im Gegensatz zu den bekannten Pressmassen eine luftfreie, kompakte Pressmasse erhalten wird.The mixture of resin, fillers and glass fibers described above is viscous. According to one embodiment of the present invention, the mixture is poured into a container or the like and allowed to thicken to a compact, almost air-free molding compound in 1 to 48 hours. With a compact molding compound, a dense mass similar to window putty is indicated, which is so viscous that it almost does not lose a given shape and can be divided into parts by cutting. This thickening is based on the effect of the magnesium oxide, which is also mixed in. The required amount can be cut off from the thickened mass and placed in the press mold or die, after which the whole is pressed to the desired molded part at elevated temperature. It is of crucial importance that, in contrast to the known molding compounds, an air-free, compact molding compound is obtained.

Temperatur und Druck sind beim Verpressen der Masse nicht kritisch und werden u.a. durch die Wandstärke des erwünschten Formteils in Relation zu der optimalen Presszeit und dem Katalysator bedingt. Übliche Temperaturen sind 100 bis 250°C übliche Drücke liegen zwischen 3 und 20 MPa. Die Presszeit wird normalerweise zwischen t und 30 Minuten liegen und vorzugsweise ca. 1 t bis 6 Minuten betragen.Temperature and pressure are not critical when pressing the mass and are among other things due to the wall thickness of the desired molded part in relation to the optimal pressing time and the catalyst. Usual temperatures are 100 to 250 ° C, usual pressures are between 3 and 20 MPa. The pressing time will normally be between t and 30 minutes and preferably about 1 t to 6 minutes.

Mit Hilfe des obenbeschriebenen Verfahrens hergestellte Formteile können bei oder kurz nach dem Verpressen mit einer harten und/oder dekorativen Oberflächenschicht versehen werden. Man kann das noch heisse und noch nicht vollständig ausgebärtete Formteil zum Beispiel kurz nach dem Verpressen mit einem pulverförmigen Harz behandeln. Zu diesem Zweck sind Epoxyharze, die freie Hydroxylgruppen enthalten, wie Methylol- oder Phenolgruppen, oder ungesättigte Polyesterharze sowie Gemische eines Epoxy- und eines Polyesterharzes geeignet. Auch können die noch freien Hydroxylgruppen des noch nicht vollständig ausgehärteten Formteils auf diese Weise eine dreidimensionale Vernetzung bewirken, wodurch eine gute Haftung zwischen Oberflächenschicht und Formteil erreicht wird.Molded parts produced using the method described above can be provided with a hard and / or decorative surface layer during or shortly after pressing. The molded part, which is still hot and not yet fully cured, can be treated with a powdery resin, for example, shortly after pressing. Epoxy resins containing free hydroxyl groups, such as methylol or phenol groups, or unsaturated polyester resins and mixtures of an epoxy and a polyester resin are suitable for this purpose. The free hydroxyl groups of the not yet fully cured molded part can also bring about three-dimensional crosslinking in this way, as a result of which good adhesion between the surface layer and molded part is achieved.

Vorzugsweise wendet man diese Behandlungsmethode an, wenn das Formteil noch eine Temperatur von minimal 150°C und vorzugsweise von 175-2000C hat. Ein Vorteil dabei ist, dass das erfindungsgemässe Formteil dank seinem hohen Gehalt an anorganischen Füllstoffen einen grossen Wärmeinhalt hat.Is preferably used in this treatment method, when the molded part still has a temperature of minimally 150 ° C and preferably from 175-200 0 C. An advantage here is that the molded part according to the invention has a high heat content thanks to its high content of inorganic fillers.

Die Behandlung mit pulverförmigen Harz kann aus Spritzen, elektrostatische Zerstäubung und Tauchen in ein Fliessbett des Pulvers bestehn. Dabei werden im allgemeinen 50 bis 300 g Pulver je m2 angebracht. Das modifizierte Epoxyharz braucht nicht monochromatisch zu sein, er sind auch systematische oder willkürliche Farbschattierungen möglichTreatment with powdered resin can consist of spraying, electrostatic atomization, and dipping into a fluid bed of the powder. In general, 50 to 300 g of powder are applied per m 2 . The modified epoxy resin does not have to be monochromatic, it is also possible to use systematic or arbitrary shades of color

Eine andere Methode zum Anbringen einer harten Oberflächenschicht besteht darin, dass eine oder mehrere vorimprägnierte Glasvlieszeangebracht werden. Dazu legt man in die Pressform oder Matrize eine oder mehrere mit einem Epoxy- oder Polyester- oder einem Gemisch dieser beiden Harze imprägnierte Glasvliesze, bevor man die Pressmasse in die Pressform oder Matrize giesst, Falls eine transparente oder teilweise transparente Schicht erwünscht ist, entspricht der Brechungsindex des Harzes nach der Aushärtung vorzugsweise ungefähr dem Brechungsindex des Glasvlieszes.Another method of applying a hard surface layer is to apply one or more pre-impregnated glass mat. To do this, one or more glass fleece impregnated with an epoxy or polyester or a mixture of these two resins is placed in the mold or die before the molding compound is poured into the mold or die. If a transparent or partially transparent layer is desired, this corresponds to Refractive index of the resin after curing preferably about the refractive index of the glass fleece.

Auf schöne Weise kann eine Dekoration dadurch angebracht werden, dass diese zwischen zwei Glasvlieszen angebracht wird. Es lässt sich für diese Dekoration eine ganze Reihe von Möglichkeiten erdenken. Man kann z.B. zwischen den Glasvlieszen feinverteilte anorganische oder organische Stoffe anbringen. Beispiele sind Metallpulver, farbige Mineralien, Polymerisatteilen usw. Auch kann eine der beiden Glasvlieszen vorher mit einem Motiv bedruckt werden, vorzugsweise mit Hilfe eines gefärbten oder pigmentierten Harzes. Such sind Kombinationen beider Methoden möglich.A decoration can be beautifully attached by placing it between two glass fleece. There are a number of possibilities for this decoration. You can e.g. Place finely divided inorganic or organic substances between the glass fleece. Examples are metal powder, colored minerals, polymer parts, etc. One of the two glass nonwovens can also be printed with a motif beforehand, preferably using a colored or pigmented resin. Combinations of both methods are possible.

Daneben können die Formteile auch auf die in der niederländischen Patentanmeldung 7305807 beschriebene Weise mit einer Dekoration versehen werden.In addition, the molded parts can also be provided with a decoration in the manner described in Dutch patent application 7305807.

Schliesslich kann die Oberfläche strukturiert werden, indem man eine Pressform mit strukturierten Wänden benutzt.Finally, the surface can be structured using a press mold with structured walls.

Bei Benutzung einer oder mehrerer Glasvliesze als harte Oberflächenschicht wird man vorzugsweise auch auf der anderen Seite des Formteils ein Glasvliesz anbringen.If one or more glass fleece is used as the hard surface layer, a glass fleece is preferably also applied to the other side of the molded part.

Die Erfindung wird anhand eines praktischen Beispiels näher erläutert. Als ungesättigtes Polyesterharz wird ein Polykondensationsprodukt von:

  • 1,5 Mol hydriertem Bisphenol A,
  • 1,5 Mol Propylenglycol,
  • 0,5 Mol Phthalsäureanhydrid,
  • 1 Mol Maleinsäureanhydrid und
  • 1 Mol Fumarsäureanhydrid

verwendet.The invention is explained in more detail using a practical example. As unsaturated Polyester resin becomes a polycondensation product of:
  • 1.5 moles of hydrogenated bisphenol A,
  • 1.5 moles of propylene glycol,
  • 0.5 mol of phthalic anhydride,
  • 1 mole of maleic anhydride and
  • 1 mole of fumaric anhydride

used.

650 Teile dieses Harzes werden gemischt mit:

  • 235 Gew.-Tlen. Styrolmonomerem,
  • 100 Gew.-Tlen. Diallylphthalat,
  • 10 Gew.-Tlen. tertiärem Butylperbenzoat und 5 Gew.-Tlen. Wasser.

Diesem Harzgemisch wird 1 Gew.-% Magnesiumoxid beigegeben.650 parts of this resin are mixed with:
  • 235 parts by weight Styrene monomer,
  • 100 parts by weight Diallyl phthalate,
  • 10 parts by weight tertiary butyl perbenzoate and 5 parts by weight. Water.

1% by weight of magnesium oxide is added to this resin mixture.

Ausgehend von diesem Harsgemisch wird eine Gemisch hergestellt, das, bezogen auf die gesamte Masse, 85 Gew.-% CalciumMagnesiumcarbonat mit einer Teilchengrösse von 0-200 Mikron und 1,5 Gew.-% Glasfasern mit einer hauptsächlich zwischen 6 und 9 mm liegenden Länge enthält. Das zähflüssige Gemisch wirk in einen Behälter gegossen. Nach 24 Stunden ist das Gemisch zu einer nahezu luftfreien, kompakten und schneidbaren Pressmasse eingedickt. Ein von dieser Masse abgeschnittener Teil wird anschliessend in einer Matrize 1130" bei einer Temperatur von 200°C und einem Druck von 150 kg/cm2 (15 MPa) zu einer Platte mit einer Stärke von ca. 8 mm verpresst. Der E-Modul dieses Materials beträgt ca. 150.000 kg/cm2 (15 GN/m2) gegenüber 115.000 kg/cm2 (11,5 GN/m2) bzw. 110.000 kg/cm2 (11 GN/M 2) für die im Handel erhältlichen auf dieselbe Weise verpressten BMC- bzw. SMC-Massen.Starting from this Hars mixture, a mixture is produced which, based on the total mass, contains 85% by weight calcium magnesium carbonate with a particle size of 0-200 microns and 1.5% by weight glass fibers with a length mainly between 6 and 9 mm contains. The viscous mixture was poured into a container. After 24 hours, the mixture has thickened to an almost air-free, compact and cuttable molding compound. A part cut from this mass is then pressed in a die 1 1 30 "at a temperature of 200 ° C and a pressure of 150 kg / cm 2 (15 MPa) to a plate with a thickness of about 8 mm. The E -Module of this material is approximately 150,000 kg / cm 2 (15 GN / m 2 ) compared to 115,000 kg / cm 2 (11.5 GN / m 2 ) or 110,000 kg / cm 2 (11 GN / M 2 ) for the Compressed BMC or SMC compounds commercially available in the same way.

Wenn die Oberflächentemperatur der gepressten Platte noch 190°C beträgt, wird ein aus festem pigmentiertem Epoxy- und Polyesterharz bestehendes Gemisch in äusserst feinem Zustand durch Zerstäubung auf der Oberfläche angebracht. Je m2 werden ca. 200 g dieses Gemisches angebracht. Nach Abkühlung ist das Resultat eine Platte, deren Oberfläche sich kaum von der Oberfläche eines mit keramischer Glasur überzogenen gusseisernen Duschbeckens unterscheiden lässt. Die Platte genügt den Normen des Commercial Standard (USA) Nr. CS 222-59 für Duschbecken. Bei 140- stündiger Behandlung unter kochendem Wasser ändert sich die schöne Oberfläche nicht.When the surface temperature of the pressed plate is still 190 ° C, a mixture consisting of solid pigmented epoxy and polyester resin is applied to the surface in an extremely fine condition by atomization. Approx. 200 g of this mixture are applied per m 2 . After cooling, the result is a plate whose surface can hardly be distinguished from the surface of a cast iron shower basin covered with ceramic glaze. The plate meets the standards of the Commercial Standard (USA) No. CS 222-59 for shower basins. When treated under boiling water for 140 hours, the beautiful surface does not change.

Eine gleiche Platte mit unbehandelter Oberfläche wird lange Zeit den Witterungsverhältnissen eines Seeklimas ausgesetzt. Die Oberfläche zeigt keine sichtbaren Veränderungen.The same plate with an untreated surface is exposed to the weather conditions of a sea climate for a long time. The surface shows no visible changes.

Der gleiche Pressversuch wird mit 0,5 bzw. 6 Gew.-% Glasfasern ausgeführt. Im ersten Fall ist die Platte sehr spröde; im zweiten Fall lässt sich das Gemisch nicht ausgiessen und nicht in eine luftfreie, kompakte Pressmasse umsetzen.The same pressing test is carried out with 0.5 or 6% by weight of glass fibers. In the first case the plate is very brittle; in the second case, the mixture cannot be poured out and cannot be converted into an air-free, compact molding compound.

Eine Pressmasse wie oben beschrieben mit den gleichen Gewichtsverhältnissen der Bestandteile, aber mit langen Glasfasern zeigt sich weniger gut zum Verpressen zu stark gebogenen, dünnwändigen Formteilen geeignet als eine Pressmasse mit kurzen, willkürlich orientierten Glasfasern. In diesem Fall stellt sich heraus, dass die Festigkeit an gebogenen Stellen weniger gut ist als bei Anwendung von kurzen Fasern. Das Bruchrisiko an stark gebogenen steifen ist zu gross, um aus dieser Masse Gebrauchsgegenstände herzustellen.A molding compound as described above with the same weight ratios of the components, but with long glass fibers is less suitable for pressing into strongly curved, thin-walled molded parts than a molding compound with short, arbitrarily oriented glass fibers. In this case, it turns out that the strength at bent points is less good than when using short fibers. The risk of breakage on strongly curved stiffeners is too great to produce everyday objects from this mass.

Bei Versuchen konnte der Füllstoffgehalt auf 95 Gew.-% gesteigert werden. Bei höheren Gehalten geht der Zusammenhang völlig verloren.In tests, the filler content was increased to 95% by weight. At higher levels, the relationship is completely lost.

Untenstehende Tabelle gibt eine übersicht über die Zusammensetzung, die Kosten und den. E-Modul eines im Handel erhältlichen 'bulkmoulding compound' (BMC), eines 'sheet moulding compound' (SMC) und eines erfindungsgemässen Gemisches.The table below gives an overview of the composition, the costs and the. Modulus of elasticity of a commercially available bulk molding compound (BMC), a sheet molding compound (SMC) and a mixture according to the invention.

Figure imgb0001
Figure imgb0001

Es stellt sich heraus, dass es ohne weiteres möglich ist, während des Pressvorgangs als Dekoration zwei vorimpregnierte Glasvliesze anzubringen, zwischen denen vorher Bronzepulver zerstäubt wurde. Diese Dekoration ist gut reproduzierbar, wenn jeweils die. gleiche Menge Pulver auf die gleiche Weise angebracht wird.It turns out that it is easily possible to apply two pre-impregnated glass fleece as decoration during the pressing process, between which bronze powder was previously atomized. This decoration is easily reproducible if the. same amount of powder is applied in the same way.

Die Erfindung betrifft schliesslich auch Formteile, deren Körper, bezogen auf das gesamte Körpergewicht, zu 80 bis 95 Gew.-% aus anorganischen Füllstoffen mit einer hauptsächlich zwischen 0 und 500 Mikron liegenden Korngrösse, zu maximal 5 Gew.-%, bezogen auf das gesamte Körpergewicht, aus Glasfasern, von denen zumindest 3/4 eine Länge von weniger als 15 mm haben und hauptsächlich als Einfäden in willkürlicher Verteilung vorhanden sind, sowie aus gehärtetem Polyesterharz, das Magnesiumoxid enthält, besteht.Finally, the invention also relates to molded parts whose bodies, based on the total body weight, are 80 to 95% by weight of inorganic fillers with a grain size mainly between 0 and 500 microns, and a maximum of 5% by weight, based on the total Body weight, made of glass fibers, from which at least 3/4 have a length of less than 15 mm and are mainly available as threads in an arbitrary distribution, and consists of hardened polyester resin containing magnesium oxide.

Die vorliegende Erfindung beschränkt sich nicht nur auf verhältnismässig komplizierte Formteile, sondern unfasst auch relativ einfache Formteile wie Fliessen oder Wandplatten.The present invention is not only limited to relatively complicated molded parts, but also includes relatively simple molded parts such as tiles or wall panels.

Claims (15)

1. Process for producing mouldings by mixing unsaturated polyester resin, inorganic fillers and magnesium oxide, thickening the resultant mixture in the presence of glass fibres, and moulding portions of the thickened compound at elevated temperature, this process being characterized in that, by the side of the unsaturated polyester resin the mixture contains 80-95% wt.-referred to the total mixture-of inorganic fillers with a particle size lying mainly between 0 and 500 microns, 1-5% wt.- referred to the total mixture-of glass fibres at least three-quarters of which are shorter than 15 mm and are present mainly as randomly distributed monofilaments, and 0.5-5% wt.- referred to the unsaturated polyester resin-of magnesium oxide, which mixture is thickened until it is compact and practically free of air.
2. Process according to Claim 1, characterized in that it contains 1-2.5% wt. of glass fibres.
3. Process according to Claims 1-2, characterized in that the glass fibres mainly have a length of 6-12 mm.
4. Process according to Claims 1-3, characterized in that the average length of the glass fibres is about 9 mm.
5. Process according to Claims 1­4, characterized in that the filler mainly has a particle size of at most 200 microns.
6. Process according to Claims 1-5, characterized in that the mixture is thickened to a compact, practically air-free moulding compound in 1-48 hours.
7. Process according to Claims 1-6, characterized in that the thickened compound is compressed at a temperature of between 100 and 250°C and a pressure of between 30 (3) and 200 (20) kg/cm2 (MPa).
8. Process according to Claims 1-7, characterized in that before the moulding has hardened completely it is treated with a pulverulent resin at a temperature of at least 150°C.
9. Process according to Claim 8, characterized in that the resin is an epoxy resin containing free hydroxyl groups, an unsaturated polyester resin, or a mixture of an epoxy and a polyester resin.
10. Process according to Claim 8 or 9, characterized in that during the treatment the temperature is 175-200°C.
11. Process according to Claims 1-7, characterized in that before the moulding compound is introduced, one or more glass fleeces impregnated with an epoxy or a polyester resin, or with a mixture of such resins, are placed in the mould.
12. Process according to Claim 11, characterized in that two glass fleeces are placed in the mould, with a decoration between them.
13. Process according to Claim 12, characterized in that the decoration consists of finely divided inorganic or organic substances.
14. Process according to Claim 12, characterized in that the decoration consists of a pigmented resin.
15. Moulding on the basis of polyester resin, with or without a surface layer, the body of this moulding consisting of a hardened mixture composed of 80-95% wt.-referred to the total mixture-of inorganic fillers with a particle size lying mainly between 0 and 500 microns, 1-5% wt.-referred to the total mixture-of glass fibres at least three-quarters of which are shorter than 15 mm and are present mainly as randomly distributed monofilaments, and 0.5-5% wt.-referred to the unsaturated polyester resin-of magnesium oxide.
EP78200045A 1977-06-24 1978-06-19 Production of articles from an unsaturated polyester resin, mineral fillers and glass fibres and articles thus obtained Expired EP0000223B1 (en)

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NLAANVRAGE7706997,A NL186016C (en) 1977-06-24 1977-06-24 PROCESS FOR MANUFACTURING ARTICLES BY MIXING UNSATURATED POLYESTER RESIN, MINERAL FILLER AND MAGNESIUM OXIDE.
NL7706997 1977-06-24

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IT1109381B (en) 1977-11-03 1985-12-16 Stamicarbon PROCEDURE FOR THE PRODUCTION OF OBJECTS FROM MINERAL CHARGES LINKED WITH THERMOSETTING RESIN
JPS5949240A (en) * 1982-09-16 1984-03-21 Dainippon Ink & Chem Inc Prepreg with both high workability and compression moldability
NL8600487A (en) * 1986-02-27 1987-09-16 Dsm Resins Bv SHEET MOLDING COMPOUND AND A TOP LAYER FOR THIS.

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FR1466894A (en) * 1965-02-05 1967-01-20 Bayer Ag Process for the preparation of strips in molding masses of polyesters containing fillers
US3631217A (en) * 1967-03-09 1971-12-28 Ppg Industries Inc Process for increasing the viscosity of polyester resins and products obtained thereby
JPS5242838B2 (en) * 1971-10-26 1977-10-26
IT1004335B (en) * 1973-03-15 1976-07-10 Koppers Co Inc COMPOSITION FROM MOLDING OF FLAME RETARDING POLYESTER
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