EP3551360A1 - Alkaline resol binders having improved flowability - Google Patents

Alkaline resol binders having improved flowability

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Publication number
EP3551360A1
EP3551360A1 EP17811304.9A EP17811304A EP3551360A1 EP 3551360 A1 EP3551360 A1 EP 3551360A1 EP 17811304 A EP17811304 A EP 17811304A EP 3551360 A1 EP3551360 A1 EP 3551360A1
Authority
EP
European Patent Office
Prior art keywords
molding material
material mixture
mixture according
sugar
mold
Prior art date
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Granted
Application number
EP17811304.9A
Other languages
German (de)
French (fr)
Other versions
EP3551360B1 (en
Inventor
Frank Lenzen
Christian Priebe
Melanie Mertscheit
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ASK Chemicals GmbH
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ASK Chemicals GmbH
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Publication date
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Publication of EP3551360A1 publication Critical patent/EP3551360A1/en
Application granted granted Critical
Publication of EP3551360B1 publication Critical patent/EP3551360B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
    • B22C1/10—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for influencing the hardening tendency of the mould material
    • 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
    • B22C1/162—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 use of a gaseous treating agent for hardening the binder
    • 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
    • B22C1/2246—Condensation polymers of aldehydes and ketones
    • B22C1/2253—Condensation polymers of aldehydes and ketones with phenols

Definitions

  • the invention relates to molding material mixtures for the production of molds, cores or feeders for metal casting comprising at least one refractory molding material, a binder based on an alkaline resole resin and at least one sugar surfactant. Furthermore, the invention relates to a process for the production of molds and cores using the molding material mixtures as well as molds, cores and feeders produced by this process.
  • Molds are essentially composed of molds and molds and cores, which represent the negative mold of the casting to be produced.
  • These forms and cores usually consist of a refractory base molding material, such as quartz sand, and a suitable binder, which gives the mold after removal from the mold sufficient mechanical strength.
  • the refractory molding base material is preferably in free-flowing form, so that it can be filled into a suitable mold after mixing with the binder, compacted and then cured. After curing, the binder provides for a firm cohesion between the particles of the molding base material, so that the casting mold obtains the required mechanical stability.
  • Molds form the outer wall of the casting during casting, cores are used to form cavities within the casting. It is not absolutely necessary that the forms and cores are made of the same material. For example, in die casting, the outer shape of the cast pieces is carried out using metallic permanent molds. Also possible is a combination of molds and cores made from differently blended molding compounds and by different processes. Feeders are voids in the mold, which are filled with liquid metal during casting together with the casting. The feeder keeps the metal in it liquid for a longer time and can thus compensate for a volume deficit in the solidification phase of the casting. If, in simplification terms, only kernels are discussed below, the statements apply to the same extent to molds and feeders based on the same molding material mixture and produced by the same process.
  • organic, inorganic and mixed organic / inorganic binder can be used, the curing of which can be done by cold or hot process.
  • Cold processes are those processes which are carried out essentially without heating the mold used for core production, generally at room temperature or at a temperature caused by a possible reaction.
  • the curing takes place, for example, in that a gas is passed through the molding mixture to be cured and thereby initiates a chemical reaction.
  • hot processes the molding material mixture is heated to a sufficiently high temperature after molding, for example by the heated mold, to expel the solvent contained in the binder and / or to initiate a chemical reaction by which the binder is cured.
  • alkaline phenolic resins as binders for molds is known per se and these are disclosed for example in EP 0323096 B2 and in EP 1228128 B1. These are alkaline resole resins that can be cured by introducing CO2.
  • Essential constituents of the binders described in said patents are oxyanions, e.g. the borate ion (EP 032096 B2) or the combination of borate and aluminate ion (EP 1228128 B1).
  • US 5376696 and WO 92/01016 A1 describe sand mixtures for ester-curing alkaline resole resins in which a surfactant solution for improving the flowability is added to the sand mixture.
  • EP 0399636 A2 describes ester-curing alkaline resole resins containing a fluorosurfactant, which may have an anionic, cationic, amphoteric or nonionic character. It improves the flowability of the molding material mixture.
  • sugar surfactants markedly improves the flowability of mixtures of alkaline resole resin and refractory molding base materials. This is surprising insofar as the surface tension of an alkaline resole resin is only insignificantly reduced by a sugar surfactant.
  • the sugar surfactant used according to the invention is either contained in the alkaline resole resin component or it is fed as pure or diluted second component directly to the molding material mixture before or during mixing.
  • the molding material mixture according to the invention thus comprises at least a) a refractory molding base material;
  • a sugar surfactant which may also be added as a sugar surfactant solution.
  • the invention relates to a method for producing a core comprising the following steps:
  • Molding material for obtaining a molding material mixture
  • the binder is alkaline Resolharze.
  • the resols are prepared by condensation of phenolic compounds and aldehyde compounds in the presence of a basic catalyst such as ammonium hydroxide or an alkali metal hydroxide. Preference is given to using alkali metal hydroxide catalysts.
  • the resoles are used in a concentration of about 0.8% by weight to about 10% by weight, preferably from about 1% by weight to about 5% by weight and more preferably from about 1% by weight to about 4% by weight, based in each case on the solids content of the resol (according to DIN EN ISO 3251) and the molding base material.
  • concentration of binder within the casting mold can vary.
  • Resoles in the sense of the present invention are aromatics which are linked to one another via methylene groups (-CH 2 -) groups and / or via ether bridges (especially -CH 2 -O-CH 2 -) and which each carry at least one -OH group (phenol compound).
  • Suitable phenol compounds are phenols, substituted phenols, such as, for example, cresols or nonylphenol, 1,2-dihydroxybenzene (pyrocatechol), 1,3-dihydroxybenzene (resorcinol), cashew nut shell oil, ie a mixture of caranol and cardol, or 1,4 Dihydroxybenzene (hydroquinone) or phenolic compounds such as bisphenol A.
  • aldehyde compounds examples include formaldehyde, paraformaldehyde and glyoxal and mixtures thereof. Particularly preferred is formaldehyde or mixtures containing predominantly formaldehyde (based on the molar amount of aldehydes).
  • the molar ratio of phenolic compound to aldehyde compound may vary in the range of 1.05: 1 to 1.05: 3, but is preferably between 1.05: 1.2 to 1.05: 2.6, more preferred between 1, 1: 1, 3 to 1, 1: 2.5.
  • resoles in which adjacent hydroxy aromatics are each linked to ortho and / or para (relative to the hydroxyl group of the incorporated phenol / aromatics) via the methylene bridges and / or the ether bridges, i. the majority of links are para and / or ortho.
  • Suitable oxyanions in the binder composition for the ReSO.sub.2 / CO2 process include borate, stannate and aluminate ions. Aluminate and borate ions are preferred.
  • the oxyanion may be used in the binder composition for the resole / CO2 process by the admixture of sodium tetraborate times x H2O, potassium tetraborate times x H2O, sodium metaborate, sodium pentaborate, sodium stannate trihydrate, sodium aluminate, potassium aluminate, aluminum hydroxide, alumina or ammonium oxyanion salt such as Ammonium borate be inserted. Borations can also be introduced by adding boric acid or boron oxide.
  • the molar ratio of the oxyanions (expressed as boron and / or aluminum and / or tin) to phenol group is preferably in the range of 0.1: 1 to 1: 1.
  • the molar ratio of boron to phenol is more preferably in the range 0.1: 1 to 0.5: 1.
  • organic aluminum, boron or tin compounds can also by introducing organic boron, aluminum and tin compounds such as aluminum alcoholates of the formula AI (OR) 3, wherein R can be independently a saturated or unsaturated, branched or unbranched hydrocarbon radical having 1 to 10 carbon atoms.
  • a solution of a boron compound such as boric acid or boric acid ester in brine is suitable as a solution of boron-containing oxyanion.
  • the solution used is a solution of a base in water, which is also used for mixing with the resole resin.
  • both organic bases e.g. Amines or ammonium compounds as well as inorganic bases such as e.g. Alkali metal hydroxides
  • alkali hydroxides e.g. Sodium hydroxide and potassium hydroxide used.
  • the molar ratio of hydroxide ions to the phenol group in the binder system is preferably 0.5: 1 to 3: 1, preferably 1, 0: 1 to 2.5: 1. It is not necessary that the entire amount of base is added already at the beginning of the condensation; Usually, the addition takes place in two or more substeps, wherein a part can be added only at the end of the manufacturing process. Mixtures of basic catalysts can also be used.
  • alkaline resoles The preparation of alkaline resoles is e.g. in EP 0323096 B2 and EP 1228128 B1. Further resol-based binders are described, for example, in US Pat. No. 4,426,467 and US Pat. No. 4,474,904.
  • the resole contains water, preferably in an amount of 15% by weight to 50% by weight, based on the binder.
  • water In the final part of the binder are resole, water, alkalis and oxyanion.
  • the water may originate from aqueous solutions which are used in binder preparation, but on the other hand it may also be added separately to the binder or be obtained as condensation water from the resol condensation.
  • water also serves, for example, to impart to the binder an application-specific viscosity (25 ° C.) of from 5 to 1200 mPas, preferably from 10 to 1100 mPas and particularly preferably from 10 to 950 mPas.
  • the viscosity is determined using a Brookfield Rotational Viscometer, Small Sample Method, Spindle No. 21 at 100 rpm and 25 ° C.
  • the alkaline resole preferably has a pH (at 25 ° C.) greater than 12.
  • the binder may contain up to about 50% by weight of additives such as e.g. Alcohols, glycols, and silanes may be added.
  • additives such as e.g. Alcohols, glycols, and silanes
  • the wettability of the molding material by the binder and its adhesion to the molding material can be increased, which in turn can lead to improved strength and increased moisture resistance.
  • silanes e.g. gamma-aminopropyltriethoxysilane or gamma-glycidoxypropyltrimethoxysilane
  • concentrations of from about 0.1 weight percent to about 4.0 weight percent, preferably from about 0.2 weight percent to about 3.0 weight percent, and especially preferably from about 0.3% by weight to about 2.5% by weight, in each case based on the weight of the molding composition.
  • esters suitable for curing the resols are known to those skilled in the art, e.g. from US 4426467, US 4474904 and US 5405881. They include lactones, organic carbonates and esters of C1 to C10 mono- and polycarboxylic acids with C1 to C10 mono- and polyalcohols. Preferred but non-limiting examples of these compounds are gamma-butyrolactone, propylene carbonate, ethylene glycol diacetate, mono-, di- and triacetin, and the dimethyl esters of succinic acid, glutaric acid and adipic acid including their known under the name DBE mixture. Due to different saponification rates of the individual esters, the curing speed of the sole runs at different rates depending on the ester used, which can also influence the strengths. By mixing two or more esters, the desired cure time can be varied within wide limits.
  • sugar surfactants are nonionic surfactants in which sugars form the hydrophilic portion of the surfactant molecule.
  • the hydrophobic component is fatty alcohol or fatty acid residues.
  • Carbohydrates used are, for example, glucose, methyl glucose, fructose, methyl fructose, lactose, ribose, sucrose, xylenose, xylitol, mannose, mannitol, isosorbitol and sorbitol.
  • the sugar building blocks can be used as monomer or up to a degree of polymerization of 30.
  • the sugar units alpha or beta 1, 4 may be glycosidically linked.
  • the hydrophilic portion is formed by linking glucose, sucrose, fructose, isosorbitol and / or sorbitol, particular preference is given to sucrose and / or glucose.
  • Fatty acids can be esterified to the free hydroxyl groups or fatty alcohols, and / or fatty alcohol ethoxylates, fatty alcohol propoxylates and / or fatty alcohol ethoxylates / fatty alcohol propoxylates can be etherified, the chain length is between C6 and C32, in particular Cs and C22, and can be branched or straight-chain and saturated or be unsaturated. Both the sugar and the fat components can be mixed with each other. Preference is given to using alkylpolyglycosides (APG), in particular alkylpolyglucosides, which have the following exemplary structure.
  • APG alkylpolyglycosides
  • n is on average from 1 to 30, preferably on average from 2 to 25 and particularly preferably on average from 2 to 10.
  • n is a saturated or unsaturated, straight-chain or branched alkyl radical of on average 5 to 31 carbon atoms and particularly preferably of 7 to 21 carbon atoms.
  • Alkylpolyglycosides are industrially produced and marketed by BASF under the trade names Plantacare or Glucopon.
  • the sugar surfactants according to the invention are preferably added to the resole resin in a concentration of 0.05 to 5.0% by weight. Preferably in a range from 0.05 to 3.0% by weight, and more preferably from 0.05 to 2.0% by weight, relative to the binder.
  • the sugar surfactants according to the invention can be added directly to the molding material mixture. This can be done as pure substance or dissolved in a carrier medium (eg water). Based on the finished molding mixture 0.005 to 0.5 wt.%, Preferably 0.01 to 0.3 wt.% Sugar surfactant is added.
  • the sugar surfactants used preferably have an HLB value between 1 1 and 16 (HLB stands for English, hydrophilic-lipophilic balance).
  • molding base material materials customary for the production of casting molds can be used.
  • quartz sand, zircon sand or chrome ore sand, olivine, vermiculite, bauxite and chamotte or mixtures thereof are suitable. If there are no technological reasons, quartz sand is preferred for economic reasons. It is not necessary to use only new sands. In terms of resource conservation and to avoid landfill costs, it is even advantageous to use the highest possible proportion of regenerated used sand. Particularly suitable are regenerates, which are obtained by washing and subsequent drying. It is also possible to use regenerates obtained by thermo-mechanical or purely mechanical treatment.
  • the average diameter of the molding materials is usually between 100 ⁇ and 600 ⁇ , preferably between 120 ⁇ and 550 ⁇ and more preferably between 150 ⁇ and 500 ⁇ .
  • the particle size can be e.g. by sieving in accordance with DIN ISO 3310.
  • synthetic molding materials can also be used as mold base materials, in particular as an additive to the above molding base materials, but also as exclusive molding base material, for example glass beads, glass granules, the spherical ceramic molding bases or aluminum silicate microbeads known under the name “Cerabeads” or “Carboaccucast” (US Pat. so-called microspheres).
  • Such aluminosilicate hollow microspheres are marketed, for example, by Omega Minerals Germany GmbH, Norderstedt, under the name “Omega Spheres.”
  • Corresponding products are also available from PQ Corporation (USA) under the name “Extendospheres”.
  • amorphous silicon dioxide to the molding base material.
  • an increase in strength is achieved.
  • This is i.a. disclosed in DE 102014106178.
  • the procedure is such that the refractory molding base material is initially charged and then the binder and the sugar surfactant are added together or successively with stirring.
  • the molding material mixture is then brought into the desired shape.
  • customary methods are used for the shaping.
  • the molding material mixture can be shot by means of a core shooter with the aid of compressed air into the tool.
  • Another possibility is to free-flow the molding material mixture from the mixer into the mold and to compact it there by shaking, stamping or pressing.
  • Preferred core manufacturing process is the Resol / CO2 process.
  • this does not preclude sparing with lower alkyl esters known under the name of Betaset, such as C1 to C3 alkyl formates, especially methyl formate, and liquid ester curing, known by the name Alphaset method.
  • Curing takes place in that the CO2, a CO2 / gas mixture (eg with air), a gas mixture (eg air) or gaseous methyl formate (Betaset method) successively (as described in detail in DE 102012103705.1) by the mold or by the molding material mixture contained therein is passed.
  • the gas stream has a temperature between 0 ° C to 140 ° C, preferably from 5 ° C to 120 ° C and more preferably from 6 ° C to 1 10 ° C.
  • Oleic acid technical oleic acid
  • Capstone FS 35 25% aqueous solution of a nonionic fluorosurfactant, manufacturer: Chemour
  • Plantacare 2000 UP 50% aqueous alkyl polyglucoside solution with C8-C16 fatty alcohol chains, manufacturer: BASF SE
  • Table 1 shows the surface tensions found (in mN / mm) at room temperature, which were obtained by adding the surfactants. If one considers the surface tension (comparison of the same amount of active substance, identification with " * "), it is surprisingly found that the APG type sugar surfactants according to the invention reduce the surface tension by only 2% (zero example to B2).
  • the oleic acid reduces the surface tension by 10% (zero example to A1), according to EP 0399 636 even a reduction by 27% is achieved (zero example to A8).
  • the reference water was 68.8 mN / mm. Determination of strength in N / cm 2 - Resol CO2 method
  • a sand mixture of quartz sand H 32, plus 3.0% NOVANOL 165 was homogeneously mixed for 2 minutes.
  • This sand mixture was transferred to a core shooter, model Laempe L 1 (opening at the sand outlet of the shooting head reduced to 5mm) and placed in a four core box (GF bar 220mm x 22.4mm x 22.4mm) with a shooting pressure of 2 bar by means of compressed air and a shooting time of 1 sec brought into the mold.
  • CO2 gas 2 liters / min for 30 sec
  • the flexural strengths were broken by means of a Biegeprüfös Fa. Multiserw after the specified time (average values of four determinations).
  • a sand mixture of quartz sand H 31, plus 2.3% AVENOL F 633 was mixed homogeneously for 2 minutes.
  • This sand mixture was transferred to a core shooter, Model Roeper H 1 (opening at the sand outlet of the shooting head 10 mm) and was placed in a two core box (GF bar 220mm x 22.4mm x 22.4 mm) with a shooting pressure of 3 bar by means of compressed air and a shooting time of 1 sec brought into the mold.
  • the sand was hardened by means of 60 ° C. warm methyl formate gas (2.0 ml liquid methyl formate, for 20 sec, 2 bar rinsing pressure).
  • the flexural strengths were determined by means of a Biegeprüfauss Fa. Multiserw after the specified time (average values of four determinations).
  • Plantacare 2000 UP the highest strengths in N / cm 2 and the highest packing density (indicated by the core weight) were achieved.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mold Materials And Core Materials (AREA)

Abstract

The invention relates to molding material mixtures for producing molds, risers or cores for metal casting, comprising at least one refractory basic molding material, a binder on the basis of an alkaline resol resin and at least one sugar surfactant. The invention also relates to a method for producing molds and cores using the molding material mixtures and to molds, risers or cores produced according to said method.

Description

Alkalische Resolbinder mit verbesserter Fließfähigkeit  Alkaline Resolbinder with improved flowability
Einleitung Die Erfindung betrifft Formstoffmischungen zur Herstellung von Formen, Kernen oder Speisern für den Metallguss umfassend mindestens einen feuerfesten Formgrundstoff, ein Bindemittel auf der Basis eines alkalischen Resolharzes und mindestens ein Zuckertensid. Weiterhin betrifft die Erfindung ein Verfahren zur Herstellung von Formen und Kernen unter Verwendung der Formstoffmischungen sowie nach diesem Verfahren hergestellte Formen, Kerne und Speiser. The invention relates to molding material mixtures for the production of molds, cores or feeders for metal casting comprising at least one refractory molding material, a binder based on an alkaline resole resin and at least one sugar surfactant. Furthermore, the invention relates to a process for the production of molds and cores using the molding material mixtures as well as molds, cores and feeders produced by this process.
Hintergrund der Erfindung Background of the invention
Gießformen setzen sich im Wesentlichen aus Formen oder Formen und Kernen zusammen, welche die Negativform des herzustellenden Gussstücks darstellen. Diese Formen und Kerne bestehen dabei in der Regel aus einem feuerfesten Formgrundstoff, beispielsweise Quarzsand, und einem geeigneten Bindemittel, das der Gießform nach der Entnahme aus dem Formwerkzeug eine ausreichende mechanische Festigkeit verleiht. Der feuerfeste Formgrundstoff liegt bevorzugt in rieselfähiger Form vor, so dass er nach dem Mischen mit dem Bindemittel in eine geeignete Hohlform eingefüllt, verdichtet und danach ausgehärtet werden kann. Nach dem Aushärten sorgt das Bindemittel für einen festen Zusammenhalt zwischen den Partikeln des Formgrundstoffs, so dass die Gießform die erforderliche mechanische Stabilität erhält. Molds are essentially composed of molds and molds and cores, which represent the negative mold of the casting to be produced. These forms and cores usually consist of a refractory base molding material, such as quartz sand, and a suitable binder, which gives the mold after removal from the mold sufficient mechanical strength. The refractory molding base material is preferably in free-flowing form, so that it can be filled into a suitable mold after mixing with the binder, compacted and then cured. After curing, the binder provides for a firm cohesion between the particles of the molding base material, so that the casting mold obtains the required mechanical stability.
Formen bilden beim Gießen die äußere Wandung für das Gussstück, Kerne werden zur Ausbildung von Hohlräumen innerhalb des Gussstücks eingesetzt. Dabei ist es nicht zwingend notwendig, dass Formen und Kerne aus demselben Material bestehen. So erfolgt z.B. beim Kokillenguss die äußere Formgebung der Gussstü- cke mit Hilfe metallischer Dauerformen. Auch ist eine Kombination von Formen und Kernen, die aus unterschiedlich zusammengesetzten Formstoffmischungen und nach unterschiedlichen Verfahren hergestellt wurden, möglich. Speiser sind Hohlräume in der Gießform, die beim Gießen gemeinsam mit dem Gussstück mit flüssigem Metall gefüllt werden. Der Speiser hält das in ihm befindliche Metall län- ger flüssig und kann somit ein Volumendefizit in der Erstarrungsphase des Gussstücks ausgleichen. Wenn nachstehend vereinfachend nur von Kernen gesprochen wird, gelten die Aussagen in gleichem Maße auch für Formen und Speiser, die auf einer gleichen Formstoffmischung basieren und nach demselben Verfahren hergestellt wurden. Zur Herstellung von Kernen können organische, anorganische und gemischt organisch/anorganische Bindemittel (Hybridsysteme) eingesetzt werden, deren Aushärtung jeweils durch kalte oder heiße Verfahren erfolgen kann. Als kalte Verfahren bezeichnet man dabei solche Verfahren, welche im Wesentlichen ohne Erhitzen des zur Kernherstellung verwendeten Formwerkzeugs durchgeführt werden, i.d.R. bei Raumtemperatur oder bei einer durch eine etwaige Reaktion verursachten Temperatur. Die Aushärtung erfolgt beispielsweise dadurch, dass ein Gas durch die zu härtende Formstoffmischung geleitet wird und dabei eine chemische Reaktion auslöst. Bei heißen Verfahren wird die Formstoffmischung nach der Formgebung z.B. durch das erwärmte Formwerkzeug auf eine ausreichend hohe Temperatur erhitzt, um das im Bindemittel enthaltene Lösemittel auszutreiben und/oder um eine chemische Reaktion zu initiieren, durch welche das Bindemittel ausgehärtet wird. Molds form the outer wall of the casting during casting, cores are used to form cavities within the casting. It is not absolutely necessary that the forms and cores are made of the same material. For example, in die casting, the outer shape of the cast pieces is carried out using metallic permanent molds. Also possible is a combination of molds and cores made from differently blended molding compounds and by different processes. Feeders are voids in the mold, which are filled with liquid metal during casting together with the casting. The feeder keeps the metal in it liquid for a longer time and can thus compensate for a volume deficit in the solidification phase of the casting. If, in simplification terms, only kernels are discussed below, the statements apply to the same extent to molds and feeders based on the same molding material mixture and produced by the same process. For the production of cores organic, inorganic and mixed organic / inorganic binder (hybrid systems) can be used, the curing of which can be done by cold or hot process. Cold processes are those processes which are carried out essentially without heating the mold used for core production, generally at room temperature or at a temperature caused by a possible reaction. The curing takes place, for example, in that a gas is passed through the molding mixture to be cured and thereby initiates a chemical reaction. In hot processes, the molding material mixture is heated to a sufficiently high temperature after molding, for example by the heated mold, to expel the solvent contained in the binder and / or to initiate a chemical reaction by which the binder is cured.
Die Verwendung alkalischer Phenolharze als Bindemittel für Gussformen ist an sich bekannt und diese sind beispielsweise in der EP 0323096 B2 und in der EP 1228128 B1 offenbart. Es handelt sich dabei um alkalische Resolharze, die sich durch Einleiten von CO2 aushärten lassen. Wesentliche Bestandteile der in den genannten Patenten beschriebenen Bindemittel sind Oxyanionen, z.B. das Borat- Ion (EP 032096 B2) bzw. die Kombination aus Borat- und Aluminat-Ion (EP 1228128 B1 ). The use of alkaline phenolic resins as binders for molds is known per se and these are disclosed for example in EP 0323096 B2 and in EP 1228128 B1. These are alkaline resole resins that can be cured by introducing CO2. Essential constituents of the binders described in said patents are oxyanions, e.g. the borate ion (EP 032096 B2) or the combination of borate and aluminate ion (EP 1228128 B1).
Aufgabe der Erfindung Object of the invention
Formstoffmischungen mit alkalischen Resolharzen weisen häufig eine schlechte Fließfähigkeit auf. Diese macht sich dadurch bemerkbar, dass feine Kernpartien unvollständig abgebildet werden, die Kerne nicht kompakt verdichtet sind und damit an Festigkeiten verlieren oder dass die Formstoffmischung im Schießkopf stockt und nicht weiterfließt. Im letzten Fall bildet sich dann ein Hohlraum aus und der Sand kann nur durch mechanisches Stopfen nachgedrückt werden. Es sind bereits verschiedene Vorschläge erfolgt, die sich diesem Problem annehmen. US 5077323 beschreibt esterhärtende alkalische Resolharze (= Alphaset Verfahren), deren Fließfähigkeit durch Zusatz von Fettsäuren, Fettalkoholen, Fettaminen, Fettsäureamiden oder Fettsäurealkanolamiden verbessert wird. US 5376696 bzw. die WO 92/01016 A1 beschreiben Sandmischungen für esterhärtende alkalische Resolharze, bei denen der Sandmischung eine Tensidlösung zur Verbesserung der Fließfähigkeit zugesetzt wird. EP 0399636 A2 beschreibt esterhärtende alkalische Resolharze, die ein Fluortensid enthalten, dieses kann einen anionischen, kationischen, amphoteren oder nichtionischen Charakter aufweisen. Es verbessert die Fließfähigkeit der Formstoffmischung. Form material blends with alkaline resole resins often have poor flowability. This manifests itself in the fact that fine core parts are incompletely imaged, the cores are not compressed compactly and thus lose strength or that the molding material mixture in the shooting head stops and does not continue to flow. In the latter case, then forms a cavity and the sand can be pressed only by mechanical plugging. There have already been several proposals to address this problem. No. 5,077,323 describes ester-hardening alkaline resole resins (= Alphaset method) whose flowability is improved by adding fatty acids, fatty alcohols, fatty amines, fatty acid amides or fatty acid alkanolamides. US 5376696 and WO 92/01016 A1 describe sand mixtures for ester-curing alkaline resole resins in which a surfactant solution for improving the flowability is added to the sand mixture. EP 0399636 A2 describes ester-curing alkaline resole resins containing a fluorosurfactant, which may have an anionic, cationic, amphoteric or nonionic character. It improves the flowability of the molding material mixture.
Es besteht aber weiter das Bedürfnis Formstoffmischungen enthaltend alkalische Resolharze dahingehend weiterzuentwickeln, dass sie eine verbesserte Fließfähigkeit aufweisen. Dadurch ließen sich auch Kerne mit komplexeren Geometrien herstellen bzw. bei massiven einfachen Kernen ließe sich der Bindergehalt absen- ken, was zum einen die Wirtschaftlichkeit des Verfahrens erhöhen und zum anderen die Menge der beim Guss auftretenden Emissionen reduzieren würde. Aufgabe der Erfindung ist es somit, die Fließfähigkeit des mit einem alkalischen Resol imprägnierten Formgrundstoffes zu verbessern. Zusammenfassung der Erfindung However, there is still a need to further develop molding material mixtures containing alkaline Resolharze that they have improved flowability. As a result, it would also be possible to produce cores of more complex geometries or, in the case of massive simple cores, the binder content could be lowered, which would increase the cost-effectiveness of the process and reduce the amount of emissions occurring during casting. The object of the invention is thus to improve the flowability of impregnated with an alkaline resole molding material. Summary of the invention
Diese Aufgabe wird durch Formstoffmischungen mit den Merkmalen des Anspruchs 1 gelöst. Vorteilhafte Weiterbildungen sind Gegenstand der abhängigen Patentansprüche und werden nachstehend beschrieben. This object is achieved by molding material mixtures with the features of claim 1. Advantageous developments are the subject of the dependent claims and are described below.
Überraschend wurde gefunden, dass ein Zusatz von Zuckertensiden die Fließfähigkeit von Gemischen aus alkalischen Resolharz und feuerfesten Formgrundstoffen deutlich verbessert. Dieses ist insofern überraschend als die Oberflächenspannung eines alkalischen Resolharzes nur unwesentlich von einem Zuckerten- sid herabgesetzt wird. Das erfindungsgemäß eingesetzte Zuckertensid ist entweder in der alkalischen Resolharz-Komponente enthalten oder es wird als zweite Komponente pur oder verdünnt direkt der Formstoffmischung vor oder während des Mischens zugeführt. Die erfindungsgemäße Formstoffmischung umfasst somit mindestens a) einen feuerfesten Formgrundstoff; Surprisingly, it has been found that addition of sugar surfactants markedly improves the flowability of mixtures of alkaline resole resin and refractory molding base materials. This is surprising insofar as the surface tension of an alkaline resole resin is only insignificantly reduced by a sugar surfactant. The sugar surfactant used according to the invention is either contained in the alkaline resole resin component or it is fed as pure or diluted second component directly to the molding material mixture before or during mixing. The molding material mixture according to the invention thus comprises at least a) a refractory molding base material;
b) ein alkalisches Resolharz als Bindemittel welches mittels CO2; Methyl- formiat (als Aerosol, gasförmig oder flüssig) oder einem anderen flüssi- gen (bei Raumtemperatur = 25°C) Ester härtbar ist; und  b) an alkaline resole resin as a binder which by means of CO2; Methyl formate (as an aerosol, gaseous or liquid) or another liquid (at room temperature = 25 ° C) ester curable; and
c) ein Zuckertensid, welches auch als Zuckertensidlösung zugegeben werden kann.  c) a sugar surfactant, which may also be added as a sugar surfactant solution.
Weiterhin betrifft die Erfindung ein Verfahren zur Herstellung eines Kerns umfas- send die folgenden Schritte: Furthermore, the invention relates to a method for producing a core comprising the following steps:
Vermischen von alkalischem Resolharz, Zuckertensid und feuerfestem Mixing of alkaline resole resin, sugar surfactant and refractory
Formgrundstoff zum Erhalt einer Formstoffmischung; Molding material for obtaining a molding material mixture;
Einbringen der Formstoffmischung in ein Formwerkzeug;  Introducing the molding material mixture into a molding tool;
Härten der Formstoffmischung mittels CO2; Methylform iat (als Aerosol, gas- förmig oder flüssig) oder einem anderen flüssigen Ester; und  Hardening of the molding material mixture by means of CO2; Methyl formate (as aerosol, gaseous or liquid) or other liquid ester; and
Entnahme des gehärteten Kerns, des Speisers oder der Form aus dem Removal of the hardened core, the feeder or the form from the
Formwerkzeug. Mold.
Detaillierte Beschreibung der Erfindung Detailed description of the invention
Das Bindemittel sind alkalische Resolharze. Die Resole werden durch Kondensation von Phenol-Verbindungen und Aldehyd-Verbindungen in Gegenwart eines basischen Katalysators, wie Ammoniumhydroxid oder eines Alkalimetallhydroxids, hergestellt. Bevorzugt werden Alkalimetallhydroxid-Katalysatoren verwendet. The binder is alkaline Resolharze. The resols are prepared by condensation of phenolic compounds and aldehyde compounds in the presence of a basic catalyst such as ammonium hydroxide or an alkali metal hydroxide. Preference is given to using alkali metal hydroxide catalysts.
Die Resole werden in einer Konzentration von ca. 0,8 Gew.% bis ca. 10 Gew.%, bevorzugt von ca. 1 Gew.% bis ca. 5 Gew.% und besonders bevorzugt von ca. 1 Gew.% bis ca. 4 Gew.% eingesetzt, jeweils bezogen auf den Feststoffgehalt des Resols (nach DIN EN ISO 3251 ) und den Formgrundstoff. Dabei kann die Kon- zentration an Bindemittel innerhalb der Gießform variieren. The resoles are used in a concentration of about 0.8% by weight to about 10% by weight, preferably from about 1% by weight to about 5% by weight and more preferably from about 1% by weight to about 4% by weight, based in each case on the solids content of the resol (according to DIN EN ISO 3251) and the molding base material. In this case, the concentration of binder within the casting mold can vary.
Resole im Sinn der vorliegenden Erfindung sind über Methylengruppen (-CH2-) Gruppen und/oder über Etherbrücken (insbesondere -CH2-O-CH2-) miteinander verbundene Aromaten, die jeweils zumindest eine -OH Gruppe tragen (Phenol-Verbindung). Geeignete Phenol-Verbindungen sind Phenole, substituierte Phenole, wie z.B. Kresole oder Nonylphenol, 1 ,2-Dihydroxybenzol (Brenzcatechin), 1 ,3- Dihydroxybenzol (Resorcin), Cashewnussschalenöl, d.h. eine Mischung aus Car- danol und Cardol, oder 1 ,4-Dihydroxybenzol (Hydrochinon) oder phenolische Ver- bindungen wie z.B. Bisphenol A. Resoles in the sense of the present invention are aromatics which are linked to one another via methylene groups (-CH 2 -) groups and / or via ether bridges (especially -CH 2 -O-CH 2 -) and which each carry at least one -OH group (phenol compound). Suitable phenol compounds are phenols, substituted phenols, such as, for example, cresols or nonylphenol, 1,2-dihydroxybenzene (pyrocatechol), 1,3-dihydroxybenzene (resorcinol), cashew nut shell oil, ie a mixture of caranol and cardol, or 1,4 Dihydroxybenzene (hydroquinone) or phenolic compounds such as bisphenol A.
Beispiele für geeignete Aldehyd-Verbindungen sind Formaldehyd, Paraformalde- hyd und Glyoxal und deren Mischungen. Besonders bevorzugt ist Formaldehyd oder Mischungen enthaltend überwiegend Formaldehyd (bezogen auf die molare Menge der Aldehyde). Examples of suitable aldehyde compounds are formaldehyde, paraformaldehyde and glyoxal and mixtures thereof. Particularly preferred is formaldehyde or mixtures containing predominantly formaldehyde (based on the molar amount of aldehydes).
Das molare Verhältnis von Phenol-Verbindung zu Aldehyd-Verbindung kann im Bereich von 1 ,05 : 1 bis 1 ,05 : 3 variieren, liegt aber bevorzugt zwischen 1 ,05 : 1 ,2 bis 1 ,05 : 2,6, besonders bevorzugt zwischen 1 ,1 :1 ,3 bis 1 ,1 : 2,5. The molar ratio of phenolic compound to aldehyde compound may vary in the range of 1.05: 1 to 1.05: 3, but is preferably between 1.05: 1.2 to 1.05: 2.6, more preferred between 1, 1: 1, 3 to 1, 1: 2.5.
Es sind solche Resole bevorzugt, in denen benachbarte Hydroxy-Aromaten jeweils an ortho- und/oder para- Position (relativ zur Hydroxy-Gruppe des eingebauten Phenols/Aromaten) über die Methylenbrücken und/oder die Etherbrücken verknüpft sind, d.h. die Mehrzahl der Verknüpfungen erfolgt para und/oder ortho. There are preferred those resoles in which adjacent hydroxy aromatics are each linked to ortho and / or para (relative to the hydroxyl group of the incorporated phenol / aromatics) via the methylene bridges and / or the ether bridges, i. the majority of links are para and / or ortho.
Beispiele geeigneter Oxyanionen in der Bindemittelzusammensetzung für das Re- S0I/CO2 Verfahren umfassen Borat-, Stannat- und Aluminiat- Ionen. Aluminat- und Borationen sind dabei bevorzugt. Das Oxyanion kann in der Bindemittelzusammensetzung für das Resol/CO2 Verfahren durch das Einmischen von Natriumtet- raborat mal x H2O, Kaliumtetraborat mal x H2O, Natriummetaborat, Natriumpen- taborat, Natriumstannat-Trihydrat, Natriumaluminat, Kaliumaluminat, Aluminiumhydroxid, Aluminiumoxid oder Ammonium Oxyanion Salz wie Ammoniumborat eingefügt werden. Borationen können auch durch Zugabe von Borsäure oder Boroxid eingebracht werden. Examples of suitable oxyanions in the binder composition for the ReSO.sub.2 / CO2 process include borate, stannate and aluminate ions. Aluminate and borate ions are preferred. The oxyanion may be used in the binder composition for the resole / CO2 process by the admixture of sodium tetraborate times x H2O, potassium tetraborate times x H2O, sodium metaborate, sodium pentaborate, sodium stannate trihydrate, sodium aluminate, potassium aluminate, aluminum hydroxide, alumina or ammonium oxyanion salt such as Ammonium borate be inserted. Borations can also be introduced by adding boric acid or boron oxide.
Das Molverhältnis der Oxyanionen (ausgedrückt als Bor und/oder Aluminium und/oder Zinn) zu Phenolgruppe ist vorzugsweise im Bereich von 0,1 : 1 bis 1 : 1 . Wenn das Oxyanion Borat ist liegt das Molverhältnis von Bor zu Phenol besonders bevorzugt im Bereich 0,1 : 1 bis 0,5 : 1 . Es ist auch möglich organische Aluminium-, Bor- oder Zinnverbindungen einzubringen. Weiterhin können die Oxyanionen auch durch Einbringen von organischen Bor-, Aluminium- und Zinnverbindungen wie z.B. Aluminiumalkoholate der Formel AI(OR)3, wobei R unabhängig ein gesättigter oder ungesättigter, verzweig- ter oder unverzweigter Kohlenwasserstoffrest mit 1 bis 10 Kohlenstoffatomen sein kann. Eine Lösung einer Borverbindung wie z.B Borsäure oder Borsäureester in Lauge eignet sich als Lösung eines borhaltigen Oxyanions. The molar ratio of the oxyanions (expressed as boron and / or aluminum and / or tin) to phenol group is preferably in the range of 0.1: 1 to 1: 1. When the oxyanion is borate, the molar ratio of boron to phenol is more preferably in the range 0.1: 1 to 0.5: 1. It is also possible to introduce organic aluminum, boron or tin compounds. Furthermore, the oxyanions can also by introducing organic boron, aluminum and tin compounds such as aluminum alcoholates of the formula AI (OR) 3, wherein R can be independently a saturated or unsaturated, branched or unbranched hydrocarbon radical having 1 to 10 carbon atoms. A solution of a boron compound such as boric acid or boric acid ester in brine is suitable as a solution of boron-containing oxyanion.
Als Lauge dient die Lösung einer Base in Wasser, die ebenfalls zum Mischen mit dem Resolharz verwendet wird. The solution used is a solution of a base in water, which is also used for mixing with the resole resin.
Als basische Katalysatoren können sowohl organische Basen wie z.B. Amine oder Ammoniumverbindungen als auch anorganische Basen wie z.B. Alkalimetallhyd- roxide verwendet werden. Als Base werden bevorzugt Alkalihydroxide wie z.B. Natriumhydroxid und Kaliumhydroxid verwendet. Das molare Verhältnis von Hydroxidionen zu der Phenolgruppe im Bindemittelsystem beträgt bevorzugt 0,5:1 bis 3:1 , bevorzugt 1 ,0 : 1 bis 2,5 : 1 . Es ist nicht notwendig, dass die gesamte Menge an Base bereits zu Beginn der Kondensation zugesetzt wird; üblicherweise erfolgt die Zugabe in zwei oder mehreren Teilschritten, wobei ein Teil auch erst am Ende des Herstellungsprozesses zugegeben werden kann. Mischungen basischer Katalysatoren können ebenfalls Verwendung finden. As basic catalysts, both organic bases, e.g. Amines or ammonium compounds as well as inorganic bases such as e.g. Alkali metal hydroxides can be used. As the base, preferred are alkali hydroxides, e.g. Sodium hydroxide and potassium hydroxide used. The molar ratio of hydroxide ions to the phenol group in the binder system is preferably 0.5: 1 to 3: 1, preferably 1, 0: 1 to 2.5: 1. It is not necessary that the entire amount of base is added already at the beginning of the condensation; Usually, the addition takes place in two or more substeps, wherein a part can be added only at the end of the manufacturing process. Mixtures of basic catalysts can also be used.
Die Herstellung von alkalischen Resolen ist z.B. in der EP 0323096 B2 und EP 1228128 B1 offenbart. Weitere Bindemittel auf Resolbasis werden beispielsweise in der US 4426467 und der US 4474904 beschrieben. The preparation of alkaline resoles is e.g. in EP 0323096 B2 and EP 1228128 B1. Further resol-based binders are described, for example, in US Pat. No. 4,426,467 and US Pat. No. 4,474,904.
Neben den bereits erwähnten Bestandteilen enthält das Resol Wasser, bevorzugt in einer Menge von 15 Gew.% bis 50 Gew.% bezogen auf das Bindemittel. Bestandteil des Bindemittels sind abschließend Resol, Wasser, Alkalien und Oxyani- on. Dabei kann das Wasser einerseits von wässrigen Lösungen stammen, die bei der Binderherstellung eingesetzt werden, andererseits kann es dem Binder aber auch separat zugesetzt werden oder als Kondensationswasser aus der Resolkon- densation stammen. Wasser dient neben seiner Funktion als Lösemittel auch beispielsweise dazu, dem Bindemittel eine anwendungsgerechte Viskosität (25°C) von 5 bis 1200 mPas, bevorzugt von 10 bis 1 100 mPas und besonders bevorzugt von 10 bis 950 mPas zu verleihen. Die Viskosität wird mit Hilfe eines Brookfield Rotationsviskosimeters, Verfahren„Small Sample", Spindel Nr. 21 bei 100 U/Min und 25°C bestimmt. Das alkalische Resol hat vorzugsweise einen pH-Wert (bei 25°C) von größer 12. In addition to the components already mentioned, the resole contains water, preferably in an amount of 15% by weight to 50% by weight, based on the binder. In the final part of the binder are resole, water, alkalis and oxyanion. On the one hand, the water may originate from aqueous solutions which are used in binder preparation, but on the other hand it may also be added separately to the binder or be obtained as condensation water from the resol condensation. In addition to its function as a solvent, water also serves, for example, to impart to the binder an application-specific viscosity (25 ° C.) of from 5 to 1200 mPas, preferably from 10 to 1100 mPas and particularly preferably from 10 to 950 mPas. The viscosity is determined using a Brookfield Rotational Viscometer, Small Sample Method, Spindle No. 21 at 100 rpm and 25 ° C. The alkaline resole preferably has a pH (at 25 ° C.) greater than 12.
Des Weiteren können dem Bindemittel bis zu ca. 50 Gew.% Zusätze wie z.B. Alkohole, Glykole, und Silane zugesetzt sein. Mit Hilfe dieser Additive kann bei- spielsweise die Benetzbarkeit des Formstoffs durch das Bindemittel und dessen Haftung auf dem Formstoff erhöht werden, was wiederum zu verbesserten Festigkeiten und einer gesteigerten Feuchtigkeitsresistenz führen kann. Furthermore, the binder may contain up to about 50% by weight of additives such as e.g. Alcohols, glycols, and silanes may be added. With the aid of these additives, for example, the wettability of the molding material by the binder and its adhesion to the molding material can be increased, which in turn can lead to improved strength and increased moisture resistance.
Besonders positiv wirkt sich in dieser Hinsicht ein Zusatz von Silanen, z.B. gamma-Aminopropyltriethoxysilan oder gamma-Glycidoxypropyltrimethoxysilan, in Konzentrationen von ca. 0,1 Gew.% bis ca. 4,0 Gew.%, vorzugsweise von ca. 0,2 Gew.% bis ca. 3,0 Gew.% und besonders bevorzugt von ca. 0,3 Gew.% bis ca. 2,5 Gew.% aus, jeweils bezogen auf das Gewicht der Formstoffzusammensetzung. Particularly beneficial in this regard is the addition of silanes, e.g. gamma-aminopropyltriethoxysilane or gamma-glycidoxypropyltrimethoxysilane, in concentrations of from about 0.1 weight percent to about 4.0 weight percent, preferably from about 0.2 weight percent to about 3.0 weight percent, and especially preferably from about 0.3% by weight to about 2.5% by weight, in each case based on the weight of the molding composition.
Die zur Härtung der Resole geeigneten Ester (Alphaset Verfahren) sind dem Fachmann z.B. aus US 4426467, US 4474904 und US 5405881 bekannt. Sie umfassen Lactone, organische Carbonate und Ester von C1 - bis C10-Mono- und Po- lycarbonsäuren mit C1 - bis C10- Mono- und Polyalkoholen. Bevorzugte aber nicht limitierende Beispiele dieser Verbindungen sind Gamma-Butyrolacton, Propylen- carbonat, Ethylenglykoldiacetat, Mono-, Di- und Triacetin sowie die Dimethylester von Bernsteinsäure, Glutarsäure und Adipinsäure inklusive deren unter der Bezeichnung DBE bekanntes Gemisch. Auf Grund unterschiedlicher Verseifungsge- schwindigkeiten der einzelnen Ester verläuft die Härtungsgeschwindigkeit der Re- sole je nach eingesetztem Ester unterschiedlich rasch, was auch die Festigkeiten beeinflussen kann. Durch Mischen von zwei oder mehreren Estern kann man die gewünschte Aushärtezeit innerhalb weiter Grenzen variieren. The esters suitable for curing the resols (Alphaset method) are known to those skilled in the art, e.g. from US 4426467, US 4474904 and US 5405881. They include lactones, organic carbonates and esters of C1 to C10 mono- and polycarboxylic acids with C1 to C10 mono- and polyalcohols. Preferred but non-limiting examples of these compounds are gamma-butyrolactone, propylene carbonate, ethylene glycol diacetate, mono-, di- and triacetin, and the dimethyl esters of succinic acid, glutaric acid and adipic acid including their known under the name DBE mixture. Due to different saponification rates of the individual esters, the curing speed of the sole runs at different rates depending on the ester used, which can also influence the strengths. By mixing two or more esters, the desired cure time can be varied within wide limits.
Weiterhin zur Härtung der Resole geeignet ist Kohlendioxid oder Methylformiat als Aerosol oder erwärmt als Gas. Die Zuckertenside sind nichtionische Tenside, bei denen Zucker den hydrophilen Anteil des Tensidmoleküls bilden. Als hydrophobe Komponente fungieren Fettalkohol- oder Fettsäure-Reste. Eingesetzte Kohlenhydrate sind z.B. Glucose, Me- thylglucose, Fructose, Methylfructose, Lactose, Ribose, Saccharose, Xylenose, Xylit, Mannose, Mannit, Isosorbit und Sorbit. Also suitable for curing the resoles is carbon dioxide or methyl formate as an aerosol or heated as a gas. The sugar surfactants are nonionic surfactants in which sugars form the hydrophilic portion of the surfactant molecule. The hydrophobic component is fatty alcohol or fatty acid residues. Carbohydrates used are, for example, glucose, methyl glucose, fructose, methyl fructose, lactose, ribose, sucrose, xylenose, xylitol, mannose, mannitol, isosorbitol and sorbitol.
Die Zuckerbausteine können als Monomer oder bis zu einem Polymerisationsgrad von 30 eingesetzt werden. Dabei können die Zuckerbausteine alpha oder beta 1 ,4 glycosidisch verknüpft sein. Bevorzugt wird der hydrophile Anteil durch Verknüp- fung von Glucose, Saccharose, Fructose, Isosorbit und/oder Sorbit gebildet, besonders bevorzugt ist Saccharose und/oder Glucose. The sugar building blocks can be used as monomer or up to a degree of polymerization of 30. The sugar units alpha or beta 1, 4 may be glycosidically linked. Preferably, the hydrophilic portion is formed by linking glucose, sucrose, fructose, isosorbitol and / or sorbitol, particular preference is given to sucrose and / or glucose.
An die freien Hydroxylgruppen können Fettsäuren verestert oder Fettalkohole, und/oder Fettal koholethoxylate, Fettalkoholpropoxylate und/oder Fettalko- holethoxylate / Fettalkoholpropoxylate verethert werden, die Kettenlänge liegt zwischen Cö und C32, insbesondere Cs und C22, und kann verzweigt oder geradkettig sein und gesättigt oder ungesättigt sein. Sowohl die Zucker- als auch die Fettbausteine können untereinander gemischt werden. Bevorzugt werden Alkylpolyglyco- side (APG), insbesondere Alkylpolyglucoside verwendet, welche folgende exemp- larische Struktur aufweisen. Fatty acids can be esterified to the free hydroxyl groups or fatty alcohols, and / or fatty alcohol ethoxylates, fatty alcohol propoxylates and / or fatty alcohol ethoxylates / fatty alcohol propoxylates can be etherified, the chain length is between C6 and C32, in particular Cs and C22, and can be branched or straight-chain and saturated or be unsaturated. Both the sugar and the fat components can be mixed with each other. Preference is given to using alkylpolyglycosides (APG), in particular alkylpolyglucosides, which have the following exemplary structure.
m steht im Mittel für 1 bis 30, bevorzugt im Mittel von 2 bis 25 und insbesondere bevorzugt im Mittel von 2 bis 10. n steht für einen gesättigten oder ungesättigten, geradkettigen oder verzweigten Alkylrest von im Mittel 5 bis 31 Kohlenstoffatomen und insbesondere bevorzugt von 7 bis 21 Kohlenstoffatomen. m is on average from 1 to 30, preferably on average from 2 to 25 and particularly preferably on average from 2 to 10. n is a saturated or unsaturated, straight-chain or branched alkyl radical of on average 5 to 31 carbon atoms and particularly preferably of 7 to 21 carbon atoms.
Alkylpolyglycoside werden großtechnisch hergestellt und von der BASF unter dem Handelsnamen Plantacare oder Glucopon vertrieben. Bevorzugt werden die erfindungsgemäßen Zuckertenside dem Resolharz in einer Konzentration von 0,05 bis 5,0 Gew. % zugesetzt. Bevorzugt in einem Bereich von 0,05 bis 3,0 Gew.% und besonders bevorzugt von 0,05 bis 2,0 Gew.%, relativ zum Bindemittel. In einer weiteren Ausführungsform können die erfindungsgemäßen Zuckertenside der Formstoffmischung direkt zugegeben werden. Dieses kann als pure Substanz oder gelöst in einem Trägermedium (z.B. Wasser) erfolgen. Bezogen auf die fertige Formstoffmischung werden 0,005 bis 0,5 Gew.%, bevorzugt 0,01 bis 0,3 Gew.% Zuckertensid zugegeben. Die verwendeten Zuckertenside haben vorzugsweise einen HLB-Wert zwischen 1 1 und 16 (HLB steht für engl, hydrophilic-lipophilic balance). Alkylpolyglycosides are industrially produced and marketed by BASF under the trade names Plantacare or Glucopon. The sugar surfactants according to the invention are preferably added to the resole resin in a concentration of 0.05 to 5.0% by weight. Preferably in a range from 0.05 to 3.0% by weight, and more preferably from 0.05 to 2.0% by weight, relative to the binder. In a further embodiment, the sugar surfactants according to the invention can be added directly to the molding material mixture. This can be done as pure substance or dissolved in a carrier medium (eg water). Based on the finished molding mixture 0.005 to 0.5 wt.%, Preferably 0.01 to 0.3 wt.% Sugar surfactant is added. The sugar surfactants used preferably have an HLB value between 1 1 and 16 (HLB stands for English, hydrophilic-lipophilic balance).
Als feuerfester Formgrundstoff (nachfolgend kurz Formgrundstoff(e)) können für die Herstellung von Gießformen übliche Materialien verwendet werden. Geeignet sind beispielsweise Quarzsand, Zirkonsand oder Chromerzsand, Olivin, Vermicu- lit, Bauxit und Schamotte bzw. Gemische davon. Sofern keine technologischen Gründe dagegensprechen, kommt aus wirtschaftlichen Gründen bevorzugt Quarzsand zum Einsatz. Es ist nicht notwendig, ausschließlich Neusande einzusetzen. Im Sinne einer Ressourcenschonung und zur Vermeidung von Deponiekosten ist es sogar vorteilhaft, einen möglichst hohen Anteil an regeneriertem Altsand zu verwenden. Besonders geeignet sind Regenerate, die durch Waschen und anschließende Trocknung erhalten werden. Einsetzbar sind auch durch thermo-mechanische oder durch rein mechanische Behandlung gewonnene Regenerate. As refractory molding base material (hereinafter abbreviated to molding base material (s)), materials customary for the production of casting molds can be used. For example, quartz sand, zircon sand or chrome ore sand, olivine, vermiculite, bauxite and chamotte or mixtures thereof are suitable. If there are no technological reasons, quartz sand is preferred for economic reasons. It is not necessary to use only new sands. In terms of resource conservation and to avoid landfill costs, it is even advantageous to use the highest possible proportion of regenerated used sand. Particularly suitable are regenerates, which are obtained by washing and subsequent drying. It is also possible to use regenerates obtained by thermo-mechanical or purely mechanical treatment.
Der mittlere Durchmesser der Formgrundstoffe liegt in der Regel zwischen 100 μιτι und 600 μιτι, bevorzugt zwischen 120 μιτι und 550 μιτι und besonders bevorzugt zwischen 150 μιτι und 500 μιτι. Die Partikelgröße lässt sich z.B. durch Sieben nach DIN ISO 3310 bestimmen. The average diameter of the molding materials is usually between 100 μιτι and 600 μιτι, preferably between 120 μιτι and 550 μιτι and more preferably between 150 μιτι and 500 μιτι. The particle size can be e.g. by sieving in accordance with DIN ISO 3310.
Weiter können als Formgrundstoffe auch künstliche Formstoffe verwendet werden, insbesondere als Zusatz zu obigen Formgrundstoffen, aber auch als ausschließlicher Formgrundstoff, wie z.B. Glasperlen, Glasgranulat, die unter der Bezeich- nung „Cerabeads" bzw. „Carboaccucast" bekannten kugelförmigen keramischen Formgrundstoffe oder Aluminiumsilikatmikrohohlkugeln (sog. Microspheres). Solche Aluminiumsilikatmikrohohlkugeln werden beispielsweise von der Omega Minerals Germany GmbH, Norderstedt, unter der Bezeichnung„Omega-Spheres" in den Handel gebracht. Entsprechende Produkte sind auch bei der PQ- Corporation (USA) unter der Bezeichnung„Extendospheres" erhältlich. Furthermore, synthetic molding materials can also be used as mold base materials, in particular as an additive to the above molding base materials, but also as exclusive molding base material, for example glass beads, glass granules, the spherical ceramic molding bases or aluminum silicate microbeads known under the name "Cerabeads" or "Carboaccucast" (US Pat. so-called microspheres). Such aluminosilicate hollow microspheres are marketed, for example, by Omega Minerals Germany GmbH, Norderstedt, under the name "Omega Spheres." Corresponding products are also available from PQ Corporation (USA) under the name "Extendospheres".
Weiterhin ist es möglich dem Formgrundstoff amorphes Siliciumdioxid zu zusetzen. Dadurch wird eine Erhöhung der Festigkeit erreicht. Dies ist u.a. in der DE 102014106178 offenbart. Bei der Herstellung einer Formstoffmischung wird i.A. so vorgegangen, dass der feuerfeste Formgrundstoff vorgelegt und anschließend das Bindemittel und das Zuckertensid gemeinsam oder nacheinander unter Rühren zugegeben werden. Selbstverständlich ist es auch möglich, erst die Komponenten ganz oder teilweise zuzugeben und danach und/oder währenddessen zu rühren. Es wird solange ge- rührt, bis eine gleichmäßige Verteilung des Bindemittels und des Zuckertensids mit dem Formgrundstoff gewährleistet ist. Furthermore, it is possible to add amorphous silicon dioxide to the molding base material. As a result, an increase in strength is achieved. This is i.a. disclosed in DE 102014106178. In the preparation of a molding material i.A. The procedure is such that the refractory molding base material is initially charged and then the binder and the sugar surfactant are added together or successively with stirring. Of course, it is also possible first to add the components completely or partially and then to stir and / or while. The mixture is stirred until a uniform distribution of the binder and of the sugar surfactant with the molding material is ensured.
Die Formstoffmischung wird anschließend in die gewünschte Form gebracht. Dabei werden für die Formgebung übliche Verfahren angewendet. Beispielsweise kann die Formstoffmischung mittels einer Kernschießmaschine mit Hilfe von Druckluft in das Werkzeug geschossen werden. Eine andere Möglichkeit besteht darin, die Formstoffmischung freifließend aus dem Mischer in das Formwerkzeug rieseln zu lassen und sie dort durch Rütteln, Stampfen oder Pressen zu verdichten. The molding material mixture is then brought into the desired shape. In this case, customary methods are used for the shaping. For example, the molding material mixture can be shot by means of a core shooter with the aid of compressed air into the tool. Another possibility is to free-flow the molding material mixture from the mixer into the mold and to compact it there by shaking, stamping or pressing.
Bevorzugtes Kernherstellungsverfahren ist das Resol/CO2 Verfahren. Dieses schließt aber die Begasung mit niedrigen Alkylestern, bekannt unter dem Namen Betaset Verfahren wie C1 - bis C3- Alkylformiate, insbesondere Methylform iat, und eine Härtung mittels flüssiger Ester nicht aus, bekannt unter dem Namen Alphaset Verfahren. Preferred core manufacturing process is the Resol / CO2 process. However, this does not preclude sparing with lower alkyl esters known under the name of Betaset, such as C1 to C3 alkyl formates, especially methyl formate, and liquid ester curing, known by the name Alphaset method.
Die Härtung erfolgt dadurch, dass CO2, ein CO2/Gasgemisch (z.B. mit Luft), ein Gasgemisch (z.B. Luft) oder gasförmiges Methylformiat (beim Betaset Verfahren) nacheinander (wie z.B. im Detail in der DE 102012103705.1 beschrieben) durch das Formwerkzeug bzw. durch die darin enthaltene Formstoffmischung geleitet wird. Der Gasstrom hat eine Temperatur zwischen 0°C bis 140°C, bevorzugt von 5°C bis 120°C und besonders bevorzugt von 6°C bis 1 10°C. Curing takes place in that the CO2, a CO2 / gas mixture (eg with air), a gas mixture (eg air) or gaseous methyl formate (Betaset method) successively (as described in detail in DE 102012103705.1) by the mold or by the molding material mixture contained therein is passed. The gas stream has a temperature between 0 ° C to 140 ° C, preferably from 5 ° C to 120 ° C and more preferably from 6 ° C to 1 10 ° C.
Experimenteller Teil Experimental part
Eingesetzte Komponenten: Components used:
NOVANOL 165 - alkalischer Resol/CO2 Binder, Lieferant ASK-Chemicals GmbH AVENOL F 633 - alkalischer Betaset Binder, Lieferant ASK-Chemicals GmbH Quarzsand H 32 - Lieferant Quarzwerke GmbH  NOVANOL 165 - Alkaline Resol / CO2 Binder, Supplier ASK-Chemicals GmbH AVENOL F 633 - Alkaline Betaset Binder, Supplier ASK-Chemicals GmbH Quarzsand H 32 - Supplier Quarzwerke GmbH
Ölsäure = technische Ölsäure Oleic acid = technical oleic acid
Capstone FS 35 = 25%ige wässrige Lösung eines nichtionischen Fluortensids, Hersteller: Chemour  Capstone FS 35 = 25% aqueous solution of a nonionic fluorosurfactant, manufacturer: Chemour
Plantacare 2000 UP: 50%ige wässrige Alkylpolyglucosidlösung mit C8-C16 Fettalkoholketten, Hersteller: BASF SE  Plantacare 2000 UP: 50% aqueous alkyl polyglucoside solution with C8-C16 fatty alcohol chains, manufacturer: BASF SE
Alle Angaben in Gew%. All data in% by weight.
Bestimmung der Oberflächenspannung Determination of the surface tension
Jeweils x% der in der u.a. Tabelle genannten Stoffe wurden einzeln zu NOVANOL 165 gegeben und klar gelöst. 200g der homogenen, klaren und luftblasenfreien Mischung wurde in einen PTFE-Becher gegeben und die Oberflächenspannung (in mN/mm) bei Raumtemperatur gemessen. Hierzu wurde ein Krüss Force Tensi- ometer 100 (Fa. Krüss) verwendet. Es wurde die Plattenmethode (angerauhte Platinplatte) nach Wilhelmy als Doppelbestimmung benutzt. Berührt eine senkrecht aufgehängte Platte eine flüssige Oberfläche oder Grenzfläche, dann wirkt auf die- se Platte eine Kraft F, die mit der Oberflächenspannung korreliert. In each case x% of the substances mentioned in the table below were added individually to NOVANOL 165 and dissolved clearly. 200g of the homogeneous, clear and bubble-free mixture was placed in a PTFE beaker and the surface tension (in mN / mm) measured at room temperature. For this purpose, a Krüss Force Tensiometer 100 (Krüss) was used. The plate method (roughened platinum plate) according to Wilhelmy was used as a duplicate determination. If a vertically suspended plate touches a liquid surface or interface, then a force F, which correlates with the surface tension, acts on this plate.
Tabelle 1 Table 1
% = Gew.% relativ zum Bindemittel % = Wt.% Relative to the binder
Tabelle 1 zeigt die gefundenen Oberflächenspannungen (in mN/mm) bei Raumtemperatur, welche durch Zusatz der Tenside erhalten wurden. Betrachtet man die Oberflächenspannung (Vergleich der selben Menge Aktivsubstanz, Kennung mit „*"), so fällt überraschenderweise auf, dass die erfindungsgemäßen Zuckertenside vom APG Typ die Oberflächenspannung nur um 2% reduzieren (Nullbeispiel zu B2). Table 1 shows the surface tensions found (in mN / mm) at room temperature, which were obtained by adding the surfactants. If one considers the surface tension (comparison of the same amount of active substance, identification with " * "), it is surprisingly found that the APG type sugar surfactants according to the invention reduce the surface tension by only 2% (zero example to B2).
Verglichen zum Stand der Technik gemäß US 5,077,323 reduziert die Ölsäure die Oberflächenspannung um 10% (Nullbeispiel zu A1 ), gemäß EP 0399 636 wird sogar eine Reduzierung um 27% erreicht (Nullbeispiel zu A8). Als Referenz diente Wasser mit dem Wert 68,8 mN/mm. Bestimmung der Festigkeit in N/cm2- Resol CO2 Verfahren Compared with the prior art according to US Pat. No. 5,077,323, the oleic acid reduces the surface tension by 10% (zero example to A1), according to EP 0399 636 even a reduction by 27% is achieved (zero example to A8). The reference water was 68.8 mN / mm. Determination of strength in N / cm 2 - Resol CO2 method
In einem Hobart Mischer wurde eine Sandmischung aus Quarzsand H 32, plus 3,0% NOVANOL 165 (ohne, bzw. mit den aufgeführten Stoffen) für 2 Minuten homogen vermischt. Diese Sandmischung wurde in eine Kernschießmaschine, Model Laempe L 1 (Öffnung am Sandaustritt des Schießkopfs auf 5mm reduziert) überführt und wurde in einen vierer Kernkasten (GF Riegel 220mm x 22,4mm x 22,4 mm) mit einem Schießdruck von 2 bar mittels Druckluft und einer Schießzeit von 1 sec in die Form gebracht. Mittels CO2 Gas (2 Liter/min für 30 sec) wurde der Sand ausgehärtet. Nach drei Schüßen, ohne Auffüllung des 1 Liter fassenden Schießkopfes, wurde die Sandmischung optisch beurteilt, ob der Sand nachfließt. In a Hobart mixer, a sand mixture of quartz sand H 32, plus 3.0% NOVANOL 165 (without, or with the listed substances) was homogeneously mixed for 2 minutes. This sand mixture was transferred to a core shooter, model Laempe L 1 (opening at the sand outlet of the shooting head reduced to 5mm) and placed in a four core box (GF bar 220mm x 22.4mm x 22.4mm) with a shooting pressure of 2 bar by means of compressed air and a shooting time of 1 sec brought into the mold. By means of CO2 gas (2 liters / min for 30 sec), the sand was cured. After three shots, without filling the 1 liter shooting head, the sand mixture was visually assessed whether the sand is flowing.
Die Biegefestigkeiten wurden mittels eine Biegeprüfgerätes der Fa. Multiserw nach der angegebenen Zeit gebrochen (Mittelwerte aus vier Bestimmungen). The flexural strengths were broken by means of a Biegeprüfgerätes Fa. Multiserw after the specified time (average values of four determinations).
Tabelle 2 Table 2
Fesl iqkeit in N/cm2 Size in N / cm 2
60 sec 24h RT Sandfluß 60 sec 24h RT sand flow
# Zusatz sofort 24h RT 98% n. 3 Schuß# Addition immediately 24h RT 98% n. 3 shot
A 0 ohne 81 139 108 stocktA 0 without 81 139 108 falters
A 1 0,25% Ölsäure* 85 144 104 stocktA 1 0.25% oleic acid * 85 144 104 stalls
A 2 0,50% Ölsäure 81 146 101 rutschtA 2 0.50% oleic acid 81 146 101 slips
A3 0,75% Ölsäure 80 137 95 rutschtA3 0.75% oleic acid 80 137 95 slips
A4 1 ,0% Ölsäure 76 131 90 rutschtA4 1, 0% oleic acid 76 131 90 slips
A5 0,25% Capstone FS 35 80 133 1 10 stocktA5 0.25% Capstone FS 35 80 133 1 10 stocked
A6 0,50% Capstone FS 35 77 130 1 1 1 stocktA6 0.50% Capstone FS 35 77 130 1 1 1 stocked
A7 0,75% Capstone FS 35 78 127 105 stocktA7 0.75% Capstone FS 35 78 127 105 falters
A8 1 ,0% Capstone FS 35* 79 129 106 stocktA8 1, 0% Capstone FS 35 * 79 129 106 stops
B1 0,25% Plantacare 2000 UP 84 155 1 17 rutschtB1 0.25% Plantacare 2000 UP 84 155 1 17 slips
B2 0,50% Plantacare 2000 UP* 83 145 1 13 rutschtB2 0.50% Plantacare 2000 UP * 83 145 1 13 slips
B3 0,75% Plantacare 2000 UP 83 139 106 rutschtB3 0.75% Plantacare 2000 UP 83 139 106 slips
B4 1 ,0% Plantacare 2000 UP 82 136 101 rutscht Tabelle 2 zeigt, dass die sofort gemessenen Biegefestigkeiten mit dem erfindungsgemäßen Plantacare 2000 UP (Beispiel B1 -B4) mit zunehmender Konzentration konstant bleiben, während sie mit zunehmenden Gehalt an Ölsäure (Beispiel A1 -A4) abfallen. In der Spalte„Sandfluß nach 3 Schuß" ist der verbliebene Sand im Schießkopf optisch beurteilt worden.„Stockt" bedeutet, dass sich über den Schießöffnungen ein Hohlraum ausgebildet hat, in denen der Sand nicht nachrutscht.„Rutscht" bedeutet, dass der Hohlraum nicht vorhanden ist und durch nachrutschenden Sand verschlossen worden ist. Dadurch kann ohne Rütteln weitergeschossen werden. Dieser Effekt ist für die erfindungsgemäßen Zuckertenside (hier Plantacare 2000 UP) überraschend, da es ein Nachrutschen des Sandes begünstigt. B4 1, 0% Plantacare 2000 UP 82 136 101 slips Table 2 shows that the immediately measured flexural strengths with the Plantacare 2000 UP according to the invention (Example B1-B4) remain constant with increasing concentration, while they decrease with increasing content of oleic acid (Example A1 -A4). In the column "Sandfluss nach 3 Schuss", the remaining sand in the shooting head has been visually assessed. "Stick" means that a cavity has formed over the shooting openings, in which the sand does not slip. "Slipping" means that the cavity is not This effect can be used without shaking, and this effect is surprising for the sugar surfactants according to the invention (here Plantacare 2000 UP), since it promotes slipping of the sand.
Bestimmung der Festigkeit in N/cm2- Betaset Verfahren Determination of strength in N / cm 2 - Betaset method
In einem Hobart Mischer wurde eine Sandmischung aus Quarzsand H 31 , plus 2,3% AVENOL F 633 (ohne, bzw. mit den aufgeführten Stoffen) für 2 Minuten homogen vermischt. Diese Sandmischung wurde in eine Kernschießmaschine, Model Roeper H 1 (Öffnung am Sandaustritt des Schießkopfs 10 mm) überführt und wurde in einen zweier Kernkasten (GF Riegel 220mm x 22,4mm x 22,4 mm) mit einem Schießdruck von 3 bar mittels Druckluft und einer Schießzeit von 1 sec in die Form gebracht. Mittels 60°C warmem Methylformiat Gas (2,0 ml flüssiges Me- thylformiat, für 20 sec, 2 bar Spüldruck) wurde der Sand ausgehärtet. Die Biegefestigkeiten wurden mittels eine Biegeprüfgerätes der Fa. Multiserw nach der angegebenen Zeit bestimmt (Mittelwerte aus vier Bestimmungen).  In a Hobart mixer, a sand mixture of quartz sand H 31, plus 2.3% AVENOL F 633 (without, or with the listed substances) was mixed homogeneously for 2 minutes. This sand mixture was transferred to a core shooter, Model Roeper H 1 (opening at the sand outlet of the shooting head 10 mm) and was placed in a two core box (GF bar 220mm x 22.4mm x 22.4 mm) with a shooting pressure of 3 bar by means of compressed air and a shooting time of 1 sec brought into the mold. The sand was hardened by means of 60 ° C. warm methyl formate gas (2.0 ml liquid methyl formate, for 20 sec, 2 bar rinsing pressure). The flexural strengths were determined by means of a Biegeprüfgerätes Fa. Multiserw after the specified time (average values of four determinations).
Tabelle 3 Table 3
A9 = Vergleich, A10 gemäß US 5077323; A11 gemäß EP 0399636: B5 erfindungsgemäß  A9 = comparison, A10 according to US 5077323; A11 according to EP 0399636: B5 according to the invention
Aus der Tabelle 3 ist ersichtlich, das durch Zusatz des erfindungsgemäßen From Table 3 it can be seen that by adding the invention
Plantacare 2000 UP, die höchsten Festigkeiten in N/cm2 und die höchste Packungsdichte (angegeben durch das Kerngewicht) erreicht wurden. Plantacare 2000 UP, the highest strengths in N / cm 2 and the highest packing density (indicated by the core weight) were achieved.

Claims

Patentansprüche claims
1 . Fornnstoffnnischung umfassend zumindest einen feuerfesten Formgrundstoff, ein alkalisches Resol und ein Zuckertensid. 1 . Fornnstoffnnischung comprising at least a refractory molding material, an alkaline resole and a sugar surfactant.
2. Formstoffmischung nach Anspruch 1 , wobei das Zuckertensid ein Zuckerester oder ein Zuckeralkylether ist. 2. Molding material mixture according to claim 1, wherein the sugar surfactant is a sugar ester or a sugar alkyl ether.
3. Formstoffmischung nach zumindest einem der vorhergehenden Ansprüche, wobei das Zuckertensid ein Alkylpolyglycosid ist, vorzugsweise mit einem Polymerisationsgrad von 1 bis 30, insbesondere 2 bis10, und einer C-Zahl des Alkohol-Restes von 6 bis 32, insbesondere 8 bis 22. 3. Molding material mixture according to at least one of the preceding claims, wherein the sugar surfactant is an alkylpolyglycoside, preferably having a degree of polymerization of 1 to 30, in particular 2 to 10, and a C number of the alcohol radical of 6 to 32, in particular 8 to 22.
4. Formstoffmischung nach zumindest einem der vorhergehenden Ansprüche, wobei das Zuckertensid und insbesondere das Alkylpolyglycosid, einen HLB-Wert 1 1 bis 16 aufweist. 4. Molding material mixture according to at least one of the preceding claims, wherein the sugar surfactant and in particular the alkylpolyglycoside, an HLB value 1 1 to 16.
5. Formstoffmischung nach zumindest einem der vorhergehenden Ansprüche, wobei das Zuckertenside mit 0,05 bis 5,0 Gew. % in der Formstoffmischung ent- halten ist, bevorzugt mit 0,05 bis 3,0 Gew.% und besonders bevorzugt mit 0,05 bis 2,0 Gew%, bezogen auf den Feststoffgehalt des alkalischen Resols. 5. Molding material mixture according to at least one of the preceding claims, wherein the sugar surfactants with 0.05 to 5.0 wt.% Contained is contained in the molding material mixture, preferably with 0.05 to 3.0 wt.% And particularly preferably 0, From 05 to 2.0% by weight, based on the solids content of the alkaline resol.
6. Formstoffmischung nach zumindest einem der vorhergehenden Ansprüche, wobei das Zuckertenside mit 0,005 bis 0,5 Gew. % in der Formstoffmischung ent- halten ist, bevorzugt mit 0,01 bis 0,3 Gew.%, bezogen auf die Formstoffmischung. 6. Molding material mixture according to at least one of the preceding claims, wherein the sugar surfactants with 0.005 to 0.5 wt.% Is contained in the molding material mixture, preferably with 0.01 to 0.3 wt.%, Based on the molding material mixture.
7. Formstoffmischung nach zumindest einem der vorhergehenden Ansprüche, wobei das alkalische Resol in einer Menge von 0,8 bis 10 Gew.%, bevorzugt von 1 bis 5 Gew.%, jeweils bezogen auf den Feststoffgehalt des Resols (nach DIN EN ISO 3251 ) und relativ zum Gewicht des feuerfesten Formgrundstoffs in der Form- stoffmischung enthalten ist. 7. Molding material mixture according to at least one of the preceding claims, wherein the alkaline resole in an amount of 0.8 to 10 wt.%, Preferably from 1 to 5 wt.%, In each case based on the solids content of the resol (according to DIN EN ISO 3251) and relative to the weight of the refractory base molding material in the molding material mixture.
8. Formstoffmischung nach zumindest einem der vorhergehenden Ansprüche, wobei das alkalische Resol Oxyanionen enthält, bevorzugt Aluminium-oxo- Verbindungen und/oder Bor-oxo-Verbindungen. 8. Molding material mixture according to at least one of the preceding claims, wherein the alkaline resole contains oxyanions, preferably aluminum oxo compounds and / or boron oxo compounds.
9. Formstoffmischung nach zumindest einem der vorhergehenden Ansprüche, wobei die Resole in Form einer wässrigen alkalischen Lösung eingesetzt werden, vorzugsweise mit einem Festkörperanteil von u 15 bis 50 Gew.%, und einem pH- Wert größer 12. 9. Molding material mixture according to at least one of the preceding claims, wherein the resoles are used in the form of an aqueous alkaline solution, preferably having a solids content of u 15 to 50 wt.%, And a pH greater than 12.
10. Formstoffmischung nach zumindest einem der vorhergehenden Ansprüche, wobei der feuerfeste Formgrundstoff Quarz-Sand, Zirkon-Sand oder Chromerzsand, Olivin, Vermiculit, Bauxit, Schamotte, Glasperlen, Glasgranulat, Aluminium- silikatmikrohohlkugeln und deren Mischungen umfasst, insbesondere mit überwie- gend runder Partikelform, und vorzugsweise zu mehr als 50 Gew.% aus Quarzsand, bezogen auf den feuerfesten Formgrundstoff, besteht. 10. Molding material mixture according to at least one of the preceding claims, wherein the refractory molding material comprises quartz sand, zircon sand or chrome ore, olivine, vermiculite, bauxite, chamotte, glass beads, glass granules, aluminum silicate hollow microspheres and mixtures thereof, in particular with predominantly rounder Particle shape, and preferably to more than 50 wt.% Of quartz sand, based on the refractory base molding material exists.
1 1 . Formstoffmischung nach zumindest einem der vorhergehenden Ansprüche, wobei größer 80 Gew.%, vorzugsweise größer gleich 90 Gew.%, und besonders bevorzugt größer gleich 95 Gew.%, der Formstoffmischung feuerfester Formgrundstoff ist. 1 1. Molding material mixture according to at least one of the preceding claims, wherein greater than 80% by weight, preferably greater than or equal to 90% by weight, and particularly preferably greater than or equal to 95% by weight, of the molding material mixture is refractory molding material.
12. Formstoffmischung nach zumindest einem der vorhergehenden Ansprüche, wobei der feuerfeste Formgrundstoff mittlere Partikeldurchmesser von 100 μιτι bis 600 μιτι, bevorzugt zwischen 120 μιτι und 550 μιτι aufweist, bestimmt durch Siebanalyse. 12. Molding material mixture according to at least one of the preceding claims, wherein the refractory molding base material average particle diameter of 100 μιτι to 600 μιτι, preferably between 120 μιτι and 550 μιτι, determined by sieve analysis.
13. Verfahren zur Herstellung eines Kerns, Speisers oder einer Form umfassend die folgenden Schritte: 13. A process for producing a core, feeder or mold comprising the following steps:
Einbringen der Formstoffmischung nach zumindest einem der vorhergehenden Ansprüche, ggf. enthaltend weitere Bestandteile, in ein Formwerkzeug;  Introducing the molding material mixture according to at least one of the preceding claims, optionally containing further constituents, into a molding tool;
Härten der Formstoffmischung im Formwerkzeug mit CO2, Methylform iat oder einem anderen bei 25°C flüssigen Ester, vorzugsweise mit CO2; und Entnahme des gehärteten Kerns, Speisers oder der Form aus dem Formwerkzeug.  Hardening of the molding material mixture in the mold with CO2, methyl formate or another at 25 ° C liquid ester, preferably with CO2; and removing the hardened core, feeder or mold from the mold.
14. Form, Speiser oder Kern herstellbar nach dem Verfahren nach Anspruch 13 für den Metallguss, insbesondere den Eisen oder Aluminium-Guss. 14. mold, feeder or core produced by the method according to claim 13 for the metal casting, in particular the iron or aluminum casting.
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Publication number Priority date Publication date Assignee Title
FR2473032A1 (en) 1980-01-07 1981-07-10 Banquy David PROCESS FOR THE PRODUCTION OF AMMONIA AND THE SYNTHESIS GAS CORRESPONDING
US4426467A (en) 1981-01-12 1984-01-17 Borden (Uk) Limited Foundry molding compositions and process
US4474904A (en) 1982-01-21 1984-10-02 Lemon Peter H R B Foundry moulds and cores
US4977209A (en) 1987-12-24 1990-12-11 Foseco International Limited Production of articles of bonded particulate material and binder compositions for use therein from phenol-formaldehyde and oxyanion
US4996249A (en) 1989-04-27 1991-02-26 Acme Resin Corporation Method to improve flowability of resin coated sand
US5077323A (en) 1989-10-10 1991-12-31 Acme Resin Corporation Method to improve flowability of alkaline phenolic resin coated sand
US5376696A (en) 1990-07-13 1994-12-27 Ashland Oil, Inc. Foundry mixes based upon reclaimed sand
AU8328191A (en) 1990-07-13 1992-02-04 Ashland Oil, Inc. Three component foundry binder system
TW256851B (en) 1992-11-18 1995-09-11 Ashland Oil Inc
JP3250915B2 (en) * 1994-09-30 2002-01-28 花王株式会社 Binder composition for mold, mold composition and method for producing mold
DE19938043C2 (en) 1999-08-12 2001-12-06 Ashland Suedchemie Kernfest Resol-based binder system containing aluminum, process for its production and use, and molding compound
JP2001219242A (en) * 2000-02-08 2001-08-14 Hodogaya Ashland Kk Binder composition for molding sand and casting mold composition
DE102007051850A1 (en) * 2007-10-30 2009-05-07 Ashland-Südchemie-Kernfest GmbH Molding compound with improved flowability
DE102012103705A1 (en) 2012-04-26 2013-10-31 Ask Chemicals Gmbh Method for producing molds and cores for casting metal, and molds and cores produced by this method
DE102012104934A1 (en) * 2012-06-06 2013-12-12 Ask Chemicals Gmbh Forstoffmischungen containing barium sulfate
DE102014106178A1 (en) 2014-05-02 2015-11-05 Ask Chemicals Gmbh Process for the layered construction of bodies comprising refractory base molding material and resoles and molds or cores produced by this process

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