EP3548200A1 - Amino acid-containing moulding material mixture for production of mouldings for the foundry industry - Google Patents
Amino acid-containing moulding material mixture for production of mouldings for the foundry industryInfo
- Publication number
- EP3548200A1 EP3548200A1 EP17823037.1A EP17823037A EP3548200A1 EP 3548200 A1 EP3548200 A1 EP 3548200A1 EP 17823037 A EP17823037 A EP 17823037A EP 3548200 A1 EP3548200 A1 EP 3548200A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- molding material
- material mixture
- formaldehyde
- binder system
- urea
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 167
- 238000000465 moulding Methods 0.000 title claims abstract description 74
- 150000001413 amino acids Chemical class 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 393
- 239000011230 binding agent Substances 0.000 claims abstract description 196
- 238000000034 method Methods 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 23
- 239000000945 filler Substances 0.000 claims abstract description 20
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 13
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 174
- 239000012778 molding material Substances 0.000 claims description 137
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 96
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 88
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 68
- 229920005989 resin Polymers 0.000 claims description 52
- 239000011347 resin Substances 0.000 claims description 52
- 239000004471 Glycine Substances 0.000 claims description 48
- 229960002449 glycine Drugs 0.000 claims description 48
- 239000004202 carbamide Substances 0.000 claims description 44
- 229940024606 amino acid Drugs 0.000 claims description 41
- 235000001014 amino acid Nutrition 0.000 claims description 41
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000004848 polyfunctional curative Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000004576 sand Substances 0.000 claims description 15
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 14
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 14
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 14
- 229960003767 alanine Drugs 0.000 claims description 14
- 235000004279 alanine Nutrition 0.000 claims description 14
- 150000002240 furans Chemical class 0.000 claims description 14
- 229960001153 serine Drugs 0.000 claims description 14
- 235000004400 serine Nutrition 0.000 claims description 14
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims description 13
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 claims description 13
- 229960004295 valine Drugs 0.000 claims description 13
- 239000004474 valine Substances 0.000 claims description 13
- 235000014393 valine Nutrition 0.000 claims description 13
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 claims description 12
- 235000004554 glutamine Nutrition 0.000 claims description 12
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 claims description 12
- 229960002743 glutamine Drugs 0.000 claims description 12
- 150000003672 ureas Chemical class 0.000 claims description 12
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 claims description 10
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 10
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 10
- 150000002989 phenols Chemical class 0.000 claims description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000006004 Quartz sand Substances 0.000 claims description 7
- -1 aluminum silicates Chemical class 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 6
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 6
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 6
- 235000014304 histidine Nutrition 0.000 claims description 6
- 229960002885 histidine Drugs 0.000 claims description 6
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 6
- 235000006109 methionine Nutrition 0.000 claims description 6
- 229930182817 methionine Natural products 0.000 claims description 6
- 229960004452 methionine Drugs 0.000 claims description 6
- 229920003987 resole Polymers 0.000 claims description 6
- 229960004441 tyrosine Drugs 0.000 claims description 6
- 235000002374 tyrosine Nutrition 0.000 claims description 6
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000010881 fly ash Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000004475 Arginine Substances 0.000 claims description 3
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 claims description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 3
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 3
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 3
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 claims description 3
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 claims description 3
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 3
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 3
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 3
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 3
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004472 Lysine Substances 0.000 claims description 3
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 3
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004473 Threonine Substances 0.000 claims description 3
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 3
- 229960003121 arginine Drugs 0.000 claims description 3
- 235000009697 arginine Nutrition 0.000 claims description 3
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 3
- 229960001230 asparagine Drugs 0.000 claims description 3
- 235000009582 asparagine Nutrition 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 229960002433 cysteine Drugs 0.000 claims description 3
- 235000018417 cysteine Nutrition 0.000 claims description 3
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229960000310 isoleucine Drugs 0.000 claims description 3
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 claims description 3
- 235000018977 lysine Nutrition 0.000 claims description 3
- 229960003646 lysine Drugs 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 229960005190 phenylalanine Drugs 0.000 claims description 3
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 3
- 229960002429 proline Drugs 0.000 claims description 3
- 235000008521 threonine Nutrition 0.000 claims description 3
- 229960002898 threonine Drugs 0.000 claims description 3
- 229960004799 tryptophan Drugs 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052849 andalusite Inorganic materials 0.000 claims description 2
- 239000002956 ash Substances 0.000 claims description 2
- 229910001570 bauxite Inorganic materials 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000010431 corundum Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 239000010903 husk Substances 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 239000010450 olivine Substances 0.000 claims description 2
- 229910052609 olivine Inorganic materials 0.000 claims description 2
- 239000010451 perlite Substances 0.000 claims description 2
- 235000019362 perlite Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 229910052845 zircon Inorganic materials 0.000 claims description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 2
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 7
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- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/224—Furan polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/02—Sand moulds or like moulds for shaped castings
Definitions
- the present invention relates to a molding material mixture for the production of moldings for the foundry industry, moldings for the foundry industry, a use of amino acids in a molding material mixture for the production of moldings for the foundry industry or for the production of moldings for the foundry industry, a process for the preparation of a molding material mixture and a Process for producing a molded article for the foundry industry.
- molten materials, ferrous metals and non-ferrous metals are converted into shaped articles with specific workpiece properties.
- the casting molds are divided into lost molds that are destroyed after each casting, and permanent molds, with each of which a large number of castings can be produced.
- the lost forms usually consist of a refractory, pourable molding material, which is solidified by means of a curable binder. Shapes are negatives that contain the pouring cavity that results in the casting being manufactured.
- Inner contours are represented by cores formed in a separate core box.
- both organic and inorganic binders can be used, the curing of which can be effected by cold or hot processes.
- Cold processes are processes in which the curing takes place essentially at room temperature without heating the molding material mixture.
- the curing is usually carried out by a chemical reaction, which can be triggered, for example, by passing a gaseous catalyst through the molding material mixture to be cured, or by adding a liquid catalyst to the molding material mixture.
- hot processes after molding, the molding material mixture is heated to a temperature high enough to expel, for example, the solvent contained in the binder or to initiate a chemical reaction by which the binder is cured by crosslinking.
- the production of the casting molds can be carried out in such a way that the filler is first mixed with the binder system, so that the grains of the refractory filler are coated with a thin film of the binder system.
- the molding material mixture obtained from the filler and binder system can then be introduced into a corresponding mold and optionally compacted in order to achieve a sufficient stability of the casting mold. Subsequently, the mold is cured. If the mold has reached at least a certain initial strength, it can be removed from the mold.
- the molding material mixture can initially be produced in larger quantities, which are then processed within a relatively long period of time, usually several hours.
- the curing of the molding material mixture takes place only after molding, with a rapid reaction is sought.
- the mold can be removed immediately after curing from the mold so that short cycle times can be realized.
- the refractory base molding material eg sand
- the curing agent can be added to high concentration of the curing agent to partial hardening or crosslinking of the binder come, resulting in an inhomogeneous molding material would result.
- the "classic" no-bake binders are often based on furan resins or phenolic resins or furan / phenolic resins. They are often offered as systems (kits) wherein one component comprises a reactive furan resin or furan / phenolic resin and the other component comprises an acid, which acid acts as a catalyst for curing the reactive resin component.
- Furan and phenolic resins show very good disintegration properties during casting. Under the action of heat of the liquid metal, the furan or phenolic resin decomposes and the strength of the mold is lost. After casting, therefore, cores, if necessary after prior shaking of the casting, can be removed from cavities.
- Furfuryl alcohol can react with itself under acid catalysis and form a homopolymer.
- furfuryl alcohol is generally not used alone, but further compounds, such as formaldehyde, are added to the furfuryl alcohol, which are polymerized into the resin.
- the resins may be added with further components which influence the properties of the resin, for example, its elasticity. Melamine and urea may be added, for example, to bind still free formaldehyde.
- Furan no-bake binders are most often prepared by first producing precondensates of, for example, urea, formaldehyde, and furfuryl alcohol under acidic conditions. These precondensates are then diluted with furfuryl alcohol.
- Resols can also be used to prepare furan / phenol no-bake binders.
- Resoles are prepared by polymerization of mixtures of phenol and formaldehyde. These resoles are then often diluted with a large amount of furfuryl alcohol.
- Furan no-bake binders are cured with an acid.
- This acid catalyzes the crosslinking of the reactive furan resin. It should be noted that the amount of acid can control the cure, the amount of acid necessary to set a cure time being binder dependent and affected by factors such as the binder's pH and the type of acid.
- aromatic sulfonic acids aromatic sulfonic acids, phosphoric acid, methanesulfonic acid and sulfuric acid are often used. In some specific cases, combinations of these are used, inter alia, in combination with other carboxylic acids. Further, certain "curing moderators" can be added to the furan no-bake binder.
- Phenolic resins as the second large group of acid-catalyzed curable no-bake binders contain resoles as reactive resin components, ie phenolic resins which have been prepared with a molar excess of formaldehyde. Phenolic resins show lower reactivity compared to furan resins and require strong sulfonic acids as catalysts. For some time no-bake binders have been used for the production of molds and cores for large and single castings. These cold-curing systems are mostly reaction products of formaldehyde with furfuryl alcohol, phenol and / or urea.
- Formaldehyde-based blends usually have very good properties.
- phenol / furan / formaldehyde mixed resins, urea / formaldehyde resins and furan / formaldehyde resins are widely used in the foundry industry.
- US 3,644,274 relates primarily to a no-bake method using certain mixtures of acid catalysts to cure for furfuryl alcohol-formaldehyde urea resins.
- US Pat. No. 3,806,491 relates to binders which can be used in the "no-bake" process
- the binders used there comprise products from the reaction of paraformaldehyde with certain ketones in a basic medium and furfuryl alcohol and / or furan resins
- Binders suitable for use in the no-bake process The binders used there are based on 2,5-bis (hydroxymethyl) furan or methyl or ethyl ethers of 2,5-bis (hydroxymethyl) furan, the binders 0.5 to 30% by weight of water and regularly a high proportion of furfuryl alcohol
- EP 0 540 837 proposes low-emission, cold-hardening binders based on furan resins and lignin from the Organosolv process
- the furan resins described there contain a high proportion on monomeric furfuryl alcohol.
- EP 1 531 018 relates to no-bake foundry binder systems of a furan resin and certain acid hardeners.
- the binder systems described therein preferably comprise 60 to 80% by weight of furfuryl alcohol.
- US 2016/0 158 828 A1 describes the production of molds by means of a rapid prototyping method.
- the molding material mixtures described in the document may contain A) at least one refractory filler and B) a binder system, wherein the binder system i) formaldehyde and ii) a thermoset, a saccharide, a synthetic polymer, a salt, a protein or an inorganic polymer ,
- EP 1 595 618 B1 describes a process for producing a ceramic mask mold.
- a casting slip is used which contains ceramic particles, a binder and a plasticizer.
- the liquefier may be amino acids, ammonium polyacrylates, or trihydric carboxyls with alcohol groups.
- the thermal insulation bodies described in the document comprise mineral wool and a binder based on a formaldehyde-phenolic resin.
- US 3 296 666 A describes a process for producing casting molds.
- synthetic resin materials natural resins, gums, proteins, carbohydrates or egg white are used as alternative binders to phenol-formaldehyde resins.
- No. 5,320,157 A describes a process for producing a core, wherein the molding material mixture used to prepare the core contains gelatin as binder.
- the binder system after curing has a high strength. Good strength is particularly important for the production of complicated, thin-walled moldings and their safe handling.
- the present invention was therefore based on the object to provide a molding material mixture available, which can be used for the production of moldings for the foundry industry and which are characterized by improved strength.
- B) a binder system comprising i) formaldehyde, a formaldehyde donor and / or precondensates of formaldehyde, and ii) an amino acid.
- moldings for the foundry industry have an improvement in strength when they are made from a molding material mixture according to the invention.
- the addition of an amino acid to a binder system which comprises formaldehyde, a formaldehyde donor and / or precondensates of formaldehyde surprisingly improved the strength of the molding produced therefrom, in comparison to moldings which, under identical conditions, consist of molding material mixtures of the same composition but without the additive an amino acid were prepared.
- molded articles which are produced from a molding material mixture according to the invention are additionally distinguished by a lower content of free formaldehyde.
- Formaldehyde has a pungent odor and is toxic at high concentrations.
- urea has hitherto usually been used as formaldehyde scavenger.
- amino acids additionally have the advantage that the nitrogen content in the molding material mixture or in the molded articles produced therefrom can be reduced since the amino acids according to the invention are the more effective formaldehyde scavengers.
- urea when using urea, no significant improvement but rather a decrease in strength is observed.
- the use of urea as a formaldehyde scavenger often results in reaction products which are not stable in mixture and lead to clouding and precipitation.
- a binder should have the lowest possible total nitrogen content, since a high nitrogen content causes surface defects, for example so-called "pinholes", as casting defects.
- the moldings for the foundry industry are preferably feeders, foundry molds or cores for the foundry industry.
- refractory fillers As pourable, refractory fillers, it is possible to use all granular fillers customarily used for the production of shaped articles (in particular feeders, foundry molds and cores) for the foundry industry, e.g. Quartz sand and special sands.
- special sand includes natural mineral sands and sintered and melted products, which are produced in granular form or transferred by crushing, grinding and Klassiervor réelle in granular form, or by other physico-chemical processes resulting inorganic mineral sands, which are used as mold bases with customary Binders are used for the manufacture of feeders, cores and molds.
- a molding material mixture according to the invention is particularly preferred, wherein the one, at least one or more pourable, refractory fillers are selected from the group consisting of quartz sand, quartz sand, olivine sand, chromium-magnesite granules, aluminum silicates, in particular J-sand and kerphalite, heavy minerals, especially chromite, zircon sand and R-sand, technical ceramics, in particular Cerabeads, chamotte, m-sand, alodur, bauxite sand and silicon carbide, feldspar sands, andalusite sands, hollow ball corundum, fly ash spheres, rice husk ash, blown glasses, foam glasses, expanded perlite, core-shell particles, hollow microspheres, fly ashes and other specialty sands.
- the one, at least one or more pourable, refractory fillers are selected from the group consisting of quartz sand, quartz s
- Preference according to the invention is given to molding material mixtures, the one, at least one of the plurality or all free-flowing, refractory fillers having an average particle diameter d50 in the range between 0.001 and 5 mm, preferably in the range from 0.01 to 3 mm, particularly preferably in the range from 0, 02 to 2.0 mm.
- the mean particle diameter d50 is determined according to DIN 66165-2, F and DIN ISO 3310-1.
- molding material mixtures the ratio of the total mass of free-flowing, refractory fillers to the total mass of other constituents of the molding material mixture in the range from 100: 5 to 100: 0.1, preferably from 100: 3 to 100: 0.4, particularly preferred from 100: 2 to 100: 0.6. Also preferred are molding mixtures according to the invention, wherein the bulk density of a mixture of all solids of the molding material mixture is 100 g / L or greater, preferably 200 g / L or greater, more preferably 1000 g / L or greater.
- the binder system additionally comprises: (a) phenols, in particular phenol, o-cresol, p-cresol, 3,5-xylenol or resorcinol, or precondensates of phenols, in particular resols,
- the binder system is used in the production of the molding with a hardener which initiates the curing of the binder.
- the curing agent is usually acids, preferably at least one organic or inorganic acid, more preferably an aromatic sulfonic acid (especially para-toluenesulfonic and / or xylenesulfonic acid), phosphoric acid, methanesulfonic acid, sulfuric acid, one or more carboxylic acids or mixtures it.
- molding mixtures according to the invention are particularly preferred, wherein the binder system is thermally curable.
- the binder additionally comprises (a) phenols, in particular phenol, o-cresol, p-cresol, 3,5-xylenol or resorcinol, or precondensates of phenols, in particular resoles, and (b) furan derivatives and / or Furfuryl alcohol or precondensates of furan derivatives and / or furfuryl alcohol.
- phenols in particular phenol, o-cresol, p-cresol, 3,5-xylenol or resorcinol
- precondensates of phenols in particular resoles
- furan derivatives and / or Furfuryl alcohol or precondensates of furan derivatives and / or furfuryl alcohol This results in phenolic / furfuryl alcohol / formaldehyde resin bonded moldings during curing.
- the binder system is curable to a phenol / furfuryl alcohol / formaldehyde resin, particularly preferably to a high polymer and solid phenol / furfuryl alcohol / formaldehyde resin is curable.
- the curing of these systems preferably takes place by addition of a hardener, the hardener being an organic or inorganic acid, particularly preferably an aromatic sulfonic acid (especially para-toluic or xylenesulfonic acid or mixtures of para-toluic and xylenesulfonic acid), phosphoric acid, methanesulfonic acid, Sulfuric acid, one or more carboxylic acids or mixtures of the aforementioned acids.
- Moldings mixtures according to the invention are particularly preferred, wherein the binder additionally comprises furan derivatives and / or furfuryl alcohol or precondensates of furan derivatives and / or furfuryl alcohol.
- the binder system is curable to a furfuryl alcohol / formaldehyde resin, preferably curable to a high polymer and solid furfuryl alcohol / formaldehyde resin.
- Moldings mixtures according to the invention are particularly preferred, wherein the binder additionally comprises urea or urea derivatives or precondensates of urea or urea derivatives.
- the binder system is curable to a urea / formaldehyde resin, preferably curable to a high polymer and solid urea / formaldehyde resin.
- the curing of these systems is preferably carried out by heating in the presence of a latent curing agent (warm box) or by adding a hardener, the hardener being an organic or inorganic acid, particularly preferably an aromatic sulfonic acid (especially para-toluic or xylene sulfonic acid or mixtures of para).
- Moldings mixtures according to the invention are particularly preferred, wherein the binder additionally comprises i) urea or urea derivatives or precondensates of urea or urea derivatives and ii) furan derivatives and / or furfuryl alcohol or precondensates of furan derivatives and / or furfuryl alcohol.
- the binder additionally comprises i) urea or urea derivatives or precondensates of urea or urea derivatives and ii) furan derivatives and / or furfuryl alcohol or precondensates of furan derivatives and / or furfuryl alcohol.
- the binder system is curable to a urea / furfuryl alcohol / formaldehyde resin, preferably curable to a high polymer and solid urea / furfuryl alcohol / formaldehyde resin.
- the curing of these systems is preferably carried out by heating in the presence of a latent curing agent (warm box) or by adding a hardener, the hardener being an organic or inorganic acid, particularly preferably an aromatic sulfonic acid (especially para-toluic or xylene sulfonic acid or mixtures of para). Toluene- and xylenesulfonic acid), phosphoric acid, methanesulfonic acid, sulfuric acid, one or more carboxylic acids or mixtures of the abovementioned acids.
- urea or urea derivatives or precondensates of urea or urea derivatives ii) furan derivatives and / or furfuryl alcohol or precondensates of furan derivatives and / or furfuryl alcohol and iii) phenols, in particular phenol, o-cresol , p-cresol, 3,5-xylenol or resorcinol, or precondensates of phenols, especially resoles.
- the binder system is curable to a urea / furfuryl alcohol / phenol / formaldehyde resin, preferably curable to a high polymer and solid urea / furfuryl alcohol / phenol / formaldehyde resin.
- the curing of these systems is preferably carried out by heating in the presence of a latent hardener (warm box) or by adding a hardener, wherein the hardener is an organic or inorganic acid, particularly preferably an aromatic sulfonic acid (in particular para-toluene or xylene sulfonic acid or mixtures of para-toluene and xylene sulfonic acid), phosphoric acid, methanesulfonic acid, sulfuric acid, one or more carboxylic acids or mixtures of the abovementioned acids ,
- molding material mixtures wherein the binder system is curable to i) phenol / furfuryl alcohol / formaldehyde resin, ii) furfuryl alcohol / formaldehyde resin, iii) urea / formaldehyde resin, iv) urea / furfuryl alcohol / formaldehyde resin or v) urea / furfuryl alcohol / phenol / formaldehyde resin
- the amino acid is selected from the group consisting of alanine, glycine, isoleucine, methionine, proline, valine, histidine, phenylalanine, tryptophan, tyrosine, asparagine, glutamine, cysteine, methionine, serine, threonine, tyrosine, lysine , Arginine and histidine, preferably selected from the group consisting of glycine, glutamine, alanine, valine and serine.
- a molding material mixture according to the invention wherein the proportion of all amino acids in the molding material mixture is 0.005 to 5.0 wt .-%, preferably 0.01 to 2.0 wt .-%, more preferably 0.03 to 1 , 0 wt .-%, based on the solids content of the entire molding material mixture.
- molding material mixtures according to the invention have particularly good properties if the proportion of all amino acids in the molding material mixture lies in the above-mentioned ranges. If the proportion of amino acids in the molding material mixture is too low, there is the possibility that the strength of the molded articles produced from the molding material mixtures will not be sufficiently improved and / or the amount of free formaldehyde will not be reduced. If the proportion of amino acids is too high, no further improvement in the properties can be observed. Likewise preferred is a molding material mixture according to the invention, wherein the molar ratio of all amino acids to available formaldehyde is 4: 1 to 1: 0.5, preferably 3: 1 to 1: 0.9, more preferably 2.5: 1 to 1: 1 ,
- molding mixtures according to the invention have particularly good properties when the molar ratio of all the amino acids to available formaldehyde is in the ranges indicated above.
- the strength of the molded body produced from the molding mixtures and the proportion of free formaldehyde in the molding material mixtures or the moldings produced therefrom show particularly good properties in the specified ranges.
- formaldehyde donors and / or precondensates of formaldehyde are selected from the group consisting of paraformaldehyde, hexamethylenetetramine, trioxane, methylolamine and methylolamine derivatives such as trimethylolmelamine or hexamethylolmelamine.
- the molding material mixture contains no proteins or peptides, such as dipeptides, tripeptides, tetrapeptides, pentapeptides or higher-order peptides). It has also been shown that it is advantageous for some embodiments of the present invention if the amino acid used is not aspartic acid but another amino acid, preferably glycine, glutamine, alanine, valine and / or serine.
- Another aspect of the present invention relates to molded articles for the foundry industry produced using a molding material mixture according to the invention.
- a molded article of the invention wherein the one or more pourable refractory fillers are bound with a cured binder and the cured binder is i) phenol / furfuryl alcohol / formaldehyde resin, ii) furfuryl alcohol / formaldehyde resin, iii) urea / formaldehyde resin, iv ) Urea / furfuryl alcohol / formaldehyde resin or v) urea / furfuryl alcohol / phenol / formaldehyde resin.
- a molding according to the invention wherein the molding is formed by curing the binder system, wherein a chemical reaction takes place between formaldehyde and / or a precondensate of formaldehyde and
- Another aspect of the present invention relates to the use of amino acids (a) in a molding material mixture for the production of moldings for the foundry industry or (b) for the production of moldings for the foundry industry.
- Another aspect of the present invention relates to the use of at least one amino acid in a molding material mixture for the foundry industry, wherein the molding material mixture in addition to the amino acid formaldehyde or a formaldehyde source.
- the amino acid is selected from the group consisting of alanine, glycine, isoleucine, methionine, proline, valine, histidine, phenylalanine, tryptophan, tyrosine, asparagine, glutamine, cysteine, methionine, serine, threonine, tyrosine, lysine , Arginine and histidine, more preferably selected from the group consisting of glycine, glutamine, alanine, valine and serine.
- a further aspect of the present invention relates to the use of at least one amino acid for the production of moldings having improved strength and / or reduced tendency to casting defects.
- Another aspect of the present invention relates to the use of molding material mixtures according to the invention for the production of moldings for the foundry industry.
- a further aspect in connection with the present invention relates to a process for producing a molding material mixture according to the invention, comprising the following steps: a) producing or providing one or more free-flowing refractory fillers, b) producing or providing a binder system, comprising i) Formaldehyde, a formaldehyde donor and / or formaldehyde precondensates, and ii) an amino acid and c) mixing all components.
- Another aspect in connection with the present invention relates to a process for the production of a molded article for the foundry industry comprising the following steps: i) producing or providing a molding material mixture according to the invention, preferably by means of a process according to the invention for a molding material mixture according to the invention, ii) molding the molding material mixture into one uncured molding; and iii) allowing the uncured molding to cure or cure to yield a molded article for the foundry industry.
- the hardening or hardening of the uncured shaped body takes place by heating.
- curing or curing is effected by adding a hardener during the production or provision of the molding material mixture according to the invention.
- the curing agent is preferably an organic or inorganic acid, more preferably a sulfonic acid (especially para-toluenesulfonic acid), phosphoric acid, methanesulfonic acid, carboxylic acid and / or sulfuric acid, or mixtures thereof.
- a further aspect in connection with the present invention relates to a kit for producing a molding material mixture according to the invention and / or for producing a molding according to the invention for the foundry industry, preferably for the production of feeders, foundry molds or cores for the foundry industry I) defines a binder system as described above for a molding material mixture according to the invention,
- a hardener preferably an organic or inorganic acid, particularly preferably an aromatic sulfonic acid (especially para-toluenesulfonic acid), phosphoric acid, carboxylic acid, methanesulfonic acid and / or sulfuric acid or mixtures thereof.
- Example 1 (according to the invention):
- the respective flexural strength values were determined in accordance with VDG leaflet P 72. To determine the flexural strengths, the test bars were placed in a Georg Fischer Strength Tester equipped with a three-point bending device (DISA-Industrie AG, Schaffhausen, CH) and the force was measured which resulted in the breakage of the test bars. The flexural strengths were after one hour, after two hours, after four hours and after 24 hours after the preparation of the test (test) moldings (storage of the cores after demolding each at room temperature 18-22 ° C, relative humidity (20-55 %). The values determined are summarized in Table 1.
- the (test) shaped bodies produced from the molding material mixture according to the invention exhibit improved flexural strength after 24 hours compared with the (test) moldings produced according to Comparative Examples 1 and 2, without adversely affecting the setting behavior.
- the content of free formaldehyde in the binder system according to the invention is lower than the content of free formaldehyde in the binder systems according to Comparative Examples 1 and 2.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 1. However, 5.7 mmol alanine instead of glycine were used.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.08%.
- Example 3 (Inventive): The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 1. However, 5.7 mmol serine was used instead of glycine.
- Example 4 (according to the invention):
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 1. However, 5.7 mmol of urea was used instead of the glycine. After cooling the binder system to room temperature (18 - 22 ° C), the binder system had a free formaldehyde content of 0.13%.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 1. However, no glycine was added. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.15%.
- the (test) moldings produced from the molding material mixture according to the invention exhibit improved flexural strength after four hours compared with the (test) moldings produced according to Comparative Examples 3 and 4, without adversely affecting the setting behavior.
- the content of free Formaldehyde in the binder system according to the invention lower than the content of free formaldehyde in the binder systems according to Comparative Examples 3 and 4.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 5. However, 4.2 mmol alanine instead of glycine were used.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a 0.05% free formaldehyde content.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 5. However, 4.2 mmol of serine were used instead of glycine.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a 0.06% free formaldehyde content.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a 0.05% free formaldehyde content.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 5. However, 4.2 mmol of glutamine were used instead of glycine. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.03%.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 5. However, 4.2 mmol of urea instead of the glycine were used.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.12%.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 5. However, no glycine was added.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.17%.
- Example 1 The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 1.
- 4.0 mmol glycine was used.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a 0.05% free formaldehyde content.
- the (test) shaped bodies according to the invention produced from the molding material mixture according to the invention show in comparison with the comparative examples 5 and 6 according to the invention. put (test) moldings after 24 hours on an improved flexural strength, without the setting behavior is adversely affected.
- the content of free formaldehyde in the binder system according to the invention is lower than the content of free formaldehyde in the binder systems according to Comparative Examples 6 and 5.
- Example 1 1 (according to the invention):
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 10. However, 4.0 mmol alanine instead of glycine were used.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a 0.05% free formaldehyde content.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 10. However, 4.0 mmol of serine were used instead of glycine.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.08%.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.07%.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 10. However, 4.0 mmol of glutamine were used instead of glycine. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.03%.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 10. However, 4.0 mmol of urea instead of the glycine were used.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a 0.05% free formaldehyde content.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 10. However, no glycine was added.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.15%.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.04%.
- the (test) shaped bodies produced from the molding material mixture according to the invention show in comparison with the comparative examples 7 and 8 put (test) moldings after 24 hours on an improved flexural strength, without the setting behavior is adversely affected.
- the content of free formaldehyde in the binder system according to the invention is lower than the content of free formaldehyde in the binder systems according to Comparative Examples 7 and 8.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 15. However, 8.3 mmol alanine instead of glycine were used.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.04%.
- Example 17 (according to the invention):
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 15. However, 8.3 mmol of serine were used instead of glycine.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a 0.05% free formaldehyde content.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.07%.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 15. However, 8.3 mmol of glutamine were used instead of glycine. After cooling the binder system to room temperature (18-22 ° C), the binder system had a 0.06% free formaldehyde content.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 15. However, 8.3 mmol urea instead of the glycine were used.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.19%.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 15. However, no glycine was added.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.27%.
- Example 1 The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 1.
- 7.7 mmol glycine were used.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.09%.
- the (test) shaped bodies according to the invention produced from the molding material mixture according to the invention show over those produced according to Comparative Example 9 (Test) moldings after 24 hours improved flexural strength, without the setting behavior is adversely affected.
- the content of free formaldehyde in the binder system according to the invention is lower than the content of free formaldehyde in the binder systems according to Comparative Example 9.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 20. However, 7.7 mmol alanine instead of glycine were used.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.08%.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 20. However, 7.7 mmol of serine were used instead of glycine.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.09%.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.07%.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 20. However, no glycine was added. After cooling the binder system to room temperature (18-22 ° C), the binder system had 0.23% free formaldehyde content.
- the molding material mixture by hand was introduced into a scholarriegelform, compacted with a hand plate and cured at 220 ° C.
- the test specimens produced were guader-shaped test bars measuring 220 mm x 22.36 mm x 22.36 mm, known as Georg Fischer test bars.
- the cold bending strength of the produced (test) shaped body is higher than in Comparative Example 1 1, in which no amino acid was added.
- the cold bending strength is particularly high.
- the hot bending strengths are not adversely affected.
- Example 25 (according to the invention): The preparation of the binder system, of the molding material mixture and of the (test) shaped body was carried out analogously to Example 24. However, 8.3 mmol of alanine were used instead of glycine.
- the cold bending strength of the produced (test) shaped body is higher than in Comparative Example 1 1, in which no amino acid was added.
- the cold bending strength is particularly high.
- the hot bending strengths are not adversely affected.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 24. However, 8.3 mmol of glutamine were used instead of glycine. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of less than 0.08%.
- the cold bending strength of the produced (test) shaped body is higher than in Comparative Example 1 1, in which no amino acid was added.
- the cold bending strength is particularly high.
- the hot bending strengths are not adversely affected.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 24. However, 8.36 mmol of serine were used instead of glycine.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of less than 0.08%.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 24. However, 8.3 mmol urea instead of glycine was used.
- the binder system After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.07%.
- the preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 24. However, no glycine was added. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.18%.
- Table 1 Comparison of the processing (WT) and curing time (ST) and the flexural strengths of the (test) moldings produced in Examples 1 to 23 and Comparative Examples 1 to 9. Hot bending strengths in [N / cm 2] - Cold bending strength [N / cm 2] - Tested tested immediately after preparation, after cooling, the baking time after ... seconds in nuclei by ... seconds baking time 220 ° C at 220 ° C
- Comparative Example 1 1 210 225 235 220 680 660 600 530
- Example 24 215 220 240 230 740 710 630 580
- Example 25 230 240 280 220 770 760 610 570
- Example 26 200 220 270 220 780 740 610 550
Abstract
The present invention relates to a moulding material mixture for production of mouldings for the foundry industry, especially for production of foundry moulds, cores or feeders, for the foundry industry, comprising A) one or more pourable refractory fillers, B) a binder system comprising i) formaldehyde, a formaldehyde donor and/or precondensates of formaldehyde, and ii) an amino acid. The present invention additionally relates to the use of amino acids in a moulding material mixture for production of mouldings for the foundry industry or for production of mouldings for the foundry industry, to a process for producing a moulding material mixture and to a process for producing a moulding for the foundry industry.
Description
HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Wiesenstraße 23, 40549 Düsseldorf HÜTTENES-ALBERTUS Chemical Works Limited Liability Company Wiesenstraße 23, 40549 Düsseldorf
Aminosäure enthaltende Formstoffmischung zur Herstellung von Formkörpern für die Gießereiindustrie Amino acid-containing molding material mixture for the production of moldings for the foundry industry
Die vorliegende Erfindung betrifft eine Formstoffmischung zur Herstellung von Formkörpern für die Gießereiindustrie, Formkörper für die Gießereiindustrie, eine Verwendung von Aminosäuren in einer Formstoffmischung zur Herstellung von Formkörpern für die Gießereiindustrie oder zur Herstellung von Formkörpern für die Gießereiindustrie, ein Verfahren zur Herstellung einer Formstoffmischung und ein Verfahren zur Herstellung eines Formkörpers für die Gießereiindustrie. The present invention relates to a molding material mixture for the production of moldings for the foundry industry, moldings for the foundry industry, a use of amino acids in a molding material mixture for the production of moldings for the foundry industry or for the production of moldings for the foundry industry, a process for the preparation of a molding material mixture and a Process for producing a molded article for the foundry industry.
In der Gießereiindustrie werden Schmelzflüssigwerkstoffe, Eisenmetalle bzw. Nichteisenmetalle in geformte Gegenstände mit bestimmten Werkstückeigenschaften überführt. Für die Formgebung der Gussstücke müssen zunächst zum Teil sehr komplizierte Gieß- formen zur Aufnahme der Metallschmelze hergestellt werden. Die Gießformen werden unterteilt in verlorene Formen, die nach jedem Guss zerstört werden, sowie Dauerformen, mit denen jeweils eine große Anzahl von Gussstücken hergestellt werden kann. Die verlorenen Formen bestehen meist aus einem feuerfesten, schüttfähigen Formstoff, der mit Hilfe eines härtbaren Bindemittels verfestigt wird. Formen sind Negative, die den auszugießenden Hohlraum enthalten, der das zu fertigende Gussstück ergibt. Bei der Herstellung der Form wird mittels eines Modells des zu
fertigenden Gussstücks der Hohlraum in den Formstoff geformt. Innenkonturen werden durch Kerne dargestellt, die in einem separaten Kernkasten geformt werden. In the foundry industry, molten materials, ferrous metals and non-ferrous metals are converted into shaped articles with specific workpiece properties. To shape the castings, it is first necessary to produce very complicated casting molds for receiving the molten metal. The casting molds are divided into lost molds that are destroyed after each casting, and permanent molds, with each of which a large number of castings can be produced. The lost forms usually consist of a refractory, pourable molding material, which is solidified by means of a curable binder. Shapes are negatives that contain the pouring cavity that results in the casting being manufactured. In the production of the mold is by means of a model of forming casting of the cavity formed in the molding material. Inner contours are represented by cores formed in a separate core box.
Zur Herstellung der Gießformen können sowohl organische als auch anorganische Bindemittel eingesetzt werden, deren Aushärtung durch kalte oder heiße Verfahren erfolgen kann. Als kalte Verfahren bezeichnet man dabei Verfahren, bei denen die Aushärtung im Wesentlichen bei Raumtemperatur ohne Erhitzen der Formstoffmischung erfolgt. Die Aushärtung erfolgt dabei meist durch eine chemische Reaktion, die beispielsweise dadurch ausgelöst werden kann, dass ein gasförmiger Katalysator durch die zu härtende Formstoffmischung geleitet wird, oder indem der Formstoffmischung ein flüssiger Kataly- sator zugesetzt wird. Bei heißen Verfahren wird die Formstoffmischung nach der Formgebung auf eine ausreichend hohe Temperatur erhitzt, um beispielsweise das im Bindemittel enthaltene Lösungsmittel auszutreiben oder um eine chemische Reaktion zu initiieren, durch welche das Bindemittel durch Vernetzen ausgehärtet wird. For the production of casting molds both organic and inorganic binders can be used, the curing of which can be effected by cold or hot processes. Cold processes are processes in which the curing takes place essentially at room temperature without heating the molding material mixture. The curing is usually carried out by a chemical reaction, which can be triggered, for example, by passing a gaseous catalyst through the molding material mixture to be cured, or by adding a liquid catalyst to the molding material mixture. In hot processes, after molding, the molding material mixture is heated to a temperature high enough to expel, for example, the solvent contained in the binder or to initiate a chemical reaction by which the binder is cured by crosslinking.
Die Herstellung der Gießformen kann dabei in der Weise verlaufen, dass der Füllstoff zunächst mit dem Bindemittelsystem vermengt wird, sodass die Körner des feuerfesten Füllstoffs mit einem dünnen Film des Bindemittelsystems überzogen sind. Die aus Füllstoff und Bindemittelsystem erhaltene Formstoffmischung kann dann in eine entsprechende Form eingebracht und gegebenenfalls verdichtet werden, um eine ausreichende Standfestigkeit der Gießform zu erreichen. Anschließend wird die Gießform ausgehärtet. Hat die Gießform zumindest eine gewisse Anfangsfestigkeit erreicht, so kann sie aus der Form entnommen werden. The production of the casting molds can be carried out in such a way that the filler is first mixed with the binder system, so that the grains of the refractory filler are coated with a thin film of the binder system. The molding material mixture obtained from the filler and binder system can then be introduced into a corresponding mold and optionally compacted in order to achieve a sufficient stability of the casting mold. Subsequently, the mold is cured. If the mold has reached at least a certain initial strength, it can be removed from the mold.
Gegenwärtig werden für die Herstellung von Gießformen vielfach organische Bindemittel, wie z. B. Polyurethan-, Furanharz-, Phenol- oder Harnstoff-Formaldehyd Harze eingesetzt, bei denen die Aushärtung des Bindemittels durch Zugabe eines Katalysators er- folgt. At present, for the production of molds often organic binders such. As polyurethane, furan resin, phenol or urea-formaldehyde resins used in which the curing of the binder by addition of a catalyst follows.
Verfahren, bei denen die Aushärtung der Formstoffmischung durch Hitze oder durch nachträgliche Zugabe eines Katalysators erfolgt, haben den Vorteil, dass die Verarbeitung der Formstoffmischung keinen besonderen zeitlichen Restriktionen unterliegt. Die Formstoffmischung lässt sich zunächst in größeren Mengen herstellen, die dann inner- halb eines längeren Zeitraums, meist mehreren Stunden, verarbeitet werden. Die Aushärtung der Formstoffmischung erfolgt erst nach der Formgebung, wobei eine rasche Reaktion angestrebt wird. Die Gießform lässt sich nach dem Aushärten unmittelbar aus dem Formwerkzeug entnehmen, sodass kurze Taktzeiten verwirklicht werden können.
Bei der Herstellung von Gießformen für große Gussstücke, beispielsweise Motorblöcke von Schiffsdieseln oder großen Maschinenteilen, wie Naben von Rotoren für Windkraftwerke, werden meist sogenannte „No-Bake-Bindemittel" verwendet. Beim „No-Bake- Verfahren" wird der feuerfeste Formgrundstoff (z.B. Sand) häufig zunächst mit einem Katalysator (Härter) belegt, anschließend das Bindemittel zugegeben und durch Mischen gleichmäßig auf den bereits mit Katalysator beschichteten Körnern des feuerfesten Formgrundstoffs verteilt. Bei diesem Verfahren wird häufig mit sogenannten kontinuierlichen Durchlaufmischern gearbeitet. Die resultierende Formstoffmischung lässt sich dann zu einem Formkörper formen. Da Bindemittel und Katalysator gleichmäßig in der FormStoffmischung verteilt sind, erfolgt auch bei großen Formkörpern die Aushärtung weitgehend gleichmäßig. Processes in which the curing of the molding material mixture by heat or by subsequent addition of a catalyst, have the advantage that the processing of the molding material mixture is not subject to any special time restrictions. The molding material mixture can initially be produced in larger quantities, which are then processed within a relatively long period of time, usually several hours. The curing of the molding material mixture takes place only after molding, with a rapid reaction is sought. The mold can be removed immediately after curing from the mold so that short cycle times can be realized. In the production of casting molds for large castings, for example engine blocks of marine diesels or large machine parts, such as hubs of rotors for wind power plants, so-called "no-bake binders" are mostly used Sand) often first with a catalyst (hardener) occupied, then added the binder and evenly distributed by mixing on the already coated with catalyst grains of the refractory base molding material. In this process is often worked with so-called continuous flow mixers. The resulting molding material mixture can then be shaped into a shaped body. Since binder and catalyst are evenly distributed in the molding material mixture, the curing is largely uniform even with large moldings.
Alternativ kann beim „No-Bake-Verfahren" der feuerfeste Formgrundstoff (z.B. Sand) zunächst mit dem Bindemittel vermischt und anschließend der Härter zugegeben werden. Bei dieser Verfahrensführung kann es, insbesondere bei der Herstellung von Gießformen für große Gussstücke, wegen einer partiellen, lokalen zu hohen Konzentration des Härters zu einer Teilhärtung bzw. Vernetzung des Bindemittels kommen, woraus ein inhomogener Formstoff resultieren würde. Alternatively, in the "no-bake process", the refractory base molding material (eg sand) can first be mixed with the binder and then the curing agent can be added To high concentration of the curing agent to partial hardening or crosslinking of the binder come, resulting in an inhomogeneous molding material would result.
Die "klassischen" No-Bake-Bindemittel beruhen häufig auf Furanharzen oder Phenolharzen oder Furan- /Phenolharzen. Sie werden oft als Systeme (Kits) angeboten, wobei eine Komponente ein reaktionsfähiges Furanharz bzw. Phenolharz oder Furan/Phenolharz und die andere Komponente eine Säure umfasst, wobei die Säure als Katalysator für die Aushärtung der reaktiven Harzkomponente wirkt. The "classic" no-bake binders are often based on furan resins or phenolic resins or furan / phenolic resins. They are often offered as systems (kits) wherein one component comprises a reactive furan resin or furan / phenolic resin and the other component comprises an acid, which acid acts as a catalyst for curing the reactive resin component.
Furan- und Phenolharze zeigen beim Guss sehr gute Zerfallseigenschaften. Unter der Hitzeeinwirkung des flüssigen Metalls zersetzt sich das Furan- oder Phenolharz und die Festigkeit der Gießform geht verloren. Nach dem Guss lassen sich daher Kerne, gegebenenfalls nach vorherigem Rütteln des Gussstücks, aus Hohlräumen entfernen. Furan and phenolic resins show very good disintegration properties during casting. Under the action of heat of the liquid metal, the furan or phenolic resin decomposes and the strength of the mold is lost. After casting, therefore, cores, if necessary after prior shaking of the casting, can be removed from cavities.
"Furan-No-Bake-Bindemittel" enthalten reaktive Furanharze, welche regelmäßig als wesentliche Komponente Furfurylalkohol umfassen. Furfurylalkohol kann unter saurer Katalyse mit sich selbst reagieren und ein Homopolymer ausbilden. Für die Herstellung von Furan-No-Bake-Bindemitteln wird im Allgemeinen nicht Furfurylalkohol alleine verwendet, sondern es werden dem Furfurylalkohol weitere Verbindungen, wie Formaldehyd, zugesetzt, die in das Harz einpolymerisiert werden. Den Harzen können noch weitere Komponenten zugegeben werden, welche die Eigenschaften des Harzes beeinflussen,
beispielsweise dessen Elastizität. Melamin und Harnstoff kann beispielsweise zugesetzt werden, um noch freies Formaldehyd zu binden. "Furan no-bake binders" contain reactive furan resins, which regularly comprise furfuryl alcohol as an essential component. Furfuryl alcohol can react with itself under acid catalysis and form a homopolymer. For the production of furan no-bake binders, furfuryl alcohol is generally not used alone, but further compounds, such as formaldehyde, are added to the furfuryl alcohol, which are polymerized into the resin. The resins may be added with further components which influence the properties of the resin, for example, its elasticity. Melamine and urea may be added, for example, to bind still free formaldehyde.
Furan-No-Bake-Bindemittel werden meist dargestellt, indem zuerst Vorkondensate aus beispielsweise Harnstoff, Formaldehyd und Furfurylalkohol unter sauren Bedingungen erzeugt werden. Diese Vorkondensate werden danach mit Furfurylalkohol verdünnt. Furan no-bake binders are most often prepared by first producing precondensates of, for example, urea, formaldehyde, and furfuryl alcohol under acidic conditions. These precondensates are then diluted with furfuryl alcohol.
Ebenso ist es vorstellbar, dass Harnstoff und Formaldehyd alleine zur Reaktion gebracht werden. Dabei entstehen so genannte UF-Harze („Urea Formaldehyde"-Harze, „Aminoplaste"). Diese werden meist anschließend mit Furfurylalkohol verdünnt. Vorteile dieser Herstellungsweise sind eine höhere Flexibilität / Variabilität in der Produktpalette und geringere Kosten, da es sich um kalte Mischprozesse handelt. It is also conceivable that urea and formaldehyde are reacted alone. This produces so-called UF resins ("urea formaldehyde" resins, "aminoplasts"). These are usually subsequently diluted with furfuryl alcohol. Advantages of this manufacturing method are a higher flexibility / variability in the product range and lower costs, because it is cold mixing processes.
Zur Herstellung von Furan-/Phenol-No-Bake-Bindemitteln können auch Resole verwendet werden. Resole werden durch Polymerisation von Gemischen aus Phenol und Formaldehyd hergestellt. Diese Resole werden dann häufig mit einer großen Menge an Furfurylalkohol verdünnt. Resols can also be used to prepare furan / phenol no-bake binders. Resoles are prepared by polymerization of mixtures of phenol and formaldehyde. These resoles are then often diluted with a large amount of furfuryl alcohol.
Furan-No-Bake-Bindemittel werden mit einer Säure gehärtet. Diese Säure katalysiert die Vernetzung des reaktiven Furanharzes. Zu beachten ist, dass über die Säuremenge die Aushärtung gesteuert werden kann, wobei die zur Einstellung einer Aushärtezeit notwendige Säuremenge Bindemittelabhängig ist und von Faktoren wie zum Beispiel dem pH Wert des Binders und der Art der Säure beeinflusst wird. Furan no-bake binders are cured with an acid. This acid catalyzes the crosslinking of the reactive furan resin. It should be noted that the amount of acid can control the cure, the amount of acid necessary to set a cure time being binder dependent and affected by factors such as the binder's pH and the type of acid.
Als Säuren werden häufig aromatische Sulfonsäuren, Phosphorsäure, Methansulfonsäure und Schwefelsäure verwendet. In einigen speziellen Fällen werden Kombinationen hiervon unter anderem auch in Kombination mit weiteren Carbonsäuren verwendet. Ferner können dem Furan-No-Bake-Bindemittel bestimmte „Härtungs- Moderatoren" zugesetzt werden. As acids, aromatic sulfonic acids, phosphoric acid, methanesulfonic acid and sulfuric acid are often used. In some specific cases, combinations of these are used, inter alia, in combination with other carboxylic acids. Further, certain "curing moderators" can be added to the furan no-bake binder.
Phenolharze als zweite große Gruppe säurekatalysiert aushärtbarer No-Bake-Bindemittel enthalten als reaktive Harzkomponente Resole, also Phenolharze, die mit einem molaren Überschuss an Formaldehyd hergestellt wurden. Phenolharze zeigen im Vergleich zu Furanharzen eine geringere Reaktivität und erfordern als Katalysatoren starke Sulfonsäuren.
Seit einiger Zeit werden No-Bake-Bindemittel für die Fertigung von Formen und Kernen für den Groß- und Einzelguss eingesetzt. Diese kalthärtenden Systeme sind meist Reaktionsprodukte aus Formaldehyd mit Furfurylalkohol, Phenol und/oder Harnstoff. Phenolic resins as the second large group of acid-catalyzed curable no-bake binders contain resoles as reactive resin components, ie phenolic resins which have been prepared with a molar excess of formaldehyde. Phenolic resins show lower reactivity compared to furan resins and require strong sulfonic acids as catalysts. For some time no-bake binders have been used for the production of molds and cores for large and single castings. These cold-curing systems are mostly reaction products of formaldehyde with furfuryl alcohol, phenol and / or urea.
Formstoffmischungen auf Basis von Formaldehyd weisen üblicherweise sehr gute Eigen- schatten auf. Insbesondere Phenol/Furan/Formaldehyd-Mischharze, Harnstoff/Formaldehydharze und Furan/Formaldehydharze werden in der Gießereiindustrie häufig eingesetzt. Formaldehyde-based blends usually have very good properties. In particular, phenol / furan / formaldehyde mixed resins, urea / formaldehyde resins and furan / formaldehyde resins are widely used in the foundry industry.
US 3,644,274 betrifft primär ein No-Bake-Verfahren unter Verwendung bestimmter Mischungen von Säurekatalysatoren zu Härtung für Furfurylalkohol-Formaldehyd- Harnstoff harze. US 3,644,274 relates primarily to a no-bake method using certain mixtures of acid catalysts to cure for furfuryl alcohol-formaldehyde urea resins.
US 3,806,491 betrifft Bindemittel, die im„No-Bake"-Verfahren eingesetzt werden können. Die dort eingesetzten Bindemittel umfassen Produkte aus der Umsetzung von Paraform- aldehyd mit bestimmten Ketonen im basischen Milieu sowie Furfurylalkohol und/oder Furanharze. US 5,491 , 180 beschreibt Harz-Bindemittel, die für den Einsatz im No-Bake-Verfahren geeignet sind. Die dort verwendeten Bindemittel basieren auf 2,5- Bis(hydroxymethyl)furan oder Methyl- oder Ethylethern des 2,5-Bis(hydroxymethyl)furans, wobei die Bindemittel 0,5 bis 30 Gew.-% Wasser enthalten und regelmäßig einen hohen Anteil an Furfurylalkohol. EP 0 540 837 schlägt emissionsarme, kalthärtende Bindemittel auf der Basis von Furanharzen und Lignin aus dem Organosolv-Verfahren vor. Die dort beschriebenen Furanharze enthalten einen hohen Anteil an monomerem Furfurylalkohol. US Pat. No. 3,806,491 relates to binders which can be used in the "no-bake" process The binders used there comprise products from the reaction of paraformaldehyde with certain ketones in a basic medium and furfuryl alcohol and / or furan resins Binders suitable for use in the no-bake process The binders used there are based on 2,5-bis (hydroxymethyl) furan or methyl or ethyl ethers of 2,5-bis (hydroxymethyl) furan, the binders 0.5 to 30% by weight of water and regularly a high proportion of furfuryl alcohol EP 0 540 837 proposes low-emission, cold-hardening binders based on furan resins and lignin from the Organosolv process The furan resins described there contain a high proportion on monomeric furfuryl alcohol.
DE 198 56 778 beschreibt Kaltharz-Bindemittel, welche durch Reaktion einer Aldehyd- Komponente, einer Keton-Komponente und einer im Wesentlichen aus Furfurylalkohol bestehenden Komponente hergestellt werden. DE 198 56 778 describes cold resin binders prepared by reacting an aldehyde component, a ketone component and a substantially furfuryl alcohol component.
EP 1 531 018 betrifft No-Bake Gießereibindemittelsysteme aus einem Furanharz und bestimmten Säurehärtern. Die darin beschriebenen Bindemittelsysteme umfassen vorzugsweise 60 bis 80 Gew.-% an Furfurylalkohol.
US 2016/0 158 828 A1 beschreibt die Herstellung von Gussformen mittels eines Rapid- Prototyping-Verfahrens. Die in dem Dokument beschriebenen Formstoffmischungen können A) zumindest einen feuerfesten Füllstoff sowie B) ein Bindemittelsystem enthalten, wobei das Bindemittelsystem i) Formaldehyd sowie ii) einen Duroplast, ein Saccharid, ein synthetisches Polymer, ein Salz, ein Protein oder ein anorganisches Polymer enthalten kann. EP 1 531 018 relates to no-bake foundry binder systems of a furan resin and certain acid hardeners. The binder systems described therein preferably comprise 60 to 80% by weight of furfuryl alcohol. US 2016/0 158 828 A1 describes the production of molds by means of a rapid prototyping method. The molding material mixtures described in the document may contain A) at least one refractory filler and B) a binder system, wherein the binder system i) formaldehyde and ii) a thermoset, a saccharide, a synthetic polymer, a salt, a protein or an inorganic polymer ,
EP 1 595 618 B1 beschreibt ein Verfahren zur Herstellung einer keramischen Maskenform. Für die Herstellung der Form wird ein Gießschiicker verwendet, der Keramikteilchen, ein Bindemittel und einen Verflüssiger enthält. Bei dem Verflüssiger kann es sich um Aminosäuren, Ammoniumpolyacrylate oder dreisäurige Carboxyle mit Alkoholgruppen handeln. EP 1 595 618 B1 describes a process for producing a ceramic mask mold. For the production of the mold, a casting slip is used which contains ceramic particles, a binder and a plasticizer. The liquefier may be amino acids, ammonium polyacrylates, or trihydric carboxyls with alcohol groups.
DE 600 05 574 T2 betrifft ein Verfahren zur Herstellung von Wärmedämmkörpern. Die in dem Dokumente beschriebenen Wärmedämmkörper umfassen Mineralwolle und ein Bindemittel auf der Basis eines Formaldehyd-Phenolharzes. DE 600 05 574 T2 relates to a process for the production of heat-insulating bodies. The thermal insulation bodies described in the document comprise mineral wool and a binder based on a formaldehyde-phenolic resin.
US 3 296 666 A beschreibt ein Verfahren zur Herstellung von Gießformen. In dem Dokument werden synthetische Harzmaterialien, natürliche Harze, Gummi, Proteine, Kohlenhydrate oder Eiklar als alternative Binder zu Phenol-Formaldehyd-Harzen eingesetzt. US 3 296 666 A describes a process for producing casting molds. In the document, synthetic resin materials, natural resins, gums, proteins, carbohydrates or egg white are used as alternative binders to phenol-formaldehyde resins.
US 5 320 157 A beschreibt ein Verfahren zur Herstellung eines Kernes, wobei die zur Herstellung des Kernes eingesetzte Formstoffmischung Gelatine als Bindemittel enthält. No. 5,320,157 A describes a process for producing a core, wherein the molding material mixture used to prepare the core contains gelatin as binder.
Bei der Herstellung von Formkörpern (wie Speisern, Gießereiformen oder Kernen) für die Gießereiindustrie ist es vorteilhaft, wenn das Bindemittelsystem nach dem Aushärten eine hohe Festigkeit aufweist. Gute Festigkeiten sind besonders wichtig für die Produktion komplizierter, dünnwandiger Formkörper und deren sichere Handhabung. In the production of moldings (such as feeders, foundry molds or cores) for the foundry industry, it is advantageous if the binder system after curing has a high strength. Good strength is particularly important for the production of complicated, thin-walled moldings and their safe handling.
Der vorliegenden Erfindung lag daher die Aufgabe zu Grunde, eine Formstoffmischung zur Verfügung zu stellen, welche zur Herstellung von Formkörpern für die Gießereiindustrie eingesetzt werden kann und die sich durch eine verbesserte Festigkeit auszeichnen. The present invention was therefore based on the object to provide a molding material mixture available, which can be used for the production of moldings for the foundry industry and which are characterized by improved strength.
Diese Aufgabe wurde erfindungsgemäß gelöst durch eine Formstoffmischung zur Herstellung von Formkörpern für die Gießereiindustrie umfassend This object has been achieved by a molding material mixture for the production of moldings for the foundry industry comprising
A) einen oder mehrere schüttfähige, feuerfeste Füllstoffe,
und A) one or more pourable, refractory fillers, and
B) ein Bindemittelsystem, umfassend i) Formaldehyd, einen Formaldehydspender und/oder Vorkondensate aus Formaldehyd, und ii) eine Aminosäure. B) a binder system comprising i) formaldehyde, a formaldehyde donor and / or precondensates of formaldehyde, and ii) an amino acid.
Es hat sich überraschenderweise gezeigt, dass Formkörpern für die Gießereiindustrie eine Verbesserung der Festigkeit aufweisen, wenn sie aus einer erfindungsgemäßen Formstoffmischung hergestellt werden. Der Zusatz einer Aminosäure zu einem Bindemit- telsystem, das Formaldehyd, einen Formaldehydspender und/oder Vorkondensate aus Formaldehyd aufweist, verbesserte dabei überraschenderweise die Festigkeit des daraus hergestellten Formkörpers, im Vergleich zu Formkörpern, die unter identischen Bedingungen aus Formstoffmischungen gleicher Zusammensetzung allerdings ohne den Zusatz einer Aminosäure hergestellt wurden. Es hat sich überraschenderweise auch gezeigt, dass Formkörper, die aus einer erfindungsgemäßen Formstoffmischung hergestellt werden, sich zusätzlich durch einen geringeren Gehalt an freiem Formaldehyd auszeichnen. Formaldehyd weist einen stechenden Geruch auf und wirkt in hohen Konzentrationen giftig. Es ist daher vorteilhaft, wenn Formkörper weniger freien Formaldehyd aufweisen und kein Formaldehyd an die Umgebung abgeben wird. Insbesondere bei der Lagerung von vielen Formkörpern auf engem Raum besteht ansonsten die Gefahr, dass die Maximale Arbeitsplatz- Konzentration (MAK) für Formaldehyd überschritten wird. Auch die Emission von Formaldehyd aus einer erfindungsgemäßen Formstoffmischung vor und während des Aushärtens kann überraschenderweise durch den Zusatz von Aminosäuren reduziert werden. Um den Gehalt an freiem Formaldehyd in Formstoffmischungen oder in aus den Formstoffmischungen hergestellten Formkörpern zu reduzieren, bestünde natürlich auch die Möglichkeit dem Bindemittelsystem weniger Formaldehyd, Formaldehydspender und/oder Vorkondensate aus Formaldehyd zuzusetzen. Allerdings würde dies zu einer signifikanten Verschlechterung der Eigenschaften (insbesondere der Festigkeit) der aus den Formstoffmischungen hergestellten Formkörper führen.
Um die Konzentration an freiem Formaldehyd in Formstoffmischungen oder in aus den Formstoffmischungen hergestellten Formkörpern zu reduzieren, wurde bisher üblicherweise Harnstoff als Formaldehydfänger verwendet. Im Vergleich zu Harnstoff haben Aminosäuren jedoch zusätzlich den Vorteil, dass der Stickstoffgehalt in der Formstoffmi- schung oder in den daraus hergestellten Formkörpern reduziert werden kann, da die erfindungsgemäßen Aminosäuren die effektiveren Formaldehydfänger sind. Zudem ist bei der Verwendung von Harnstoff keine signifikante Verbesserung sondern eher eine Herabsetzung der Festigkeit zu beobachten. Zudem entstehen bei der Verwendung von Harnstoff als Formaldehydfänger nicht selten Reaktionsprodukte, die in Mischung nicht stabil sind und zu Eintrübungen und Niederschlägen führen. It has surprisingly been found that moldings for the foundry industry have an improvement in strength when they are made from a molding material mixture according to the invention. The addition of an amino acid to a binder system which comprises formaldehyde, a formaldehyde donor and / or precondensates of formaldehyde surprisingly improved the strength of the molding produced therefrom, in comparison to moldings which, under identical conditions, consist of molding material mixtures of the same composition but without the additive an amino acid were prepared. Surprisingly, it has also been found that molded articles which are produced from a molding material mixture according to the invention are additionally distinguished by a lower content of free formaldehyde. Formaldehyde has a pungent odor and is toxic at high concentrations. It is therefore advantageous if moldings have less free formaldehyde and will not release formaldehyde to the environment. In particular, when storing many moldings in a confined space, there is otherwise the danger that the maximum workplace concentration (MAK) for formaldehyde will be exceeded. The emission of formaldehyde from a molding material mixture according to the invention before and during curing can surprisingly be reduced by the addition of amino acids. In order to reduce the content of free formaldehyde in molding material mixtures or in moldings produced from the molding material mixtures, it would of course also be possible to add less formaldehyde, formaldehyde donors and / or precondensates of formaldehyde to the binder system. However, this would lead to a significant deterioration of the properties (in particular the strength) of the molded articles produced from the molding material mixtures. In order to reduce the concentration of free formaldehyde in molding material mixtures or in moldings produced from the molding material mixtures, urea has hitherto usually been used as formaldehyde scavenger. In comparison with urea, however, amino acids additionally have the advantage that the nitrogen content in the molding material mixture or in the molded articles produced therefrom can be reduced since the amino acids according to the invention are the more effective formaldehyde scavengers. In addition, when using urea, no significant improvement but rather a decrease in strength is observed. In addition, the use of urea as a formaldehyde scavenger often results in reaction products which are not stable in mixture and lead to clouding and precipitation.
Insbesondere im Eisen- und Stahlguss, dabei vor allem im Edelstahlguss, ist ein möglichst niedriger Gesamtgehalt an Stickstoff erwünscht, da Stickstoff zu Gussfehlern führen kann. Für den Einsatz im Bereich des Stahlgusses und auch des Graugusses sollte ein Bindemittel einen möglichst geringen Gesamtgehalt an Stickstoff aufweisen, da durch einen hohen Stickstoffgehalt Oberflächenfehler, beispielsweise sogenannte „Pinholes" (Nadelstichporen), als Gussfehler auftreten. Especially in iron and steel casting, especially in stainless steel casting, the lowest possible total nitrogen content is desired, since nitrogen can lead to casting defects. For use in the field of cast steel and gray cast iron, a binder should have the lowest possible total nitrogen content, since a high nitrogen content causes surface defects, for example so-called "pinholes", as casting defects.
Erfindungsgemäß bevorzugt handelt es sich bei den Formkörpern für die Gießereiindustrie um Speiser, Gießereiformen oder Kerne für die Gießereiindustrie. According to the invention, the moldings for the foundry industry are preferably feeders, foundry molds or cores for the foundry industry.
Als schüttfähiger, feuerfester Füllstoffe können alle üblicherweise für die Herstellung von Formkörpern (insbesondere Speisern, Gießereiformen und Kernen) für die Gießereiindustrie eingesetzten körnigen Füllstoffe verwendet werden, z.B. Quarzsand und Spezial- sande. Der Begriff Spezialsand umfasst natürliche Mineralsande sowie Sinter- und Schmelzprodukte, die in körniger Form hergestellt bzw. durch Brech-, Mahl- und Klassiervorgänge in körnige Form überführt werden, bzw. durch andere physikalisch- chemische Vorgänge entstandene anorganische Mineralsande, die als Formgrundstoffe mit gießereiüblichen Bindemitteln für die Fertigung von Speisern, Kernen und Formen verwendet werden. As pourable, refractory fillers, it is possible to use all granular fillers customarily used for the production of shaped articles (in particular feeders, foundry molds and cores) for the foundry industry, e.g. Quartz sand and special sands. The term special sand includes natural mineral sands and sintered and melted products, which are produced in granular form or transferred by crushing, grinding and Klassiervorgänge in granular form, or by other physico-chemical processes resulting inorganic mineral sands, which are used as mold bases with customary Binders are used for the manufacture of feeders, cores and molds.
Gemäß einer bevorzugten Ausgestaltung der vorliegenden Erfindung ist eine erfindungsgemäße Formstoffmischung besonders bevorzugt, wobei der eine, zumindest einer der mehreren oder sämtliche schüttfähige, feuerfeste Füllstoffe ausgewählt sind aus der Gruppe bestehend aus Quarzsand, Quarzgutsand, Olivinsand, Chrom-Magnesit- Granulat, Aluminiumsilikate, insbesondere J-Sand und Kerphalite, Schwermineralien, insbesondere Chromit, Zirkonsand und R-Sand, technische Keramik, insbesondere
Cerabeads, Schamotte, M-Sand, Alodur, Bauxitsand und Siliciumcarbid, feldspathaltige Sande, Andalusitsande, Hohlkugelkorund, Spheres aus Flugaschen, Reisschalenaschen, Blähgläser, Schaumgläser, geblähte Perlite, Kern-Hülle-Partikel, Mikrohohlkugeln, Flugaschen und weitere Spezialsande. Erfindungsgemäß bevorzugt sind Formstoffmischungen, wobei der eine, zumindest einer der mehreren oder sämtliche schüttfähige, feuerfeste Füllstoffe einen mittleren Partikeldurchmesser d50 im Bereich zwischen 0,001 und 5 mm, vorzugsweise im Bereich von 0,01 bis 3 mm aufweisen, besonders bevorzugt im Bereich von 0,02 bis 2,0 mm aufweisen. Der mittleren Partikeldurchmesser d50 wird nach DIN 66165-2, F und DIN ISO 3310-1 bestimmt. According to a preferred embodiment of the present invention, a molding material mixture according to the invention is particularly preferred, wherein the one, at least one or more pourable, refractory fillers are selected from the group consisting of quartz sand, quartz sand, olivine sand, chromium-magnesite granules, aluminum silicates, in particular J-sand and kerphalite, heavy minerals, especially chromite, zircon sand and R-sand, technical ceramics, in particular Cerabeads, chamotte, m-sand, alodur, bauxite sand and silicon carbide, feldspar sands, andalusite sands, hollow ball corundum, fly ash spheres, rice husk ash, blown glasses, foam glasses, expanded perlite, core-shell particles, hollow microspheres, fly ashes and other specialty sands. Preference according to the invention is given to molding material mixtures, the one, at least one of the plurality or all free-flowing, refractory fillers having an average particle diameter d50 in the range between 0.001 and 5 mm, preferably in the range from 0.01 to 3 mm, particularly preferably in the range from 0, 02 to 2.0 mm. The mean particle diameter d50 is determined according to DIN 66165-2, F and DIN ISO 3310-1.
Ebenfalls erfindungsgemäß bevorzugt sind Formstoffmischungen, wobei das Verhältnis der Gesamtmasse an schüttfähiger, feuerfester Füllstoffe zu der Gesamtmasse sonstiger Bestandteile der Formstoffmischung im Bereich von 100 : 5 bis 100 : 0,1 , bevorzugt von 100 : 3 bis 100 : 0,4, besonders bevorzugt von 100 : 2 bis 100 : 0,6 liegt. Ebenfalls bevorzugt sind erfindungsgemäße Formstoffmischungen, wobei die Schüttdichte einer Mischung sämtlicher Feststoffe der Formstoff mischung 100 g/L oder größer ist, vorzugsweise 200 g/L oder größer ist, besonders bevorzugt 1000 g/L oder größer ist. Also preferred according to the invention are molding material mixtures, the ratio of the total mass of free-flowing, refractory fillers to the total mass of other constituents of the molding material mixture in the range from 100: 5 to 100: 0.1, preferably from 100: 3 to 100: 0.4, particularly preferred from 100: 2 to 100: 0.6. Also preferred are molding mixtures according to the invention, wherein the bulk density of a mixture of all solids of the molding material mixture is 100 g / L or greater, preferably 200 g / L or greater, more preferably 1000 g / L or greater.
Erfindungsgemäß bevorzugt sind Formstoffmischungen, wobei das Bindemittelsystem zusätzlich umfasst: (a) Phenole, insbesondere Phenol, o-Kresol, p-Kresol, 3,5-Xylenol oder Resorcin, oder Vorkondensate aus Phenolen, insbesondere Resole, Preference according to the invention is given to molding material mixtures, wherein the binder system additionally comprises: (a) phenols, in particular phenol, o-cresol, p-cresol, 3,5-xylenol or resorcinol, or precondensates of phenols, in particular resols,
(b) Furanderivate und/oder Furfurylalkohol oder Vorkondensate aus Furanderivaten und/oder Furfurylalkohol und/oder (c) Harnstoff oder Harnstoffderivate oder Vorkondensate aus Harnstoff oder Harnstoffderivaten. (b) furan derivatives and / or furfuryl alcohol or precondensates of furan derivatives and / or furfuryl alcohol and / or (c) urea or urea derivatives or precondensates of urea or urea derivatives.
In einer bevorzugten Ausgestaltung der vorliegenden erfindungsgemäßen Formstoffmischung wird das Bindemittelsystem bei der Herstellung der Formkörper mit einem Härter
versetzt, der die Aushärtung des Bindemittels initiiert. Bei dem Härter handelt es sich üblicherweise um Säuren, vorzugsweise um zumindest eine organische oder anorganische Säure, besonders bevorzugt eine aromatische Sulfonsäure (insbesondere para- Toluolsulfon- und/oder Xylolsulfonsäure), Phosphorsäure, Methansulfonsäure, Schwefel- säure, eine oder mehrere Carbonsäuren oder Mischungen daraus. In a preferred embodiment of the present molding material mixture according to the invention, the binder system is used in the production of the molding with a hardener which initiates the curing of the binder. The curing agent is usually acids, preferably at least one organic or inorganic acid, more preferably an aromatic sulfonic acid (especially para-toluenesulfonic and / or xylenesulfonic acid), phosphoric acid, methanesulfonic acid, sulfuric acid, one or more carboxylic acids or mixtures it.
In einer alternativen bevorzugten Ausgestaltung sind erfindungsgemäße Formstoffmischungen besonders bevorzugt, wobei das Bindemittelsystem thermisch härtbar ist. In an alternative preferred embodiment, molding mixtures according to the invention are particularly preferred, wherein the binder system is thermally curable.
Besonders bevorzugt sind erfindungsgemäße Formstoffmischungen, wobei das Bindemittel zusätzlich (a) Phenole, insbesondere Phenol, o-Kresol, p-Kresol, 3,5-Xylenol oder Resorcin, oder Vorkondensate aus Phenolen, insbesondere Resole, und (b) Furanderivate und/oder Furfurylalkohol oder Vorkondensate aus Furanderivaten und/oder Furfurylalkohol umfasst. Hierdurch entstehen während des Härtens Phe- nol/Furfurylalkohol/Formaldehydharz-gebundene Formstoffe. Es ist somit erfindungsgemäß bevorzugt, wenn das Bindemittelsystem zu einem Phe- nol/Furfurylalkohol/Formaldehydharz aushärtbar ist, besonders bevorzugt zu einem hochpolymeren und festen Phenol/Furfurylalkohol/Formaldehydharz aushärtbar ist. Erfindungsgemäß bevorzugt erfolgt die Aushärtung dieser Systeme durch Zugabe eines Härters, wobei der Härter eine organische oder anorganische Säure ist, besonders bevorzugt eine aromatische Sulfonsäure (insbesondere para-Toluol- oder Xylolsulfonsäure oder Mischungen aus para-Toluol- und Xylolsulfonsäure), Phosphorsäure, Methansulfonsäure, Schwefelsäure, eine oder mehrere Carbonsäuren oder Mischungen aus den voran genannten Säuren ist. Particular preference is given to molding mixtures according to the invention, where the binder additionally comprises (a) phenols, in particular phenol, o-cresol, p-cresol, 3,5-xylenol or resorcinol, or precondensates of phenols, in particular resoles, and (b) furan derivatives and / or Furfuryl alcohol or precondensates of furan derivatives and / or furfuryl alcohol. This results in phenolic / furfuryl alcohol / formaldehyde resin bonded moldings during curing. It is thus preferred according to the invention if the binder system is curable to a phenol / furfuryl alcohol / formaldehyde resin, particularly preferably to a high polymer and solid phenol / furfuryl alcohol / formaldehyde resin is curable. According to the invention, the curing of these systems preferably takes place by addition of a hardener, the hardener being an organic or inorganic acid, particularly preferably an aromatic sulfonic acid (especially para-toluic or xylenesulfonic acid or mixtures of para-toluic and xylenesulfonic acid), phosphoric acid, methanesulfonic acid, Sulfuric acid, one or more carboxylic acids or mixtures of the aforementioned acids.
Besonders bevorzugt sind erfindungsgemäße Formstoffmischungen, wobei das Bindemittel zusätzlich Furanderivate und/oder Furfurylalkohol oder Vorkondensate aus Furanderivaten und/oder Furfurylalkohol umfasst. Hierdurch entstehen während des Härtens Furfurylalkohol/Formaldehydharz-gebundenen Formstoffe. Es ist somit erfindungsgemäß bevorzugt, wenn das Bindemittelsystem zu einem Furfurylalkohol/Formaldehydharz aushärtbar ist, vorzugsweise zu einem hochpolymeren und festen Furfurylalkohol/Formaldehydharz aushärtbar ist. Besonders bevorzugt sind erfindungsgemäße Formstoffmischungen, wobei das Bindemittel zusätzlich Harnstoff oder Harnstoffderivate oder Vorkondensate aus Harnstoff oder Harnstoffderivaten umfasst. Hierdurch entstehen während des Härtens Harnstoff/Formaldehydharz-gebundenen Formstoffe. Es ist somit erfindungsgemäß bevorzugt,
wenn das Bindemittelsystem zu einem Harnstoff/Formaldehydharz aushärtbar ist, vorzugsweise zu einem hochpolymeren und festen Harnstoff/Formaldehydharz aushärtbar ist. Erfindungsgemäß bevorzugt erfolgt die Aushärtung dieser Systeme durch Erhitzen in Anwesenheit eines latenten Härters (Warmbox) oder durch Zugabe eines Härters, wobei der Härter eine organische oder anorganische Säure, besonders bevorzugt eine aromatische Sulfonsäure (insbesondere para-Toluol- oder Xylolsulfonsäure oder Mischungen aus para-Toluol- und Xylolsulfonsäure), Phosphorsäure, Methansulfonsäure, Schwefelsäure, eine oder mehrere Carbonsäuren oder Mischungen aus den voran genannten Säuren ist. Besonders bevorzugt sind erfindungsgemäße Formstoffmischungen, wobei das Bindemittel zusätzlich i) Harnstoff oder Harnstoffderivate oder Vorkondensate aus Harnstoff oder Harnstoffderivaten und ii) Furanderivate und/oder Furfurylalkohol oder Vorkondensate aus Furanderivaten und/oder Furfurylalkohol umfasst. Hierdurch entstehen während des Härtens Harnstoff/Furfurylalkohol/Formaldehydharz-gebundenen Formstoffe. Es ist somit erfindungsgemäß bevorzugt, wenn das Bindemittelsystem zu einem Harn- stoff/Furfurylalkohol/Formaldehydharz aushärtbar ist, vorzugsweise zu einem hochpolymeren und festen Harnstoff/Furfurylalkohol/Formaldehydharz aushärtbar ist. Erfindungsgemäß bevorzugt erfolgt die Aushärtung dieser Systeme durch Erhitzen in Anwesenheit eines latenten Härters (Warmbox) oder durch Zugabe eines Härters, wobei der Härter eine organische oder anorganische Säure, besonders bevorzugt eine aromatische Sulfonsäure (insbesondere para-Toluol- oder Xylolsulfonsäure oder Mischungen aus para-Toluol- und Xylolsulfonsäure), Phosphorsäure, Methansulfonsäure, Schwefelsäure, eine oder mehrere Carbonsäuren oder Mischungen aus den voran genannten Säuren ist. Moldings mixtures according to the invention are particularly preferred, wherein the binder additionally comprises furan derivatives and / or furfuryl alcohol or precondensates of furan derivatives and / or furfuryl alcohol. As a result, furfuryl alcohol / formaldehyde resin bonded moldings are formed during curing. It is thus preferred according to the invention if the binder system is curable to a furfuryl alcohol / formaldehyde resin, preferably curable to a high polymer and solid furfuryl alcohol / formaldehyde resin. Moldings mixtures according to the invention are particularly preferred, wherein the binder additionally comprises urea or urea derivatives or precondensates of urea or urea derivatives. This results in hardening urea / formaldehyde-bonded moldings. It is thus preferred according to the invention when the binder system is curable to a urea / formaldehyde resin, preferably curable to a high polymer and solid urea / formaldehyde resin. According to the invention, the curing of these systems is preferably carried out by heating in the presence of a latent curing agent (warm box) or by adding a hardener, the hardener being an organic or inorganic acid, particularly preferably an aromatic sulfonic acid (especially para-toluic or xylene sulfonic acid or mixtures of para). Toluene- and xylenesulfonic acid), phosphoric acid, methanesulfonic acid, sulfuric acid, one or more carboxylic acids or mixtures of the abovementioned acids. Moldings mixtures according to the invention are particularly preferred, wherein the binder additionally comprises i) urea or urea derivatives or precondensates of urea or urea derivatives and ii) furan derivatives and / or furfuryl alcohol or precondensates of furan derivatives and / or furfuryl alcohol. As a result, urea / furfuryl alcohol / formaldehyde resin bonded moldings are formed during curing. It is thus preferred according to the invention if the binder system is curable to a urea / furfuryl alcohol / formaldehyde resin, preferably curable to a high polymer and solid urea / furfuryl alcohol / formaldehyde resin. According to the invention, the curing of these systems is preferably carried out by heating in the presence of a latent curing agent (warm box) or by adding a hardener, the hardener being an organic or inorganic acid, particularly preferably an aromatic sulfonic acid (especially para-toluic or xylene sulfonic acid or mixtures of para). Toluene- and xylenesulfonic acid), phosphoric acid, methanesulfonic acid, sulfuric acid, one or more carboxylic acids or mixtures of the abovementioned acids.
Besonders bevorzugt sind erfindungsgemäße Formstoffmischungen, wobei das Bindemit- tel zusätzlich i) Harnstoff oder Harnstoffderivate oder Vorkondensate aus Harnstoff oder Harnstoffderivaten, ii) Furanderivate und/oder Furfurylalkohol oder Vorkondensate aus Furanderivaten und/oder Furfurylalkohol und iii) Phenole, insbesondere Phenol, o-Kresol, p-Kresol, 3,5-Xylenol oder Resorcin, oder Vorkondensate aus Phenolen, insbesondere Resole umfasst. Hierdurch entstehen während des Härtens Harn- stoff/Furfurylalkohol/Phenol/Formaldehydharz-gebundenen Formstoffe. Es ist somit erfindungsgemäß bevorzugt, wenn das Bindemittelsystem zu einem Harn- stoff/Furfurylalkohol/Phenol/Formaldehydharz aushärtbar ist, vorzugsweise zu einem hochpolymeren und festen Harnstoff/Furfurylalkohol/Phenol/Formaldehydharz aushärtbar ist. Erfindungsgemäß bevorzugt erfolgt die Aushärtung dieser Systeme durch Erhitzen in Anwesenheit eines latenten Härters (Warmbox) oder durch Zugabe eines Härters, wobei
der Härter eine organische oder anorganische Säure, besonders bevorzugt eine aromatische Sulfonsäure (insbesondere para-Toluol- oder Xylolsulfonsäure oder Mischungen aus para-Toluol- und Xylolsulfonsäure), Phosphorsäure, Methansulfonsäure, Schwefelsäure, eine oder mehrere Carbonsäuren oder Mischungen aus den voran genannten Säuren ist. I) urea or urea derivatives or precondensates of urea or urea derivatives, ii) furan derivatives and / or furfuryl alcohol or precondensates of furan derivatives and / or furfuryl alcohol and iii) phenols, in particular phenol, o-cresol , p-cresol, 3,5-xylenol or resorcinol, or precondensates of phenols, especially resoles. As a result, urea / furfuryl alcohol / phenol / formaldehyde resin bonded molding materials are formed during curing. It is thus preferred according to the invention if the binder system is curable to a urea / furfuryl alcohol / phenol / formaldehyde resin, preferably curable to a high polymer and solid urea / furfuryl alcohol / phenol / formaldehyde resin. According to the invention, the curing of these systems is preferably carried out by heating in the presence of a latent hardener (warm box) or by adding a hardener, wherein the hardener is an organic or inorganic acid, particularly preferably an aromatic sulfonic acid (in particular para-toluene or xylene sulfonic acid or mixtures of para-toluene and xylene sulfonic acid), phosphoric acid, methanesulfonic acid, sulfuric acid, one or more carboxylic acids or mixtures of the abovementioned acids ,
Erfindungsgemäß bevorzugt sind daher Formstoffmischungen, wobei das Bindemittelsystem aushärtbar ist zu einem i) Phenol/Furfurylalkohol/Formaldehydharz, ii) Furfurylalkohol/Formaldehydharz, iii) Harnstoff/Formaldehydharz, iv) Harnstoff/Furfurylalkohol/Formaldehydharz oder v) Harnstoff/Furfurylalkohol/Phenol/Formaldehydharz Therefore preferred according to the invention are molding material mixtures wherein the binder system is curable to i) phenol / furfuryl alcohol / formaldehyde resin, ii) furfuryl alcohol / formaldehyde resin, iii) urea / formaldehyde resin, iv) urea / furfuryl alcohol / formaldehyde resin or v) urea / furfuryl alcohol / phenol / formaldehyde resin
Bevorzugt sind erfindungsgemäße Formstoffmischungen, wobei die Aminosäure ausgewählt ist aus der Gruppe bestehend aus Alanin, Glycin, Isoleucin, Methionin, Prolin, Valin, Histidin, Phenylalanin, Tryptophan, Tyrosin, Aspargin, Glutamin, Cystein, Methionin, Serin, Threonin, Tyrosin, Lysin, Arginin und Histidin, vorzugsweise ausgewählt ist aus der Gruppe bestehend aus Glycin, Glutamin, Alanin, Valin und Serin. Preference is given to molding mixtures according to the invention, wherein the amino acid is selected from the group consisting of alanine, glycine, isoleucine, methionine, proline, valine, histidine, phenylalanine, tryptophan, tyrosine, asparagine, glutamine, cysteine, methionine, serine, threonine, tyrosine, lysine , Arginine and histidine, preferably selected from the group consisting of glycine, glutamine, alanine, valine and serine.
Eigene Untersuchungen haben gezeigt, dass insbesondere die Aminosäuren Glycin, Glutamin, Alanin, Valin und Serin gute Eigenschaften bei der Verwendung in erfindungsgemäßen Formstoffmischungen aufweisen. Durch den Zusatz dieser Aminosäuren lässt sich die Festigkeit der aus den Formstoffmischungen hergestellten Formkörper besonders gut verbessern, ohne dass andere Eigenschaften der hergestellten Formkörper oder der Formstoff mischung verschlechtert werden. Zudem lässt sich der Gehalt an freiem Formaldehyd in der Formstoffmischung und in den aus der Formstoffmischung hergestellten Formkörpern reduzieren. Von den Aminosäuren ist Glycin besonders bevorzugt.
Bevorzugt sind erfindungsgemäße Formstoffmischungen, wobei die Aminosäure eine o Aminosäure ist. Our own investigations have shown that especially the amino acids glycine, glutamine, alanine, valine and serine have good properties when used in molding material mixtures according to the invention. By adding these amino acids, the strength of the molded body produced from the molding mixtures can be particularly well improved without other properties of the molded body or the molding material mixture are deteriorated. In addition, the content of free formaldehyde in the molding material mixture and in the moldings produced from the molding material mixture can be reduced. Of the amino acids, glycine is particularly preferred. Preference is given to molding mixtures according to the invention, where the amino acid is an amino acid.
Ebenfalls bevorzugt ist eine erfindungsgemäße Formstoffmischung, wobei der Anteil an sämtlichen Aminosäuren in der Formstoffmischung 0,005 bis 5,0 Gew.-% beträgt, vor- zugsweise 0,01 bis 2,0 Gew.-% beträgt, besonders bevorzugt 0,03 bis 1 ,0 Gew.-% beträgt, bezogen auf den Feststoffanteil der gesamten Formstoffmischung. Also preferred is a molding material mixture according to the invention, wherein the proportion of all amino acids in the molding material mixture is 0.005 to 5.0 wt .-%, preferably 0.01 to 2.0 wt .-%, more preferably 0.03 to 1 , 0 wt .-%, based on the solids content of the entire molding material mixture.
Es hat sich in eigenen Untersuchungen gezeigt, dass erfindungsgemäße Formstoffmischungen besonders gute Eigenschaften aufweisen, wenn der Anteil an sämtlichen Aminosäuren in der Formstoffmischung in den oben aufgeführten Bereichen liegt. Bei zu geringen Anteilen an Aminosäuren in der Formstoffmischung besteht die Möglichkeit, dass die Festigkeit der aus den Formstoffmischungen hergestellten Formkörper nicht ausreichend verbessert wird und/oder dass die Menge an freiem Formaldehyd nicht reduziert wird. Bei zu hohen Anteilen an Aminosäuren ist keine weitere Verbesserung der Eigenschaften zu beobachten. Ebenfalls bevorzugt ist eine erfindungsgemäße Formstoffmischung, wobei das Molverhältnis aus sämtlichen Aminosäuren zu verfügbarem Formaldehyd 4 : 1 bis 1 : 0,5 beträgt, vorzugsweise 3 : 1 bis 1 : 0,9, besonders bevorzugt 2,5 : 1 bis 1 : 1 beträgt. It has been shown in own investigations that molding material mixtures according to the invention have particularly good properties if the proportion of all amino acids in the molding material mixture lies in the above-mentioned ranges. If the proportion of amino acids in the molding material mixture is too low, there is the possibility that the strength of the molded articles produced from the molding material mixtures will not be sufficiently improved and / or the amount of free formaldehyde will not be reduced. If the proportion of amino acids is too high, no further improvement in the properties can be observed. Likewise preferred is a molding material mixture according to the invention, wherein the molar ratio of all amino acids to available formaldehyde is 4: 1 to 1: 0.5, preferably 3: 1 to 1: 0.9, more preferably 2.5: 1 to 1: 1 ,
In eigenen Untersuchungen hat sich gezeigt, dass erfindungsgemäße Formstoffmischungen besonders gute Eigenschaften aufweisen, wenn das Molverhältnis aus sämtlichen Aminosäuren zu verfügbarem Formaldehyd in den oben angegebenen Bereichen liegt. Insbesondere die Festigkeit der aus den Formstoffmischungen hergestellten Formkörper und der Anteil an freiem Formaldehyd in den Formstoffmischungen bzw. den daraus hergestellten Formkörpern zeigen in den angegebenen Bereichen besonders gute Eigenschaften. Ebenfalls bevorzugt ist eine erfindungsgemäße Formstoffmischung, wobei die Formaldehydspender und/oder Vorkondensate aus Formaldehyd ausgewählt sind aus der Gruppe bestehend aus Paraformaldehyd, Hexamethylentetramin, Trioxan, Methylolamin und Methylolaminderivaten wie Trimethylolmelamin oder Hexamethylolmelamin. In our own investigations, it has been found that molding mixtures according to the invention have particularly good properties when the molar ratio of all the amino acids to available formaldehyde is in the ranges indicated above. In particular, the strength of the molded body produced from the molding mixtures and the proportion of free formaldehyde in the molding material mixtures or the moldings produced therefrom show particularly good properties in the specified ranges. Also preferred is a molding material mixture according to the invention, wherein the formaldehyde donors and / or precondensates of formaldehyde are selected from the group consisting of paraformaldehyde, hexamethylenetetramine, trioxane, methylolamine and methylolamine derivatives such as trimethylolmelamine or hexamethylolmelamine.
In einer bevorzugten Ausgestaltung der vorliegenden Erfindung, enthält die Formstoffmi- schung keine Proteine oder Peptide, wie beispielsweise Dipeptide, Tripeptide, Tetrapeptide, Pentapeptide oder höherwertige Peptide). Es hat sich ebenfalls gezeigt,
dass es einigen Ausgestaltungen der vorliegenenden Erfindung Vorteile hat, wenn als Aminosäure nicht Asparginsäure, sondern eine andere Aminosäure, vorzugsweise Glycin, Glutamin, Alanin, Valin und/oder Serin, eingesetzt wird. In a preferred embodiment of the present invention, the molding material mixture contains no proteins or peptides, such as dipeptides, tripeptides, tetrapeptides, pentapeptides or higher-order peptides). It has also been shown that it is advantageous for some embodiments of the present invention if the amino acid used is not aspartic acid but another amino acid, preferably glycine, glutamine, alanine, valine and / or serine.
Ein weiterer Aspekt der vorliegenden Erfindung betrifft Formkörper für die Gießereiindustrie hergestellt unter Verwendung einer erfindungsgemäßen Formstoffmischung. Another aspect of the present invention relates to molded articles for the foundry industry produced using a molding material mixture according to the invention.
Ebenfalls bevorzugt ist ein erfindungsgemäßer Formkörper, wobei der eine oder die mehreren schüttfähigen, feuerfesten Füllstoffe mit einem gehärteten Bindemittel gebunden sind und das gehärtete Bindemittel ein i) Phenol/Furfurylalkohol/Formaldehydharz, ii) Furfurylalkohol/Formaldehydharz, iii) Harnstoff/Formaldehyd harz, iv) Harnstoff/Furfurylalkohol/Formaldehydharz oder v) Harnstoff/Furfurylalkohol/Phenol/Formaldehydharz ist. Also preferred is a molded article of the invention wherein the one or more pourable refractory fillers are bound with a cured binder and the cured binder is i) phenol / furfuryl alcohol / formaldehyde resin, ii) furfuryl alcohol / formaldehyde resin, iii) urea / formaldehyde resin, iv ) Urea / furfuryl alcohol / formaldehyde resin or v) urea / furfuryl alcohol / phenol / formaldehyde resin.
Bevorzugt ist ein erfindungsgemäßer Formkörper, wobei der Formkörper ausgebildet wird durch Härten des Bindemittelsystems, wobei eine chemische Reaktion stattfindet zwischen Formaldehyd und/oder einem Vorkondensat aus Formaldehyd und Preference is given to a molding according to the invention, wherein the molding is formed by curing the binder system, wherein a chemical reaction takes place between formaldehyde and / or a precondensate of formaldehyde and
(a) Phenolen, insbesondere Phenol, o-Kresol, p-Kresol, 3,5-Xylenol oder Resorcin, oder Vorkondensaten aus Phenolen, insbesondere Resole, (a) phenols, in particular phenol, o-cresol, p-cresol, 3,5-xylenol or resorcinol, or precondensates of phenols, in particular resols,
(b) Furanderivaten und/oder Furfurylalkohol oder Vorkondensaten aus Furanderivaten und/oder Furfurylalkohol und/oder (b) furan derivatives and / or furfuryl alcohol or precondensates of furan derivatives and / or furfuryl alcohol and / or
(c) Harnstoff oder Harnstoffderivaten oder Vorkondensate aus Harnstoff oder Harnstoffderivaten.
Ein weiterer Aspekt der vorliegenden Erfindung betrifft die Verwendung von Aminosäuren (a) in einer Formstoffmischung zur Herstellung von Formkörpern für die Gießereiindustrie oder (b) zur Herstellung von Formkörpern für die Gießereiindustrie. (c) urea or urea derivatives or precondensates of urea or urea derivatives. Another aspect of the present invention relates to the use of amino acids (a) in a molding material mixture for the production of moldings for the foundry industry or (b) for the production of moldings for the foundry industry.
Ein weiterer Aspekt der vorliegenden Erfindung betrifft die Verwendung zumindest einer Aminosäure in einer Formstoffmischung für die Gießereiindustrie, wobei die Formstoffmischung neben der Aminosäure Formaldehyd oder eine Formaldehydquelle enthält. Hierbei ist es bevorzugt, dass die Aminosäure ausgewählt ist aus der Gruppe bestehend aus Alanin, Glycin, Isoleucin, Methionin, Prolin, Valin, Histidin, Phenylalanin, Tryptophan, Tyrosin, Aspargin, Glutamin, Cystein, Methionin, Serin, Threonin, Tyrosin, Lysin, Arginin und Histidin, besonders bevorzugt ausgewählt ist aus der Gruppe bestehend aus Glycin, Glutamin, Alanin, Valin und Serin. Another aspect of the present invention relates to the use of at least one amino acid in a molding material mixture for the foundry industry, wherein the molding material mixture in addition to the amino acid formaldehyde or a formaldehyde source. It is preferred that the amino acid is selected from the group consisting of alanine, glycine, isoleucine, methionine, proline, valine, histidine, phenylalanine, tryptophan, tyrosine, asparagine, glutamine, cysteine, methionine, serine, threonine, tyrosine, lysine , Arginine and histidine, more preferably selected from the group consisting of glycine, glutamine, alanine, valine and serine.
Ein weiterer Aspekt der vorliegenden Erfindung betrifft die Verwendung zumindest einer Aminosäure zur Herstellung von Formkörpern mit verbesserter Festigkeit und/oder verringerter Neigung zu Gussfehlern. Ein weiterer Aspekt der vorliegenden Erfindung betrifft die Verwendung von erfindungsgemäßen Formstoffmischungen zur Herstellung von Formkörpern für die Gießereiindustrie. A further aspect of the present invention relates to the use of at least one amino acid for the production of moldings having improved strength and / or reduced tendency to casting defects. Another aspect of the present invention relates to the use of molding material mixtures according to the invention for the production of moldings for the foundry industry.
Ein weiterer Aspekt im Zusammenhang mit der vorliegenden Erfindung betrifft ein Verfahren zur Herstellung einer erfindungsgemäßen Formstoffmischung, umfassend die folgen- den Schritte: a) Herstellen oder Bereitstellen von einem oder mehreren schüttfähigen, feuerfesten Füllstoffen, b) Herstellen oder Bereitstellen eines Bindemittelsystems, umfassend i) Formaldehyd, einen Formaldehydspender und/oder Vorkondensate aus Formaldehyd, und ii) eine Aminosäure
und c) Vermischen aller Komponenten. A further aspect in connection with the present invention relates to a process for producing a molding material mixture according to the invention, comprising the following steps: a) producing or providing one or more free-flowing refractory fillers, b) producing or providing a binder system, comprising i) Formaldehyde, a formaldehyde donor and / or formaldehyde precondensates, and ii) an amino acid and c) mixing all components.
Ein weiterer Aspekt im Zusammenhang mit der vorliegenden Erfindung betrifft ein Verfahren zur Herstellung eines Formkörpers für die Gießereiindustrie umfassend die folgenden Schritte: i) Herstellen oder Bereitstellen einer erfindungsgemäßen Formstoffmischung, vorzugsweise mittels eines erfindungsgemäßen Verfahrens zur einer erfindungsgemäßen Formstoffmischung, ii) Formen der Formstoffmischung zu einem ungehärteten Formkörper und iii) Aushärten oder Aushärtenlassen des ungehärteten Formkörpers, sodass ein Formkörper für die Gießereiindustrie resultiert. Another aspect in connection with the present invention relates to a process for the production of a molded article for the foundry industry comprising the following steps: i) producing or providing a molding material mixture according to the invention, preferably by means of a process according to the invention for a molding material mixture according to the invention, ii) molding the molding material mixture into one uncured molding; and iii) allowing the uncured molding to cure or cure to yield a molded article for the foundry industry.
In einer bevorzugten Ausgestaltung des erfindungsgemäßen Verfahrens zur Herstellung eines Formkörpers für die Gießereiindustrie erfolgt das Aushärten oder das Aushärtenlassen des ungehärteten Formkörpers durch Erhitzen. In a preferred embodiment of the method according to the invention for producing a shaped body for the foundry industry, the hardening or hardening of the uncured shaped body takes place by heating.
In einer alternativen bevorzugten Ausgestaltung des erfindungsgemäßen Verfahrens zur Herstellung eines Formkörpers für die Gießereiindustrie erfolgt das Aushärten oder das Aushärtenlassen durch Zugeben eines Härters während des Herstellens oder Bereitstellens der erfindungsgemäßen Formstoffmischung. Bei dem Härter handelt es vorzugsweise um eine organische oder anorganische Säure, besonders bevorzugt um eine Sulfonsäure (insbesondere para-Toluolsulfonsäure), Phosphorsäure, Methansulfonsäure, Carbonsäure und/oder Schwefelsäure oder um Mischungen daraus. In an alternative preferred embodiment of the method according to the invention for producing a shaped body for the foundry industry, curing or curing is effected by adding a hardener during the production or provision of the molding material mixture according to the invention. The curing agent is preferably an organic or inorganic acid, more preferably a sulfonic acid (especially para-toluenesulfonic acid), phosphoric acid, methanesulfonic acid, carboxylic acid and / or sulfuric acid, or mixtures thereof.
Ein weiterer Aspekt im Zusammenhang mit der vorliegenden Erfindung betrifft ein Kit zur Herstellung einer erfindungsgemäßen Formstoffmischung und/oder zur Herstellung eines erfindungsgemäßen Formkörpers für die Gießereiindustrie, vorzugsweise zur Herstellung von Speisern, Gießereiformen oder Kernen für die Gießereiindustrie, umfassend
I) ein Bindemittelsystem wie weiter oben für eine erfindungsgemäße Formstoffmischung definiert, A further aspect in connection with the present invention relates to a kit for producing a molding material mixture according to the invention and / or for producing a molding according to the invention for the foundry industry, preferably for the production of feeders, foundry molds or cores for the foundry industry I) defines a binder system as described above for a molding material mixture according to the invention,
II) optional einen oder mehrere schüttfähige, feuerfeste Füllstoffe und III) optional einen Härter, vorzugsweise eine organische oder anorganische Säure, besonders bevorzugt eine aromatische Sulfonsäure (insbesondere para- Toluolsulfonsäure), Phosphorsäure, Carbonsäure, Methansulfonsäure und/oder Schwefelsäure oder Mischungen daraus. II) optionally one or more pourable, refractory fillers and III) optionally a hardener, preferably an organic or inorganic acid, particularly preferably an aromatic sulfonic acid (especially para-toluenesulfonic acid), phosphoric acid, carboxylic acid, methanesulfonic acid and / or sulfuric acid or mixtures thereof.
Im Rahmen der vorliegenden Erfindung werden vorzugsweise mehrere der vorstehend als bevorzugt bezeichneten Aspekte gleichzeitig verwirklicht; insbesondere bevorzugt sind die sich aus den beigefügten Ansprüchen ergebenden Kombinationen solcher Aspekte und der entsprechenden Merkmale. In the context of the present invention, preferably several of the aspects described above as being preferred are realized simultaneously; Especially preferred are the combinations of such aspects and the corresponding features resulting from the appended claims.
Im Folgenden wird die vorliegende Erfindung anhand ausgewählter Beispiele näher erläutert. Beispiele: In the following, the present invention will be explained in more detail with reference to selected examples. Examples:
Beispiel 1 (erfindunqsqemäß): Example 1 (according to the invention):
Herstellung eines Bindemittelsvstems: Preparation of a binder system:
Zu 100 g eines handelsüblichen Phenol-Furankaltharzes der Firma Hüttenes-Albertus mit der Bezeichnung XA20 (Furfurylalkohol: 78 %, freies Phenol: 4,5 %, Wassergehalt: 2 %, freier Formaldehyd Gehalt: 0, 171 % (entsprechend 5,7 mmol); erhältlich von Hüttenes- Albertus Chemische Werke GmbH) wurde bei einer Temperatur von 40 °C 0,43 g Glycin (5,7 mmol) gegeben und für 60 Minuten gerührt. Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,09 % auf.
Herstellung einer Formstoffmischunq: To 100 g of a commercial phenol Furankaltharzes the company Hüttenes-Albertus with the name XA20 (furfuryl alcohol: 78%, free phenol: 4.5%, water content: 2%, free formaldehyde content: 0, 171% (corresponding to 5.7 mmol available from Hüttenes-Albertus Chemische Werke GmbH) at a temperature of 40 ° C was added 0.43 g of glycine (5.7 mmol) and stirred for 60 minutes. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.09%. Production of a molding material mixture:
Bei Raumtemperatur (18 - 22 °C) und einer relativen Luftfeuchtigkeit (RLF) von 40 - 55 % wurden 100 Gewichtsteile Quarzsand H32 (Quarzwerke Frechen) in einen Labor- mischer (BOSCH) gegeben, mit 0,5 Gewichtsteilen Härter (Aktivator 100 SR; para- Toluolsulfonsäure 65 %, <0,5 % H2S04) versetzt und für 30 Sekunden gemischt. Anschließend wurde 1 ,0 Gewichtsteil des hergestellten Bindemittelsystems zugegeben und für weitere 45 Sekunden gemischt. Die Temperatur der hergestellten Formstoffmischung betrug 18 - 22 °C. Herstellung von (Prüf-)Formkörpern: At room temperature (18-22 ° C) and a relative humidity (RLF) of 40-55%, 100 parts by weight of quartz sand H32 (Quarzwerke Frechen) were placed in a laboratory mixer (BOSCH) with 0.5 parts by weight of hardener (activator 100 SR para-toluenesulphonic acid 65%, <0.5% H 2 S0 4 ) and mixed for 30 seconds. Subsequently, 1.0 part by weight of the prepared binder system was added and mixed for a further 45 seconds. The temperature of the molding mixture produced was 18-22 ° C. Production of (test) shaped bodies:
Anschließend wurde die Formstoffmischung von Hand in eine Prüfriegelform eingebracht und mit einer Handplatte verdichtet. Als Prüfkörper wurden quaderförmige Prüfriegel mit den Abmessungen 220 mm x 22,36 mm x 22,36 mm, sogenannte Georg-Fischer- Prüfriegel, hergestellt. Ermittlung der Verarbeitungs- (WT) und Aushärtezeit (ST): Subsequently, the molding material mixture was introduced by hand in a Prüfriegelform and compacted with a hand plate. Cuboid test bars measuring 220 mm x 22.36 mm x 22.36 mm, known as Georg Fischer test bars, were produced as test specimens. Determination of processing (WT) and curing time (ST):
Zur Ermittlung der Verarbeitungs- (WT) und Aushärtezeit (ST) der Formstoffmischung wurde anhand eines Georg-Fischer-Prüfriegels mit dem Prüfstift gemäß VDG-Merkblatt P 72 das Abbindeverhalten beobachtet. To determine the processing (WT) and curing time (ST) of the molding material mixture, the setting behavior was observed with the test pin according to VDG leaflet P 72 using a Georg Fischer test strip.
Ermittlung des Biegefestigkeitswertes: Die jeweiligen Biegefestigkeitswerte wurden gemäß VDG-Merkblatt P 72 ermittelt. Zur Bestimmung der Biegefestigkeiten wurden die Prüfriegel in ein Georg-Fischer- Festigkeitsprüfgerät, ausgerüstet mit einer Drei-Punkt-Biegevorrichtung (DISA-Industrie AG, Schaffhausen, CH), eingelegt und die Kraft gemessen, welche zum Bruch der Prüfriegel führte. Die Biegefestigkeiten wurden nach einer Stunde, nach zwei Stunden, nach vier Stunden und nach 24 Stunden nach der Herstellung der zu prüfenden (Prüf-)Formkörper (Lagerung der Kerne nach Entformen jeweils bei Raumtemperatur 18-22 °C, relative Luftfeuchtigkeit (20-55 %) gemessen.
Die ermittelten Werte sind in Tabelle 1 zusammengefasst. Determination of the flexural strength value: The respective flexural strength values were determined in accordance with VDG leaflet P 72. To determine the flexural strengths, the test bars were placed in a Georg Fischer Strength Tester equipped with a three-point bending device (DISA-Industrie AG, Schaffhausen, CH) and the force was measured which resulted in the breakage of the test bars. The flexural strengths were after one hour, after two hours, after four hours and after 24 hours after the preparation of the test (test) moldings (storage of the cores after demolding each at room temperature 18-22 ° C, relative humidity (20-55 %). The values determined are summarized in Table 1.
Die aus der erfindungsgemäßen Formstoffmischung hergestellten erfindungsgemäßen (Prüf-) Formkörper zeigen gegenüber den gemäß Vergleichsbeispielen 1 und 2 hergestellten (Prüf-) Formkörpern nach 24 Stunden eine verbesserte Biegefestigkeit auf, ohne dass das Abbindeverhalten negativ beeinflusst wird. Zusätzlich ist der Gehalt an freiem Formaldehyd in dem erfindungsgemäßen Bindemittelsystem geringer als der Gehalt an freiem Formaldehyd in den Bindemittelsystemen gemäß Vergleichsbeispielen 1 und 2. The (test) shaped bodies produced from the molding material mixture according to the invention exhibit improved flexural strength after 24 hours compared with the (test) moldings produced according to Comparative Examples 1 and 2, without adversely affecting the setting behavior. In addition, the content of free formaldehyde in the binder system according to the invention is lower than the content of free formaldehyde in the binder systems according to Comparative Examples 1 and 2.
Beispiel 2 (erfindunqsqemäß): Example 2 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 1. Allerdings wurden 5,7 mmol Alanin statt Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 1. However, 5.7 mmol alanine instead of glycine were used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,08 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.08%.
Beispiel 3 (erfindunqsqemäß): Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 1 . Allerdings wurden 5,7 mmol Serin statt Glycin eingesetzt. Example 3 (Inventive): The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 1. However, 5.7 mmol serine was used instead of glycine.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,09 % auf. Beispiel 4 (erfindunqsqemäß): After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.09%. Example 4 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 1. Allerdings wurden 5,7 mmol Valin statt Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 1. However, 5.7 mmol of valine instead of glycine were used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,09 % auf.
Verqleichsbeispiel 1 (nicht erfindunqsqemäß): After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.09%. Comparative Example 1 (not according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-)Formkörper erfolgte analog zu Beispiel 1. Allerdings wurde 5,7 mmol Harnstoff statt des Glycins verwendet. Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,13 % auf. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 1. However, 5.7 mmol of urea was used instead of the glycine. After cooling the binder system to room temperature (18 - 22 ° C), the binder system had a free formaldehyde content of 0.13%.
Verqleichsbeispiel 2 (nicht erfindunqsqemäß): Comparative Example 2 (not according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 1. Allerdings wurde kein Glycin hinzugegeben. Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,15 % auf. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 1. However, no glycine was added. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.15%.
Beispiel 5 (erfindunqsqemäß): Example 5 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 1 . Allerdings wurden 100 g eines handelsüblichen Phenol-Furankaltharzes der Firma Hüttenes-Albertus mit der Bezeichnung Kaltharz 7864 (Furfurylalkohol: 40 %, freies Phenol: 4 %, Wassergehalt: 2 %, freier Formaldehyd Gehalt: 0, 125 % (entspricht 4,2 mmol); erhältlich von Hüttenes-Albertus Chemische Werke GmbH), statt des in Beispiel 1 eingesetzten Phenol-Furankaltharzes mit der Bezeichnung XA20 verwendet. Allerdings wurden 4,2 mmol Glycin eingesetzt. Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,04 % auf. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 1. However, 100 g of a commercial phenol Furankaltharzes Hüttenes-Albertus with the name Kaltharz 7864 (furfuryl alcohol: 40%, free phenol: 4%, water content: 2%, free formaldehyde content: 0, 125% (corresponds to 4.2 mmol available from Hüttenes-Albertus Chemische Werke GmbH), instead of the phenol furan-tooth resin used in Example 1, designated XA20. However, 4.2 mmol glycine was used. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.04%.
Die ermittelten Werte sind in Tabelle 1 zusammengefasst. The values determined are summarized in Table 1.
Die aus der erfindungsgemäßen Formstoffmischung hergestellten erfindungsgemäßen (Prüf-) Formkörper zeigen gegenüber den gemäß Vergleichsbeispielen 3 und 4 herge- stellten (Prüf-) Formkörpern nach vier Stunden eine verbesserte Biegefestigkeit auf, ohne dass das Abbindeverhalten negativ beeinflusst wird. Zusätzlich ist der Gehalt an freiem
Formaldehyd in dem erfindungsgemäßen Bindemittelsystem geringer als der Gehalt an freiem Formaldehyd in den Bindemittelsystemen gemäß Vergleichsbeispielen 3 und 4. The (test) moldings produced from the molding material mixture according to the invention exhibit improved flexural strength after four hours compared with the (test) moldings produced according to Comparative Examples 3 and 4, without adversely affecting the setting behavior. In addition, the content of free Formaldehyde in the binder system according to the invention lower than the content of free formaldehyde in the binder systems according to Comparative Examples 3 and 4.
Beispiel 6 (erfindunqsqemäß): Example 6 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 5. Allerdings wurden 4,2 mmol Alanin statt Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 5. However, 4.2 mmol alanine instead of glycine were used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,05 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a 0.05% free formaldehyde content.
Beispiel 7 (erfindunqsqemäß): Example 7 (Inventive):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 5. Allerdings wurden 4,2 mmol Serin statt Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 5. However, 4.2 mmol of serine were used instead of glycine.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,06 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a 0.06% free formaldehyde content.
Beispiel 8 (erfindunqsqemäß): Example 8 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 5. Allerdings wurden 4,2 mmol Valin statt Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 5. However, 4.2 mmol of valine instead of glycine were used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,05 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a 0.05% free formaldehyde content.
Beispiel 9 (erfindunqsqemäß): Example 9 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 5. Allerdings wurden 4,2 mmol Glutamin statt Glycin eingesetzt.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,03 % auf. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 5. However, 4.2 mmol of glutamine were used instead of glycine. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.03%.
Verqleichsbeispiel 3 (nicht erfindunqsqemäß): Comparative Example 3 (not according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 5. Allerdings wurden 4,2 mmol Harnstoff statt des Glycins verwendet. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 5. However, 4.2 mmol of urea instead of the glycine were used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,12 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.12%.
Verqleichsbeispiel 4 (nicht erfindunqsqemäß): Comparative Example 4 (not according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 5. Allerdings wurde kein Glycin hinzugegeben. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 5. However, no glycine was added.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,17 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.17%.
Beispiel 10 (erfindunqsqemäß): Example 10 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 1 . Allerdings wurden 100 g eines handelsüblichen Phenol-Furankaltharzes der Firma Hüttenes-Albertus mit der Bezeichnung Kaltharz 81 17 (Furfurylalkohol: 50 %, freies Phenol: 3 - 4 %, Wassergehalt: 2 %, freier Formaldehyd Gehalt: 0,120 % (entspricht 4 mmol); erhältlich von Hüttenes-Albertus Chemische Werke GmbH) statt des in Beispiel 1 eingesetzten Phenol-Furankaltharzes mit der Bezeichnung XA20 verwendet. Allerdings wurden 4,0 mmol Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 1. However, 100 g of a commercial phenolic furan-resin Hüttenes-Albertus with the name cold resin 81 17 (furfuryl alcohol: 50%, free phenol: 3-4%, water content: 2%, free formaldehyde content: 0.120% (equivalent to 4 mmol) available from Hüttenes-Albertus Chemische Werke GmbH) instead of the phenol furan-red resin used in Example 1, designated XA20. However, 4.0 mmol glycine was used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,05 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a 0.05% free formaldehyde content.
Die ermittelten Werte sind in Tabelle 1 zusammengefasst. The values determined are summarized in Table 1.
Die aus der erfindungsgemäßen Formstoffmischung hergestellten erfindungsgemäßen (Prüf-) Formkörper zeigen gegenüber den gemäß Vergleichsbeispielen 5 und 6 herge-
stellten (Prüf-) Formkörpern nach 24 Stunden eine verbesserte Biegefestigkeit auf, ohne dass das Abbindeverhalten negativ beeinflusst wird. Zusätzlich ist der Gehalt an freiem Formaldehyd in dem erfindungsgemäßen Bindemittelsystem geringer als der Gehalt an freiem Formaldehyd in den Bindemittelsystemen gemäß Vergleichsbeispielen 6 und 5. The (test) shaped bodies according to the invention produced from the molding material mixture according to the invention show in comparison with the comparative examples 5 and 6 according to the invention. put (test) moldings after 24 hours on an improved flexural strength, without the setting behavior is adversely affected. In addition, the content of free formaldehyde in the binder system according to the invention is lower than the content of free formaldehyde in the binder systems according to Comparative Examples 6 and 5.
Beispiel 1 1 (erfindunqsqemäß): Example 1 1 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 10. Allerdings wurden 4,0 mmol Alanin statt Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 10. However, 4.0 mmol alanine instead of glycine were used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,05 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a 0.05% free formaldehyde content.
Beispiel 12 (erfindunqsqemäß): Example 12 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 10. Allerdings wurden 4,0 mmol Serin statt Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 10. However, 4.0 mmol of serine were used instead of glycine.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,08 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.08%.
Beispiel 13 (erfindunqsqemäß): Example 13 (Inventive):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 10. Allerdings wurden 4,0 mmol Valin statt Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 10. However, 4.0 mmol of valine instead of glycine were used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,07 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.07%.
Beispiel 14 (erfindunqsqemäß): Example 14 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 10. Allerdings wurden 4,0 mmol Glutamin statt Glycin eingesetzt.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,03 % auf. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 10. However, 4.0 mmol of glutamine were used instead of glycine. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.03%.
Verqleichsbeispiel 5 (nicht erfindunqsqemäß): Comparative Example 5 (not according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 10. Allerdings wurden 4,0 mmol Harnstoff statt des Glycins verwendet. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 10. However, 4.0 mmol of urea instead of the glycine were used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,05 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a 0.05% free formaldehyde content.
Verqleichsbeispiel 6 (nicht erfindunqsqemäß): Comparative Example 6 (not according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 10. Allerdings wurde kein Glycin hinzugegeben. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 10. However, no glycine was added.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,15 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.15%.
Beispiel 15 (erfindunqsqemäß): Example 15 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 1 . Allerdings wurden 100 g eines handelsüblichen Phenol-Furankaltharzes der Firma Hüttenes-Albertus mit der Bezeichnung Kaltharz 8500 (Furfurylalkohol: 57 %, freies Phenol: 1 ,1 - 1 ,8 %, Wassergehalt: 8 - 10 %, freier Formaldehyd Gehalt: 0,25 % (entspricht 8,3 mmol); erhältlich von Hüttenes-Albertus Chemische Werke GmbH) statt des in Beispiel 1 eingesetzten Phenol-Furankaltharzes mit der Bezeichnung XA20 verwendet. Allerdings wurden 8,3 mmol Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 1. However, 100 g of a commercial phenol Furankaltharzes Hüttenes-Albertus with the name Kaltharz 8500 (furfuryl alcohol: 57%, free phenol: 1, 1 - 1, 8%, water content: 8 - 10%, free formaldehyde content: 0, 25% (equivalent to 8.3 mmol), available from Hüttenes-Albertus Chemische Werke GmbH) instead of the phenol furan-tooth resin used in Example 1, designated XA20. However, 8.3 mmol glycine was used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,04 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.04%.
Die ermittelten Werte sind in Tabelle 1 zusammengefasst. The values determined are summarized in Table 1.
Die aus der erfindungsgemäßen Formstoffmischung hergestellten erfindungsgemäßen (Prüf-) Formkörper zeigen gegenüber den gemäß Vergleichsbeispielen 7 und 8 herge-
stellten (Prüf-) Formkörpern nach 24 Stunden eine verbesserte Biegefestigkeit auf, ohne dass das Abbindeverhalten negativ beeinflusst wird. Zusätzlich ist der Gehalt an freiem Formaldehyd in dem erfindungsgemäßen Bindemittelsystem geringer als der Gehalt an freiem Formaldehyd in den Bindemittelsystemen gemäß Vergleichsbeispielen 7 und 8. The (test) shaped bodies produced from the molding material mixture according to the invention show in comparison with the comparative examples 7 and 8 put (test) moldings after 24 hours on an improved flexural strength, without the setting behavior is adversely affected. In addition, the content of free formaldehyde in the binder system according to the invention is lower than the content of free formaldehyde in the binder systems according to Comparative Examples 7 and 8.
Beispiel 16 (erfindunqsqemäß): Example 16 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 15. Allerdings wurden 8,3 mmol Alanin statt Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 15. However, 8.3 mmol alanine instead of glycine were used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,04 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.04%.
Beispiel 17 (erfindunqsqemäß): Example 17 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 15. Allerdings wurden 8,3 mmol Serin statt Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 15. However, 8.3 mmol of serine were used instead of glycine.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,05 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a 0.05% free formaldehyde content.
Beispiel 18 (erfindunqsqemäß): Example 18 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 15. Allerdings wurden 8,3 mmol Valin statt Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 15. However, 8.36 mmol of valine instead of glycine were used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,07 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.07%.
Beispiel 19 (erfindunqsqemäß): Example 19 (Inventive):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 15. Allerdings wurden 8,3 mmol Glutamin statt Glycin eingesetzt.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,06 % auf. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 15. However, 8.3 mmol of glutamine were used instead of glycine. After cooling the binder system to room temperature (18-22 ° C), the binder system had a 0.06% free formaldehyde content.
Vergleichsbeispiel 7 (nicht erfindunqsqemäß): Comparative Example 7 (not according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 15. Allerdings wurden 8,3 mmol Harnstoff statt des Glycins verwendet. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 15. However, 8.3 mmol urea instead of the glycine were used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,19 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.19%.
Vergleichsbeispiel 8 (nicht erfindunqsqemäß): Comparative Example 8 (not according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 15. Allerdings wurde kein Glycin hinzugegeben. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 15. However, no glycine was added.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,27 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.27%.
Beispiel 20 (erfindungsgemäß): Example 20 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 1 . Allerdings wurden 100 g eines handelsüblichen Furankaltharzes der Firma Hüttenes-Albertus mit der Bezeichnung Kaltharz TDE 20 (Furfurylalkohol: 70 %, Wassergehalt: 5 - 7 %, freier Formaldehyd Gehalt: 0,23 % (entspricht 7,7 mmol); erhältlich von Hüttenes-Albertus Chemische Werke GmbH) statt des in Beispiel 1 eingesetzten Phenol-Furankaltharzes mit der Bezeichnung XA20 verwendet. Allerdings wurden 7,7 mmol Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 1. However, 100 g of a commercially available furan-talc resin from Hüttenes-Albertus designated cold resin TDE 20 (furfuryl alcohol: 70%, water content: 5-7%, free formaldehyde content: 0.23% (equivalent to 7.7 mmol), available from Hüttenes -Albertus Chemische Werke GmbH) instead of the phenol furan-red resin used in Example 1, designated XA20. However, 7.7 mmol glycine were used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,09 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.09%.
Die ermittelten Werte sind in Tabelle 1 zusammengefasst. The values determined are summarized in Table 1.
Die aus der erfindungsgemäßen Formstoffmischung hergestellten erfindungsgemäßen (Prüf-) Formkörper zeigen gegenüber den gemäß Vergleichsbeispiel 9 hergestellten
(Prüf-) Formkörpern nach 24 Stunden eine verbesserte Biegefestigkeit auf, ohne dass das Abbindeverhalten negativ beeinflusst wird. Zusätzlich ist der Gehalt an freiem Formaldehyd in dem erfindungsgemäßen Bindemittelsystem geringer als der Gehalt an freiem Formaldehyd in den Bindemittelsystemen gemäß Vergleichsbeispiel 9. The (test) shaped bodies according to the invention produced from the molding material mixture according to the invention show over those produced according to Comparative Example 9 (Test) moldings after 24 hours improved flexural strength, without the setting behavior is adversely affected. In addition, the content of free formaldehyde in the binder system according to the invention is lower than the content of free formaldehyde in the binder systems according to Comparative Example 9.
Beispiel 21 (erfindunqsqemäß): Example 21 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 20. Allerdings wurden 7,7 mmol Alanin statt Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 20. However, 7.7 mmol alanine instead of glycine were used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,08 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.08%.
Beispiel 22 (erfindunqsqemäß): Example 22 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 20. Allerdings wurden 7,7 mmol Serin statt Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 20. However, 7.7 mmol of serine were used instead of glycine.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,09 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.09%.
Beispiel 23 (erfindunqsqemäß): Example 23 (according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 20. Allerdings wurden 7,7 mmol Valin statt Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 20. However, 7.7 mmol of valine instead of glycine were used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,07 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.07%.
Verqleichsbeispiel 9 (nicht erfindunqsqemäß): Comparative Example 9 (not according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 20. Allerdings wurde kein Glycin hinzugegeben.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,23 % auf. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 20. However, no glycine was added. After cooling the binder system to room temperature (18-22 ° C), the binder system had 0.23% free formaldehyde content.
Beispiel 24 (erfindunqsqemäß): Example 24 (according to the invention):
Herstellung eines Bindemittelsvstems: Zu 100 g eines handelsüblichen Phenol-Furan-Warmbox-Harzes der Firma Hüttenes- Albertus mit der Bezeichnung„Furesan 7682" (Furfurylalkohol: 57 %, freies Phenol: 1 ,0 - 1 ,6 %, Wassergehalt: 8 - 10 %, freier Formaldehyd-Gehalt: 0,25 % (entspricht 8,3 mmol); erhältlich von Hüttenes-Albertus Chemische Werke GmbH) wurden bei einer Temperatur von 40 °C 0,62 g Glycin (8,3 mmol) gegeben und für 60 Minuten gerührt. Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,07 % auf. Preparation of a binder system: To 100 g of a commercial phenol-furan-warmbox resin from Hüttenes-Albertus with the name "Furesan 7682" (furfuryl alcohol: 57%, free phenol: 1, 0 - 1, 6%, water content: 8 - 10%, free formaldehyde content: 0.25% (equivalent to 8.3 mmol), available from Hüttenes-Albertus Chemische Werke GmbH) were added at a temperature of 40 ° C 0.62 g glycine (8.3 mmol) and stirred for 60 minutes After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.07%.
Herstellung einer Formstoffmischunq: Production of a molding material mixture:
Bei Raumtemperatur (18-22 °C) und einer rel. Lufttemperatur (40-55%) werden in einen Labormischer (BOSCH) 100 GT Quarzsand H32 gegeben, mit 0,3% Härter (Furedur 2) versetzt und 15 sec vermischt. Im Anschluss wird das Sand/Härter-Gemisch mit 1 ,5 GT Harz versehen und weitere 150 sec gemischt. Die Temperatur der hergestellten Formstoffmischung beträgt 18 - 22 °C. At room temperature (18-22 ° C) and a rel. Air temperature (40-55%) are placed in a laboratory mixer (BOSCH) 100 GT quartz sand H32, mixed with 0.3% hardener (Furedur 2) and mixed for 15 sec. Subsequently, the sand / hardener mixture is provided with 1, 5 GT resin and mixed for a further 150 sec. The temperature of the molding mixture produced is 18-22 ° C.
Herstellung von (Prüf-) Formkörpern: Production of (test) shaped bodies:
Anschließend wurde die Formstoffmischung von Hand in eine Prüfriegelform eingebracht, mit einer Handplatte verdichtet und bei 220°C gehärtet. Als Prüfkörper wurden guader- förmige Prüfriegel mit den Abmessungen 220 mm x 22,36 mm x 22,36 mm, sogenannte Georg-Fischer-Prüfriegel, hergestellt. Subsequently, the molding material mixture by hand was introduced into a Prüfriegelform, compacted with a hand plate and cured at 220 ° C. The test specimens produced were guader-shaped test bars measuring 220 mm x 22.36 mm x 22.36 mm, known as Georg Fischer test bars.
Es wurden verschiedene Prüfformkörper hergestellt, wobei diese 15, 30, 60 oder 120 sec bei 220 °C gehärtet wurden. Von den hergestellten (Prüf-) Formkörpern wurden die Heißbiegefestigkeit (Biegefestigkeit direkt nach dem Entformen des heißen (Prüf-) Formkörpers) und die Kaltbiegefestigkeit (Biegefestigkeit des erkalteten (Prüf-) Formkörpers nach 24 Stunden) gemäß der in Beispiel 1 beschriebenen Bestimmungsmethode bestimmt.
Die Ergebnisse sind in Tabelle 2 zusammengefasst. Various shaped bodies were produced, these being cured at 220 ° C. for 15, 30, 60 or 120 seconds. Of the prepared test specimens, hot bending strength (flexural strength immediately after demolding of the hot (test) shaped body) and cold bending strength (flexural strength of the cooled (test) shaped body after 24 hours) were determined according to the method of determination described in Example 1. The results are summarized in Table 2.
Die Kaltbiegefestigkeit des hergestellten (Prüf-) Formkörpers ist höher als bei Vergleichsbeispiel 1 1 , in dem keine Aminosäure zugesetzt wurde. Bei den Proben mit einer kurzen Backzeit (15 und 30 Sekunden) ist die Kaltbiegefestigkeit besonders hoch. Die Heißbie- gefestigkeiten werden nicht negativ beeinflusst. The cold bending strength of the produced (test) shaped body is higher than in Comparative Example 1 1, in which no amino acid was added. For samples with a short baking time (15 and 30 seconds), the cold bending strength is particularly high. The hot bending strengths are not adversely affected.
Diese Ergebnisse sind besonders überraschend, da bei Phenol-Furan-Warmbox-Harzen bisher angenommen wurde, dass hohe Biegefestigkeiten (insbesondere bei kurzen Backzeiten) nur mit einem hohen Gehalt an freiem Formaldehyd erreicht werden können. These results are particularly surprising because it has hitherto been assumed in phenol-furan-warmbox resins that high flexural strengths (in particular with short baking times) can only be achieved with a high content of free formaldehyde.
Beispiel 25 (erfindunqsqemäß): Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 24. Allerdings wurden 8.3 mmol Alanin statt Glycin eingesetzt. Example 25 (according to the invention): The preparation of the binder system, of the molding material mixture and of the (test) shaped body was carried out analogously to Example 24. However, 8.3 mmol of alanine were used instead of glycine.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von unter 0,08 % auf. Die Ergebnisse sind in Tabelle 2 zusammengefasst. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of less than 0.08%. The results are summarized in Table 2.
Die Kaltbiegefestigkeit des hergestellten (Prüf-) Formkörpers ist höher als bei Vergleichsbeispiel 1 1 , in dem keine Aminosäure zugesetzt wurde. Bei den Proben mit einer kurzen Backzeit (15 und 30 Sekunden) ist die Kaltbiegefestigkeit besonders hoch. Die Heißbiegefestigkeiten werden nicht negativ beeinflusst. Diese Ergebnisse sind besonders überraschend, da bei Phenol-Furan-Warmbox-Harzen bisher angenommen wurde, dass hohe Biegefestigkeiten (insbesondere bei kurzen Backzeiten) nur mit einem hohen Gehalt an freiem Formaldehyd erreicht werden können. The cold bending strength of the produced (test) shaped body is higher than in Comparative Example 1 1, in which no amino acid was added. For samples with a short baking time (15 and 30 seconds), the cold bending strength is particularly high. The hot bending strengths are not adversely affected. These results are particularly surprising because it has hitherto been assumed in phenol-furan-warmbox resins that high flexural strengths (in particular with short baking times) can only be achieved with a high content of free formaldehyde.
Beispiel 26 (erfindunqsqemäß): Example 26 (Inventive):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Form- körper erfolgte analog zu Beispiel 24. Allerdings wurden 8,3 mmol Glutamin statt Glycin eingesetzt.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von unter 0,08 % auf. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 24. However, 8.3 mmol of glutamine were used instead of glycine. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of less than 0.08%.
Die Ergebnisse sind in Tabelle 2 zusammengefasst. The results are summarized in Table 2.
Die Kaltbiegefestigkeit des hergestellten (Prüf-) Formkörpers ist höher als bei Vergleichsbeispiel 1 1 , in dem keine Aminosäure zugesetzt wurde. Bei den Proben mit einer kurzen Backzeit (15 und 30 Sekunden) ist die Kaltbiegefestigkeit besonders hoch. Die Heißbiegefestigkeiten werden nicht negativ beeinflusst. The cold bending strength of the produced (test) shaped body is higher than in Comparative Example 1 1, in which no amino acid was added. For samples with a short baking time (15 and 30 seconds), the cold bending strength is particularly high. The hot bending strengths are not adversely affected.
Diese Ergebnisse sind besonders überraschend, da bei Phenol-Furan-Warmbox-Harzen bisher angenommen wurde, dass hohe Biegefestigkeiten (insbesondere bei kurzen Backzeiten) nur mit einem hohen Gehalt an freiem Formaldehyd erreicht werden können. These results are particularly surprising because it has hitherto been assumed in phenol-furan-warmbox resins that high flexural strengths (in particular with short baking times) can only be achieved with a high content of free formaldehyde.
Beispiel 27 (erfindunqsqemäß): Example 27 (Inventive):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 24. Allerdings wurden 8,3 mmol Serin statt Glycin eingesetzt. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 24. However, 8.36 mmol of serine were used instead of glycine.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von unter 0,08 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of less than 0.08%.
Verqleichsbeispiel 10 (nicht erfindunqsqemäß): Comparative Example 10 (not according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 24. Allerdings wurde 8,3 mmol Harnstoff statt des Glycins verwendet. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 24. However, 8.3 mmol urea instead of glycine was used.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,07 % auf. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.07%.
Verqleichsbeispiel 1 1 (nicht erfindunqsqemäß): Comparative Example 1 1 (not according to the invention):
Die Herstellung des Bindemittelsystems, der Formstoffmischung und der (Prüf-) Formkörper erfolgte analog zu Beispiel 24. Allerdings wurde kein Glycin hinzugegeben.
Nach dem Abkühlen des Bindemittelsystems auf Raumtemperatur (18 - 22 °C) wies das Bindemittelsystem einen Gehalt an freiem Formaldehyd von 0,18 % auf. The preparation of the binder system, the molding material mixture and the (test) shaped body was carried out analogously to Example 24. However, no glycine was added. After cooling the binder system to room temperature (18-22 ° C), the binder system had a free formaldehyde content of 0.18%.
Ergebnisse: Results:
Tabelle 1 : Vergleich der Verarbeitungs- (WT) und Aushärtezeit (ST) sowie der Biegefestigkeiten der in den Beispielen 1 bis 23 und den Vergleichsbeispielen 1 bis 9 hergestellten (Prüf-) Formkörper.
Heißbiegefestigkeiten in [N/cm2] - Kaltbiegefestigkeiten [N/cm2] - geprüft sofort nach Herstellung geprüft nach dem Erkalten der nach ... Sekunden Backzeit bei Kerne nach ... Sekunden Backzeit 220 °C bei 220 °C Table 1: Comparison of the processing (WT) and curing time (ST) and the flexural strengths of the (test) moldings produced in Examples 1 to 23 and Comparative Examples 1 to 9. Hot bending strengths in [N / cm 2] - Cold bending strength [N / cm 2] - Tested tested immediately after preparation, after cooling, the baking time after ... seconds in nuclei by ... seconds baking time 220 ° C at 220 ° C
15" 30" 60" 120" 15" 30" 60" 120" 15 "30" 60 "120" 15 "30" 60 "120"
Vergleichsbeispiel 1 1 210 225 235 220 680 660 600 530Comparative Example 1 1 210 225 235 220 680 660 600 530
Beispiel 24 215 220 240 230 740 710 630 580Example 24 215 220 240 230 740 710 630 580
Beispiel 25 230 240 280 220 770 760 610 570Example 25 230 240 280 220 770 760 610 570
Beispiel 26 200 220 270 220 780 740 610 550 Example 26 200 220 270 220 780 740 610 550
Tabelle 2: Vergleich der Heißbiegefestigkeiten und Kaltbiegefestigkeiten der in den Table 2: Comparison of the hot bending strengths and cold bending strengths of the
Beispielen 24 bis 26 und in Vergleichsbeispiel 1 1 hergestellten (Prüf-) Formkörper.
Examples 24 to 26 and in Comparative Example 1 1 prepared (test) moldings.
Claims
1. Formstoffmischung zur Herstellung von Formkörpern für die Gießereiindustrie, vorzugsweise zur Herstellung von Gießereiformen, Kernen oder Speisern, für die Gießereiindustrie, umfassend 1. molding material mixture for the production of moldings for the foundry industry, preferably for the production of foundry molds, cores or feeders, for the foundry industry, comprising
A) einen oder mehrere schüttfähige, feuerfeste Füllstoffe, A) one or more pourable, refractory fillers,
B) ein Bindemittelsystem, umfassend i) Formaldehyd, einen Formaldehydspender und/oder Vorkondensate aus Formaldehyd, und ii) eine Aminosäure. B) a binder system comprising i) formaldehyde, a formaldehyde donor and / or precondensates of formaldehyde, and ii) an amino acid.
2. Formstoffmischung nach Anspruch 1 , wobei die Aminosäure ausgewählt ist aus der Gruppe bestehend aus Alanin, Glycin, Isoleucin, Methionin, Prolin, Valin, Histi- din, Phenylalanin, Tryptophan, Tyrosin, Aspargin, Glutamin, Cystein, Methionin, Serin, Threonin, Tyrosin, Lysin, Arginin und Histidin, 2. Molding material mixture according to claim 1, wherein the amino acid is selected from the group consisting of alanine, glycine, isoleucine, methionine, proline, valine, histidine, phenylalanine, tryptophan, tyrosine, asparagine, glutamine, cysteine, methionine, serine, threonine , Tyrosine, lysine, arginine and histidine,
3. Formstoffmischung nach Anspruch 1 , wobei die Aminosäure ausgewählt ist aus der Gruppe bestehend aus Glycin, Glutamin, Alanin, Valin und Serin. 3. The molding material mixture according to claim 1, wherein the amino acid is selected from the group consisting of glycine, glutamine, alanine, valine and serine.
4. Formstoffmischung nach Anspruch 1 , wobei die Aminosäure Glycin ist. 4. The molding material mixture according to claim 1, wherein the amino acid is glycine.
5. Formstoffmischung nach einem der vorherigen Ansprüche, wobei der eine, zumindest einer der mehreren oder sämtliche schüttfähige, feuerfeste Füllstoffe ausgewählt sind aus der Gruppe bestehend aus Quarzsand, Quarzgutsand, Olivinsand, Chrom-Magnesit-Granulat, Aluminiumsilikate, insbesondere J-Sand und Kerphalite, Schwermineralien, insbesondere Chromit, Zirkonsand und R-Sand, technische Keramik, insbesondere Cerabeads, Schamotte, M-Sand, Alodur, Bauxitsand und Siliciumcarbid, feldspathaltige Sande, Andalusitsande, Hohlkugelkorund, Spheres aus Flugaschen, Reisschalenaschen, Blähgläser, Schaumgläser, geblähte Perlite, Kern-Hülle-Partikel, Flugaschen und weitere Spezialsande.
5. Molding material mixture according to one of the preceding claims, wherein the one, at least one of the plurality or all free-flowing refractory fillers are selected from the group consisting of quartz sand, quartz sand, olivine, chromium-magnesite granules, aluminum silicates, in particular J-sand and Kerphalite Heavy minerals, in particular chromite, zircon sand and R-sand, technical ceramics, in particular cerabeads, chamotte, M-sand, Alodur, bauxite sand and silicon carbide, feldspathic sands, andalusite sands, hollow spherical corundum, fly ash particles, rice husk ash, blown glass, foam glass, expanded perlite, Core-shell particles, fly ash and other special sands.
Formstoffmischung nach einem der vorherigen Ansprüche, wobei der eine, zumindest einer der mehreren oder sämtliche schüttfähige, feuerfeste Füllstoffe einen mittleren Partikeldurchmesser d50 im Bereich zwischen 0,001 und 5 mm, vorzugsweise im Bereich von 0,01 bis 3 mm aufweisen, besonders bevorzugt im Bereich von 0,02 bis 2,0 mm aufweisen Molding material mixture according to one of the preceding claims, wherein the one, at least one of the plurality or all pourable, refractory fillers have a mean particle diameter d50 in the range between 0.001 and 5 mm, preferably in the range of 0.01 to 3 mm, particularly preferably in the range of 0.02 to 2.0 mm
Formstoffmischung nach einem der vorherigen Ansprüche, wobei das Verhältnis der Gesamtmasse an schüttfähiger, feuerfester Füllstoffe zu der Gesamtmasse sonstiger Bestandteile der Formstoffmischung im Bereich von 100 : 5 bis 100 : 0,1 , bevorzugt von 100 : 3 bis 100 : 0,4, besonders bevorzugt von 100 : 2 bis 100 : 0,6 liegt. Molding material mixture according to one of the preceding claims, wherein the ratio of the total mass of pourable, refractory fillers to the total mass of other components of the molding material mixture in the range of 100: 5 to 100: 0.1, preferably from 100: 3 to 100: 0.4, especially preferably from 100: 2 to 100: 0.6.
Formstoffmischung nach einem der vorherigen Ansprüche, wobei das Bindemittelsystem zusätzlich umfasst: a) Phenole, insbesondere Phenol, o-Kresol, p-Kresol, 3,5-Xylenol oder Resorcin, oder Vorkondensate aus Phenolen, insbesondere Resole, und/oder b) Furanderivate und/oder Furfurylalkohol oder Vorkondensate aus Furanderivaten und/oder Furfurylalkohol und/oder c) Harnstoff oder Harnstoffderivate oder Vorkondensate aus Harnstoff oder Harnstoffderivaten. Molding material mixture according to one of the preceding claims, wherein the binder system additionally comprises: a) phenols, in particular phenol, o-cresol, p-cresol, 3,5-xylenol or resorcinol, or precondensates of phenols, especially resoles, and / or b) furan derivatives and / or furfuryl alcohol or precondensates of furan derivatives and / or furfuryl alcohol and / or c) urea or urea derivatives or precondensates of urea or urea derivatives.
Formstoffmischung nach einem der vorherigen Ansprüche, wobei das Bindemittelsystem aushärtbar ist zu einem i) Phenol/Furfurylalkohol/Formaldehydharz, ii) Furfurylalkohol/Formaldehydharz, iii) Harnstoff/Formaldehydharz,
iv) Harnstoff/Furfurylalkohol/Formaldehydharz oder v) Harnstoff/Furfurylalkohol/Phenol/Formaldehydharz. Molding material mixture according to one of the preceding claims, wherein the binder system is curable to i) phenol / furfuryl alcohol / formaldehyde resin, ii) furfuryl alcohol / formaldehyde resin, iii) urea / formaldehyde resin, iv) urea / furfuryl alcohol / formaldehyde resin or v) urea / furfuryl alcohol / phenol / formaldehyde resin.
10. Formstoffmischung nach einem der vorherigen Ansprüche, wobei der Anteil an sämtlichen Aminosäuren in der Formstoffmischung 0,005 bis 2 Gew.-% beträgt, vorzugsweise 0,01 bis 1 Gew.-% beträgt, besonders bevorzugt 0,03 bis 0,5 Gew.- % beträgt, bezogen auf den Feststoffanteil der gesamten Formstoffmischung. 10. Molding material mixture according to one of the preceding claims, wherein the proportion of all amino acids in the molding material mixture is 0.005 to 2 wt .-%, preferably 0.01 to 1 wt .-%, more preferably 0.03 to 0.5 wt. -%, based on the solids content of the entire molding material mixture.
1 1. Formstoffmischung nach einem der vorherigen Ansprüche, wobei das Molverhältnis aus sämtlichen Aminosäuren zu verfügbarem Formaldehyd 4 : 1 bis 1 : 0,5 beträgt, vorzugsweise 3 : 1 bis 1 : 0,9, besonders bevorzugt 2,5 : 1 bis 1 : 1 beträgt. 1. The molding material mixture according to claim 1, wherein the molar ratio of all amino acids to available formaldehyde is 4: 1 to 1: 0.5, preferably 3: 1 to 1: 0.9, particularly preferably 2.5: 1 to 1 : 1 is.
12. Formkörper für die Gießereiindustrie hergestellt unter Verwendung einer Formstoffmischung wie in einem der Ansprüche 1 bis 1 1 definiert. 12. Moldings for the foundry industry produced using a molding material mixture as defined in any one of claims 1 to 1 1 defined.
13. Verwendung zumindest einer Aminosäure in einer Formstoffmischung für die Gießereiindustrie, wobei die Formstoffmischung neben der Aminosäure Formaldehyd oder eine Formaldehydquelle enthält. 13. Use of at least one amino acid in a molding material mixture for the foundry industry, wherein the molding material mixture in addition to the amino acid formaldehyde or a formaldehyde source.
14. Verfahren zur Herstellung einer Formstoffmischung nach einem der Ansprüche 1 bis 1 1 , umfassend die folgenden Schritte: a) Herstellen oder Bereitstellen von einem oder mehreren schüttfähigen, feuerfesten Füllstoffen, b) Herstellen oder Bereitstellen eines Bindemittelsystems, umfassend i) Formaldehyd, einen Formaldehydspender und/oder Vorkondensate aus Formaldehyd, und ii) eine Aminosäure
und c) Vermischen aller Komponenten. 14. A process for preparing a molding material mixture according to any one of claims 1 to 1 1, comprising the following steps: a) producing or providing one or more pourable refractory fillers, b) preparing or providing a binder system comprising i) formaldehyde, a formaldehyde donor and / or precondensates of formaldehyde, and ii) an amino acid and c) mixing all components.
15. Verfahren zur Herstellung eines Formkörpers für die Gießereiindustrie umfassend die folgenden Schritte: 15. A process for producing a molded article for the foundry industry, comprising the following steps:
Herstellen oder Bereitstellen einer Formstoffmischung nach einem sprüche 1 bis 1 1 ii) Formen der Formstoffmischung zu einem ungehärteten Formkörper und Producing or providing a molding material mixture according to a claims 1 to 1 1 ii) molding the molding material mixture to form an uncured molding and
Aushärten oder Aushärtenlassen des ungehärteten Formkörpers, sodass Formkörper für die Gießereiindustrie resultiert. Curing or curing of the uncured molding so that moldings for the foundry industry results.
16. Kit zur Herstellung einer Formstoffmischung nach einem der Ansprüche 1 bis 1 1 und/oder zur Herstellung eines Formkörpers nach Anspruch 12 umfassend 16. Kit for preparing a molding material mixture according to any one of claims 1 to 1 1 and / or for producing a shaped article according to claim 12 comprising
I) ein Bindemittelsystem wie in einem der Ansprüche 1 bis 1 1 definiert, I) a binder system as defined in any one of claims 1 to 11,
II) optional einen oder mehrere schüttfähige, feuerfeste Füllstoffe wie in einem der Ansprüche 1 bis 1 1 definiert und optional einen Härter, vorzugsweise eine organische oder anorganische Säure, besonders bevorzugt eine Sulfonsäure (insbesondere para- Toluolsulfonsäure), Phosphorsäure, Carbonsäure, Methansulfonsäure und/oder Schwefelsäure oder Mischungen daraus.
II) optionally one or more free-flowing, refractory fillers as defined in any one of claims 1 to 1 1 and optionally a hardener, preferably an organic or inorganic acid, more preferably a sulfonic acid (especially para-toluenesulfonic acid), phosphoric acid, carboxylic acid, methanesulfonic acid and / or sulfuric acid or mixtures thereof.
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| PCT/EP2017/080602 WO2018099887A1 (en) | 2016-11-29 | 2017-11-28 | Amino acid-containing moulding material mixture for production of mouldings for the foundry industry |
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| DE102018118291A1 (en) * | 2018-07-27 | 2020-01-30 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Sizing composition to reduce formaldehyde emissions |
| DE102019106021A1 (en) | 2019-03-08 | 2020-09-10 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Formaldehyde scavenger for binder systems |
| CN111545738B (en) * | 2020-05-18 | 2021-08-27 | 西峡龙成冶金材料有限公司 | Drainage sand and preparation method and application thereof |
| KR20230132480A (en) * | 2021-01-22 | 2023-09-15 | 오엘리콘 멧코 아게, 볼렌 | Implanted thermal barrier coating system |
| RU210048U1 (en) * | 2021-12-07 | 2022-03-25 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Волгоградский государственный технический университет" (ВолгГТУ) | Casting shape |
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2017
- 2017-11-28 WO PCT/EP2017/080602 patent/WO2018099887A1/en unknown
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- 2017-11-28 CN CN201780073951.3A patent/CN110049835A/en active Pending
- 2017-11-28 US US16/464,859 patent/US11338356B2/en active Active
- 2017-11-28 KR KR1020197018635A patent/KR102421482B1/en active IP Right Grant
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- 2017-11-28 ES ES17823037T patent/ES2874780T3/en active Active
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- 2017-11-28 EA EA201991323A patent/EA038564B1/en unknown
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| CN110049835A (en) | 2019-07-23 |
| KR102421482B1 (en) | 2022-07-15 |
| ES2874780T3 (en) | 2021-11-05 |
| US11338356B2 (en) | 2022-05-24 |
| DE102016123051A1 (en) | 2018-05-30 |
| BR112019010872A2 (en) | 2019-10-01 |
| BR112019010872B1 (en) | 2023-01-10 |
| PL3548200T3 (en) | 2021-11-22 |
| JP7069200B2 (en) | 2022-05-17 |
| KR20190090828A (en) | 2019-08-02 |
| MX2019006187A (en) | 2019-07-10 |
| EP3548200B1 (en) | 2021-06-09 |
| EA038564B1 (en) | 2021-09-15 |
| WO2018099887A1 (en) | 2018-06-07 |
| US20190283116A1 (en) | 2019-09-19 |
| EA201991323A1 (en) | 2019-10-31 |
| JP2019535537A (en) | 2019-12-12 |
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