EP0000223A1 - 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

Info

Publication number
EP0000223A1
EP0000223A1 EP78200045A EP78200045A EP0000223A1 EP 0000223 A1 EP0000223 A1 EP 0000223A1 EP 78200045 A EP78200045 A EP 78200045A EP 78200045 A EP78200045 A EP 78200045A EP 0000223 A1 EP0000223 A1 EP 0000223A1
Authority
EP
European Patent Office
Prior art keywords
polyester resin
mixture
resin
unsaturated polyester
articles
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.)
Granted
Application number
EP78200045A
Other languages
German (de)
French (fr)
Other versions
EP0000223B1 (en
Inventor
René Leopold Eduard Van Gasse
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stamicarbon BV
Original Assignee
Stamicarbon BV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Stamicarbon BV filed Critical Stamicarbon BV
Publication of EP0000223A1 publication Critical patent/EP0000223A1/en
Application granted granted Critical
Publication of EP0000223B1 publication Critical patent/EP0000223B1/en
Expired legal-status Critical Current

Links

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 producing molded parts by mixing unsaturated polyester resin, mineral fillers and magnesium oxide, thickening this mixture in the presence of glass fibers and pressing parts of the thickened mass at elevated temperature.
  • 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 aforementioned mixtures.
  • the mixture contains 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 mixture as a whole. at least 3/4 of which have a length of less than 15 mm and are mainly present as random threads and contain 0.5 to 5% by weight of a alkali metal oxide, preferably magnesium oxide, based on the unsaturated polyester resin, which mixture is thickened until it is compact and almost air-free.
  • a alkali metal oxide preferably magnesium oxide
  • 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 to produce molded parts lower than when using the known mixtures.
  • a further requirement for the method according to the invention is that the mass is compact and almost free of air before it is pressed.
  • the unsaturated polyester resin can be any suitable polyhydric alcohol and polyhydric reaction product 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 caused, among other things, by the wall thickness of the desired molded part in relation to the optimum pressing time and the catalyst. Usual temperatures are 100 to 250 ° C, usual pressures are between 3 and 20 MPa.
  • the pressing time is usually between and 30 minutes and preferably approx. 1 up 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 the pressing.
  • the molded part which is still hot and not yet fully cured, can be used, for example, shortly after pressing with a powdered one to treat.
  • 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 can also not fully cured molded part in this way cause a three-dimensional crosslinking, whereby good adhesion between the surface layer and molded part is achieved.
  • This treatment method is preferably used if the molded part still has a temperature of at least 150 ° C. and preferably of 175-200 ° 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.
  • 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 .
  • One of the two glass fleece can also be printed with a motif beforehand, preferably with the help of a colored or pigmented resin. Combinations of both methods are also possible.
  • molded parts can also be provided with a decoration in the manner described in Dutch patent application 7305807.
  • An unsaturated polyester resin is a polycondensation product from:
  • a part cut from this mass is then pressed in a die 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 approx. 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 ) b between 110,000 kg / cm 2 (11 GN / m 2 ) for the commercially available BMC or SMC compounds pressed 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 in strongly curved places is too great to make everyday items from this mass.
  • the present invention is not limited to relatively complicated molded parts, but also includes relatively simple molded parts such as tiles or wall panels.
  • the modified epoxy resin does not need to be monochromatic, and systematic or arbitrary shades of color are also possible.
  • the invention also relates to molded parts whose bodies contain 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 mass, of glass fibers, of which at least 3/4 of a length of less than 15 mm and mainly as threads in an arbitrary distribution, as well as hardened polyester resin containing a magnesium compound.

Abstract

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.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung Formteilen durch Vermischung von ungesättigen Polyesterharz, mineralischen FUllstoffen 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 producing molded parts by mixing unsaturated polyester resin, mineral 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 enthalter sind im Handel bereits seit langer Zeit als

Figure imgb0001
(DMC) bekannt. Diese Massen enthalten relativ
Figure imgb0002
und ziemlich lange, gebündelte Glasfasern. Für die Herstellung dünnwandiger, willkürlich geformter und/oder stark gebegener Formteile sind derartige Massen weniger gut geeignet. Die Glasfasern orientieren sich während des Pressvorgans in bestimmten Richtungen, wodurch die Polymerisationsschwindung nicht gleichmässig abgefangen wird, so dass die
Figure imgb0003
Festigkeit und Elastizität nicht homogen ist. Weiterhin wirken die an der Oberfläche des Formteils liegenden Glasfaserbundel 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 been on the market for a long time
Figure imgb0001
(DMC) known. These masses contain relatively
Figure imgb0002
and rather long, bundled glass fibers. Such compositions are less suitable for the production of thin-walled, arbitrarily shaped and / or strongly bent molded parts. The glass fibers orient themselves in certain directions during the pressing process, as a result of which the polymerization shrinkage is not evenly absorbed, so that the
Figure imgb0003
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 unfavorable 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 vorgenannten 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 aforementioned mixtures.

Nach der vorliegenden Erfindung wird dies erreicht, wenn das Gemisch neben dem ungesättigten Polyesterharz 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.-% eines Erkalkalimetalloxides, vorzugsweise 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, the mixture contains 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 mixture as a whole. at least 3/4 of which have a length of less than 15 mm and are mainly present as random threads and contain 0.5 to 5% by weight of a alkali metal oxide, preferably 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 sehr 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 erfindungsgemässe 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 to produce molded parts lower than when using the known mixtures. A further requirement for the method according to the invention is that the mass is compact and almost free of air before it is pressed.

Figure imgb0004
Figure imgb0004

Das ungesättigte Polyesterharz kann jedes geeignete Reaktionsprodukt von mehrwertigen Alkoholen und mehrwertigen

Figure imgb0005
Säuren oder säurebildendenAnhydriden sein.The unsaturated polyester resin can be any suitable polyhydric alcohol and polyhydric reaction product
Figure imgb0005
Acids or acid-forming anhydrides.

Von den Alkoholen können Propylenglycol, Athylenglycol, Pentandiol, Butandiol, Butylenglycol und Dipropylenglycol genannt werden. Von den Säuren sind Maleinsäureanhydrid, Phthalsäureanhydrid, Isophthalsäureanhydriet, Adipinsäure u. dgl. gebräuchlich.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 ebenfalls 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 AusfUhrungsform der vorliegenden Erfindung giesst man das Gemisch in einen Behälter o. dgl. und lässt man es in 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 erwünschten 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. Ubliche Temperaturen sind 100 bis 250 °C, Übliche Drücke liegen zwischen 3 und 20 MPa. Die Presszeit wird normalerweise zwischen

Figure imgb0006
und 30 Minuten liegen und vorzugsweiseca. 1
Figure imgb0007
 bis 6 Minuten betragen.Temperature and pressure are not critical when pressing the mass and are caused, among other things, by the wall thickness of the desired molded part in relation to the optimum pressing time and the catalyst. Usual temperatures are 100 to 250 ° C, usual pressures are between 3 and 20 MPa. The pressing time is usually between
Figure imgb0006
 and 30 minutes and preferably approx. 1
Figure imgb0007
 up 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 ausgehärtet Formteil zum Beispiel kurz nach dem Verpressen mit einem pulverförmigen

Figure imgb0008
behandeln. Zu diesem Zweck sind Epoxyharzs, 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
Figure imgb0009
nicht vollständig ausgehärteten Formteils auf diese Weise eine dreidimensionale Vernetzung bewirken, wodurch eine gute Haftung zwischen Oberflächenschicht und Formteil erreicht wird. Vorzugsweise wendet man diese Behandlungsmethode an, wenn das Formteil noch eine Temperatur von minimal 150°C und vorzugsweise von 175-200 °C hat. Ein Vorteil dabei ist, dass das erfindungsgemässe Formteil dank seinem hohen Gehalt an anorganischen Füllstoffen einen grossen Wärmeinhalt hat.Molded parts produced using the method described above can be provided with a hard and or decorative surface layer during or shortly after the pressing. The molded part, which is still hot and not yet fully cured, can be used, for example, shortly after pressing with a powdered one
Figure imgb0008
to treat. 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 can also
Figure imgb0009
not fully cured molded part in this way cause a three-dimensional crosslinking, whereby good adhesion between the surface layer and molded part is achieved. This treatment method is preferably used if the molded part still has a temperature of at least 150 ° C. and preferably of 175-200 ° 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 pulverförmigem Harz kann aus Spritzen, elektrostatische Zerstäubung und Tauchen in ein Fliessbett des Pulvers bestehen. Dabei werden im allgemeinen 50 bis 300 g Pulver je m2 angebracht.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 .

Figure imgb0010
Figure imgb0010

Figure imgb0011
Metallpofver, farbige Mineralien, Polymerisatteilen usw. Auch kann eine der beiden Glasvlieszen vorher mit einem Motiv bedruckt werden, vorzugsweise mit Hilfe eines gefärbten oder pigmentierten Harzes. Auch sind Kombinationen beider Methoden möglich.
Figure imgb0011
Metal powder, colored minerals, polymer parts, etc. One of the two glass fleece can also be printed with a motif beforehand, preferably with the help of a colored or pigmented resin. Combinations of both methods are also 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.

Figure imgb0012
Figure imgb0012

Figure imgb0013
Figure imgb0013

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

Figure imgb0014
The invention is explained in more detail using a practical example. An unsaturated polyester resin is a polycondensation product from:
Figure imgb0014

Mol Fumarsäureanhydrid. verwendet.Mole of fumaric anhydride. used.

650 Teile dieses Harzes werden gemischt mit:

Figure imgb0015
Diesem Harzgemisch wird 1 Gew.-% Magnesiumoxid beigegeben.650 parts of this resin are mixed with:
Figure imgb0015
 1% by weight of magnesium oxide is added to this resin mixture.

Figure imgb0016
Figure imgb0016

Ein von dieser Masse abgeschnittener Teil wird anschliessend in einer Matrize 1'30 " bei einer Temperatur von 200 C und einem Druck von 150 kg/cm 2 ( 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/m2) für die im Handel erhältlichen auf dieselbe Weise verpressten BMC- bzw. SMC-Massen.A part cut from this mass is then pressed in a die 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 approx. 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 ) b between 110,000 kg / cm 2 (11 GN / m 2 ) for the commercially available BMC or SMC compounds pressed in the same way.

Als 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

Figure imgb0017
ca. 200 g dieses Gemisches angebracht. Nach Abkühlung ist das Resultat eine Platte, deren Oberfläche sich kaum von der Oberfläche eines mit keramischer Glasur Uberzogenen 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 state by atomization. Each m 2
Figure imgb0017
about 200 g of this mixture attached. 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, dünnwandigen 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 stellen 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 in strongly curved places is too great to make everyday items 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 erfindungsgemassen Gemisches.

Figure imgb0018
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 imgb0018

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 can be reproduced well if the same amount of powder is applied in the same way.

Die vorliegende Erfindung beschränkt sich nicht nur auf verhältnismässig komplizierte Formteile, sondern unfasst auch relativ einfache Formteile wie Fliesen oder Wandplatten. Das modifizierte Epoxyharz braucht nichtmonochromatisch zu sein, er sind auch systematische oder willkürliche Farbschattierungen möglich.The present invention is not limited to relatively complicated molded parts, but also includes relatively simple molded parts such as tiles or wall panels. The modified epoxy resin does not need to be monochromatic, and systematic or arbitrary shades of color are also possible.

Die Erfindung betrifft schlieslich auch Formteile, deren Körper zu 80 bis 95 Gew.-% aus anorganischen Füllstoffen mit einer hauptsächlich zwischen 0 und 500 Mikron liegenden Korngrösse, zu maximal 5 Gew.-%, bezogen auf die gesamte Masse, aus Glasfasern, von denen zumindest 3/4 eine Länge von weniger als 15 mm haben und hauptsächlich als Einfäden in willkürlicher Verteilung vornanden sind, sowie aus gehärtetem Polyesterharz, das eine Hagnesiumverbindung enthält, besteht.Finally, the invention also relates to molded parts whose bodies contain 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 mass, of glass fibers, of which at least 3/4 of a length of less than 15 mm and mainly as threads in an arbitrary distribution, as well as hardened polyester resin containing a magnesium compound.

Claims (12)

Figure imgb0019
Figure imgb0019
 6. Verfahren nach den Ansprüchen 1-5, dadurch gekennzeichnet, dass das Gemisch 1 bis 48 Stunden lang zu einer kompakten, nahezu luftfreien Pressmasse eingedickt wird.6. The method according to claims 1-5, characterized in that the mixture is thickened for 1 to 48 hours to a compact, almost air-free molding compound. 7. Verfahren nach den Ansprüchen 1-6, dadurch gekennzeichnet, dass die eingedickte Masse bei einer Temperatur zwischen 100 und 250 °C und einem Druck zwischen 30 (3) und 200 (20) kg/cm2 (MPa) verpresst wird.7. The method according to claims 1-6, characterized in that the thickened mass at a temperature between 100 and 250 ° C and a pressure between 3 0 (3) and 2 00 (2 0 ) kg / cm 2 (MPa) pressed becomes. 8. Verfahren nach den Ansprüchen 1-7, dadurch gekennzeichnet, dass das Formteil in noch nicht ganz ausgehärtetem Zustand bei einer Temperatur von mindestens 150 °C mit einem pulverförmigen Harz behandelt wird.8. The method according to claims 1-7, characterized in that the molded part is treated in a not yet fully cured state at a temperature of at least 150 ° C with a powdery resin. 9. Verfahren nach den Ansprüchen 1-8, dadurch gekennzeichnet, dass das Harz ein Epoxyharz mit freien Hydroxylgruppen, ein ungesättigtes Polyesterharz oder ein Gemisch eines Epoxy- und eines Polyesterharzes ist.9. The method according to claims 1-8, characterized in that the resin is an epoxy resin with free hydroxyl groups, an unsaturated polyester resin or a mixture of an epoxy and a polyester resin. 10. Verfahren nach Anspruch 8 oder 9, dadurch gekennzeichnet, dass die Temperatur während der Behandlung 175 bis 200 °C beträgt.10. The method according to claim 8 or 9, characterized in that the temperature during the treatment is 175 to 200 ° C. 11. Verfahren nach den Ansprüchen 1-7, dadurch gekennzeichnet, dass vor dem Einbringen der Pressmasse in die Pressform eine oder mehrere Glasvliesze angebracht werden, die mit einem Epoxy-oder Polyesterharz oder einem Gemisch dieser Harze imprägniert sind.11. The method according to claims 1-7, characterized in that before the introduction of the molding compound into the mold, one or more glass fleece are attached, which are impregnated with an epoxy or polyester resin or a mixture of these resins. 12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, dass zwei Glasvliesze angebracht werden, zwischen denen sich eine Dekoration befindet.12. The method according to claim 11, characterized in that two glass fleece are attached, between which there is a decoration. 13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass die Dekoration aus feinverteilten anorganischen oder organischen Stoffen besteht.13. The method according to claim 12, characterized in that the decoration consists of finely divided inorganic or organic substances. 14. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass die Dekoration aus einem pigmentierten Harz bestehe14. The method according to claim 12, characterized in that the decoration consists of a pigmented resin 15. Formteil, dessen Körper zu 80 bis 95 Gew.-% aus anorganischen Füllstoffen mit einer hauptsächlich zwischen 0 und 500 Mikron liegenden Kurngrösse, zu 1-5 Gew.-%,bezogen auf das gesamte Gemisch, aus Glasfasern, von denen zumindest 3/4 eine Lange von weniger als 15 mm haben und hauptsächlich als willkürlich verteilte Einfäden vorhanden sind, und aus gehärteten Polyesterharz, das eine Magnesiumverbindung enthält, besteht.15. molded part, the body of which consists of 80 to 95% by weight of inorganic fillers with a core size mainly between 0 and 500 microns, 1-5% by weight, based on the mixture as a whole, of glass fibers, of which at least 3 / 4 have a length of less than 15 mm and mainly as arbitrary distributed threads are present, and consists of hardened polyester resin containing a magnesium compound. 16. Verfahren nach Anspruch 1, wie im wesentlichen beschrieben und anhand des Beispiels näher erläutert.16. The method according to claim 1, as essentially described and explained in more detail using the example.
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)

Applications Claiming Priority (2)

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

Publications (2)

Publication Number Publication Date
EP0000223A1 true EP0000223A1 (en) 1979-01-10
EP0000223B1 EP0000223B1 (en) 1983-03-02

Family

ID=19828778

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78200045A Expired EP0000223B1 (en) 1977-06-24 1978-06-19 Production of articles from an unsaturated polyester resin, mineral fillers and glass fibres and articles thus obtained

Country Status (5)

Country Link
EP (1) EP0000223B1 (en)
JP (1) JPS5411174A (en)
DE (1) DE2862193D1 (en)
IT (1) IT1105043B (en)
NL (1) NL186016C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0242891A2 (en) * 1986-02-27 1987-10-28 Dsm Resins B.V. Sheet moulding compound and an upper layer for it

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2861438D1 (en) 1977-11-03 1982-02-04 Stamicarbon Process for making objects from mineral fillers bonded with a thermosetting resin
JPS5949240A (en) * 1982-09-16 1984-03-21 Dainippon Ink & Chem Inc Prepreg with both high workability and compression moldability

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
DE2243991A1 (en) * 1971-09-07 1973-03-22 Mitsubishi Gas Chemical Co PROCESS FOR COLORING MOLDED OBJECTS MADE FROM UNSATURATED POLYESTER RESINS
DE2252566A1 (en) * 1971-10-26 1973-05-10 Asahi Chemical Ind GLASS FIBER REINFORCED MOLDED BODY
DE2410787A1 (en) * 1973-03-15 1974-09-19 Koppers Co Inc POLYMERIZABLE MOLDING COMPOUNDS AND METHOD FOR MANUFACTURING FLAME RETARDANT POLYESTER MOLDED BODIES THEREOF
DE2509236A1 (en) * 1975-03-04 1976-09-16 Bayer Ag Low shrinkage moulding compsn - contg unsatd polyester, glass fibres and diatomaceous earth
US3986992A (en) * 1975-04-16 1976-10-19 Scm Corporation Low shrink thermosetting polyesters

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
DE2243991A1 (en) * 1971-09-07 1973-03-22 Mitsubishi Gas Chemical Co PROCESS FOR COLORING MOLDED OBJECTS MADE FROM UNSATURATED POLYESTER RESINS
DE2252566A1 (en) * 1971-10-26 1973-05-10 Asahi Chemical Ind GLASS FIBER REINFORCED MOLDED BODY
DE2410787A1 (en) * 1973-03-15 1974-09-19 Koppers Co Inc POLYMERIZABLE MOLDING COMPOUNDS AND METHOD FOR MANUFACTURING FLAME RETARDANT POLYESTER MOLDED BODIES THEREOF
DE2509236A1 (en) * 1975-03-04 1976-09-16 Bayer Ag Low shrinkage moulding compsn - contg unsatd polyester, glass fibres and diatomaceous earth
US3986992A (en) * 1975-04-16 1976-10-19 Scm Corporation Low shrink thermosetting polyesters

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0242891A2 (en) * 1986-02-27 1987-10-28 Dsm Resins B.V. Sheet moulding compound and an upper layer for it
EP0242891A3 (en) * 1986-02-27 1990-03-28 Dsm Resins Bv Sheet moulding compound and an upper layer for it

Also Published As

Publication number Publication date
NL186016C (en) 1990-09-03
DE2862193D1 (en) 1983-04-07
IT7850016A0 (en) 1978-06-23
IT1105043B (en) 1985-10-28
JPS6244571B2 (en) 1987-09-21
NL7706997A (en) 1978-12-28
JPS5411174A (en) 1979-01-27
EP0000223B1 (en) 1983-03-02

Similar Documents

Publication Publication Date Title
CH417943A (en) Process for the production of dimensionally stable injection molded articles from polyesters of aromatic dicarboxylic acids
DE2301617B2 (en) Process for the production of a decorative layer on a substrate by spraying on or spraying on a mortar mass based on cement, resin and aggregates and applying a final synthetic resin layer
DE2414973A1 (en) HAIRABLE POLYESTER MATERIAL
DE1569234A1 (en) Phenol-based resin mixture
DE2158561A1 (en) Unsaturated polyester compositions and their use for making hot-press, impregnated precursors
DE1966942C3 (en) Process for making fiberglass articles
DE2419527A1 (en) PROCESS FOR MANUFACTURING DECORATIVE PLASTIC ARTICLES, AND MOLDED BODIES, MANUFACTURED IN ACCORDANCE WITH THIS PROCESS
WO1998028356A1 (en) Material containing polyreactions products and method for the production thereof
DE2646145A1 (en) ARTICLES MADE OF PHENOLIC RESIN AND PROCESS FOR THEIR PRODUCTION
DE2241130A1 (en) COMPOSITE HIGH FIRE RESISTANCE AND METHOD FOR MANUFACTURING THE SAME
EP0000223B1 (en) Production of articles from an unsaturated polyester resin, mineral fillers and glass fibres and articles thus obtained
DE966278C (en) Process for the production of self-adhesive masses, especially for dental purposes
DE2211942C3 (en) Binder composition for glass wool products
DE1960199C3 (en) Thermosetting mixture based on an unsaturated glycidyl ester resin
DE2231205A1 (en) DECORATIVE LAYER AND METHOD OF MANUFACTURING IT
DE1006153B (en) Process for the production of heat-curable molding compounds
DE1812250B2 (en) PROCESS FOR THE PRODUCTION OF SMALL ELASTOMERIC POLYURETHANE PARTICLES
DE1469890B1 (en) Polyester molding compound
DE2315494A1 (en) LIQUID UNSATURATED POLYESTER COMPOSITIONS AND METHODS OF CONTROLLING THE RATE OF VISCOSITY INCREASE OF THESE MATERIALS
DE1077426B (en) Process for the production of laminated bodies with a layered structure from epoxy and polyester resin-bonded fiber material layers
DE2208299B2 (en) Process for the production of hollow glass fiber reinforced synthetic resin objects
DE1629732A1 (en) Process and device for the continuous production of dust-free preformed molding compounds
DE2235537B2 (en) Process for mixing fibrous materials with binders in the dry state
DE1061512B (en) Process for improving the adhesion of unsaturated polyester resin compositions to glass
DE1303355C2 (en) METHOD AND DEVICE FOR MANUFACTURING CHIPBOARD

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE DE FR GB LU SE

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR GB LU SE

REF Corresponds to:

Ref document number: 2862193

Country of ref document: DE

Date of ref document: 19830407

ET Fr: translation filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

EPTA Lu: last paid annual fee
EAL Se: european patent in force in sweden

Ref document number: 78200045.9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19960430

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19960501

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19960515

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19960523

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19960611

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19960801

Year of fee payment: 19

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970619

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970619

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19970620

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19970630

BERE Be: lapsed

Owner name: DSM N.V.

Effective date: 19970630

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19970619

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980227

EUG Se: european patent has lapsed

Ref document number: 78200045.9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980303

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT