CN116234647A - Adhesive composition for casting mold - Google Patents
Adhesive composition for casting mold Download PDFInfo
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- CN116234647A CN116234647A CN202080105309.0A CN202080105309A CN116234647A CN 116234647 A CN116234647 A CN 116234647A CN 202080105309 A CN202080105309 A CN 202080105309A CN 116234647 A CN116234647 A CN 116234647A
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- mold
- composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 284
- 239000000853 adhesive Substances 0.000 title claims description 64
- 230000001070 adhesive effect Effects 0.000 title claims description 64
- 238000005266 casting Methods 0.000 title claims description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 119
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims abstract description 99
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 98
- 238000007493 shaping process Methods 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 51
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- SOGYZZRPOIMNHO-UHFFFAOYSA-N [2-(hydroxymethyl)furan-3-yl]methanol Chemical compound OCC=1C=COC=1CO SOGYZZRPOIMNHO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims description 77
- 239000003795 chemical substances by application Substances 0.000 claims description 62
- 239000007849 furan resin Substances 0.000 claims description 58
- 238000004519 manufacturing process Methods 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 19
- 150000001299 aldehydes Chemical class 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 150000002240 furans Chemical class 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 description 18
- 239000006087 Silane Coupling Agent Substances 0.000 description 16
- 239000004576 sand Substances 0.000 description 16
- NSQYDLCQAQCMGE-UHFFFAOYSA-N 2-butyl-4-hydroxy-5-methylfuran-3-one Chemical compound CCCCC1OC(C)=C(O)C1=O NSQYDLCQAQCMGE-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 13
- 239000004202 carbamide Substances 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 229930040373 Paraformaldehyde Natural products 0.000 description 9
- 238000004898 kneading Methods 0.000 description 9
- 229920002866 paraformaldehyde Polymers 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- -1 Furanyl alcohol Chemical compound 0.000 description 7
- 229920001864 tannin Polymers 0.000 description 7
- 239000001648 tannin Substances 0.000 description 7
- 235000018553 tannin Nutrition 0.000 description 7
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 4
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 3
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZWRLWJAFBLTMSQ-UHFFFAOYSA-N Docosa-7,10,14-triensaeure Natural products C1C(C)=C2CC(C)(C)CC2C(O)C2=COC=C21 ZWRLWJAFBLTMSQ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229920002770 condensed tannin Polymers 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- YKASHPSKFYVZRC-UHFFFAOYSA-M furan-2-ylmethyl(trimethyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)CC1=CC=CO1 YKASHPSKFYVZRC-UHFFFAOYSA-M 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical class NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000007696 Kjeldahl method Methods 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- RNKXUVJWMOMTHV-UHFFFAOYSA-N [4-(hydroxymethyl)furan-3-yl]methanol Chemical group OCC1=COC=C1CO RNKXUVJWMOMTHV-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- IZALUMVGBVKPJD-UHFFFAOYSA-N benzene-1,3-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=C1 IZALUMVGBVKPJD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- HDNHWROHHSBKJG-UHFFFAOYSA-N formaldehyde;furan-2-ylmethanol Chemical compound O=C.OCC1=CC=CO1 HDNHWROHHSBKJG-UHFFFAOYSA-N 0.000 description 1
- RRPGUZROISYLGY-UHFFFAOYSA-N formaldehyde;furan-2-ylmethanol;phenol Chemical compound O=C.OCC1=CC=CO1.OC1=CC=CC=C1 RRPGUZROISYLGY-UHFFFAOYSA-N 0.000 description 1
- QFFUJMYTIBZKQL-UHFFFAOYSA-N formaldehyde;furan-2-ylmethanol;urea Chemical compound O=C.NC(N)=O.OCC1=CC=CO1 QFFUJMYTIBZKQL-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- IZWIQVOZAJLLOH-UHFFFAOYSA-N furan-2-ylmethanediol Chemical compound OC(O)C1=CC=CO1 IZWIQVOZAJLLOH-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- ZQDWYQDJDCIFKC-UHFFFAOYSA-N methanesulfonic acid;phosphoric acid Chemical class CS(O)(=O)=O.OP(O)(O)=O ZQDWYQDJDCIFKC-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229940054441 o-phthalaldehyde Drugs 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallyl group Chemical group C1(=C(C(=CC=C1)O)O)O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- WIJVUKXVPNVPAQ-UHFFFAOYSA-N silyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)O[SiH3] WIJVUKXVPNVPAQ-UHFFFAOYSA-N 0.000 description 1
- GRJISGHXMUQUMC-UHFFFAOYSA-N silyl prop-2-enoate Chemical class [SiH3]OC(=O)C=C GRJISGHXMUQUMC-UHFFFAOYSA-N 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
- B22C1/10—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for influencing the hardening tendency of the mould material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Mold Materials And Core Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a binder composition for mold shaping, which contains furanmethanol (component A), dimethylolfuran (component B), resin (component C) and water (component D) and satisfies the following conditions (1) to (5). Condition (1): the content of the component A in the binder composition for mold shaping is 30.0 mass% or less; condition (2): the content of the component D in the binder composition for mold shaping is 25.0 mass% or less; condition (3): the content of the component B in the binder composition for mold shaping is 39.0 mass% or more and 95.0 mass% or less relative to the total of the contents of the component B and the component C; condition (4): the nitrogen content in the component C is 2.7 mass% or more and 22.0 mass% or less; condition (5): when the content of the component B in the binder composition for mold shaping is y and the nitrogen content of the component C is x, the following formula (1) is satisfied: 2.97x+15.2.ltoreq.y (1). According to the present invention, a binder composition having a low content of monomeric furanmethanol, which can greatly improve the mold strength in a low-temperature environment, can be provided.
Description
Technical Field
The present invention relates to an adhesive composition for mold shaping.
Background
In general, acid-curable molds are manufactured by: a binder composition for mold molding containing an acid-curable resin and a curing agent composition containing sulfonic acid, sulfuric acid, phosphoric acid, etc. are added to refractory particles such as silica sand, these are kneaded, and then the obtained kneaded sand is filled into a master such as a wood mold to cure the acid-curable resin. As the acid-curable resin, a furan resin, a phenol resin, or the like is used, and as the furan resin, a furanmethanol-urea-formaldehyde resin, a furanmethanol-phenol-formaldehyde resin, other known modified furan resins, or the like is used. The method for producing a mold can perform a molding operation with a high degree of freedom, and the mold has excellent thermal properties, so that a high-quality casting can be produced, and is widely used for casting machine parts, construction machine parts, automobile parts, and the like.
An important condition for producing a mold is to improve the working environment at the time of producing the mold (at the time of curing the resin), and in particular, it is desired to reduce the amount of the monomer-like furanmethanol in the furanic resin in order to reduce the amount of the furanic methanol volatilized at the time of producing the mold.
For example, japanese patent application laid-open No. 2014-501175 discloses the following: by using a binder composition having a small content of monomeric furanmethanol, the release of furanmethanol and formaldehyde during kneading and molding can be reduced.
In addition, japanese patent application laid-open No. 56-61420 discloses a method for producing a phenol-furanmethanol-formaldehyde resin for mold molding, which contains a small amount of furanmethanol in a monomer form, wherein the furanmethanol skeleton is introduced into the resin structure at a high ratio by sufficiently performing the reaction.
Further, japanese patent application laid-open No. 2013-151019 discloses the following: by using a binder composition containing 5-hydroxymethylfurfural and 2, 5-dimethylolfuran instead of furanmethanol, the mold release time can be shortened in the same usable time, thereby improving the mold productivity and the curing speed and the mold strength.
Disclosure of Invention
The invention relates to a binder composition for mold shaping, which contains furanmethanol (component A), dimethylolfuran (component B), resin (component C) and water (component D)
The following conditions (1) to (5) are satisfied.
Condition (1): the content of the component A in the binder composition for mold shaping is 30.0 mass% or less
Condition (2): the content of the component D in the binder composition for mold shaping is 25.0 mass% or less
Condition (3): the content of the component B in the adhesive composition for mold shaping is 39.0 mass% or more and 95.0 mass% or less relative to the total of the contents of the component B and the component C
Condition (4): the nitrogen content in the component C is 2.7 to 22.0 mass% inclusive
Condition (5): when the content of the component B in the binder composition for mold shaping is y and the nitrogen content of the component C is x, the following formula (1) is satisfied
2.97x+15.2≤y (1)
The present invention also provides a molding composition comprising the above binder composition for molding and a curing agent composition comprising a curing agent for curing the binder composition for molding.
The present invention also provides a molding composition containing refractory particles, the binder composition for molding, and a curing agent composition containing a curing agent for curing the binder composition for molding.
The present invention also provides a method for producing a mold, comprising: a mixing step of mixing refractory particles, the binder composition for mold molding, and a curing agent composition containing a curing agent for curing the binder composition for mold molding to obtain a composition for mold molding; and a curing step of filling the molding composition into a mold frame and curing the molding composition.
Detailed Description
The conventionally proposed adhesive composition having a small content of the monomeric furanmethanol has insufficient mold strength, particularly in a low-temperature (e.g., 5 ℃ or lower) environment, and has room for improvement.
The invention provides a binder composition for mold molding, a composition for mold molding, and a method for producing a mold, wherein the strength of a mold in a low-temperature environment can be greatly improved and the content of monomeric furanmethanol is small.
The invention relates to a binder composition for mold shaping, which contains furanmethanol (component A), dimethylolfuran (component B), resin (component C) and water (component D)
The following conditions (1) to (5) are satisfied.
Condition (1): the content of the component A in the binder composition for mold shaping is 30.0 mass% or less
Condition (2): the content of the component D in the binder composition for mold shaping is 25.0 mass% or less
Condition (3): the content of the component B in the adhesive composition for mold shaping is 39.0 mass% or more and 95.0 mass% or less relative to the total of the contents of the component B and the component C
Condition (4): the nitrogen content in the component C is 2.7 to 22.0 mass% inclusive
Condition (5): when the content of the component B in the binder composition for mold shaping is y and the nitrogen content of the component C is x, the following formula (1) is satisfied
2.97x+15.2≤y (1)
The present invention also provides a molding composition comprising the above binder composition for molding and a curing agent composition comprising a curing agent for curing the binder composition for molding.
The present invention also provides a molding composition containing refractory particles, the binder composition for molding, and a curing agent composition containing a curing agent for curing the binder composition for molding.
The present invention also provides a method for producing a mold, comprising: a mixing step of mixing refractory particles, the binder composition for mold molding, and a curing agent composition containing a curing agent for curing the binder composition for mold molding to obtain a composition for mold molding; and a curing step of filling the molding composition into a mold frame and curing the molding composition.
According to the present invention, there can be provided a binder composition for mold molding, a composition for mold molding, and a method for producing a mold, which can greatly improve the mold strength in a low-temperature environment and have a small content of monomeric furanmethanol.
An embodiment of the present invention will be described below.
Adhesive composition for mold shaping
The binder composition for mold shaping of the present embodiment (hereinafter, also simply referred to as binder composition) contains furanmethanol (component a), dimethylolfuran (component B), resin (component C), and water (component D), and satisfies the following conditions (1) to (5).
Condition (1): the content of the component A in the binder composition for mold shaping is 30.0 mass% or less
Condition (2): the content of the component D in the binder composition for mold shaping is 25.0 mass% or less
Condition (3): the content of the component B in the adhesive composition for mold shaping is 39.0 mass% or more and 95.0 mass% or less relative to the total of the contents of the component B and the component C
Condition (4): the nitrogen content in the component C is 2.7 to 22.0 mass% inclusive
Condition (5): when the content of the component B in the binder composition for mold shaping is y and the nitrogen content of the component C is x, the following formula (1) is satisfied
2.97x+15.2≤y (1)
According to the above adhesive composition, it is possible to provide an adhesive composition which can greatly improve the mold strength in a low-temperature environment and has a small content of monomeric furanmethanol. The reason why the above adhesive composition exerts such an effect is still uncertain, but it is considered as follows.
The dimethylolfuran (component B) has excellent reactivity with the furanmethanol (component a) as compared with the resin (component C), and reduces the viscosity of the adhesive composition. When the content of dimethylolfuran (component B) is increased, the reactivity is improved, the viscosity of the binder composition is also reduced, and the kneading with refractory particles is also improved, so that the mold strength is improved. On the other hand, since the dimethylolfuran (component B) has a high melting point, the storage stability becomes poor if the content increases (condition (3)). In addition, if the nitrogen content in the resin increases, the crosslinking reaction proceeds, and the mold strength increases. On the other hand, if the nitrogen content in the resin increases, the viscosity of the binder composition increases, the kneading property with the refractory particles decreases, and the strength decreases (condition (4)). Therefore, it is considered that as the nitrogen content in the resin increases, the viscosity is decreased by increasing the content of dimethylolfuran (component B) relative to the total of the contents of dimethylolfuran (component B) and the resin (component C), and thus the mold strength can be improved (condition (5)).
[ Furanyl alcohol (component A) ]
The content of the component a in the adhesive composition is 30.0 mass% or less, preferably 25.0 mass% or less, more preferably 20.0 mass% or less, and even more preferably 15.0 mass% or less, from the viewpoint of improving the working environment. The content of the component a in the adhesive composition is preferably more than 0 mass%, more preferably 5.0 mass% or more, still more preferably 10.0 mass% or more, still more preferably 15.0 mass% or more, and still more preferably 20.0 mass% or more, from the viewpoint of improving the mold strength. The content of component a can be measured by the method described in the examples.
[ Dimethylolfuran (component B) ]
The component B is preferably 2, 5-dimethylolfuran and/or 3, 4-dimethylolfuran, more preferably 2, 5-dimethylolfuran, from the viewpoint of reducing the content of the monomeric furanmethanol and greatly improving the mold strength in a low-temperature environment.
The content of the component B in the binder composition is preferably 18.0 mass% or more, more preferably 20.0 mass% or more, still more preferably 21.0 mass% or more, still more preferably 22.0 mass% or more, still more preferably 39.0 mass% or more, still more preferably 51.0 mass% or more, and still more preferably 63.0 mass% or more, from the viewpoint of reducing the content of the monomeric furanmethanol and greatly improving the mold strength in a low-temperature environment. The content of the component B in the adhesive composition is preferably 70.0 mass% or less, more preferably 68.0 mass% or less, further preferably 65.0 mass% or less, and still further preferably 63.0 mass% or less, from the viewpoint of improving storage stability. The content of component B can be measured by the method described in examples.
[ resin (component C) ]
The component C is not particularly limited as long as it is a resin used as a binder for mold shaping. As the resin used as the binder for mold molding, an acid-curable resin may be exemplified, and as the acid-curable resin, at least one selected from the group consisting of furan resins, condensates of melamine and aldehydes, condensates of urea and aldehydes, and condensates of ethylene urea and aldehydes may be exemplified. The component C preferably contains a furan resin from the viewpoint of reducing the content of the monomeric furanmethanol and greatly improving the mold strength in a low-temperature environment. The component C does not include furanmethanol.
The furan resin is obtained by polymerizing a monomer composition containing furanmethanol, and can be used without any particular limitation as long as it can be used as a binder for molding. From the viewpoint of reducing the content of monomeric furanmethanol and greatly improving the mold strength in a low-temperature environment, the furanic resin preferably contains one or more selected from the following condensates and one or more selected from two or more cocondensates selected from them: a condensate of furanmethanol and urea; a condensate of furanmethanol and melamine; a condensate of furanmethanol and ethylene urea; condensates of furanmethanol, urea and aldehydes (urea-modified furan resins); condensates of furanmethanols, melamines and aldehydes; condensates of furanmethanol, ethyleneurea and aldehydes; a furanmethanol condensate; a condensate of furanmethanol and aldehydes; and condensates of furanmethanol, phenols and aldehydes, more preferably, the furanresin contains at least one selected from urea-modified furanresins, furanmethanol condensates and condensates of furanmethanol and aldehydes, and at least one selected from co-condensates of two or more selected from them.
The aldehydes include: formaldehyde, acetaldehyde, glyoxal, furfural, terephthalaldehyde, hydroxymethylfurfural, and the like, and one or more of these may be used appropriately. Formaldehyde is preferably used from the viewpoint of improving the mold strength, and furfural, terephthalaldehyde, and hydroxymethylfurfural are preferably used from the viewpoint of reducing the formaldehyde generation amount during molding.
Examples of the phenols include: phenol, cresol, resorcinol, bisphenol a, bisphenol C, bisphenol E, bisphenol F, and the like, and one or more of these may be used.
The furan resin can be produced by a known method. For example, in the case where the furan resin is a urea-modified furan resin, the urea-modified furan resin can be obtained by reacting 0.6 to 30.0 parts by mass of urea and 0.4 to 50.0 parts by mass of paraformaldehyde with 100.0 parts by mass of furanmethanol.
The total content of one or more selected from the urea-modified furan resin, the furanmethanol condensate and the condensate of furanmethanol and aldehydes, and one or more selected from the two or more cocondensates selected from them, in the furan resin is preferably 90 mass% or more, more preferably 95 mass% or more, still more preferably 98 mass% or more, still more preferably substantially 100 mass%, from the viewpoint of reducing the content of monomeric furanmethanol and greatly improving the mold strength in a low-temperature environment. In the present specification, "substantially" means an amount that can contain impurities.
The content of the furan resin in the component C is preferably 80 mass% or more, more preferably 90 mass% or more, further preferably 95 mass% or more, further preferably 98 mass% or more, further preferably substantially 100 mass%, further preferably 100 mass% from the viewpoint of reducing the content of the monomeric furanmethanol and greatly improving the mold strength in a low-temperature environment.
The nitrogen content (in this specification, nitrogen content means the content of nitrogen atoms) in the component C is 2.7 mass% or more, preferably 2.8 mass% or more, more preferably 3.7 mass% or more, and even more preferably 4.6 mass% or more, from the viewpoint of greatly improving the mold strength in a low-temperature environment by increasing the crosslinking density of the resin. The nitrogen content in the component C is 22.0 mass% or less, preferably 21.0 mass% or less, more preferably 17.0 mass% or less, and even more preferably 13.9 mass% or less, from the viewpoint of maintaining good kneading with the refractory aggregate and suppressing a decrease in mold strength. The nitrogen content in the component C can be measured by the method described in the examples.
The content of the component C in the adhesive composition is preferably 5.0 mass% or more, more preferably 6.0 mass% or more, and even more preferably 7.0 mass% or more, from the viewpoint of greatly improving the mold strength in a low-temperature environment by increasing the crosslinking density of the resin. The content of the component C in the binder composition is preferably 45.0 mass% or less, more preferably 43.0 mass% or less, and even more preferably 42.0 mass% or less, from the viewpoint of maintaining good kneading with the refractory aggregate and suppressing a decrease in mold strength.
The nitrogen content in the binder composition is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, from the viewpoint of greatly improving the mold strength in a low-temperature environment by increasing the crosslinking density of the resin. The nitrogen content in the binder composition is preferably 3.5 mass% or less, more preferably 3.2 mass% or less, and even more preferably 3.0 mass% or less, from the viewpoint of maintaining good kneading with refractory aggregate and suppressing a decrease in mold strength. The nitrogen content in the binder composition can be measured by the method described in examples.
The content of the component B in the adhesive composition is 39.0 mass% or more, preferably 51.0 mass% or more, and more preferably 63.0 mass% or more, based on the total of the content of the component B and the content of the component C, in view of greatly improving the mold strength in a low-temperature environment by increasing the crosslinking density of the resin. From the viewpoint of improving the storage stability, the content of the component B in the adhesive composition is 95.0 mass% or less, preferably 92.0 mass% or less, more preferably 90.0 mass% or less, and even more preferably 78.0 mass% or less, based on the total of the content of the component B and the content of the component C.
When the content of the component B in the binder composition is y and the nitrogen content of the component C is x, the binder composition satisfies the above formula (1) from the viewpoint of reducing the content of the monomeric furanmethanol and greatly improving the mold strength in a low-temperature environment.
In the adhesive composition, from the viewpoint of reducing the content of the monomeric furanmethanol and greatly improving the mold strength in a low-temperature environment, it is preferable that the content of the component B in the adhesive composition is 39.0 to 95.0 mass% with respect to the total of the contents of the component B and the component C, and the nitrogen content in the component C is 2.7 to 22.0 mass%, and the formula (1) is satisfied.
In the adhesive composition, from the viewpoint of reducing the content of the monomeric furanmethanol and greatly improving the mold strength in a low-temperature environment, it is preferable that the content of the component B in the adhesive composition is 51.0 to 95.0 mass% with respect to the total of the contents of the component B and the component C, and the nitrogen content in the component C is 2.7 to 22.0 mass%, and the formula (1) is satisfied.
In the adhesive composition, from the viewpoint of reducing the content of the monomeric furanmethanol and greatly improving the mold strength in a low-temperature environment, it is more preferable that the content of the component B in the adhesive composition is 63.0 to 95.0 mass% with respect to the total of the contents of the component B and the component C, and the nitrogen content in the component C is 2.7 to 22.0 mass%, and the formula (1) is satisfied.
In the adhesive composition, from the viewpoint of reducing the content of the monomeric furanmethanol and greatly improving the mold strength in a low-temperature environment, it is further preferable that the content of the component B in the adhesive composition is 63.0 to 95.0 mass% with respect to the total of the contents of the component B and the component C, and the nitrogen content in the component C is 3.7 to 17.0 mass%, and the formula (1) is satisfied.
In the adhesive composition, from the viewpoint of reducing the content of the monomeric furanmethanol and greatly improving the mold strength in a low-temperature environment, it is still more preferable that the content of the component B in the adhesive composition is 63.0 to 95.0 mass% with respect to the total of the contents of the component B and the component C, and the nitrogen content in the component C is 4.6 to 13.9 mass%, and satisfies the following formula (2).
1.32x+57.4≤y (2)
In the adhesive composition, from the viewpoint of improving the storage stability, it is further preferable that the content of the component B in the adhesive composition is 63.0 to 78.0 mass% with respect to the total of the contents of the component B and the component C, and the nitrogen content in the component C is 4.6 to 13.9 mass%, and satisfies the formula (2).
[ Water (component D) ]
The content of the component D in the adhesive composition is 25.0 mass% or less, preferably 20.0 mass% or less, from the viewpoint of improving the mold strength. The content of the component D in the adhesive composition is preferably 5.0 mass% or more, more preferably 8.0 mass% or more, and even more preferably 10.0 mass% or more, from the viewpoint of adjusting the viscosity of the adhesive composition. The content of component D can be measured by the method described in the examples.
[ curing accelerator ]
The binder composition may contain a curing accelerator from the viewpoint of improving the mold strength. The curing accelerator is preferably one or more selected from the group consisting of phenol derivatives, aromatic dialdehydes, and tannins from the viewpoint of improving the mold strength.
Examples of the phenol derivative include: resorcinol, cresol, hydroquinone, phloroglucinol, methylenebisphenol, and the like. The content of the phenol derivative in the binder composition is preferably 1 to 25% by mass, more preferably 2 to 15% by mass, and even more preferably 3 to 10% by mass, from the viewpoint of improving the mold strength.
Examples of the aromatic dialdehyde include: terephthalaldehyde, o-phthalaldehyde, m-phthalaldehyde, and the like, derivatives of these, and the like. These derivatives refer to compounds having a substituent such as an alkyl group on the aromatic ring of an aromatic compound having two formyl groups as a basic skeleton, and the like. The content of the aromatic dialdehyde in the adhesive composition is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass, from the viewpoints of sufficiently dissolving the aromatic dialdehyde in the furan resin and suppressing the odor of the aromatic dialdehyde itself.
Examples of the tannins include condensed tannins and hydrolyzed tannins. Examples of the condensed tannins and the hydrolyzed tannins include tannins having a pyrogallol skeleton and a resorcinol skeleton. Further, bark extracts containing these tannins, extracts extracted from natural substances such as leaves, fruits, seeds derived from plants, and galls parasitic to plants may be added. The content of tannins in the binder composition is preferably 0.2 to 10% by mass, more preferably 1.0 to 7% by mass, and even more preferably 1.9 to 5% by mass, from the viewpoint of improving the curing speed and the viewpoint of improving the mold strength.
The viscosity of the binder composition at 25 ℃ is preferably 70mpa·s or less, more preferably 50mpa·s or less, from the viewpoints of workability in producing the composition for a mold and in producing a mold. The viscosity of the adhesive composition at 25℃can be measured by the method described in examples.
The adhesive composition may further contain an additive such as a silane coupling agent. For example, if the binder composition contains a silane coupling agent, the final strength of the obtained mold can be further improved, and thus it is preferable. As the silane coupling agent, use can be made of: aminosilanes such as N- β - (aminoethyl) - γ -aminopropyl methyldimethoxysilane, N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane, N- β - (aminoethyl) - γ -aminopropyl triethoxysilane, and 3-aminopropyl trimethoxysilane; epoxy silanes such as 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, and 3-glycidoxypropyl triethoxysilane; ureido silanes, mercapto silanes, thio silanes, methacryloxy silanes, acryloxy silanes, and the like. Aminosilanes, epoxysilanes, ureidosilanes are preferred. More preferred are aminosilanes and epoxysilanes. Among the aminosilanes, N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxysilane is preferred. Among epoxysilanes, 3-glycidoxypropyl methyldimethoxy silane is preferred.
The content of the silane coupling agent in the adhesive composition is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, from the viewpoint of improving the mold strength. From the same viewpoint, the content of the silane coupling agent in the adhesive composition is preferably 5 mass% or less, more preferably 3 mass% or less, further preferably 1 mass% or less, further preferably 0.5 mass% or less.
The adhesive composition for mold molding of the present embodiment is suitably used for molding of self-curing molds. Here, the self-hardening mold is a mold as follows: when the binder composition and the curing agent are mixed in sand, the polymerization reaction advances with the lapse of time, and the mold is cured. The temperature of the sand used in this case is in the range of-20 to 50 ℃, preferably 0 to 40 ℃. For sand at such a temperature, a curing agent is added to the sand in an amount selected to be suitable therefor, whereby the mold can be properly cured.
Composition for mold shaping
The composition for mold molding of the present embodiment contains the above-described binder composition, and a curing agent composition containing a curing agent for curing the binder composition for mold molding. The molding composition of the present embodiment has the same effects as the binder composition described above.
[ curing agent composition ]
The curing agent composition may be used without any particular limitation as long as it contains a curing agent that cures the adhesive composition. As the curing agent, an acid-based curing agent may be exemplified, and one or more of the following curing agents, which have been conventionally known, may be used: sulfonic acid-based compounds such as xylene sulfonic acid (particularly metaxylene sulfonic acid), toluene sulfonic acid (particularly p-toluene sulfonic acid), and methane sulfonic acid; phosphoric acid compounds such as phosphoric acid and acid phosphate esters; sulfuric acid. From the viewpoint of operability, these compounds are preferably aqueous solutions. The curing agent composition may further contain at least one solvent selected from alcohols, ether alcohols and esters, and carboxylic acids.
The content of the solvent in the curing agent composition may be appropriately adjusted depending on the temperature of the working environment or the temperature of the refractory particles to obtain a desired reaction rate and mold strength, and is generally preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more, from the viewpoint of dissolving the curing agent composition. The content of the solvent in the curing agent composition is preferably 90 mass% or less, more preferably 80 mass% or less, and still more preferably 70 mass% or less, from the viewpoint of improving the mold strength.
The content of the curing agent in the curing agent composition is preferably 10 mass% or more, more preferably 20 mass% or more, and still more preferably 30 mass% or more, from the viewpoint of improving the mold strength. The content of the curing agent in the curing agent composition is preferably 95 mass% or less, more preferably 90 mass% or less, and still more preferably 80 mass% or less, from the viewpoint of dissolving the curing agent composition.
The mass ratio of the binder composition to the curing agent is preferably 10 to 60 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 10 to 30 parts by mass, based on 100 parts by mass of the binder composition, from the viewpoint of improving the curing speed and improving the mold strength.
[ composition for casting mold ]
The molding composition of the present embodiment contains refractory particles, the binder composition, and the curing agent composition. The molding composition of the present embodiment has the same effects as the binder composition described above.
[ refractory particles ]
As the refractory particles, one or more of conventionally known refractory particles such as silica sand, chrome sand, zircon sand, olivine sand, alumina sand, mullite sand, and synthetic mullite sand may be used, and a substance obtained by recovering the used refractory particles, a substance obtained by performing a regeneration treatment, and the like may be used. Among them, silica sand is preferably contained.
In the composition for a mold, the mass ratio of the refractory particles, the binder composition, and the curing agent may be appropriately set, and from the viewpoint of improving the curing speed and the mold strength, the binder composition is preferably 0.5 to 1.5 parts by mass and the curing agent is preferably in the range of 0.07 to 1 part by mass relative to 100 parts by mass of the refractory particles.
Method for producing mold
The method for manufacturing a mold according to the present embodiment includes: a mixing step of mixing the refractory particles, the binder composition, and the curing agent composition to obtain a composition for a mold; and a curing step of filling the molding composition into a mold frame and curing the molding composition. The method for producing the mold has the same effect as the binder composition.
The order of adding and mixing the binder composition, the curing agent composition, and the refractory particles in the mixing step is not particularly limited, and the binder composition and the curing agent composition may be mixed to produce a composition for molding a mold, and then the composition for molding a mold may be mixed with the refractory particles, or the binder composition, the curing agent composition, and the refractory particles may be added and mixed separately, but from the viewpoints of storage stability and productivity of a mold, it is preferable to mix the binder composition, the curing agent composition, and the refractory particles to obtain a composition for molding a mold. In addition, from the viewpoint of improving the mold strength, it is preferable to add and mix the curing agent composition to the refractory particles, and then add and mix the binder composition. In the case of using two or more types of the curing agent compositions, each curing agent composition may be added after mixing, or each curing agent composition may be added separately.
In the above-described mixing step, as a method for mixing the raw materials, a known general method can be used, and examples thereof include a method for adding the raw materials by a batch mixer and kneading them, and a method for supplying the raw materials to a continuous mixer and kneading them.
In the method for manufacturing a mold according to the present embodiment, a mold can be manufactured directly by a conventional mold manufacturing process, in addition to the mixing step.
For the above embodiments, the present invention also discloses the following compositions, methods of manufacture or uses.
1 > an adhesive composition for molding comprising furanmethanol (component A), dimethylolfuran (component B), a resin (component C) and water (component D)
The following conditions (1) to (5) are satisfied.
Condition (1): the content of the component A in the binder composition for mold shaping is 30.0 mass% or less
Condition (2): the content of the component D in the binder composition for mold shaping is 25.0 mass% or less
Condition (3): the content of the component B in the adhesive composition for mold shaping is 39.0 mass% or more and 95.0 mass% or less relative to the total of the contents of the component B and the component C
Condition (4): the nitrogen content in the component C is 2.7 to 22.0 mass% inclusive
Condition (5): when the content of the component B in the binder composition for mold shaping is y and the nitrogen content of the component C is x, the following formula (1) is satisfied
2.97x+15.2≤y (1)
A binder composition for mold molding comprising furanmethanol (component A), dimethylolfuran (component B), a resin (component C) and water (component D) as described in < 2 > and < 1
The following conditions (1) to (5) are satisfied.
Condition (1): the content of the component A in the binder composition for mold shaping is 5.0 mass% or more and 30.0 mass% or less
Condition (2): the content of the component D in the binder composition for mold shaping is 5.0 mass% or more and 25.0 mass% or less
Condition (3): the content of the component B in the adhesive composition for mold shaping is 39.0 mass% or more and 95.0 mass% or less relative to the total of the contents of the component B and the component C
Condition (4): the nitrogen content in the component C is 2.7 to 22.0 mass% inclusive
Condition (5): when the content of the component B in the binder composition for mold shaping is y and the nitrogen content of the component C is x, the following formula (1) is satisfied
2.97x+15.2≤y (1)
A binder composition for molding, as described in < 3 > or < 1 > or < 2 >, wherein the content of the component A is 10.0 mass% or more and 30.0 mass% or less.
A binder composition for molding as defined in any one of < 4 > to < 1 > to < 3 >, wherein the content of the component A is 15.0% by mass or more and 30.0% by mass or less.
A binder composition for mold shaping as defined in any one of < 5 > to < 1 > to < 4 >, wherein the content of component D is 8.0 mass% or more and 25.0 mass% or less.
A binder composition for mold shaping as defined in any one of < 6 > to < 1 > to < 5 >, wherein the content of component D is 10.0% by mass or more and 20.0% by mass or less.
A binder composition for mold shaping according to any one of < 7 > to < 1 > to < 6 > satisfying the following conditions (3) to (5).
Condition (3): the content of the component B in the adhesive composition for mold shaping is 51.0-95.0 mass% relative to the total of the content of the component B and the content of the component C
Condition (4): the nitrogen content in the component C is 2.7 to 22.0 mass% inclusive
Condition (5): when the content of the component B in the binder composition for mold shaping is y and the nitrogen content of the component C is x, the following formula (1) is satisfied
2.97x+15.2≤y (1)
A binder composition for mold shaping according to any one of < 8 > to < 1 > to < 7 > satisfying the following conditions (3) to (5).
Condition (3): the content of the component B in the adhesive composition for mold shaping is 63.0 to 95.0 mass% inclusive of the total of the content of the component B and the content of the component C
Condition (4): the nitrogen content in the component C is 2.7 to 22.0 mass% inclusive
Condition (5): when the content of the component B in the binder composition for mold shaping is y and the nitrogen content of the component C is x, the following formula (1) is satisfied
2.97x+15.2≤y (1)
A binder composition for mold shaping as defined in any one of < 9 > to < 1 > to < 8 >, wherein the component C contains a furan resin and the content of the furan resin in the component C is 80% by mass or more.
A binder composition for mold shaping as defined in any one of < 10 > to < 1 > to < 9 >, wherein the component C contains a furan resin and the content of the furan resin in the component C is 90% by mass or more.
A binder composition for mold shaping as defined in any one of < 11 > to < 1 > to < 10 >, wherein the component C contains a furan resin and the content of the furan resin in the component C is 95% by mass or more.
The binder composition for mold shaping according to any one of < 12 > to < 1 > to < 11 >, wherein the component C contains a furan resin, and the content of the furan resin in the component C is 98 mass% or more.
A binder composition for mold shaping as defined in any one of < 13 > to < 1 > to < 12 >, wherein the component C contains a furan resin and the content of the furan resin in the component C is substantially 100% by mass.
The binder composition for mold molding of any one of < 14 > to < 9 > to < 13 >, wherein the furan resin contains at least one selected from urea-modified furan resins, furan-methanol condensates and condensates of furan-methanol and aldehydes, and at least one selected from co-condensates of two or more selected from them.
The binder composition for mold molding as defined in < 15 > and < 14 >, wherein the total content of at least one selected from the urea-modified furan resin, the furanmethanol condensate and the condensate of furanmethanol and aldehydes, and at least one selected from the two or more cocondensates selected from the above-mentioned furan resins is 90% by mass or more.
A binder composition for mold molding as defined in < 16 > or < 14 > or < 15 > wherein the total content of at least one selected from the urea-modified furan resin, the furanmethanol condensate and the condensate of furanmethanol and aldehydes in the furan resin and at least one selected from the co-condensates of two or more selected from them is 95% by mass or more.
The binder composition for mold shaping according to any one of < 17 > to < 14 > to < 16 >, wherein the total content of at least one selected from the urea-modified furan resin, the furanmethanol condensate and the condensate of furanmethanol and aldehydes in the furan resin, and at least one selected from the two or more cocondensates selected from them is 98% by mass or more.
The binder composition for mold molding of any one of < 18 > to < 14 > to < 17 >, wherein the total content of at least one selected from the urea-modified furan resin, the furanmethanol condensate and the condensate of furanmethanol and aldehydes in the furan resin and at least one selected from the co-condensates of two or more selected from them is substantially 100% by mass.
A composition for molding comprising the binder composition for molding as defined in any one of < 1 > to < 18 > and a curing agent composition comprising a curing agent for curing the binder composition for molding.
A molding composition comprising refractory particles, the binder composition for molding as defined in any one of < 1 > to < 18 > and a curing agent composition comprising a curing agent for curing the binder composition for molding.
The composition for casting mold of < 21 > and < 20 > wherein the binder composition is 0.5 to 1.5 parts by mass and the curing agent is 0.07 to 1 part by mass based on 100 parts by mass of the refractory particles.
< 22 > a method of manufacturing a mold, comprising: a mixing step of mixing refractory particles, the binder composition for mold molding described in any one of < 1 > to < 18 >, and a curing agent composition containing a curing agent for curing the binder composition for mold molding to obtain a composition for mold molding; and a curing step of filling the molding composition into a mold frame and curing the molding composition.
Examples
Hereinafter, embodiments and the like specifically showing the present invention will be described.
Method for measuring physical Properties
[ Water content ]
The measurement was performed by using an automatic moisture measuring apparatus (AQV-2200A, manufactured by Pingzhou industries Co., ltd.) based on the Kapph method shown in JIS K0068.
[ Furanol and Dimethylolfuran content ]
The measurement was performed by gas chromatography using a gas chromatograph (GC-2014S, manufactured by Shimadzu corporation) under the following conditions.
Standard curve: is prepared from furanmethanol and dihydroxymethyl furan.
Internal standard solution: 1, 6-hexanediol
Column: PEG-20M Chromosorb WAW DMCS 60/80 mesh (GL Science Co., ltd.)
Column temperature: 80-200 ℃ (8 ℃/min)
Injection temperature: 210 DEG C
Detector temperature: carrier gas at 250 ℃): 50mL/min (He)
[ Nitrogen content ]
The measurement was performed based on the Kjeldahl method shown in JIS K6451-2.
[ viscosity ]
The viscosity was measured at 100rpm using an E-type viscometer (RE-80R, manufactured by Tokyo Co., ltd.) at 25℃using a standard spindle (cone angle: 1℃34', cone radius: 24 mm).
< method for producing resin >
[ Urea-modified Furan resin ]
To a three-necked flask, 609g of furanmethanol, 0.7g of a 25% by mass aqueous sodium hydroxide solution, 188g of 92% by mass paraformaldehyde and 140g of urea were charged, and the mixture was reacted at 100℃for 45 minutes under normal pressure. Then, 1.4g of glutaric acid was charged, and the reaction was further carried out at 100℃for 45 minutes. Then, 52g of urea was added and reacted at 70℃for 30 minutes. After the reaction, the pH was adjusted to 10 with a 25 mass% aqueous sodium hydroxide solution. The obtained composition was distilled under reduced pressure at 110℃under an internal pressure of 5mmHg using a rotary evaporator to remove water and a part of furanmethanol. The composition of the obtained reactant was 71.9 mass% of urea-modified furan resin and 28.1 mass% of furanmethanol. In addition, the nitrogen content of the obtained reactant was 14.5 mass%, and the nitrogen content of the urea-modified furan resin was 20.2 mass%.
[ Furanol condensate ]
Into a three-necked flask, 492g of furanmethanol and 8g of glutaric acid were charged, and the mixture was reacted at 100℃for 5 hours under normal pressure. Then, the pH was adjusted to 10 with a 25 mass% aqueous sodium hydroxide solution. The obtained composition was distilled under reduced pressure at 110℃under an internal pressure of 5mmHg using a rotary evaporator to remove water and a part of furanmethanol. The composition of the obtained reactant was 79.0 mass% of a furanmethanol condensate and 21.0 mass% of furanmethanol.
[2, 5-Dimethylolfuran (BHMF) ]
To a three-necked flask, 615g of furanmethanol, 205g of 92 mass% paraformaldehyde and 41g of glutaric acid were charged, and the mixture was reacted at 100℃for 3 hours under normal pressure. Thereafter, the pH was adjusted to 10 with a 48% aqueous sodium hydroxide solution. The obtained composition was distilled under reduced pressure at 110℃under an internal pressure of 5mmHg using a rotary evaporator, whereby furanmethanol and water were removed. After the obtained residue was completely dissolved in chloroform heated to 40 ℃, cooling was performed at 5 ℃, whereby crystals of BHMF were obtained. Then, the same operation was repeated twice. The purity of the obtained crystals was 100 mass%.
Preparation of adhesive composition
Production example 1
Resin a was obtained by the procedure described in paragraph 0055 of JP-A2013-151019 < production of condensate 1 >. The unreacted furanmethanol and moisture of the resin a were measured, and based on the measurement results, the adhesive composition of production example 1 was prepared using the resin a, furanmethanol, water and a silane coupling agent so that the furanmethanol content was 50 mass%, the water content was 10 mass%, and the silane coupling agent content was 0.15 mass%.
PREPARATION EXAMPLE 2
The adhesive composition of production example 2 was obtained by using the resin a, the furanmethanol, the water and the silane coupling agent, and preparing the adhesive composition such that the furanmethanol content was 50 mass%, the water content was 20 mass%, and the silane coupling agent content was 0.15 mass%.
PREPARATION EXAMPLE 3
To a three-necked flask, 587g of furanmethanol, 1.0g of a 25% by mass aqueous sodium hydroxide solution, 159g of 92% by mass paraformaldehyde and 29g of glutaric acid were charged, and the mixture was reacted at 125℃under normal pressure for 3 hours. Then, the mixture was cooled to 90℃and 35g of urea was added thereto, followed by heating to 105℃and reacting at the same temperature for 2 hours. After the reaction, the mixture was cooled to 75℃and 7g of urea was added thereto, followed by reaction at the same temperature for 20 minutes to obtain a resin b. The furanmethanol in the resin b was 20.0 mass%, the BHMF was 29.5 mass%, the water was 6.8 mass%, and the nitrogen content was 2.4 mass%. To the resin b, 1.5g of a silane coupling agent, 36g of furanmethanol, and 145g of water were added and mixed to obtain an adhesive composition of production example 3. The content of furanmethanol in the adhesive composition of production example 3 was 20.0 mass%, the content of BHMF was 24.1 mass%, the content of furan resin was 32.9 mass%, the content of water was 20.0 mass%, and the nitrogen content in furan resin was 6.0 mass%.
PREPARATION EXAMPLE 4
Into a three-necked flask, 588g of furanmethanol, 1.0g of a 25% by mass aqueous sodium hydroxide solution, 159g of 92% by mass paraformaldehyde and 29g of benzoic acid were charged, and the mixture was reacted at 125℃for 2 hours under normal pressure. Thereafter, the mixture was cooled to 90℃and 10g of 92 mass% paraformaldehyde and 50g of urea were charged, and the temperature was raised to 105℃to react at the same temperature for 2 hours. After the reaction, the mixture was cooled to 75℃and 11g of urea was added thereto, followed by reaction at the same temperature for 20 minutes to obtain a resin c. The furanmethanol in the above resin c was 22.0 mass%, BHMF was 26.4 mass%, water was 7.4 mass%, and the nitrogen content was 3.3 mass%. To the resin c, 1.5g of a silane coupling agent, 13g of furanmethanol, and 138g of water were added and mixed to obtain an adhesive composition of production example 4. The content of furanmethanol in the adhesive composition of production example 4 was 20.0 mass%, the content of BHMF was 22.4 mass%, the content of furan resin was 34.6 mass%, the content of water was 20.0 mass%, and the nitrogen content in furan resin was 8.1 mass%.
PREPARATION EXAMPLE 5
359g of the resin c, 121g of furanmethanol, 173g of water, 345g of BHMF and 1.5g of silane coupling agent were charged into a three-necked flask, and stirred at 40℃for 30 minutes to obtain an adhesive composition of production example 5. The content of furanmethanol in the adhesive composition of production example 5 was 20.0 mass%, the content of BHMF was 44.0 mass%, the content of furan resin was 14.7 mass%, the content of water was 20.0 mass%, and the nitrogen content in furan resin was 8.1 mass%.
Production example 6
Into a three-necked flask, 569g of furanmethanol, 0.9g of a 25% by mass aqueous sodium hydroxide solution, 154g of 92% by mass paraformaldehyde and 28g of glutaric acid were charged, and the mixture was reacted at 125℃under normal pressure for 3 hours. Then, the mixture was cooled to 90℃and 58g of ethylene urea was added thereto, followed by heating to 105℃and reacting at the same temperature for 3 hours. After the reaction, the mixture was cooled to 75℃and 8g of urea was added thereto, followed by reaction at the same temperature for 20 minutes to obtain a resin d. The furanmethanol in the resin d was 20.6 mass%, the BHMF was 28.0 mass%, the water was 6.5 mass%, and the nitrogen content was 2.8 mass%. To the resin d, 1.5g of a silane coupling agent, 31g of furanmethanol, and 147g of water were added and mixed to obtain an adhesive composition of production example 6. The content of furanmethanol in the adhesive composition of production example 6 was 20.0 mass%, the content of BHMF was 23.0 mass%, the content of furan resin was 34.1 mass%, the content of water was 20.0 mass%, and the nitrogen content in furan resin was 6.7 mass%.
PREPARATION EXAMPLE 7
To a three-necked flask, 587g of furanmethanol, 1.0g of a 25% by mass aqueous sodium hydroxide solution, 195g of 92% by mass paraformaldehyde and 29g of glutaric acid were charged, and the mixture was reacted at 125℃for 2 hours under normal pressure. Then, the mixture was cooled to 90℃and 28g of melamine was added thereto, followed by heating to 105℃and reacting at the same temperature for 2 hours. After the reaction, the mixture was cooled to 75℃and 8g of urea was added thereto, followed by reaction at the same temperature for 20 minutes to obtain a resin e. The furanmethanol in the resin e was 19.3 mass%, the BHMF was 27.5 mass%, the water was 7.3 mass%, and the nitrogen content was 2.8 mass%. To the resin e, 1.5g of a silane coupling agent, 43g of furanmethanol, and 141g of water were added and mixed to obtain an adhesive composition of production example 7. The content of furanmethanol in the adhesive composition of production example 7 was 20.0 mass%, the content of BHMF was 22.4 mass%, the content of furan resin was 34.6 mass%, the content of water was 20.0 mass%, and the nitrogen content in furan resin was 6.6 mass%.
Production example 8
According to the method for producing KH-Y described in Japanese patent application laid-open No. 2014-501175, the adhesive composition of production example 6 was produced in the following steps. To a three-necked flask, 197g of furanmethanol, 196g of 92% paraformaldehyde and 4.7g of benzoic acid were charged, and the mixture was reacted at 110℃for 1 hour under normal pressure. To the reaction mixture were further added 394g of furanmethanol and 9.4g of benzoic acid, and the mixture was heated to 135℃and refluxed for 5 hours. The temperature after the completion of the reaction was 125 ℃. Then, 60g of urea was charged and cooled to 60℃over about 40 minutes, whereby resin f was obtained. The furanmethanol in the above resin f was 23.2 mass%, BHMF was 14.8 mass%, water was 7.3 mass%, and the nitrogen content was 3.3 mass%. 1.5g of a silane coupling agent and 137g of water were added to the resin f and mixed to obtain an adhesive composition of production example 8. The content of furanmethanol in the adhesive composition of production example 8 was 20.0 mass%, the content of BHMF was 12.7 mass%, the content of furan resin was 45.7 mass%, the content of water was 20.0 mass%, and the nitrogen content in furan resin was 6.1 mass%.
Examples 1 to 21 and comparative examples 1 to 9 >
[ production of adhesive composition for Molding
The urea-modified furan resin, the furanmethanol-formaldehyde resin, the BHMF, the furanmethanol, the water, and the silane coupling agent obtained in the production example were mixed at 40 ℃ for 30 minutes to obtain binder compositions for mold molding of examples 1 to 16 and comparative examples 1 to 8. The binder compositions for mold molding of examples 17 to 21, comparative example 9 and reference examples 1 and 2 were prepared by using the compositions of production examples 1 to 8 described above.
[ production of composition for casting mold ]
The curing agent composition was added to 100 parts by mass of furan-regenerated silica sand at 5℃and 55% RH, and then 0.8 parts by mass of the binder composition for mold molding shown in Table 1 was added thereto, followed by mixing, to obtain a composition for mold. The curing agent composition used was a xylene sulfonic acid/sulfuric acid-based curing agent (Kao Lighter U.S. Pat. No. 3, kao Lighter C-21: manufactured by Kao-Quaker Co.). The amount of the curing agent composition to be added was 0.32 part by mass based on 100 parts by mass of the furan-regenerated silica sand, and the ratio of Kao light ler US-3 to Kao light ler C-21 was adjusted so that the compressive strength of the following sample was 0.20 to 0.35MPa/30 minutes. When the amount added is 0.32 parts by mass, the compressive strength is not satisfied, only Kao Lighter US-3 is used, and the amount added is increased so as to satisfy the compressive strength.
[ evaluation of compression Strength of mold ]
Immediately after kneading, the molding composition was filled into a cylindrical sample frame having a diameter of 50mm and a height of 50mm, and after 30 minutes, the molding was released, and the compressive strength (MPa) was measured by the method described in JIS Z2604-1976, and this strength was defined as "compressive strength after 30 minutes". The "compressive strength after 30 minutes" was used as a standard for curing speed, and the curing dose was confirmed to be appropriate. The sample frame was filled with the composition for a mold in the same manner, and after 2 hours, the mold was released, and after 24 hours after filling, the compressive strength (MPa) was measured by the method described in JIS Z2604-1976, and was "compressive strength after 24 hours". The higher the value, the higher the mold strength. The evaluation results are shown in tables 1 and 2.
TABLE 1
TABLE 2
Claims (7)
1. A binder composition for molding comprising a furanmethanol component A, a dimethylolfuran component B, a resin component C, and a water component D,
the adhesive composition for mold shaping satisfies the following conditions (1) to (5):
condition (1): the content of the component A in the binder composition for mold shaping is 30.0 mass% or less;
condition (2): the content of the component D in the binder composition for mold shaping is 25.0 mass% or less;
condition (3): the content of the component B in the binder composition for mold shaping is 39.0 mass% or more and 95.0 mass% or less relative to the total of the content of the component B and the content of the component C;
condition (4): the nitrogen content in the component C is 2.7 mass% or more and 22.0 mass% or less;
condition (5): when the content of the component B in the binder composition for mold shaping is set to y and the nitrogen content of the component C is set to x, the following formula (1) is satisfied:
2.97x+15.2≤y (1)。
2. the binder composition for mold shaping according to claim 1, wherein the component C contains a furan resin, and the content of the furan resin in the component C is 80 mass% or more.
3. The binder composition for mold molding according to claim 2, wherein the furan resin contains at least one selected from urea-modified furan resins, furan-methanol condensates and condensates of furan-methanol and aldehydes, and at least one selected from co-condensates of two or more selected from them.
4. The binder composition for mold shaping according to claim 3, wherein the total content of at least one selected from the group consisting of the urea-modified furan resin, the furanmethanol condensate and the condensate of furanmethanol and aldehydes, and at least one selected from the group consisting of two or more cocondensates selected from the above is at least 90 mass%.
5. A composition for mold molding comprising the binder composition for mold molding according to any one of claims 1 to 4, and a curing agent composition comprising a curing agent for curing the binder composition for mold molding.
6. A composition for casting mold comprising refractory particles, the binder composition for casting mold according to any one of claims 1 to 4, and a curing agent composition comprising a curing agent for curing the binder composition for casting mold.
7. A method for manufacturing a mold, comprising the steps of:
a mixing step of mixing refractory particles, the binder composition for mold shaping according to any one of claims 1 to 4, and a curing agent composition containing a curing agent for curing the binder composition for mold shaping to obtain a composition for mold shaping; and
And a curing step of filling the molding composition into a mold frame and curing the molding composition.
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/JP2020/042460 WO2022102089A1 (en) | 2020-11-13 | 2020-11-13 | Binder composition for forming mold |
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| CN116234647A true CN116234647A (en) | 2023-06-06 |
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| JP (1) | JP7102639B1 (en) |
| CN (1) | CN116234647A (en) |
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| JP3114516B2 (en) * | 1994-08-19 | 2000-12-04 | 花王株式会社 | Binder composition for mold production and method for producing mold |
| JP5486241B2 (en) * | 2009-08-26 | 2014-05-07 | 花王株式会社 | Binder composition for mold making |
| JP5563875B2 (en) * | 2010-04-16 | 2014-07-30 | 花王株式会社 | Kit for producing a mold composition |
| DE202011110617U1 (en) * | 2010-12-16 | 2015-04-29 | Hüttenes-Albertus Chemische Werke GmbH | Low-emission cold-curing binder for the foundry industry |
| JP6010426B2 (en) * | 2011-10-31 | 2016-10-19 | 花王株式会社 | Binder composition for mold making |
| DE102017112681A1 (en) * | 2017-06-08 | 2018-12-13 | Ask Chemicals Gmbh | Process for the preparation of three-dimensionally layered shaped bodies |
| JP7175822B2 (en) * | 2019-03-28 | 2022-11-21 | 群栄化学工業株式会社 | Sand composition, method for producing same, and method for producing mold |
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