EP0032596B1 - Process for producing lost moulds - Google Patents
Process for producing lost moulds Download PDFInfo
- Publication number
- EP0032596B1 EP0032596B1 EP80200997A EP80200997A EP0032596B1 EP 0032596 B1 EP0032596 B1 EP 0032596B1 EP 80200997 A EP80200997 A EP 80200997A EP 80200997 A EP80200997 A EP 80200997A EP 0032596 B1 EP0032596 B1 EP 0032596B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- percent
- molds
- phenolic
- binder
- 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
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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
- B22C1/167—Mixtures of inorganic and organic binding agents
-
- 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
- B22C1/18—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 inorganic agents
- B22C1/186—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 inorganic agents contaming ammonium or metal silicates, silica sols
- B22C1/188—Alkali metal silicates
Definitions
- the invention relates to a method for producing lost molds according to the preamble of claim 1. Such a method is known from DE-B 13 02 716.
- Aqueous solutions of sodium or potassium silicates are often used as cold-curing binders for basic molding materials for lost molds.
- decay-promoting additives such as. B. coal dust, wood flour, starch, sugar derivatives added. It is also known to add urea, melanin, phenol, furfuryl alcohol or furfuryl alcohol-urea-formaldehyde condensates, which in turn are combined with other resinous substances such as ketone formaldehyde resins, hydrocarbon resins, rosin, tall resins and the like. a. can be modified to support the tendency to decay.
- these prior art additives are inadequate, especially when these binders are used to make intricately shaped and narrow passage molds.
- isocyanates used as binders are cured by gassing with amines. These amines have hygroscopic properties and are highly toxic.
- the object is achieved by processes for the production of lost molds from a molding material mixture of sand or other molding raw materials and by gassing with carbon dioxide-curable binders based on alkali silicates and 0.3-3 percent by weight of phenolic or furan resins, and optionally additives known per se, such as silanes, polyhydric alcohols and polysaccharides, the molding material mixture being introduced into molds and hardened, characterized in that the phenolic or furan resin has 0.1-1.5 percent by weight of a dry substance and the alkali silicate is 2-5 percent by weight.
- Quartz sand is preferably used as the basic molding material.
- other conventional molding materials such as chromite, zircon or olivine sand, chamotte, magnesite, sillimanite or corundum.
- Phenolic or furan resins are preferably used as condensation resins.
- 0.1-1.5% by weight of a dry substance is added to the condensation resin.
- small amounts (0.1-0.5%) of an aminosilane are sometimes added.
- dry matter is understood to mean metal soaps soluble in organic solvents, the main metals being Co, Mn and. Pb come into consideration, while as the organic component mostly carboxylic acid residues are present, such as. As naphthenates, octoates, linoleates, resinates or caprylates. These dry substances transfer the atmospheric oxygen through continuous regeneration, so that only small amounts of these substances are needed.
- This binder is mixed thoroughly with the basic molding material. Then 2-5% by weight of alkali silicate is added as the second binder component and mixed.
- An alkali silicate is an aqueous solution of sodium or potassium silicate which is commercially available under the name of water glass and in which 0.2-3% by weight of lithium hydroxide or a hydroxide of an alkaline earth metal have been dissolved.
- This solution can additionally be admixed with substances known to promote disintegration, such as glycerin, starch, sugar derivatives or cellulose.
- the mixture produced by thoroughly mixing the basic molding material with the two binder components is introduced into molds and hardened by gassing with carbon dioxide.
- the strength of which already decreases considerably after storage for several days the strength of the shaped articles produced by the process according to the invention increases over the course of the storage time. Nevertheless, the decay after the casting is significantly improved.
- Binder consisting of:
- Binder consisting of:
- Binder consisting of:
- Binder consisting of:
- a pure cobalt octoate e.g. octa-solingen cobalt
- Molding material mixtures were produced with the binders of Comparative Examples 1-3 and Inventive Examples 4-7. 3 or 4 parts by weight of binder were used per 100 parts by weight of quartz sand (e.g. AFS 55). In the case of Examples 2-7, the sand was only 2 min. mixed with component I and then with component 11. Cylindrical test specimens (50 x 50 mm) were rammed from the mixtures. The cores were precured by gassing with CO 2 for 6-10 s. The shear strength was measured after 10 min. as well as 1, 5, 24, 48 and 72 hours, moisture absorption after 8 weeks and decay at 500 and 1000 ° C.
- quartz sand e.g. AFS 55
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von verlorenen Formen nach dem Oberbegriff des Anspruchs 1. Ein derartiges Verfahren ist aus der DE-B 13 02 716 bekannt.The invention relates to a method for producing lost molds according to the preamble of claim 1. Such a method is known from DE-B 13 02 716.
Als kalthärtende Bindemittel für Formgrundstoffe für verlorene Formen werden vielfach wäßrige Lösungen von Natrium- oder Kaliumsilikaten (Wasserglas) verwendet.Aqueous solutions of sodium or potassium silicates (water glass) are often used as cold-curing binders for basic molding materials for lost molds.
Die Härtung erfolgt meist durch Begasen mit Kohlendioxid (C02-Verfahren). Durch die chemische Reaktion des Silikats mit dem C02 erfolgt die Verfestigung. Die so hergestellten Kerne haben 2 entscheidende Nachteile gegenüber nach warmhärtenden Verfahren gefertigten :
- 1. Die hohe Hygroskopizität. Durch Feuchtigkeitsaufnahme ist bereits nach kurzer Zeit ein wesentlicher Festigkeitsabfall zu verzeichnen, der sich bis zur Unbrauchbarkeit der Formkörper fortsetzt.
- 2. Der schlechte Zerfall nach dem Abgießgen wie z. B. bei den nach dem eingangs genannten Verfahren hergestellten Formen, besonders bei hohen Temperaturen (Stahlguß). Ursache dafür ist das Sintern des Silikats und Carbonats.
- 1. The high hygroscopicity. As a result of moisture absorption, a significant drop in strength can be observed after a short time, which continues until the molded articles are unusable.
- 2. The bad decay after pouring such as. B. in the molds produced by the method mentioned above, especially at high temperatures (cast steel). The reason for this is the sintering of the silicate and carbonate.
Um besonders den letztgenannten Nachteil zu verringern, werden bekanntlich seit langem zerfallsfördernde Zusätze, wie z. B. Kohlenstaub, Holzmehl, Stärke, Zuckerderivate zugesetzt. Bekannt ist auch die Zugabe von Harnstoff-, Melanin-, Phenol-, Furfurylalkohol- oder Furfurylalkohol-Harnstoff-Formaldehyd-Kondensaten, die ihrerseits mit weiteren harzartigen Stoffen wie Ketonformaldehydharzen, Kohlenwasserstoffharzen, Kolophonium, Tallharzen u. a. modifiziert sein können, um die Zerfallsneigung zu unterstützen. Diese dem Stand der Technik entsprechenden Zusätze sind jedoch unzureichend, vor allem, wenn diese Bindemittel zur Herstellung von kompliziert gestalteten und mit engen Durchgängen versehenen Formen verwendet werden.In order to reduce the latter disadvantage in particular, it is known that decay-promoting additives, such as. B. coal dust, wood flour, starch, sugar derivatives added. It is also known to add urea, melanin, phenol, furfuryl alcohol or furfuryl alcohol-urea-formaldehyde condensates, which in turn are combined with other resinous substances such as ketone formaldehyde resins, hydrocarbon resins, rosin, tall resins and the like. a. can be modified to support the tendency to decay. However, these prior art additives are inadequate, especially when these binders are used to make intricately shaped and narrow passage molds.
Ferner ist eine andere Härtungsmethode bekannt, bei der als Bindemittel verwendete Isocyanate durch Begasen mit Aminen ausgehärtet werden. Diese Amine haben hygroskopische Eigenschaften und sind hochgiftig.Another curing method is also known in which isocyanates used as binders are cured by gassing with amines. These amines have hygroscopic properties and are highly toxic.
Da das Amin teilweise unverändert aus dem Prozeß hervorgeht, muß es abgeleitet oder vernichtet werden. Hier müssen die entsprechenden Sicherheitsvorschriften beachtet werden, da diese leichtflüchtigen Amine im bestimmten Verhältnis mit Luft explosive Gemische bilden und ferner ätzend auf Haut, Augen und Schleimhäute wirken. Eine Cold-Box-Anlage zur automatischen Formfertigung ist, da all diese Sicherheitsvorschriften eingehalten werden müssen, sehr aufwendig und teuer.Since some of the amine emerges unchanged from the process, it must be derived or destroyed. The relevant safety regulations must be observed here, since these volatile amines form explosive mixtures with air in a certain ratio and also have a corrosive effect on the skin, eyes and mucous membranes. A cold box system for automatic mold production is very complex and expensive because all these safety regulations have to be observed.
Da auch die so hergestellten Formen und Kerne bei Lagerung hygroskopisch sind und somit an Festigkeit verlieren, müssen sie in den meisten Fällen geschlichtet oder in Öfen vor Gebrauch getrocknet werden.Since the molds and cores produced in this way are hygroscopic when stored and therefore lose strength, in most cases they have to be sized or dried in ovens before use.
Um diese Nachteile der derzeit gebräuchlichen kalthärtenden Verfahren zur Herstellung von verlorenen Formen zu überwinden, war es Aufgabe der vorliegenden Erfindung, ein entsprechendes umweltfreundliches Verfahren zu finden, mit dem sich auch komplizierte Formen herstellen lassen, die nach dem Abgießen leicht zerfallen. Die so hergestellten Formen sollen bei Lagerung feuchtigkeitsbeständig sein, ohne einen Festigkeitsabfall zu zeigen.In order to overcome these disadvantages of the currently used cold-hardening process for the production of lost molds, it was an object of the present invention to find a corresponding environmentally friendly process which can also be used to produce complicated molds which easily disintegrate after casting. The molds produced in this way are said to be moisture-resistant during storage without showing a decrease in strength.
Die Aufgabe wird gelöst durch Verfahren zur Herstellung von verlorenen Formen aus einer Formstoffmischung aus Sand oder anderen Formgrundstoffen und durch Begasen mit Kohlendioxid härtbaren Bindemitteln auf Basis von Alkalisilikaten und 0,3-3 Gewichtsprozent Phenol- oder Furanharzen sowie gegebenenfalls an sich bekannten Zusatzstoffen wie Silanen, mehrwertigen Alkoholen und Polysaccariden, wobei die Formstoffmischung in Formen eingebracht und gehärtet wird, dadurch gekennzeichnet, daß das Phenol- oder Furanharz 0,1-1,5 Gewichtsprozent eines Trockenstoffes aufweist sowie das Alkalisilikat 2-5 Gewichtsprozent beträgt.The object is achieved by processes for the production of lost molds from a molding material mixture of sand or other molding raw materials and by gassing with carbon dioxide-curable binders based on alkali silicates and 0.3-3 percent by weight of phenolic or furan resins, and optionally additives known per se, such as silanes, polyhydric alcohols and polysaccharides, the molding material mixture being introduced into molds and hardened, characterized in that the phenolic or furan resin has 0.1-1.5 percent by weight of a dry substance and the alkali silicate is 2-5 percent by weight.
Es ist bekannt, die Festigkeit von Formkörpern zu verbessern, indem man dem Formgrundstoff vor der Zugabe des wasserglashaltigen Bindemittels ein Kondensationsharz beimischt.It is known to improve the strength of moldings by adding a condensation resin to the base material before adding the water glass-containing binder.
Überraschenderweise wurde nun gefunden, daß man sowohl eine höhere Festigkeit als auch eine bessere Lagerfähigkeit der Formkörper erhält, wenn dem Kondensationsharz eine geringe Menge eines Trockenstoffes zugefügt wird. Die Zugabe des Trockenstoffs bewirkt den weiteren, nicht vorhersehbaren Effekt, daß der Zerfall der Formkörper nach dem Abgießen, speziell bei hohen Temperaturen, wesentlich verbessert wird. Eine weitere Steigerung der Festigkeit der Formkörper wird erreicht, indem man dem Wasserglas Zusätze von Lithiumhydroxid oder einem Erdalkalimetallhydroxid beifügt. Dadurch wird die Feuchtigkeitsaufnahme der Formkörper sehr stark herabgesetzt, so daß auch die hohen Festigkeitswerte nach mehreren Wochen Lagerung nicht abfallen.Surprisingly, it has now been found that both a higher strength and a better shelf life of the moldings are obtained if a small amount of a dry substance is added to the condensation resin. The addition of the drying agent has the further, unforeseeable effect that the disintegration of the shaped bodies after casting, especially at high temperatures, is significantly improved. A further increase in the strength of the moldings is achieved by adding lithium hydroxide or an alkaline earth metal hydroxide to the water glass. As a result, the moisture absorption of the moldings is reduced considerably, so that even the high strength values do not drop after several weeks of storage.
Damit werden auf einfache Weise durch Zusetzen geringer Mengen nicht toxischer Stoffe zu den Bindemitteln die Nachteile eines eingeführten Verfahrens überwunden. Dies hat den weiteren Vorteil, daß der Formenhersteller, der bislang nach dem CO2-Verfahren gearbeitet hat, weder umzulernen, noch einen Verfahrensschritt umzuändern braucht, und daß für die Einführung des neuen Verfahrens keine neuen Investitionen notwendig sind.The disadvantages of an established method are thus overcome in a simple manner by adding small amounts of non-toxic substances to the binders. This has the further advantage that the mold manufacturer, who has previously worked according to the CO2 process, does not have to relearn or change a process step, and that no new investments are necessary to introduce the new process.
Als Formgrundstoff wird bevorzugt Quarzsand verwendet. Es lassen sich jedoch auch die anderen gebräuchlichen Formstoffe einzetzen, wie Chromit-, Zirkon- oder Olivinsand, Schamotte, Magnesit, Sillimanit oder Korund.Quartz sand is preferably used as the basic molding material. However, it is also possible to use the other conventional molding materials, such as chromite, zircon or olivine sand, chamotte, magnesite, sillimanite or corundum.
Als Kondensationsharze werden bevorzugt Phenol- oder Furanharze verwendet. Dabei zählt man zu den Furanharzen sowohl die Furfurylalkohol-Formaldehyd-Kondensate wie auch die verschiedenen modifizierten Furanharze, wie z. B. Furfurylalkohol-Harnstoff-Formaldehyd-Kondensate, Furfurylalkohol-Phenol-Formaldehyd-Kondensate oder Furfurylalkohol-Keton-Formaldehyd-Kondensate, die ihrerseits mit weiteren harzartigen Stoffen modifiziert sein können. Dem Kondensationsharz werden 0,1-1,5 Gew.-% eines Trockenstoffes zugegeben. Desgleichen werden mitunter geringe Mengen (0,1-0,5 %) eines Aminosilans zugefügt.Phenolic or furan resins are preferably used as condensation resins. One counts the furan resins both the furfuryl alcohol-formaldehyde condensates and the various modified furan resins, such as. B. furfuryl alcohol-urea-formaldehyde condensates, furfuryl alcohol-phenol-formaldehyde condensates or furfuryl alcohol-ketone-formaldehyde condensates, which in turn can be modified with other resinous substances. 0.1-1.5% by weight of a dry substance is added to the condensation resin. Likewise, small amounts (0.1-0.5%) of an aminosilane are sometimes added.
Unter Trockenstoff versteht man nach DIN 55901 in organischen Lösungsmitteln lösliche Metallseifen, wobei als Metalle vornehmlich, Co, Mn u. Pb in Betracht kommen, während als organische Komponente meist Carbonsäurereste vorhanden sind, wie z. B. Naphthenate, Octoate, Linoleate, Resinate oder Caprylate. Diese Trockenstoffe übertragen den Luftsauerstoff durch fortwährende Regenerierung, so daß man lediglich geringe Mengen dieser Stoffe braucht.According to DIN 55901, dry matter is understood to mean metal soaps soluble in organic solvents, the main metals being Co, Mn and. Pb come into consideration, while as the organic component mostly carboxylic acid residues are present, such as. As naphthenates, octoates, linoleates, resinates or caprylates. These dry substances transfer the atmospheric oxygen through continuous regeneration, so that only small amounts of these substances are needed.
Dieses Bindemittel wird mit dem Formgrundstoff gründlich gemischt. Sodann werden 2-5 Gew.-% Alkalisilikat als 2. Bindemittelkomponente zugegeben und gemischt.This binder is mixed thoroughly with the basic molding material. Then 2-5% by weight of alkali silicate is added as the second binder component and mixed.
Als Alkalisilikat dient eine wäßrige Lösung von Natrium- oder Kaliumsilikat, die unter der Bezeichnung Wasserglas im Handel ist und in der gegebenenfalls 0,2-3 Gew.-% Lithiumhydroxid oder eines Hydroxids eines Erdalkalimetalls gelöst wurden. Dieser Lösung können zusätzlich noch als zerfallsfördernde Zusätze bekannte Stoffe wie Glyzerin, Stärke, Zuckerderivate oder Cellulose beigegeben werden.An alkali silicate is an aqueous solution of sodium or potassium silicate which is commercially available under the name of water glass and in which 0.2-3% by weight of lithium hydroxide or a hydroxide of an alkaline earth metal have been dissolved. This solution can additionally be admixed with substances known to promote disintegration, such as glycerin, starch, sugar derivatives or cellulose.
Die durch gründliches Mischen des Formgrundstoffes mit den beiden Bindemittelkomponenten hergestellte Mischung wird in Formen eingebracht und durch Begasen mit Kohlendioxid gehärtet. Im Gegensatz zu den bislang nach dem CO2-Verfahren gehärteten Formen, deren Festigkeit bereits nach mehrtätiger Lagerung beträchtlich abnimmt, nimmt die Festigkeit der nach dem erfindungsgemäßen Verfahren hergestellten Formkörper im Laufe der Lagerzeit zu. Trotzdem aber ist der Zerfall nach dem Abguß wesentlich verbessert.The mixture produced by thoroughly mixing the basic molding material with the two binder components is introduced into molds and hardened by gassing with carbon dioxide. In contrast to the forms hitherto hardened by the CO2 process, the strength of which already decreases considerably after storage for several days, the strength of the shaped articles produced by the process according to the invention increases over the course of the storage time. Nevertheless, the decay after the casting is significantly improved.
Die folgenden Beispiele, in denen Bindemittel verschiedener Zusammensetzung sowie die Eigenschaften der damit hergestellten Formkörper aufgeführt sind, dienen der Erläuterung der Erfindung :The following examples, in which binders of different compositions and the properties of the moldings produced therewith are listed, serve to illustrate the invention:
Bindemittel bestehend aus :
Bindemittel bestehend aus :
Bindemittel bestehend aus :
Bindemittel bestehend aus :
- Komponente 1 : 49,8 Gew.-Teile Furanharz
0,2 Gew.-Teile eines Gemisches aus Metallnaphthenaten (Co 1,5 - Pb 22 - Mn 1,5) wie z. B. Siccatol-Mischtrockner - Komponente II : 50,0 Gew.-Teile Na-Silicat aus Beispiel 1
- Component 1: 49.8 parts by weight of furan resin
0.2 parts by weight of a mixture of metal naphthenates (Co 1.5 - Pb 22 - Mn 1, 5 ) such as. B. Siccatol mixer dryer - Component II: 50.0 parts by weight of Na silicate from Example 1
Bindemittel bestehend aus :
Bindemittel der Zusammensetzung wie in Beispiel 5 aufgeführt; in der Komponente II wurde jedoch das Lithiumhydroxid durch Bariumhydroxid ersetzt.Binder of the composition as listed in Example 5; in component II, however, the lithium hydroxide was replaced by barium hydroxide.
Bindemittel der Zusammensetzung wie in Beispiel 5 aufgeführt ; in der Komponente I wurde jedoch das Gemisch aus Naphthenaten durch ein reines Kobaltoctoat (z. B. Octa-Solingen-Kobalt) ersetzt.Binder of the composition as listed in Example 5; in component I, however, the mixture of naphthenates was replaced by a pure cobalt octoate (e.g. octa-solingen cobalt).
Mit den Bindemitteln der Vergleichsbeispiele 1-3 und der Erfindungsbeispiele 4-7 wurden Formstoffmischungen hergestellt. Es wurden 3 beziehungsweise 4 Gewichtsteile Bindemittel auf 100 Gewichtsteile Quarzsand (z. B. AFS 55) eingesetzt. Im Falle der Beispiele 2-7 wurde der Sand erst 2 min. mit der Komponente I und anschließend mit der Komponente 11 gemischt. Aus den Mischungen wurden zylindrische Prüfkörper (50 x 50 mm) gerammt. Die Kerne wurden durch Begasen mit C02 während 6-10 s vorgehärtet. Gemessen wurde die Scherfestigkeit nach 10 min. sowie 1, 5, 24, 48 und 72 Std., die Feuchtigkeitsaufnahme nach 8 Wochen und der Zerfall bei 500 und 1 000 °C.Molding material mixtures were produced with the binders of Comparative Examples 1-3 and Inventive Examples 4-7. 3 or 4 parts by weight of binder were used per 100 parts by weight of quartz sand (e.g. AFS 55). In the case of Examples 2-7, the sand was only 2 min. mixed with component I and then with component 11. Cylindrical test specimens (50 x 50 mm) were rammed from the mixtures. The cores were precured by gassing with CO 2 for 6-10 s. The shear strength was measured after 10 min. as well as 1, 5, 24, 48 and 72 hours, moisture absorption after 8 weeks and decay at 500 and 1000 ° C.
Die erhaltenen Ergebnisse sind in der folgenden Tabelle zusammengefaßt.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803002113 DE3002113A1 (en) | 1980-01-22 | 1980-01-22 | METHOD FOR PRODUCING LOST FORMS |
| DE3002113 | 1980-01-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0032596A1 EP0032596A1 (en) | 1981-07-29 |
| EP0032596B1 true EP0032596B1 (en) | 1983-02-16 |
Family
ID=6092618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80200997A Expired EP0032596B1 (en) | 1980-01-22 | 1980-10-21 | Process for producing lost moulds |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0032596B1 (en) |
| DE (2) | DE3002113A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2814357A1 (en) * | 1977-04-04 | 1978-10-19 | Hitachi Ltd | BINDERS FOR MOLDS |
| DE2842114A1 (en) * | 1977-09-28 | 1979-03-29 | Hitachi Ltd | MOLD BINDERS |
| DE2733874B2 (en) * | 1976-07-28 | 1979-06-13 | Hitachi, Ltd, Tokio | Self-hardening water-decomposing form and process for its manufacture |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1302716B (en) * | 1963-03-20 | 1970-10-22 |
-
1980
- 1980-01-22 DE DE19803002113 patent/DE3002113A1/en not_active Withdrawn
- 1980-10-21 DE DE8080200997T patent/DE3062062D1/en not_active Expired
- 1980-10-21 EP EP80200997A patent/EP0032596B1/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2733874B2 (en) * | 1976-07-28 | 1979-06-13 | Hitachi, Ltd, Tokio | Self-hardening water-decomposing form and process for its manufacture |
| DE2814357A1 (en) * | 1977-04-04 | 1978-10-19 | Hitachi Ltd | BINDERS FOR MOLDS |
| DE2842114A1 (en) * | 1977-09-28 | 1979-03-29 | Hitachi Ltd | MOLD BINDERS |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0032596A1 (en) | 1981-07-29 |
| DE3062062D1 (en) | 1983-03-24 |
| DE3002113A1 (en) | 1981-07-30 |
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| 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 |
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