DE102005009636A1 - Binding system, useful for sand molding based on hardenable acid resin component, comprises a nitrogenous compound as resin component and arylsulfonic acid as hardener - Google Patents

Binding system, useful for sand molding based on hardenable acid resin component, comprises a nitrogenous compound as resin component and arylsulfonic acid as hardener Download PDF

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DE102005009636A1
DE102005009636A1 DE200510009636 DE102005009636A DE102005009636A1 DE 102005009636 A1 DE102005009636 A1 DE 102005009636A1 DE 200510009636 DE200510009636 DE 200510009636 DE 102005009636 A DE102005009636 A DE 102005009636A DE 102005009636 A1 DE102005009636 A1 DE 102005009636A1
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Prior art keywords
resin
resin component
acid
hardener
binder system
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DE200510009636
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DE102005009636B4 (en
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Harald Heere
Christian Froschauer
Robert Adam
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Bayerische Motoren Werke AG
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Bayerische Motoren Werke AG
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B22C1/224—Furan polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08L61/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C09D161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof

Abstract

Binding system (I) for sand molding based on hardenable acid resin component, particularly furfuryl alcohol, comprises at least a nitrogenous compound as resin component with a nitrogen content of 2-6 wt.% related to the total resin and an arylsulfonic acid as hardener with 10-65% parts by weight. An independent claim is included for a preparation of sand molding in generative ways of 3D-printing process with the help of acid-hardenable binder system, comprising using the resin component and the hardener of (I).

Description

Die Erfindung bezieht sich auf ein Bindemittelsystem für Sandformen sowie auf ein Verfahren zum Herstellen einer Sandform, nach dem Oberbegriff des Patentanspruchs 1 bzw. 6.The This invention relates to a binder system for sand molds and to a method of making a sand mold after which Preamble of claim 1 or 6.

Aus der DE 102 24 981 A1 ist ein generatives 3D-Druckverfahren zur Herstellung von Sandformen mit Hilfe eines Zweikomponenten-Bindemittelsystems bekannt, bei dem ein Formsand/Harzgemisch in übereinanderliegenden Schichten aufgebracht und an jeder einzelnen Schicht mit dem Härter des Bindemittelsystems bedruckt wird, so dass ein individuell geformter Festkörper entsteht, der nach Ablauf der Reaktionszeit des Bindemittelsystems als integrale Metallgussform aus dem umliegenden, ungebundenen Materialbett entnommen werden kann. An ein hierfür, aber auch generell zur Sandformherstellung geeignetes Bindemittelsystem werden hinsichtlich kurzer Reaktionszeiten, geringer Ausgasung während des Gussvorgangs und erzielbarer Sandformfestigkeit hohe Anforderungen gestellt.From the DE 102 24 981 A1 is a generative 3D printing process for producing sand molds using a two-component binder system known in which a molding sand / resin mixture applied in superimposed layers and printed on each individual layer with the hardener of the binder system, so that an individually shaped solid is formed, the can be removed as an integral metal mold from the surrounding, unbound material bed after the reaction time of the binder system. To a, but also generally suitable for sand mold production binder system high demands are made in terms of short reaction times, low outgassing during the casting process and achievable sand mold strength.

So ist aus der DE 101 36 365 A1 ein CO2-härtbares Bindemittelsystem bekannt, bei welchem der Harzkomponente mindestens eine stickstoffhaltige Verbindung, insbesondere Harnstoffharz, zugemischt ist, um dadurch die mechanische Festigkeit der resultierenden Sandform zu erhöhen. Nachteilig dabei ist, dass die so gefertigten Sandformen ein verstärktes Ausgasungsverhalten während des Abgusses aufweisen, was zum Einschluss von Gasblasen bei der Erstarrung der Metallschmelze und demzufolge zu Porositäten und Lunkerbildungen im Gussteil führt.So is out of the DE 101 36 365 A1 a CO 2 curable binder system is known in which the resin component at least one nitrogen-containing compound, in particular urea resin, is mixed, thereby increasing the mechanical strength of the resulting sand mold. The disadvantage here is that the sand molds thus produced have an increased outgassing behavior during the casting, which leads to the inclusion of gas bubbles in the solidification of the molten metal and consequently to porosities and voids forming in the casting.

Aufgabe der Erfindung ist es, ein generatives 3D-Druckverfahren und ein hierfür geeignetes Bindemittelsystem der eingangs genannten Art zu schaffen, welches ein geringes Ausgasungsverhalten während des Gussvorgangs und zugleich eine hohe Festigkeit der mit dem Bindemittelsystem gefertigten Sandformen gewährleistet.task The invention is a generative 3D printing method and a therefor to provide a suitable binder system of the type mentioned, which has a low outgassing behavior during the casting process and at the same time high strength of the sand molds made with the binder system guaranteed.

Diese Aufgabe wird erfindungsgemäß durch das im Patentanspruch 1 gekennzeichnete Bindemittelsystem bzw. das im Patentanspruch 6 gekennzeichnete Verfahren gelöst.These The object is achieved by the characterized in claim 1 binder system or in the Claim 6 characterized solved method.

Grundlage der Erfindung ist die Erkenntnis, dass eine Festigkeitserhöhung durch Zugabe einer stickstoffhaltigen Verbindung nicht zwangsläufig mit einer erhöhten Ausgasung des Bindemittelsystems während des Abgusses verbunden ist, sondern sich das gussstörende Ausgasungsverhalten überraschenderweise durch eine Stickstoffzugabe zur säurehärtbaren Harzkomponente sogar noch signifikant verringern lässt, wenn der Stickstoffanteil an der Gesamtharzmenge innerhalb definierter Grenzen gehalten und zusätzlich ein spezieller Härter mit einem, bezogen auf die Harzmenge, ebenfalls begrenzten Gewichtsanteil verwendet wird, mit dem Ergebnis, dass die resultierenden Sandformen eine hohe Bruch- und Biegefestigkeit aufweisen und dennoch eine qualitativ hochwertige, von Porositäten und Lunkern weitgehend freie und maßgenaue Gussteilfertigung sicherstellen.basis The invention is the realization that an increase in strength by Addition of a nitrogen-containing compound is not necessarily with a increased Outgassing of the binder system connected during the casting is, but the cast-disturbing Outgassing behavior surprisingly by adding nitrogen to the acid-curable resin component even still significantly reduce, if the nitrogen content of the total amount of resin within defined Limits kept and in addition a special hardener with a, based on the amount of resin, also limited weight fraction is used, with the result that the resulting sand molds have a high breaking and bending strength and yet a high quality, largely of porosities and voids free and accurate to measure Ensure casting production.

Ein weiterer, vor allem in Verbindung mit dem generativen 3D-Druckverfahren wesentlicher Aspekt des erfindungsgemäßen Bindemittelsystems liegt in den verkürzten Reaktionszeiten und den sich daraus ergebenden, höheren Produktionsgeschwindigkeiten. Dabei wird der Formsand vorzugsweise mit dem Härter des Bindemittelsystems vorgemischt und das Sand/Härtergemisch schichtweise mit der stickstoffhaltig angereicherten Harzkomponente bedruckt, wodurch die Sandformfestigkeit nochmals gesteigert werden kann.One more, especially in connection with the generative 3D printing process essential aspect of the binder system according to the invention in the shortened Reaction times and the resulting, higher production speeds. The molding sand is preferably with the hardener of the binder system premixed and the sand / hardener mixture layer by layer with the nitrogen-containing enriched resin component printed, whereby the sand resistance are increased again can.

Eine besonders bevorzugte Ausgestaltung des erfindungsgemäßen Verfahrens betrifft die Reinigung des Druckkopfes: Während das generative 3D-Drucken mit einer durch eine stickstoffhaltige Verbindung, etwa Harnstoffharz, angereicherten Harzkomponente bisher zumeist daran scheiterte, dass die verstopfungsgefährdeten Druckerdüsen nicht oder nur mit unvertretbar großem Aufwand gereinigt werden konnten, lassen sich die Druckerdüsen von den Harzrückständen des erfindungsgemäßen Bindemittelsystems problemlos mit Hilfe eines aromatischen Alkohols, vorzugsweise Benzylalkohol, befreien.A particularly preferred embodiment of the method according to the invention concerns the cleaning of the printhead: During generative 3D printing with a nitrogen-containing compound, such as urea resin, enriched resin component so far mostly failed because the clog-prone printer nozzles not be cleaned or only with unreasonable effort could, the printer nozzles from the resin residues of the inventive binder system easily with the help of an aromatic alcohol, preferably benzyl alcohol, to free.

Als besonders vorteilhaft hat es sich erwiesen, als stickstoffhaltige Verbindung ein Harnstoffharz mit einem Gewichtsanteil an der Gesamtharzmenge von etwa 4% und als Härter Xylolsulfonsäure mit 30 bis 50 Gew.-%, bezogen auf das Gesamtharz, auszuwählen.When It has proven to be particularly advantageous as a nitrogen-containing Compound a urea resin with a weight fraction of the total amount of resin of about 4% and as a hardener Xylene sulfonic acid with 30 to 50 wt .-%, based on the total resin to select.

Die Erfindung wird nachfolgend anhand eines Ausführungsbeispiels in Verbindung mit der Zeichnung näher beschrieben, in deren einziger Figur eine generative 3D-Druckanlage in stark schematisierter Darstellung gezeigt ist.The Invention will be described below with reference to an embodiment in connection closer to the drawing described in their only figure, a generative 3D printing system is shown in a highly schematic representation.

Die in der Zeichnung gezeigte Druckanlage enthält einen Formsandbehälter 1, Vorratsbehälter 2 bis 4 für den Härter bzw. die Harzkomponente eines säurehärtbaren Bindemittelsystems sowie einen Reinigungsmittelbehälter 5. Als Härter ist eine Arylsulfonsäure, nämlich im Ausführungsbeispiel Xylolsulfonsäure vorgesehen, die Harzkomponente im Behälter 3 ist Furfurylalkohol, der Behälter 4 enthält Harnstoffharz oder eine äquivalente stickstoffhaltige Verbindung und das Reinigungsmittel im Behälter 5 besteht aus einem aromatischen Alkohol, z. B. Benzylalkohol.The printing unit shown in the drawing contains a molding sand container 1 , Storage container 2 to 4 for the hardener or the resin component of an acid-hardening binder system and a detergent container 5 , As a hardener is an arylsulfonic acid, namely in the embodiment xylene sol fonsäure provided, the resin component in the container 3 is furfuryl alcohol, the container 4 contains urea resin or an equivalent nitrogen-containing compound and the cleaning agent in the container 5 consists of an aromatic alcohol, eg. B. benzyl alcohol.

Der Formsand und die Xylolsulfonsäure werden zunächst im einem Mischer 6 vorgemischt und anschließend in übereinanderliegenden Schichten 7.1...7.n auf einen Träger 8 aufgebracht. Dabei wird jede einzelne Materialschicht 7 jeweils in einem individuell vorgegebenen Flächenbereich mittels eines Druckkopfes 9, welcher nach Art eines Tintenstrahldruckers mit selektiv ansteuerba ren Harzdüsen 10 ausgestattet ist, mit dem zuvor in einem Mischbehälter 11 mit Harnstoffharz angereicherten Furfuryalkohol bedruckt, so dass die Schichten 7.1...7.n in den bedruckten Materialzonen sukzessive aushärten und sich zu einem dreidimensional geformten Festkörper 12 verbinden, welcher aus dem umliegenden, ungebundenen Materialbett entnommen werden kann und dann z. B. einen – in der Zeichnung schraffiert dargestellten – Formkern einer (nicht gezeigten) Metallgussform bildet.The molding sand and the xylenesulfonic acid are first mixed in a mixer 6 premixed and then in superimposed layers 7.1 ... 7.n on a carrier 8th applied. Thereby every single material layer becomes 7 each in an individually predetermined surface area by means of a print head 9 , which in the manner of an ink jet printer with selectively asteuerba ren resin nozzles 10 equipped with the previously in a mixing vessel 11 imprinted with urea resin-enriched furfury alcohol, so that the layers 7.1 ... 7.n in the printed material zones successively harden and become a three-dimensionally shaped solid 12 connect, which can be removed from the surrounding, unbound material bed and then z. B. a - shown in the drawing hatched - mold core of a (not shown) metal mold forms.

Im Hinblick auf kurze Aushärtzeiten, eine hohe Sandformfestigkeit und ein geringes Ausgasungsverhalten der Sandform 12 während des Metallgussvorgangs beträgt der Stickstoffanteil der Harnstoffzugabe an der Gesamtharzmenge 2 bis 6 Gew.-% und das Gewichtsverhältnis der Xylolsulfonsäure zur Gesamtharzmenge liegt zwischen 0,1 und 0,65. Als besonders günstig hat sich ein Stickstoffanteil von etwa 4 Gew.-% und ein Härter/Harzverhältnis von 0,3 bis 0,5 erwiesen.With regard to short curing times, a high sand resistance and a low outgassing behavior of the sand mold 12 During the metal casting operation, the nitrogen content of the urea addition to the total resin amount is 2 to 6 wt% and the weight ratio of the xylenesulfonic acid to the total resin amount is between 0.1 and 0.65. A nitrogen content of about 4% by weight and a hardener / resin ratio of 0.3 to 0.5 have proven particularly favorable.

Sehr einfach ist auch die Druckkopfreinigung, da sich Rückstände des Furfurylalkohol/Harnstoffharzgemisches mühelos mit Benzylalkohol aus den Druckerdüsen 10 entfernen lassen.Very easy is also the head cleaning, as residues of furfuryl alcohol / urea resin mixture effortlessly with benzyl alcohol from the printer nozzles 10 have it removed.

Claims (10)

Bindemittelsystem für Sandformen, auf der Basis einer säurehärtbaren Harzkomponente, insbesondere Furfurylalkohol, dadurch gekennzeichnet, dass der Harzkomponente mindestens eine stickstoffhaltige Verbindung mit einem Stickstoffanteil von 2 bis 6 Gew.-%, bezogen auf die Gesamtharzmenge, zugegeben und als Härter eine Arylsulfonsäure mit einem Gewichtsanteil von 10 bis 65% der Gesamtharzmenge vorgesehen ist.Binder system for sand molds, based on an acid-curable resin component, in particular furfuryl alcohol, characterized in that the resin component at least one nitrogen-containing compound having a nitrogen content of 2 to 6 wt .-%, based on the total amount of resin added and as a hardener an arylsulfonic acid with a weight fraction from 10 to 65% of the total amount of resin is provided. Bindemittelsystem nach Anspruch 1, dadurch gekennzeichnet, dass der Stickstoffanteil der stickstoffhaltigen Verbindung an der Gesamtharzmenge bei etwa 4 Gew.-% liegt.Binder system according to claim 1, characterized in that that the nitrogen content of the nitrogenous compound at the Total amount of resin is about 4 wt .-%. Bindemittelsystem nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die stickstoffhaltige Verbindung aus der Gruppe Harnstoff, Harnstoff/Formaldehydharze, Melamin und Melamin/Formaldehydharze ausgewählt ist.Binder system according to claim 1 or 2, characterized characterized in that the nitrogen-containing compound is selected from the group Urea, urea / formaldehyde resins, melamine and melamine / formaldehyde resins selected is. Bindemittelsystem nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Gewichtsanteil der Arylsulfonsäure zwischen 30 und 50% liegt.Binder system according to one of the preceding claims, characterized characterized in that the weight fraction of the arylsulfonic between 30 and 50% lies. Bindemittelsystem nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass als Härter Xylolsulfonsäure vorgesehen ist.Binder system according to one of the preceding claims, characterized characterized as a hardener xylene sulfonic acid is provided. Verfahren zum Herstellen einer Sandform im Wege des generativen 3D-Druckverfahrens mit Hilfe eines säurehärtbaren Bindemittelsystems, dadurch gekennzeichnet, dass der Harzkomponente des Bindemittelsystems mindestens eine stickstoffhaltige Verbindung mit einem Stickstoffanteil von 2 bis 6 Gew.-%, bezogen auf das Gesamtharz, zugesetzt und als Härter eine Arylsulfonsäure mit einem Gewichtsanteil von 10 bis 65% der Gesamtharzmenge verwendet wird.Method for producing a sand mold by way of generative 3D printing process with the help of an acid hardening Binder system, characterized in that the resin component of the binder system at least one nitrogen-containing compound with a nitrogen content of 2 to 6 wt .-%, based on the total resin, added and as a hardener an arylsulfonic acid used with a proportion by weight of 10 to 65% of the total amount of resin becomes. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass der Formsand mit der Arylsulfonsäure vorgemischt und das Sand/Säuregemisch schichtweise mit der stickstoffhaltigen Harzkomponente bedruckt wird.Method according to Claim 6, characterized that the molding sand premixed with the arylsulfonic acid and the sand / acid mixture Layered with the nitrogen-containing resin component becomes. Verfahren nach Anspruch 6 oder 7, dadurch gekennzeichnet, dass zur Druckkopfreinigung ein aromatischer Alkohol, vorzugsweise Benzylalkohol verwendet wird.Method according to claim 6 or 7, characterized that for printhead cleaning an aromatic alcohol, preferably Benzyl alcohol is used. Verfahren nach einem der Ansprüche 6 bis 8, dadurch gekennzeichnet, dass die Harzkomponente aus einer Mischung aus Furfurylalkohol und Harnstoffharz mit einem Stickstoffanteil von etwa 4 Gew.-%, bezogen auf die Gesamtharzmenge, besteht.Method according to one of claims 6 to 8, characterized that the resin component of a mixture of furfuryl alcohol and Urea resin with a nitrogen content of about 4 wt .-%, based on the total amount of resin, consists. Verfahren nach einem der Ansprüche 6 bis 9, dadurch gekennzeichnet, dass als Härter Xylolsulfonsäure mit einem Gewichtsanteil von 30 bis 50% der Gesamtharzmenge verwendet wird.Method according to one of claims 6 to 9, characterized that as a hardener xylene sulfonic acid used at a weight fraction of 30 to 50% of the total amount of resin becomes.
DE102005009636.0A 2005-03-03 2005-03-03 Method of generating a sand mold generatively Expired - Fee Related DE102005009636B4 (en)

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