JP6499852B2 - Mold making kit - Google Patents
Mold making kit Download PDFInfo
- Publication number
- JP6499852B2 JP6499852B2 JP2014250058A JP2014250058A JP6499852B2 JP 6499852 B2 JP6499852 B2 JP 6499852B2 JP 2014250058 A JP2014250058 A JP 2014250058A JP 2014250058 A JP2014250058 A JP 2014250058A JP 6499852 B2 JP6499852 B2 JP 6499852B2
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- Japan
- Prior art keywords
- mass
- mold
- composition
- preferable
- curing agent
- 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.)
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- 239000000203 mixture Substances 0.000 claims description 210
- 239000011230 binding agent Substances 0.000 claims description 98
- 239000003795 chemical substances by application Substances 0.000 claims description 91
- -1 furanaldehyde compound Chemical class 0.000 claims description 48
- 239000004202 carbamide Substances 0.000 claims description 37
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 33
- AKEUNCKRJATALU-UHFFFAOYSA-N 2,6-dihydroxybenzoic acid Chemical compound OC(=O)C1=C(O)C=CC=C1O AKEUNCKRJATALU-UHFFFAOYSA-N 0.000 claims description 30
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 18
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- 229960001755 resorcinol Drugs 0.000 claims description 10
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 8
- 229940079877 pyrogallol Drugs 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- 239000007849 furan resin Substances 0.000 claims description 7
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 150000002240 furans Chemical class 0.000 claims description 4
- QAVITTVTXPZTSE-UHFFFAOYSA-N (5-formylfuran-2-yl)methyl acetate Chemical compound CC(=O)OCC1=CC=C(C=O)O1 QAVITTVTXPZTSE-UHFFFAOYSA-N 0.000 claims description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 87
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 239000002253 acid Substances 0.000 description 25
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 22
- 239000004576 sand Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000006087 Silane Coupling Agent Substances 0.000 description 14
- 238000005266 casting Methods 0.000 description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 13
- 238000000465 moulding Methods 0.000 description 13
- 150000001299 aldehydes Chemical class 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 125000004434 sulfur atom Chemical group 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000003672 ureas Chemical class 0.000 description 6
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 4
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052815 sulfur oxide Inorganic materials 0.000 description 4
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 239000004593 Epoxy Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- 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 2
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 description 2
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-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
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 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
- 150000002148 esters Chemical class 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 235000011087 fumaric acid Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
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- 229910052863 mullite Inorganic materials 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
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- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
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- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 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
- 150000003739 xylenols Chemical class 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
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- DZEPFNDOOWFEKN-UHFFFAOYSA-N 2,5-bis(methoxymethyl)furan Chemical compound COCC1=CC=C(COC)O1 DZEPFNDOOWFEKN-UHFFFAOYSA-N 0.000 description 1
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- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
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- CLAHOZSYMRNIPY-UHFFFAOYSA-N 2-hydroxyethylurea Chemical compound NC(=O)NCCO CLAHOZSYMRNIPY-UHFFFAOYSA-N 0.000 description 1
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-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
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- JOFDQONITRMYMX-UHFFFAOYSA-N [5-(methoxymethyl)furan-2-yl]methanol Chemical compound COCC1=CC=C(CO)O1 JOFDQONITRMYMX-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 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
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 230000008901 benefit Effects 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
- 238000011088 calibration curve Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- WUESWDIHTKHGQA-UHFFFAOYSA-N cyclohexylurea Chemical compound NC(=O)NC1CCCCC1 WUESWDIHTKHGQA-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient 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
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 150000003016 phosphoric acids 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
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- MOVRCMBPGBESLI-UHFFFAOYSA-N prop-2-enoyloxysilicon Chemical compound [Si]OC(=O)C=C MOVRCMBPGBESLI-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000243 solution Substances 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 compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 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
- B22C1/16—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Mold Materials And Core Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、鋳型造型用キットに関する。 The present invention relates to a mold making kit.
一般に、酸硬化性鋳型は、珪砂等の耐火性粒子に、酸硬化性樹脂を含有する鋳型造型用粘結剤組成物と、スルホン酸、硫酸、リン酸等を含有する硬化剤組成物とを添加し、これらを混練した後、得られた混練砂を木型等の原型に充填し、酸硬化性樹脂を硬化させて製造される。酸硬化性樹脂には、フラン樹脂やフェノール樹脂等が用いられており、フラン樹脂には、フルフリルアルコール、フルフリルアルコール・尿素・ホルムアルデヒド樹脂、フルフリルアルコール・ホルムアルデヒド樹脂、フルフリルアルコール・フェノール・ホルムアルデヒド樹脂、その他公知の変性フラン樹脂等が用いられている。このような鋳型の製造方法は自由度の高い造型作業が可能であり、また鋳型の熱的性質に優れることから高品質の鋳物が製造できるため、機械部品や建設機械部品、あるいは自動車用部品等の鋳物を鋳造する際に広く使用されている。 In general, an acid-curable mold comprises a binder composition for mold making containing an acid-curable resin on a refractory particle such as silica sand, and a curing agent composition containing a sulfonic acid, sulfuric acid, phosphoric acid or the like. After these are added and kneaded, the obtained kneaded sand is filled into a mold such as a wooden mold and the acid curable resin is cured. Furan resin, phenol resin, etc. are used for acid curable resins. Furan resin includes furfuryl alcohol, furfuryl alcohol / urea / formaldehyde resin, furfuryl alcohol / formaldehyde resin, furfuryl alcohol / phenol, Formaldehyde resin and other known modified furan resins are used. Such a mold manufacturing method is capable of molding work with a high degree of freedom, and because it is excellent in the thermal properties of the mold, it can manufacture high-quality castings, so machine parts, construction machine parts, automobile parts, etc. It is widely used in casting of castings.
鋳型の造型、あるいは鋳型を用いて所望の鋳物を鋳造する上で重要な項目として、鋳造時の作業環境の改善が挙げられる。酸硬化性鋳型には硬化剤として有機スルホン酸、硫酸等の硫黄原子を含有する酸が使用されるため、特に鋳造時における二酸化硫黄等のＳＯｘやその他成分の熱分解ガスが作業環境を悪化させる恐れがある。そのため、ＳＯｘの発生を抑制することが望まれている。 An important item in casting a mold or casting a desired casting using the mold is to improve the working environment during casting. Acid curable molds use organic sulfonic acid, sulfuric acid and other acids as curing agents, and SOx such as sulfur dioxide and other pyrolytic gases during casting deteriorate the working environment. There is a fear. Therefore, it is desired to suppress the generation of SOx.
下記特許文献１では、硫黄原子を含有する酸の替りに２，６−ジヒドロキシ安息香酸を硬化剤として用いることによりＳＯ２ガスの発生を低減する技術が開示されている。 In the following Patent Document 1, a technique for reducing generation of SO 2 gas by using 2,6-dihydroxybenzoic acid as a curing agent instead of an acid containing a sulfur atom is disclosed.
また、鋳型の造型、あるいは鋳型を用いて所望の鋳物を鋳造する上で重要な別の項目として、鋳型の硬化速度、及び鋳型の強度が挙げられる。鋳型の硬化速度が遅いと鋳型の生産性が落ち、鋳型の強度が不足すると鋳型が割れたり、鋳造時の中子割れが発生したりして、作業者に危険が及んだり、得られる鋳物が不良品になる恐れがある。 Other important items for mold making or casting a desired casting using the mold include mold curing speed and mold strength. If the mold curing speed is slow, the productivity of the mold will decrease, and if the mold strength is insufficient, the mold will crack or the core will crack at the time of casting. May become defective.
下記特許文献２では、フルフラール誘導体とフルフリル化尿素樹脂を含有する鋳型造型用粘結剤組成物を用いることにより、鋳型の硬化速度及び鋳型の強度を向上させる技術が開示されている。 In the following Patent Document 2, a technique for improving the mold curing speed and the mold strength by using a binder composition for mold making containing a furfural derivative and a furfurylated urea resin is disclosed.
また、反応速度は温度に影響されるため、所望の硬化速度及び鋳型強度を得るために硬化剤の濃度を調整することが有る。例えば、作業環境の温度が低く、特に耐火性粒子が低温の場合は反応速度が低下するため、所望の硬化速度及び鋳型強度が得られるように、硬化剤組成物中の硬化剤の濃度を上げることが有る（例えば、特許文献３、４）。 In addition, since the reaction rate is affected by temperature, the concentration of the curing agent may be adjusted to obtain a desired curing rate and mold strength. For example, when the temperature of the working environment is low, especially when the refractory particles are low temperature, the reaction rate decreases, so the concentration of the curing agent in the curing agent composition is increased so that the desired curing rate and mold strength are obtained. (For example, Patent Documents 3 and 4).
しかし、硬化剤として硫黄原子を含有する酸を用いる場合、低温条件下で所望の硬化速度及び鋳型強度を得るために当該酸の使用量を増やすと二酸化硫黄等のＳＯｘの発生量が増え、作業環境は悪化する。 However, when an acid containing a sulfur atom is used as a curing agent, increasing the amount of the acid used to obtain a desired curing rate and mold strength under low temperature conditions will increase the amount of SOx generated, such as sulfur dioxide. The environment gets worse.
硫黄原子を含有する酸の替りに、例えば、２，６−ジヒドロキシ安息香酸を硬化剤として使用すると、ＳＯｘの発生量は抑制できるものの、作業環境の温度によっては所望の鋳型強度が得られないことがあることが明らかになった。 For example, when 2,6-dihydroxybenzoic acid is used as a curing agent instead of an acid containing a sulfur atom, the amount of SOx generated can be suppressed, but the desired mold strength cannot be obtained depending on the temperature of the working environment. It became clear that there is.
本発明は、硬化剤として硫黄原子を含有する酸を用いなくとも、作業環境の温度に係わらず、所望の鋳型強度を得ることが出来る鋳型造型用キットを提供する。 The present invention provides a mold making kit that can obtain a desired mold strength regardless of the temperature of the working environment without using an acid containing a sulfur atom as a curing agent.
本発明の鋳型造型用キットは、粘結剤組成物と硬化剤組成物からなる、鋳型用組成物を製造するための鋳型造型用キットであって、前記粘結剤組成物が、フランアルデヒド化合物を含有し、前記硬化剤組成物が、カルボキシル基をもたない芳香族ヒドロキシ化合物、及びカルボン酸を含有する。 The mold making kit of the present invention is a mold making kit for producing a mold composition comprising a binder composition and a curing agent composition, wherein the binder composition is a furanaldehyde compound. And the curing agent composition contains an aromatic hydroxy compound having no carboxyl group and a carboxylic acid.
本発明によれば、硬化剤として硫黄原子を含有する酸を用いなくとも、作業環境の温度に係わらず、所望の鋳型強度を得ることが出来る鋳型造型用キットを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, even if it does not use the acid containing a sulfur atom as a hardening | curing agent, the mold for mold making which can obtain desired mold intensity | strength irrespective of the temperature of a working environment can be provided.
＜鋳型造型用キット＞
本実施形態の鋳型造型用キットは、粘結剤組成物と硬化剤組成物からなる、鋳型用組成物を製造するための鋳型造型用キットであって、前記粘結剤組成物が、フランアルデヒド化合物を含有し、前記硬化剤組成物が、カルボキシル基をもたない芳香族ヒドロキシ化合物、及びカルボン酸を含有する。当該鋳型造型用キットは、作業環境の温度に係わらず、カルボン酸を硬化剤として使用した場合でも、所望の鋳型強度を得ることが出来る。このような効果を奏する理由は定かではないが、以下の様に考えられる。
<Mold making kit>
The mold making kit of this embodiment is a mold making kit for producing a mold composition, comprising a binder composition and a curing agent composition, wherein the binder composition is furanaldehyde. A compound is contained, and the curing agent composition contains an aromatic hydroxy compound having no carboxyl group and a carboxylic acid. The mold making kit can obtain a desired mold strength even when carboxylic acid is used as a curing agent, regardless of the temperature of the working environment. The reason for such an effect is not clear, but is considered as follows.
硫黄原子を含有する酸の替りに２，６−ジヒドロキシ安息香酸を硬化剤として用いた場合、当該２，６−ジヒドロキシ安息香酸が有するカルボキシル基が反応性触媒として作用し、鋳型の硬化速度を向上させることができるとともに、２，６−ジヒドロキシ安息香酸が粘結剤組成物中のフランアルデヒド化合物と反応し、高分子量化するため鋳型強度を向上させることが出来る。すなわち、フランアルデヒド化合物の硬化剤として２，６−ジヒドロキシ安息香酸を用いることにより、所望の鋳型強度を得ることが出来る。しかし、温度に応じた硬化速度を得るために２，６−ジヒドロキシ安息香酸の配合量を減らすと、フランアルデヒド化合物と反応する量も減ることになり高分子量化が抑制されるため、鋳型強度が低下する。本実施形態の鋳型造型用キットは、硬化剤組成物中にカルボン酸、及びカルボキシル基を有さない芳香族ヒドロキシ化合物を含有するため、触媒作用を有するカルボン酸の配合量を減らしても、カルボキシル基を有さない芳香族ヒドロキシ化合物がフランアルデヒド化合物と反応して高分子量化する。そのため、本実施形態の鋳型造型用キットによれば、硬化剤として硫黄原子を含有する酸を用いなくとも、作業環境の温度に係わらず、所望の鋳型強度を得ることが出来る。 When 2,6-dihydroxybenzoic acid is used as a curing agent instead of an acid containing a sulfur atom, the carboxyl group of the 2,6-dihydroxybenzoic acid acts as a reactive catalyst, improving the mold curing rate. In addition, 2,6-dihydroxybenzoic acid reacts with the furanaldehyde compound in the binder composition to increase the molecular weight, so that the template strength can be improved. That is, a desired mold strength can be obtained by using 2,6-dihydroxybenzoic acid as a curing agent for the furanaldehyde compound. However, if the blending amount of 2,6-dihydroxybenzoic acid is decreased in order to obtain a curing rate according to the temperature, the amount reacting with the furanaldehyde compound is also decreased and the high molecular weight is suppressed. descend. The mold making kit of the present embodiment contains a carboxylic acid and an aromatic hydroxy compound having no carboxyl group in the curing agent composition, so that even if the amount of the carboxylic acid having a catalytic action is reduced, carboxyl An aromatic hydroxy compound having no group reacts with the furanaldehyde compound to increase the molecular weight. Therefore, according to the mold making kit of this embodiment, a desired mold strength can be obtained regardless of the temperature of the working environment without using an acid containing a sulfur atom as a curing agent.
〔粘結剤組成物〕
前記粘結剤組成物は、フランアルデヒド化合物を含有する。
[Binder composition]
The binder composition contains a furanaldehyde compound.
［フランアルデヒド化合物］
前記フランアルデヒド化合物は、鋳型強度向上の観点から、フルフラール、５−ヒドロキシメチルフルフラール、及び５−アセトキシメチルフルフラールからなる群より選ばれる少なくとも１種以上が好ましく、フルフラール、及び５−ヒドロキシメチルフルフラールからなる群より選ばれる少なくとも１種以上がより好ましく、フルフラールが更に好ましい。
[Furanaldehyde compound]
The furanaldehyde compound is preferably at least one selected from the group consisting of furfural, 5-hydroxymethylfurfural, and 5-acetoxymethylfurfural, from the viewpoint of improving template strength, and comprises furfural and 5-hydroxymethylfurfural. At least one selected from the group is more preferred, and furfural is more preferred.
前記粘結剤組成物中の前記フランアルデヒド化合物の含有量は、鋳型強度向上の観点から、５質量％以上が好ましく、１０質量％以上がより好ましく、２０質量％以上が更に好ましく、４０質量％以上がより更に好ましい。前記粘結剤組成物中の前記フランアルデヒド化合物の含有量は、鋳型強度向上の観点から、９０質量％以下が好ましく、８５質量％以下がより好ましく、８０質量％以下が更に好ましく、７５質量％以下がより更に好ましい。また、前記粘結剤組成物中の前記フランアルデヒド化合物の含有量は、鋳型強度向上の観点から、５〜９０質量％が好ましく、１０〜８５質量％がより好ましく、２０〜８０質量％が更に好ましく、４０〜７５質量％がより更に好ましい。 The content of the furanaldehyde compound in the binder composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and 40% by mass from the viewpoint of improving the mold strength. The above is even more preferable. The content of the furanaldehyde compound in the binder composition is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, and 75% by mass from the viewpoint of improving the mold strength. The following is even more preferable. Further, the content of the furanaldehyde compound in the binder composition is preferably 5 to 90% by mass, more preferably 10 to 85% by mass, and further preferably 20 to 80% by mass from the viewpoint of improving the mold strength. Preferably, 40 to 75% by mass is even more preferable.
［その他の成分］
前記粘結剤組成物は、本実施形態の鋳型造型用キットの効果を損なわない範囲で他の成分を含有していても良い。当該他の成分としては、以下の成分が例示できる。なお、本実施形態の効果発現の観点から、前記粘結剤組成物はカルボキシル基を有さない芳香族ヒドロキシ化合物を含有しない。
[Other ingredients]
The binder composition may contain other components as long as the effects of the mold making kit of the present embodiment are not impaired. Examples of the other components include the following components. In addition, from the viewpoint of manifesting the effects of the present embodiment, the binder composition does not contain an aromatic hydroxy compound having no carboxyl group.
（尿素及び尿素誘導体からなる群より選ばれる１種以上の化合物）
前記粘結剤組成物は、鋳型強度向上の観点から、尿素及び尿素誘導体からなる群より選ばれる１種以上の化合物（以下、「尿素等」とも称する）が含まれていても良い。
(One or more compounds selected from the group consisting of urea and urea derivatives)
The binder composition may contain one or more compounds selected from the group consisting of urea and urea derivatives (hereinafter also referred to as “urea etc.”) from the viewpoint of improving the mold strength.
前記粘結剤組成物中の尿素及び尿素誘導体からなる群より選ばれる１種以上の化合物とは、ホルムアルデヒドやフルフリルアルコール等と縮合反応していない尿素及び尿素誘導体からなる群より選ばれる１種以上の化合物であり、未反応分として残存したものでも、別途添加されたものでも何れでも良い。 The one or more compounds selected from the group consisting of urea and urea derivatives in the binder composition are one type selected from the group consisting of urea and urea derivatives that are not condensed with formaldehyde, furfuryl alcohol or the like. These compounds may be any of those remaining as unreacted components or those added separately.
尿素及び尿素誘導体からなる群より選ばれる１種以上の化合物としては、例えば、尿素；エチレン尿素、プロピレン尿素、ブチレン尿素、ヒダントイン等のアルキレン尿素；メチル尿素、１，１−ジメチル尿素、１，３−ジメチル尿素等のアルキル尿素；シクロヘキシル尿素、１，３−ジシクロヘキシル尿素等のシクロヘキシル尿素；フェニル尿素、１，１−ジフェニル尿素、１，３−ジフェニル尿素等のアリール尿素；２−ヒドロキシエチル尿素等のアルキル基の炭素数が２以上のヒドロキシアルキル尿素；アゾジカルボンアミド等が挙げられる。これらの化合物は単独でも或いは２種以上の混合でも用いることが出来る。硬化速度の向上、鋳型強度の向上及びホルムアルデヒド発生量低減の観点から尿素及びエチレン尿素が好ましく、経済性の観点から尿素が更に好ましい。 Examples of one or more compounds selected from the group consisting of urea and urea derivatives include, for example, urea; alkylene urea such as ethylene urea, propylene urea, butylene urea, and hydantoin; methyl urea, 1,1-dimethyl urea, 1, 3 -Alkylureas such as dimethylurea; cyclohexylureas such as cyclohexylurea and 1,3-dicyclohexylurea; arylureas such as phenylurea, 1,1-diphenylurea and 1,3-diphenylurea; 2-hydroxyethylurea and the like Examples thereof include hydroxyalkylurea having an alkyl group with 2 or more carbon atoms; azodicarbonamide and the like. These compounds can be used alone or in combination of two or more. Urea and ethylene urea are preferable from the viewpoint of improving the curing rate, improving the mold strength, and reducing the amount of formaldehyde generated, and urea is more preferable from the viewpoint of economy.
前記粘結剤組成物中の尿素等の含有量は、鋳型強度向上の観点から、０．５質量％以上が好ましく、１質量％以上がより好ましく、１．５質量％以上が更に好ましい。前記粘結剤組成物中の尿素等の含有量は、前記粘結剤組成物中の尿素等の溶解性の観点から、８質量％以下が好ましく、７質量％以下がより好ましく、６質量％以下が更に好ましい。また、前記粘結剤組成物中の尿素等の含有量は、鋳型の硬化速度向上の観点、及び前記粘結剤組成物中の尿素の溶解性の観点から、０．５〜８質量％が好ましく、１〜７質量％がより好ましく、１．５〜６質量％が更に好ましい。 The content of urea or the like in the binder composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 1.5% by mass or more from the viewpoint of improving the mold strength. From the viewpoint of solubility of urea or the like in the binder composition, the content of urea or the like in the binder composition is preferably 8% by mass or less, more preferably 7% by mass or less, and 6% by mass. The following is more preferable. The content of urea or the like in the binder composition is 0.5 to 8% by mass from the viewpoint of improving the curing rate of the mold and the solubility of urea in the binder composition. Preferably, 1-7 mass% is more preferable, and 1.5-6 mass% is still more preferable.
（酸硬化性樹脂）
前記粘結剤組成物には、粘結剤成分として従来公知の酸硬化性樹脂が含まれていても良い。当該酸硬化性樹脂としては、フルフリルアルコール、フルフリルアルコールの縮合物、フルフリルアルコールとアルデヒド類の縮合物、フルフリルアルコールと尿素とアルデヒド類の縮合物（尿素変性フラン樹脂）、尿素とエチレン尿素とアルデヒド類の縮合物（尿素・エチレン尿素共縮合樹脂）、メラミンとアルデヒド類の縮合物、及び尿素とアルデヒド類の縮合物よりなる群から選ばれる１種からなるものや、これらの群から選ばれる２種以上の混合物からなるものが例示できる。また、これらの群から選ばれる２種以上の共縮合物からなるものも使用できる。このうち、鋳型の硬化速度向上と鋳型強度向上の観点から、フルフリルアルコール、フルフリルアルコールの縮合物及びフルフリルアルコールと尿素とアルデヒド類の縮合物から選ばれる１種以上、並びにこれらの共縮合物を使用するのが好ましい。フルフリルアルコールは、非石油資源である植物から製造できるため、地球環境の観点からは、フルフリルアルコールを使用するのが好ましい。
(Acid curable resin)
The binder composition may contain a conventionally known acid curable resin as a binder component. Examples of the acid curable resin include furfuryl alcohol, condensate of furfuryl alcohol, condensate of furfuryl alcohol and aldehydes, condensate of furfuryl alcohol, urea and aldehydes (urea-modified furan resin), urea and ethylene. Condensates of urea and aldehydes (urea / ethylene urea co-condensation resin), ones selected from the group consisting of condensates of melamine and aldehydes, and condensates of urea and aldehydes, and from these groups What consists of 2 or more types of mixtures chosen can be illustrated. Moreover, what consists of 2 or more types of cocondensates chosen from these groups can also be used. Among these, from the viewpoint of improving the mold curing speed and mold strength, at least one selected from furfuryl alcohol, a condensate of furfuryl alcohol, a condensate of furfuryl alcohol, urea, and aldehydes, and their cocondensation It is preferable to use a product. Since furfuryl alcohol can be produced from a plant which is a non-petroleum resource, it is preferable to use furfuryl alcohol from the viewpoint of the global environment.
前記粘結剤組成物中の前記酸硬化性樹脂の含有量は、鋳型強度向上の観点から、５質量％以上が好ましく、１０質量％以上がより好ましく、２５質量％以上が更に好ましい。前記粘結剤組成物中の前記酸硬化性樹脂の含有量は、同様の観点から、９０質量％以下が好ましく、８０質量％以下がより好ましく、６０質量％以下が更に好ましい。前記粘結剤組成物中の前記酸硬化性樹脂の含有量は、同様の観点から、５〜９０質量％が好ましく、１０〜８０質量％がより好ましく、２５〜６０質量％が更に好ましい。 The content of the acid curable resin in the binder composition is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 25% by mass or more from the viewpoint of improving the mold strength. From the same viewpoint, the content of the acid curable resin in the binder composition is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 60% by mass or less. From the same viewpoint, the content of the acid curable resin in the binder composition is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 25 to 60% by mass.
（硬化促進剤）
前記粘結剤組成物には、鋳型強度向上の観点から、硬化促進剤が含まれていても良い。硬化促進剤としては、鋳型強度向上の観点から、下記一般式（１）で表される化合物（以下、硬化促進剤（１）という）、及び芳香族ジアルデヒドからなる群より選ばれる１種以上が好ましい。
(Curing accelerator)
The binder composition may contain a curing accelerator from the viewpoint of improving the mold strength. As the curing accelerator, from the viewpoint of improving the mold strength, at least one selected from the group consisting of a compound represented by the following general formula (1) (hereinafter referred to as curing accelerator (1)) and an aromatic dialdehyde. Is preferred.
〔式中、Ｘ１及びＸ２は、それぞれ水素原子、ＣＨ３又はＣ２Ｈ５の何れかを表す。〕
[Wherein, X 1 and X 2 each represent a hydrogen atom, CH 3 or C 2 H 5 . ]
前記硬化促進剤（１）としては、２，５−ビスヒドロキシメチルフラン、２，５−ビスメトキシメチルフラン、２，５−ビスエトキシメチルフラン、２−ヒドロキシメチル−５−メトキシメチルフラン、２−ヒドロキシメチル−５−エトキシメチルフラン、２−メトキシメチル−５−エトキシメチルフランが挙げられる。なかでも、鋳型強度向上の観点から、２，５−ビスヒドロキシメチルフランを使用するのが好ましい。 Examples of the curing accelerator (1) include 2,5-bishydroxymethyl furan, 2,5-bismethoxymethyl furan, 2,5-bisethoxymethyl furan, 2-hydroxymethyl-5-methoxymethyl furan, 2- Examples include hydroxymethyl-5-ethoxymethylfuran and 2-methoxymethyl-5-ethoxymethylfuran. Of these, 2,5-bishydroxymethylfuran is preferably used from the viewpoint of improving the mold strength.
前記芳香族ジアルデヒドとしては、テレフタルアルデヒド、フタルアルデヒド及びイソフタルアルデヒド等、並びにそれらの誘導体等が挙げられる。それらの誘導体とは、基本骨格としての２つのホルミル基を有する芳香族化合物の芳香環にアルキル基等の置換基を有する化合物等を意味する。鋳型強度向上の観点から、テレフタルアルデヒド及びテレフタルアルデヒドの誘導体が好ましく、テレフタルアルデヒドがより好ましい。 Examples of the aromatic dialdehyde include terephthalaldehyde, phthalaldehyde and isophthalaldehyde, and derivatives thereof. These derivatives mean compounds having a substituent such as an alkyl group on the aromatic ring of an aromatic compound having two formyl groups as the basic skeleton. From the viewpoint of improving the mold strength, terephthalaldehyde and terephthalaldehyde derivatives are preferable, and terephthalaldehyde is more preferable.
前記粘結剤組成物中の硬化促進剤の含有量は、鋳型強度向上の観点から、０．５質量％以上が好ましく、１質量％以上がより好ましく、２質量％以上が更に好ましい。前記粘結剤組成物中の硬化促進剤の含有量は、硬化促進剤の溶解性の観点及び鋳型強度向上の観点から、５０質量％以下が好ましく、４０質量％以下がより好ましく、３０質量％以下が更に好ましい。 The content of the curing accelerator in the binder composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 2% by mass or more from the viewpoint of improving the mold strength. The content of the curing accelerator in the binder composition is preferably 50% by mass or less, more preferably 40% by mass or less, and more preferably 30% by mass from the viewpoint of solubility of the curing accelerator and improvement of mold strength. The following is more preferable.
［水］
前記粘結剤組成物には、さらに水が含まれてもよい。例えば、フルフリルアルコールとアルデヒド類の縮合物などの各種縮合物を合成する場合、水溶液状の原料を使用したり縮合水が生成したりするため、縮合物は、通常、水との混合物の形態で得られる。このような縮合物を前記粘結剤組成物に使用するにあたり、水は必要に応じて、トッピング等で除去しても構わないが、硬化反応速度を維持できる限り、製造の際にあえて除去する必要はない。また、前記粘結剤組成物及び鋳型造型用組成物を取扱いやすい粘度に調整する目的などで、水をさらに添加してもよい。
[water]
The binder composition may further contain water. For example, when synthesizing various condensates such as a condensate of furfuryl alcohol and aldehydes, an aqueous raw material is used or condensed water is generated. Therefore, the condensate is usually in the form of a mixture with water. It is obtained by. In using such a condensate in the binder composition, water may be removed by topping, if necessary, but it is intentionally removed during production as long as the curing reaction rate can be maintained. There is no need. Further, water may be further added for the purpose of adjusting the binder composition and the mold making composition to a viscosity that is easy to handle.
前記粘結剤組成物を取扱いやすい粘度に調整する目的で水をさらに添加する場合、前記粘結剤組成物中の水の含有量は０質量％以上が好ましく、０．５質量％以上がより好ましく、０．７質量％以上が更に好ましい。ただし、鋳型の硬化速度向上の観点から、前記粘結剤組成物中の水の含有量は３０質量％以下が好ましく、５質量％以下がより好ましく、３．５質量％以下が更に好ましい。また、前記粘結剤組成物中の水の含有量は、前記粘結剤組成物を取扱いやすい粘度に調整する観点、及び鋳型の硬化速度向上の観点から、０〜３０質量％が好ましく、０．５〜５質量％がより好ましく、０．７〜３．５質量％が更に好ましい。 When water is further added for the purpose of adjusting the binder composition to an easy-to-handle viscosity, the water content in the binder composition is preferably 0% by mass or more, more preferably 0.5% by mass or more. Preferably, 0.7 mass% or more is more preferable. However, from the viewpoint of improving the curing rate of the mold, the content of water in the binder composition is preferably 30% by mass or less, more preferably 5% by mass or less, and even more preferably 3.5% by mass or less. Further, the content of water in the binder composition is preferably 0 to 30% by mass from the viewpoint of adjusting the binder composition to an easy-to-handle viscosity and improving the curing rate of the mold. More preferably, 5-5 mass% is more preferable, and 0.7-3.5 mass% is still more preferable.
前記粘結剤組成物には、更にシランカップリング剤等の添加剤が含まれていてもよい。例えば、前記粘結剤組成物にシランカップリング剤が含まれていると、得られる鋳型の最終強度をより向上させることができるため好ましい。シランカップリング剤としては、Ｎ−β−（アミノエチル）−γ−アミノプロピルメチルジメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリエトキシシラン、３−アミノプロピルトリメトキシシラン等のアミノシランや、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−グリシドキシプロピルジメトキシメチルシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリエトキシシラン等のエポキシシラン、ウレイドシラン、メルカプトシラン、スルフィドシラン、メタクリロキシシラン、アクリロキシシランなどが用いられる。好ましくは、アミノシラン、エポキシシラン、ウレイドシランである。より好ましくはアミノシラン、エポキシシランであり、更に好ましくはエポキシシランである。エポキシシランの中でも、３−グリシドキシプロピルジメトキシメチルシランが好ましい。 The binder composition may further contain an additive such as a silane coupling agent. For example, it is preferable that the binder composition contains a silane coupling agent because the final strength of the obtained mold can be further improved. As the silane coupling agent, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl)- aminosilanes such as γ-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, Epoxy silanes such as 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, ureidosilane, mercaptosilane, sulfide silane, methacryloxysilane, acryloxysilane, and the like are used. Amino silane, epoxy silane, and ureido silane are preferable. More preferred are aminosilanes and epoxysilanes, and even more preferred are epoxysilanes. Among epoxy silanes, 3-glycidoxypropyl dimethoxymethyl silane is preferable.
前記粘結剤組成物中のシランカップリング剤の含有量は、最終的な鋳型強度向上の観点から、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましい。前記粘結剤組成物中のシランカップリング剤の含有量は、同様の観点から、５質量％以下が好ましく、４質量％以下がより好ましい。前記粘結剤組成物中のシランカップリング剤の含有量は、同様の観点から、０．０１〜５質量％が好ましく、０．０５〜４質量％がより好ましい。 The content of the silane coupling agent in the binder composition is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more from the viewpoint of improving the final mold strength. From the same viewpoint, the content of the silane coupling agent in the binder composition is preferably 5% by mass or less, and more preferably 4% by mass or less. From the same viewpoint, the content of the silane coupling agent in the binder composition is preferably 0.01 to 5% by mass, and more preferably 0.05 to 4% by mass.
〔硬化剤組成物〕
前記硬化剤組成物は、カルボキシル基を有さない芳香族ヒドロキシ化合物、及びカルボン酸を含有する。
[Curing agent composition]
The said hardening | curing agent composition contains the aromatic hydroxy compound which does not have a carboxyl group, and carboxylic acid.
［カルボキシル基を有さない芳香族ヒドロキシ化合物］
前記芳香族ヒドロキシ化合物は、カルボキシル基を有さない芳香族ヒドロキシ化合物であれば特に限定されない。当該芳香族ヒドロキシ化合物としては、フェノール、クレゾール、キシレノール、クミルフェノール、ノニルフェノール、ブチルフェノール、フェニルフェノール、エチルフェノール、オクチルフェノール、アミルフェノール、ナフトール、レゾルシン、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＣ、カテコール、ハイドロキノン、ピロガロール、及びフロログリシン、フェノール類とホルムアルデヒドの縮合物からなる群より選ばれる少なくとも１種以上が例示でき、鋳型強度向上の観点から、ピロガロール、レゾルシン、及びフェノール類とホルムアルデヒドの縮合物からなる群より選ばれる少なくとも１種以上が好ましく、ピロガロール、及びレゾルシンからなる群より選ばれる少なくとも１種以上がより好ましい。
[Aromatic hydroxy compound having no carboxyl group]
The aromatic hydroxy compound is not particularly limited as long as it is an aromatic hydroxy compound having no carboxyl group. Examples of the aromatic hydroxy compound include phenol, cresol, xylenol, cumylphenol, nonylphenol, butylphenol, phenylphenol, ethylphenol, octylphenol, amylphenol, naphthol, resorcin, bisphenol A, bisphenol F, bisphenol C, catechol, hydroquinone, Examples include at least one selected from the group consisting of pyrogallol, phloroglysin, and phenols and formaldehyde condensates, and from the viewpoint of improving mold strength, pyrogallol, resorcin, and from the group consisting of phenols and formaldehyde condensates At least one selected from the group consisting of pyrogallol and resorcin is more preferable.
前記硬化剤組成物中の前記芳香族ヒドロキシ化合物の含有量は、作業環境の温度や耐火性粒子の温度に応じて、所望の反応速度及び鋳型強度を得るために適宜調整されるが、一般的には、鋳型強度向上の観点から、１質量％以上が好ましく、３質量％以上がより好ましく、１５質量％以上が更に好ましい。同様に、前記硬化剤組成物中の前記芳香族ヒドロキシ化合物の含有量は、鋳型強度向上の観点から、８０質量％以下が好ましく、６０質量％以下がより好ましく、３５質量％以下が更に好ましい。また、前記硬化剤組成物中の前記芳香族ヒドロキシ化合物の含有量は、鋳型強度向上の観点から、１〜８０質量％が好ましく、３〜６０質量％がより好ましく、１５〜３５質量％が更に好ましい。また、硬化剤組成物中に前記芳香族ヒドロキシ化合物が存在しても粘度の経時変化が少ないため、取扱い上も好ましい。 The content of the aromatic hydroxy compound in the curing agent composition is appropriately adjusted in order to obtain a desired reaction rate and mold strength according to the temperature of the working environment and the temperature of the refractory particles. From the viewpoint of improving the mold strength, it is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 15% by mass or more. Similarly, the content of the aromatic hydroxy compound in the curing agent composition is preferably 80% by mass or less, more preferably 60% by mass or less, and still more preferably 35% by mass or less from the viewpoint of improving the mold strength. Further, the content of the aromatic hydroxy compound in the curing agent composition is preferably 1 to 80% by mass, more preferably 3 to 60% by mass, and further preferably 15 to 35% by mass from the viewpoint of improving the mold strength. preferable. In addition, even when the aromatic hydroxy compound is present in the curing agent composition, the change in viscosity with time is small, which is preferable in handling.
［カルボン酸］
前記カルボン酸は、カルボン酸であれば特に限定されない。当該カルボン酸としては、鋳型強度向上及び臭気低減の観点から、２，６−ジヒドロキシ安息香酸、シュウ酸、マレイン酸、ピルビン酸、マロン酸、２−フランカルボン酸、フタル酸、フマル酸、乳酸、クエン酸、リンゴ酸からなる群より選ばれる少なくとも１種以上が例示でき、鋳型強度向上の観点から、２，６−ジヒドロキシ安息香酸、シュウ酸、マレイン酸からなる群より選ばれる少なくとも１種以上が好ましく、２，６−ジヒドロキシ安息香酸がより好ましい。
[carboxylic acid]
The carboxylic acid is not particularly limited as long as it is a carboxylic acid. As the carboxylic acid, 2,6-dihydroxybenzoic acid, oxalic acid, maleic acid, pyruvic acid, malonic acid, 2-furancarboxylic acid, phthalic acid, fumaric acid, lactic acid, from the viewpoint of improving template strength and reducing odor, Examples include at least one selected from the group consisting of citric acid and malic acid, and at least one selected from the group consisting of 2,6-dihydroxybenzoic acid, oxalic acid and maleic acid from the viewpoint of improving the template strength. Preferably, 2,6-dihydroxybenzoic acid is more preferable.
前記硬化剤組成物中の前記カルボン酸の含有量は、作業環境の温度や耐火性粒子の温度に応じて、所望の反応速度及び鋳型強度を得るために適宜調整されるが、一般的には、鋳型強度向上の観点から、１質量％以上が好ましく、３質量％以上がより好ましく、１０質量％以上が更に好ましい。同様に、前記硬化剤組成物中の前記カルボン酸の含有量は、鋳型強度向上の観点から、８０質量％以下が好ましく、６０質量％以下がより好ましく、５０質量％以下が更に好ましい。また、前記硬化剤組成物中の前記カルボン酸の含有量は、鋳型強度向上の観点から、１〜８０質量％が好ましく、３〜６０質量％がより好ましく、１０〜５０質量％が更に好ましい。 The content of the carboxylic acid in the curing agent composition is appropriately adjusted in order to obtain a desired reaction rate and mold strength, depending on the temperature of the working environment and the temperature of the refractory particles. From the viewpoint of improving the mold strength, it is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 10% by mass or more. Similarly, the content of the carboxylic acid in the curing agent composition is preferably 80% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less from the viewpoint of improving the mold strength. In addition, the content of the carboxylic acid in the curing agent composition is preferably 1 to 80% by mass, more preferably 3 to 60% by mass, and still more preferably 10 to 50% by mass from the viewpoint of improving the mold strength.
前記カルボン酸及びカルボキシル基を有さない芳香族ヒドロキシ化合物は、硬化剤として用いる際には１種又は２種以上を組み合わせて用いることができる。
The aromatic hydroxy compound having no carboxylic acid and carboxyl groups, when used as a curing agent Ru can be used singly or in combination of two or more kinds.
［その他の成分］
前記硬化剤組成物及び鋳型造型用組成物には、カルボキシル基を有さない芳香族ヒドロキシ化合物、及びカルボン酸以外の硬化剤成分として、公知の酸性物質が本実施形態の効果を阻害しない程度に含有されても良い。前記酸性物質としては、例えば、リン酸等のリン酸系化合物、あるいは硝酸等の無機酸などの１種又は２種以上の混合物が例示できる。
[Other ingredients]
In the curing agent composition and the mold making composition, as a curing agent component other than the aromatic hydroxy compound having no carboxyl group and the carboxylic acid, a known acidic substance does not inhibit the effect of the present embodiment. It may be contained. Examples of the acidic substance include one or a mixture of two or more of phosphoric acid compounds such as phosphoric acid or inorganic acids such as nitric acid.
前記硬化剤組成物中の前記酸性物質の含有量は、作業環境の温度や耐火性粒子の温度に応じて、所望の反応速度及び鋳型強度を得るために適宜調整されるが、一般的には、鋳型硬化速度向上の観点から、１質量％以上が好ましく、５質量％以上がより好ましく、１０質量％以上が更に好ましい。前記硬化剤組成物中の前記酸性物質の含有量は、同様の観点から、５０質量％以下が好ましく、４５質量％以下がより好ましく、４０質量％以下が更に好ましい。また、前記硬化剤組成物中の前記酸性物質の含有量は、同様の観点から、１〜５０質量％が好ましく、５〜４５質量％がより好ましく、１０〜４０質量％が更に好ましい。 The content of the acidic substance in the curing agent composition is appropriately adjusted in order to obtain a desired reaction rate and mold strength, depending on the temperature of the working environment and the temperature of the refractory particles. From the viewpoint of improving the mold curing speed, it is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more. From the same viewpoint, the content of the acidic substance in the curing agent composition is preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less. Moreover, 1-50 mass% is preferable from the same viewpoint, as for content of the said acidic substance in the said hardening | curing agent composition, 5-45 mass% is more preferable, and 10-40 mass% is still more preferable.
更に、前記硬化剤組成物及び前記鋳型造型用組成物には、アルコール類、エーテルアルコール類及びエステル類よりなる群から選ばれる１種以上の溶剤を含有させることができる。これらの中でも、鋳型強度の向上の観点から、アルコール類、エーテルアルコール類が好ましく、アルコール類がより好ましい。 Further, the curing agent composition and the mold making composition may contain one or more solvents selected from the group consisting of alcohols, ether alcohols and esters. Among these, alcohols and ether alcohols are preferable and alcohols are more preferable from the viewpoint of improving the mold strength.
鋳型強度向上の観点から、前記アルコール類としては、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、ベンジルアルコールが好ましく、エーテルアルコール類としては、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノヘキシルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノヘキシルエーテル、ジエチレングリコールモノフェニルエーテル、エチレングリコールモノフェニルエーテルが好ましく、エステル類としては、酢酸ブチル、安息香酸ブチル、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテートが好ましい。 From the viewpoint of improving mold strength, the alcohols are preferably methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, and benzyl alcohol, and the ether alcohols are ethylene glycol monoethyl ether, ethylene glycol mono Butyl ether, ethylene glycol monohexyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, ethylene glycol monophenyl ether are preferred, and esters include butyl acetate, butyl benzoate, ethylene glycol monophenyl Butyl ether acetate, diethylene glycol mono Chill ether acetate is preferable.
前記硬化剤組成物中の前記溶剤の含有量は、作業環境の温度や耐火性粒子の温度に応じて、所望の反応速度及び鋳型強度を得るために適宜調整されるが、一般的には、鋳型強度向上の観点および硬化剤組成物を溶解させる観点から、５質量％以上が好ましく、１０質量％以上がより好ましく、２０質量％以上が更に好ましい。前記硬化剤組成物中の前記溶剤の含有量は、同様の観点から、９０質量％以下が好ましく、８０質量％以下がより好ましく、７０質量％以下が更に好ましい。また、前記硬化剤組成物中の前記溶剤の含有量は、同様の観点から、５〜９０質量％が好ましく、１０〜８０質量％がより好ましく、２０〜７０質量％が更に好ましい。 The content of the solvent in the curing agent composition is appropriately adjusted in order to obtain a desired reaction rate and mold strength, depending on the temperature of the working environment and the temperature of the refractory particles. From the viewpoint of improving the mold strength and from the viewpoint of dissolving the curing agent composition, the content is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. From the same viewpoint, the content of the solvent in the curing agent composition is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less. Moreover, 5-90 mass% is preferable from the same viewpoint, as for content of the said solvent in the said hardening | curing agent composition, 10-80 mass% is more preferable, and 20-70 mass% is still more preferable.
前記粘結剤組成物と前記硬化剤組成物の比率は、鋳型強度向上の観点から、前記粘結剤組成物１００質量部に対して、硬化剤組成物が２０質量部以上が好ましく、３０質量部以上がより好ましく、６０質量部以上が更に好ましい。前記粘結剤組成物と前記硬化剤組成物の比率は、同様の観点から、前記粘結剤組成物１００質量部に対して、硬化剤組成物が１００質量部以下が好ましく、９０質量部以下がより好ましく、８０質量部以下がより好ましい。また、前記粘結剤組成物と前記硬化剤組成物の比率は、鋳型強度向上の観点から、前記粘結剤組成物１００質量部に対して、硬化剤組成物が２０〜１００質量部が好ましく、３０〜９０質量部がより好ましく、６０〜８０質量部が更に好ましい。 The ratio of the binder composition and the curing agent composition is preferably 20 parts by mass or more, and 30 parts by mass with respect to 100 parts by mass of the binder composition from the viewpoint of improving mold strength. Part or more is more preferable, and 60 parts by mass or more is more preferable. From the same viewpoint, the ratio of the binder composition and the curing agent composition is preferably 100 parts by mass or less, and 90 parts by mass or less with respect to 100 parts by mass of the binder composition. Is more preferable, and 80 parts by mass or less is more preferable. Further, the ratio of the binder composition to the curing agent composition is preferably 20 to 100 parts by mass of the curing agent composition with respect to 100 parts by mass of the binder composition from the viewpoint of improving the mold strength. 30-90 mass parts is more preferable, and 60-80 mass parts is still more preferable.
本実施形態の鋳型造型用キットは自硬性鋳型の造型に好適に用いられる。ここで自硬性鋳型とは、砂に粘結剤組成物と硬化剤を混合すると、時間の経過と共に重合反応が進行し、鋳型が硬化する鋳型である。その際に用いられる砂の温度としては、−２０℃〜５０℃の範囲であり、好ましくは０℃〜４０℃である。このような温度の砂に対して、それに適した量の硬化剤を選択し砂に添加する事で、鋳型を適切に硬化できる。 The mold making kit of this embodiment is suitably used for making a self-hardening mold. Here, the self-hardening mold is a mold in which, when a binder composition and a curing agent are mixed with sand, a polymerization reaction proceeds with time, and the mold is cured. As temperature of the sand used in that case, it is the range of -20 degreeC-50 degreeC, Preferably it is 0 degreeC-40 degreeC. The mold can be appropriately cured by selecting a suitable amount of a curing agent for the sand at such a temperature and adding it to the sand.
＜鋳型造型用組成物＞
本実施形態の鋳型造型用組成物は、前記鋳型造型用キットを構成する前記粘結剤組成物及び前記硬化剤組成物を含有する。当該鋳型造型用組成物は、作業環境の温度に係わらず、カルボン酸を硬化剤として使用した場合でも、所望の鋳型強度を得ることが出来る。このような効果を奏する理由は定かではないが、鋳型造型用キットと同様の理由が考えられる。
<Mold molding composition>
The mold molding composition of the present embodiment contains the binder composition and the curing agent composition that constitute the mold molding kit. The mold molding composition can obtain a desired mold strength even when carboxylic acid is used as a curing agent, regardless of the temperature of the working environment. The reason for such an effect is not clear, but the same reason as the mold making kit can be considered.
〔その他の成分〕
前記鋳型造型用組成物は、本実施形態の効果を阻害しない程度に酸硬化性樹脂、硬化促進剤、水、シランカップリング剤等の添加剤、酸性物質、溶剤、及びカルボン酸類等を添加しても良い。酸硬化性樹脂、硬化促進剤、水、シランカップリング剤等の添加剤、酸性物質、溶剤、及びカルボン酸類は、前記粘結剤組成物に用いることができる成分、及び前記硬化剤組成物に用いることができる成分と同様のもの及び量を用いることが出来る。
[Other ingredients]
The mold molding composition is added with an acid curable resin, a curing accelerator, water, an additive such as a silane coupling agent, an acidic substance, a solvent, and carboxylic acids to the extent that the effects of the present embodiment are not impaired. May be. Acid curable resins, curing accelerators, water, additives such as silane coupling agents, acidic substances, solvents, and carboxylic acids are components that can be used in the binder composition, and the curing agent composition. The same components and amounts that can be used can be used.
＜鋳型の製造方法＞
本実施形態の鋳型の製造方法は、前記鋳型造型用キットを構成する粘結剤組成物及び硬化剤組成物と、耐火性粒子とを混合する混合工程を有する。当該鋳型の製造方法は、作業環境の温度に係わらず、カルボン酸を硬化剤として使用した場合でも、所望の鋳型強度を得ることが出来る。このような効果を奏する理由は定かではないが、鋳型造型用キットと同様の理由が考えられる。
<Mold production method>
The method for producing a mold according to this embodiment includes a mixing step of mixing the binder composition and the curing agent composition constituting the mold making kit and the refractory particles. The mold production method can obtain a desired mold strength even when carboxylic acid is used as a curing agent, regardless of the temperature of the working environment. The reason for such an effect is not clear, but the same reason as the mold making kit can be considered.
〔耐火性粒子〕
前記耐火性粒子としては、珪砂、クロマイト砂、ジルコン砂、オリビン砂、アルミナ砂、ムライト砂、合成ムライト砂等の従来公知のもの１種又は２種以上を使用でき、また、使用済みの耐火性粒子を回収したものや再生処理したものなども使用できる。これらの中でも珪砂を含むことが好ましい。
(Fireproof particles)
As the refractory particles, one or more conventionally known ones such as silica sand, chromite sand, zircon sand, olivine sand, alumina sand, mullite sand, and synthetic mullite sand can be used, and used fire resistance. Those obtained by collecting or regenerating particles can also be used. Among these, it is preferable to contain silica sand.
前記混合工程において、前記粘結剤組成物及び前記硬化剤組成物、並びに耐火性粒子を添加・混合する順序に特に限定は無く、前記粘結剤組成物と前記硬化剤組成物とを混合し鋳型造型用組成物を製造した後、当該鋳型造型用組成物と耐火性粒子とを混合しても良く、前記粘結剤組成物、前記硬化剤組成物、及び耐火性粒子をそれぞれ添加・混合しても良いが、保存安定性及び鋳型の生産性の観点からは、前記粘結剤組成物、前記硬化剤組成物、及び耐火性粒子を混合し、鋳型用組成物を得るのが好ましい。また、鋳型強度向上の観点から、耐火性粒子に硬化剤組成物を添加して混合し、ついで粘結剤組成物を添加して混合することが好ましい。また、２種以上の硬化剤組成物を用いる場合は、各硬化剤組成物を混合してから添加しても良く、各硬化剤組成物を別々に添加しても良い。 In the mixing step, the order of adding and mixing the binder composition and the curing agent composition, and the refractory particles is not particularly limited, and the binder composition and the curing agent composition are mixed. After producing the mold molding composition, the mold molding composition and the refractory particles may be mixed, and the binder composition, the curing agent composition, and the refractory particles are added and mixed, respectively. However, from the viewpoint of storage stability and mold productivity, it is preferable to mix the binder composition, the curing agent composition, and refractory particles to obtain a mold composition. Further, 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. Moreover, when using 2 or more types of hardening | curing agent compositions, you may add after mixing each hardening | curing agent composition, and you may add each hardening | curing agent composition separately.
前記耐火性粒子と前記粘結剤組成物と前記硬化剤組成物との比率は作業環境の温度や耐火性粒子の温度に応じて、所望の反応速度及び鋳型強度を得るために適宜設定できるが、一般的には最終的な鋳型強度向上の観点から、前記耐火性粒子１００質量部に対して、前記粘結剤組成物が０．５質量部以上が好ましく、経済性の観点及び鋳物品質向上の観点から、前記耐火性粒子１００質量部に対して、３．０質量部以下が好ましく、１．５質量部以下がより好ましい。最終的な鋳型強度向上の観点から、前記耐火性粒子１００質量部に対して、前記硬化剤組成物が０．０７質量部以上が好ましく、０．４０質量部以上がより好ましく、経済性の観点及び鋳物品質向上の観点から、前記耐火性粒子１００質量部に対して、２．０質量部以下が好ましく、１．０質量部以下がより好ましい。また、前記耐火性粒子と前記粘結剤組成物と前記硬化剤組成物との比率は、最終的な鋳型強度向上の観点、並びに経済性の観点及び鋳物品質向上の観点から、前記耐火性粒子１００質量部に対して、前記粘結剤組成物が０．５〜３．０質量部が好ましく、０．５〜１．５質量部がより好ましい。最終的な鋳型強度向上の観点、並びに経済性の観点及び鋳物品質向上の観点から、前記耐火性粒子１００質量部に対して、前記硬化剤組成物が０．０７〜２．０質量部が好ましく、０．４０〜１．０質量部がより好ましい。 The ratio of the refractory particles, the binder composition and the curing agent composition can be set as appropriate in order to obtain a desired reaction rate and mold strength depending on the temperature of the working environment and the temperature of the refractory particles. In general, from the viewpoint of improving the final mold strength, the binder composition is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the refractory particles. From this viewpoint, 3.0 parts by mass or less is preferable and 1.5 parts by mass or less is more preferable with respect to 100 parts by mass of the refractory particles. From the viewpoint of improving the final mold strength, the curing agent composition is preferably 0.07 parts by mass or more, more preferably 0.40 parts by mass or more, with respect to 100 parts by mass of the refractory particles. And from a viewpoint of a casting quality improvement, 2.0 mass parts or less are preferable with respect to 100 mass parts of the said refractory particles, and 1.0 mass part or less is more preferable. In addition, the ratio of the refractory particles, the binder composition and the curing agent composition is determined from the viewpoint of improving the final mold strength, the economical viewpoint, and the casting quality. The binder composition is preferably 0.5 to 3.0 parts by mass and more preferably 0.5 to 1.5 parts by mass with respect to 100 parts by mass. From the viewpoint of final mold strength improvement, economical viewpoint and casting quality improvement, 0.07 to 2.0 parts by mass of the curing agent composition is preferable with respect to 100 parts by mass of the refractory particles. 0.40 to 1.0 part by mass is more preferable.
〔その他の成分〕
前記混合工程では、本実施形態の効果を阻害しない程度に酸硬化性樹脂、硬化促進剤、水、シランカップリング剤等の添加剤、酸性物質、溶剤、及びカルボン酸類等を添加しても良い。酸硬化性樹脂、硬化促進剤、水、シランカップリング剤等の添加剤、酸性物質、溶剤、及びカルボン酸類は、前記粘結剤組成物に用いることができる成分、及び前記硬化剤組成物に用いることができる成分と同様のもの及び量を用いることが出来る。
[Other ingredients]
In the mixing step, an acid curable resin, a curing accelerator, water, an additive such as a silane coupling agent, an acidic substance, a solvent, and a carboxylic acid may be added to the extent that the effects of the present embodiment are not impaired. . Acid curable resins, curing accelerators, water, additives such as silane coupling agents, acidic substances, solvents, and carboxylic acids are components that can be used in the binder composition, and the curing agent composition. The same components and amounts that can be used can be used.
前記混合工程において、各原料を混合する方法としては、公知一般の手法を用いることが出来、例えば、バッチミキサーにより各原料を添加して混練する方法や、連続ミキサーに各原料を供給して混練する方法が挙げられる。 In the mixing step, as a method of mixing the raw materials, a known general method can be used, for example, a method of adding each raw material by a batch mixer and kneading, or a method of supplying each raw material to a continuous mixer and kneading. The method of doing is mentioned.
本実施形態の鋳型の製造方法において、当該混合工程以外は従来の鋳型の製造プロセスをそのまま利用して鋳型を製造することができる。好ましい鋳型の製造方法として、前記鋳型造型用組成物と耐火性粒子とを混合して鋳型用組成物を得る混合工程、及び前記鋳型用組成物を型枠に詰め、当該鋳型用組成物を硬化させる硬化工程を有する鋳型の製造方法が挙げられる。 In the mold manufacturing method of the present embodiment, the mold can be manufactured using the conventional mold manufacturing process as it is except for the mixing step. As a preferred method for producing a mold, a mixing step of obtaining a mold composition by mixing the mold molding composition and refractory particles, and filling the mold composition into a mold, and curing the mold composition The manufacturing method of the casting_mold | template which has a hardening process to make is mentioned.
上述した実施形態に関し、本発明はさらに以下の組成物、製造方法、或いは用途を開示する。 In relation to the above-described embodiment, the present invention further discloses the following composition, production method, or application.
＜１＞粘結剤組成物と硬化剤組成物からなる、鋳型用組成物を製造するための鋳型造型用キットであって、前記粘結剤組成物が、フランアルデヒド化合物を含有し、前記硬化剤組成物が、カルボキシル基をもたない芳香族ヒドロキシ化合物、及びカルボン酸を含有する鋳型造型用キット。
＜２＞前記フランアルデヒド化合物は、フルフラール、５−ヒドロキシメチルフルフラール、及び５−アセトキシメチルフルフラールからなる群より選ばれる少なくとも１種以上が好ましく、フルフラール、及び５−ヒドロキシメチルフルフラールからなる群より選ばれる少なくとも１種以上がより好ましく、フルフラールが更に好ましい＜１＞に記載の鋳型造型用キット。
＜３＞前記粘結剤組成物中の前記フランアルデヒド化合物の含有量は、５質量％以上が好ましく、１０質量％以上がより好ましく、２０質量％以上が更に好ましく、４０質量％以上がより更に好ましく、９０質量％以下が好ましく、８５質量％以下がより好ましく、８０質量％以下が更に好ましく、７５質量％以下がより更に好ましく、５〜９０質量％が好ましく、１０〜８５質量％がより好ましく、２０〜８０質量％が更に好ましく、４０〜７５質量％がより更に好ましい＜１＞又は＜２＞に記載の鋳型造型用キット。
＜４＞前記粘結剤組成物が更に、尿素及び尿素誘導体からなる群より選ばれる１種以上の化合物を含有する＜１＞〜＜３＞いずれかに記載の鋳型造型用キット。
＜５＞前記粘結剤組成物中の尿素及び尿素誘導体からなる群より選ばれる１種以上の化合物の含有量が、０．５質量％以上が好ましく、１質量％以上がより好ましく、１．５質量％以上が更に好ましく、８質量％以下が好ましく、７質量％以下がより好ましく、６質量％以下が更に好ましく、０．５〜８質量％が好ましく、１〜７質量％がより好ましく、１．５〜６質量％が更に好ましい＜１＞〜＜４＞いずれかに記載の鋳型造型用キット。
＜６＞前記粘結剤組成物が更に、酸硬化性樹脂を含有する＜１＞〜＜５＞いずれかに記載の鋳型造型用キット。
＜７＞前記酸硬化性樹脂が、フルフリルアルコール、フルフリルアルコールの縮合物、フルフリルアルコールとアルデヒド類の縮合物、フルフリルアルコールと尿素とアルデヒド類の縮合物（尿素変性フラン樹脂）、尿素とエチレン尿素とアルデヒド類の縮合物（尿素・エチレン尿素共縮合樹脂）、メラミンとアルデヒド類の縮合物、及び尿素とアルデヒド類の縮合物よりなる群から選ばれる１種からなるものや、これらの群から選ばれる２種以上の混合物からなるもの、並びにこれらの群から選ばれる２種以上の共縮合物からなるものが好ましく、フルフリルアルコール、フルフリルアルコールの縮合物及びフルフリルアルコールと尿素とアルデヒド類の縮合物から選ばれる１種以上、並びにこれらの共縮合物がより好ましく、フルフリルアルコールが更に好ましい＜１＞〜＜６＞いずれかに記載の鋳型造型用キット。
＜８＞前記粘結剤組成物中の前記酸硬化性樹脂の含有量が、５質量％以上が好ましく、１０質量％以上がより好ましく、２５質量％以上が更に好ましく、９０質量％以下が好ましく、８０質量％以下がより好ましく、６０質量％以下が更に好ましく、５〜９０質量％が好ましく、１０〜８０質量％がより好ましく、２５〜６０質量％が更に好ましい＜１＞〜＜７＞いずれかに記載の鋳型造型用キット。
＜９＞前記粘結剤組成物が更に、硬化促進剤を含有する＜１＞〜＜８＞いずれかに記載の鋳型造型用キット。
＜１０＞前記硬化促進剤が、前記硬化促進剤（１）、及び芳香族ジアルデヒドからなる群より選ばれる１種以上が好ましい＜１＞〜＜９＞いずれかに記載の鋳型造型用キット。
＜１１＞前記粘結剤組成物中の硬化促進剤の含有量が、０．５質量％以上が好ましく、１質量％以上がより好ましく、２質量％以上が更に好ましく、５０質量％以下が好ましく、４０質量％以下がより好ましく、３０質量％以下が更に好ましい＜１＞〜＜１０＞いずれかに記載の鋳型造型用キット。
＜１２＞前記粘結剤組成物が更に、水を含有する＜１＞〜＜１１＞いずれかに記載の鋳型造型用キット。
＜１３＞前記粘結剤組成物中の水の含有量が、０量％以上が好ましく、０．５質量％以上がより好ましく、０．７質量％以上が更に好ましく、３０質量％以下が好ましく、５質量％以下がより好ましく、３．５質量％以下が更に好ましく、０〜３０質量％が好ましく、０．５〜５質量％がより好ましく、０．７〜３．５質量％が更に好ましい＜１＞〜＜１２＞いずれかに記載の鋳型造型用キット。
＜１４＞前記粘結剤組成物が更に、シランカップリング剤を含有する＜１＞〜＜１３＞いずれかに記載の鋳型造型用キット。
＜１５＞前記粘結剤組成物中のシランカップリング剤の含有量が、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、５質量％以下が好ましく、４質量％以下がより好ましく、０．０１〜５質量％が好ましく、０．０５〜４質量％がより好ましい＜１＞〜＜１４＞いずれかに記載の鋳型造型用キット。
＜１６＞前記粘結剤組成物が、カルボキシル基を有さない芳香族ヒドロキシ化合物を含有しない＜１＞〜＜１５＞いずれかに記載の鋳型造型用キット。
＜１７＞前記芳香族ヒドロキシ化合物が、フェノール、クレゾール、キシレノール、クミルフェノール、ノニルフェノール、ブチルフェノール、フェニルフェノール、エチルフェノール、オクチルフェノール、アミルフェノール、ナフトール、レゾルシン、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＣ、カテコール、ハイドロキノン、ピロガロール、及びフロログリシン、フェノール類とホルムアルデヒドの縮合物からなる群より選ばれる少なくとも１種以上が好ましく、ピロガロール、レゾルシン、及びフェノール類とホルムアルデヒドの縮合物からなる群より選ばれる少なくとも１種以上がより好ましく、ピロガロール、及びレゾルシンからなる群より選ばれる少なくとも１種以上が更に好ましい＜１＞〜＜１６＞いずれかに記載の鋳型造型用キット。
＜１８＞前記硬化剤組成物中の前記芳香族ヒドロキシ化合物の含有量が、１質量％以上が好ましく、３質量％以上がより好ましく、１５質量％以上が更に好ましく、８０質量％以下が好ましく、６０質量％以下がより好ましく、３５質量％以下が更に好ましく、１〜８０質量％が好ましく、３〜６０質量％がより好ましく、１５〜３５質量％が更に好ましい＜１＞〜＜１７＞いずれかに記載の鋳型造型用キット。
＜１９＞前記カルボン酸が、２，６−ジヒドロキシ安息香酸、シュウ酸、マレイン酸、ピルビン酸、マロン酸、２−フランカルボン酸、フタル酸、フマル酸、乳酸、クエン酸、リンゴ酸からなる群より選ばれる少なくとも１種以上が好ましく、２，６−ジヒドロキシ安息香酸、シュウ酸、マレイン酸からなる群より選ばれる少なくとも１種以上がより好ましく、２，６−ジヒドロキシ安息香酸が更に好ましい＜１＞〜＜１８＞いずれかに記載の鋳型造型用キット。
＜２０＞前記硬化剤組成物中の前記カルボン酸の含有量が、１質量％以上が好ましく、３質量％以上がより好ましく、１０質量％以上が更に好ましく、８０質量％以下が好ましく、６０質量％以下がより好ましく、５０質量％以下が更に好ましく、１〜８０質量％が好ましく、３〜６０質量％がより好ましく、１０〜５０質量％が更に好ましい＜１＞〜＜１９＞いずれかに記載の鋳型造型用キット。
＜２１＞前記硬化剤組成物が、更に溶剤を含有することを特徴とする＜１＞〜＜２０＞いずれかに記載の鋳型造型用キット。
＜２２＞前記硬化剤組成物中の前記溶剤の含有量が、５質量％以上が好ましく、１０質量％以上がより好ましく、２０質量％以上が更に好ましく、９０質量％以下が好ましく、８０質量％以下がより好ましく、７０質量％以下が更に好ましく、５〜９０質量％が好ましく、１０〜８０質量％がより好ましく、２０〜７０質量％が更に好ましい＜１＞〜＜２１＞いずれかに記載の鋳型造型用キット。
＜２３＞前記粘結剤組成物と前記硬化剤組成物の比率が、前記粘結剤組成物１００質量部に対して、硬化剤組成物が２０質量部以上が好ましく、３０質量部以上がより好ましく、６０質量部以上が更に好ましく、１００質量部以下が好ましく、９０質量部以下がより好ましく、８０質量部以下がより好ましく、２０〜１００質量部が好ましく、３０〜９０質量部がより好ましく、６０〜８０質量部が更に好ましい＜１＞〜＜２２＞いずれかに記載の鋳型造型用キット。
＜２４＞＜１＞〜＜２３＞いずれかに記載の鋳型造型用キットを構成する前記粘結剤組成物及び前記硬化剤組成物を含有する、鋳型造型用組成物。
＜２５＞＜１＞〜＜２３＞いずれかに記載の鋳型造型用キットを構成する前記粘結剤組成物及び前記硬化剤組成物と、耐火性粒子とを混合してなる鋳型用組成物。
＜２６＞＜２４＞又は＜２５＞に記載の鋳型用組成物を鋳型製造用の型枠に充填し、前記鋳型用組成物を硬化させる、鋳型の製造方法。
＜２７＞前記＜１＞〜＜２３＞いずれかに記載の鋳型造型用キットを構成する粘結剤組成物及び硬化剤組成物と、耐火性粒子とを混合する混合工程を有する、鋳型の製造方法。
＜２８＞前記混合工程が、前記粘結剤組成物と前記硬化剤組成物とを混合し鋳型造型用組成物を製造した後、当該鋳型造型用組成物と耐火性粒子とを混合する工程、又は前記粘結剤組成物、前記硬化剤組成物、及び耐火性粒子をそれぞれ添加・混合する工程が好ましく、前記粘結剤組成物、前記硬化剤組成物、及び耐火性粒子を混合する工程がより好ましい＜２７＞に記載の鋳型の製造方法。
＜２９＞前記耐火性粒子と前記粘結剤組成物と前記硬化剤組成物との比率が、前記耐火性粒子１００質量部に対して、前記粘結剤組成物が０．５質量部以上が好ましく、３．０質量部以下が好ましく、１．５質量部以下がより好ましく、前記耐火性粒子１００質量部に対して、前記硬化剤組成物が０．０７質量部以上が好ましく、０．４０質量部以上がより好ましく、２．０質量部以下が好ましく、１．０質量部以下がより好ましく、前記耐火性粒子１００質量部に対して、前記粘結剤組成物が０．５〜３．０質量部が好ましく、０．５〜１．５質量部がより好ましく、前記硬化剤組成物が０．０７〜２．０質量部が好ましく、０．４０〜１．０質量部がより好ましい＜２７＞又は＜２８＞に記載の鋳型の製造方法。
＜３０＞＜１＞〜＜２３＞いずれかに記載のキットの、鋳型を製造するための使用。
<1> A mold making kit for producing a mold composition, comprising a binder composition and a curing agent composition, wherein the binder composition contains a furanaldehyde compound and the curing A mold making kit, wherein the agent composition contains an aromatic hydroxy compound having no carboxyl group and a carboxylic acid.
<2> The furanaldehyde compound is preferably at least one selected from the group consisting of furfural, 5-hydroxymethylfurfural, and 5-acetoxymethylfurfural, and selected from the group consisting of furfural and 5-hydroxymethylfurfural. The mold making kit according to <1>, wherein at least one or more are more preferable, and furfural is more preferable.
<3> The content of the furanaldehyde compound in the binder composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and even more preferably 40% by mass or more. Preferably, 90 mass% or less is preferable, 85 mass% or less is more preferable, 80 mass% or less is more preferable, 75 mass% or less is still more preferable, 5-90 mass% is preferable, and 10-85 mass% is more preferable. The mold making kit according to <1> or <2>, further preferably 20 to 80% by mass, and still more preferably 40 to 75% by mass.
<4> The mold making kit according to any one of <1> to <3>, wherein the binder composition further contains one or more compounds selected from the group consisting of urea and urea derivatives.
<5> The content of one or more compounds selected from the group consisting of urea and urea derivatives in the binder composition is preferably 0.5% by mass or more, more preferably 1% by mass or more. 5 mass% or more is further preferable, 8 mass% or less is preferable, 7 mass% or less is more preferable, 6 mass% or less is further more preferable, 0.5-8 mass% is preferable, 1-7 mass% is more preferable, The mold making kit according to any one of <1> to <4>, further preferably 1.5 to 6% by mass.
<6> The mold making kit according to any one of <1> to <5>, wherein the binder composition further contains an acid curable resin.
<7> The acid curable resin is furfuryl alcohol, a furfuryl alcohol condensate, a furfuryl alcohol / aldehyde condensate, a furfuryl alcohol / urea / aldehyde condensate (urea-modified furan resin), urea Condensate of ethylene urea and aldehyde (urea / ethylene urea co-condensation resin), condensate of melamine and aldehyde, and one selected from the group consisting of condensate of urea and aldehyde, Those composed of a mixture of two or more selected from the group, and those composed of two or more cocondensates selected from these groups are preferred. Furfuryl alcohol, a condensate of furfuryl alcohol, and furfuryl alcohol and urea One or more selected from condensates of aldehydes, and their cocondensates are more preferred, furfuryl Alcohol is more preferred <1> to <6> kit mold formation according to any one.
<8> The content of the acid curable resin in the binder composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 25% by mass or more, and preferably 90% by mass or less. 80 mass% or less is more preferable, 60 mass% or less is more preferable, 5-90 mass% is preferable, 10-80 mass% is more preferable, 25-60 mass% is still more preferable <1>-<7> any A mold making kit according to claim 1.
<9> The mold making kit according to any one of <1> to <8>, wherein the binder composition further contains a curing accelerator.
<10> The mold making kit according to any one of <1> to <9>, wherein the curing accelerator is preferably at least one selected from the group consisting of the curing accelerator (1) and an aromatic dialdehyde.
<11> The content of the curing accelerator in the binder composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and preferably 50% by mass or less. 40% by mass or less, more preferably 30% by mass or less, and the mold making kit according to any one of <1> to <10>.
<12> The mold making kit according to any one of <1> to <11>, wherein the binder composition further contains water.
<13> The content of water in the binder composition is preferably 0% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.7% by mass or more, and preferably 30% by mass or less. 5 mass% or less is more preferable, 3.5 mass% or less is more preferable, 0-30 mass% is preferable, 0.5-5 mass% is more preferable, 0.7-3.5 mass% is still more preferable <1>-<12> The mold making kit as described in any one of.
<14> The mold making kit according to any one of <1> to <13>, wherein the binder composition further contains a silane coupling agent.
<15> The content of the silane coupling agent in the binder composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 5% by mass or less, and 4% by mass or less. Is more preferable, 0.01-5 mass% is preferable, and 0.05-4 mass% is more preferable <1>-<14> Kit for mold making in any one.
<16> The mold making kit according to any one of <1> to <15>, wherein the binder composition does not contain an aromatic hydroxy compound having no carboxyl group.
<17> The aromatic hydroxy compound is phenol, cresol, xylenol, cumylphenol, nonylphenol, butylphenol, phenylphenol, ethylphenol, octylphenol, amylphenol, naphthol, resorcin, bisphenol A, bisphenol F, bisphenol C, catechol, Preferably, at least one selected from the group consisting of hydroquinone, pyrogallol, and phloroglysin, a condensate of phenols and formaldehyde, and at least one selected from the group consisting of pyrogallol, resorcin, and a condensate of phenols and formaldehyde Any one of <1> to <16>, more preferably at least one selected from the group consisting of pyrogallol and resorcin. For mold formation kit according.
<18> The content of the aromatic hydroxy compound in the curing agent composition is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 15% by mass or more, and preferably 80% by mass or less, 60 mass% or less is more preferable, 35 mass% or less is more preferable, 1-80 mass% is preferable, 3-60 mass% is more preferable, 15-35 mass% is still more preferable <1>-<17> 2. A mold making kit according to 1.
<19> The group consisting of 2,6-dihydroxybenzoic acid, oxalic acid, maleic acid, pyruvic acid, malonic acid, 2-furancarboxylic acid, phthalic acid, fumaric acid, lactic acid, citric acid and malic acid. At least one selected from the group consisting of 2,6-dihydroxybenzoic acid, oxalic acid and maleic acid is more preferable, and 2,6-dihydroxybenzoic acid is more preferable <1>. ~ <18> The mold making kit according to any one of the above.
<20> The content of the carboxylic acid in the curing agent composition is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 10% by mass or more, preferably 80% by mass or less, and 60% by mass. % Or less is more preferable, 50 mass% or less is more preferable, 1-80 mass% is preferable, 3-60 mass% is more preferable, 10-50 mass% is still more preferable <1>-<19> Mold making kit.
<21> The mold making kit according to any one of <1> to <20>, wherein the curing agent composition further contains a solvent.
<22> The content of the solvent in the curing agent composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, preferably 90% by mass or less, and 80% by mass. The following is more preferable, 70% by mass or less is further preferable, 5 to 90% by mass is preferable, 10 to 80% by mass is more preferable, and 20 to 70% by mass is still more preferable <1> to <21>. Mold making kit.
<23> The ratio of the binder composition to the curing agent composition is preferably 20 parts by mass or more, more preferably 30 parts by mass or more with respect to 100 parts by mass of the binder composition. Preferably, 60 parts by mass or more is more preferable, 100 parts by mass or less is preferable, 90 parts by mass or less is more preferable, 80 parts by mass or less is more preferable, 20 to 100 parts by mass is preferable, and 30 to 90 parts by mass is more preferable. The mold making kit according to any one of <1> to <22>, more preferably 60 to 80 parts by mass.
<24><1>-<23> The composition for mold making containing the said binder composition and the said hardening | curing agent composition which comprise the kit for mold making in any one.
<25> A composition for a mold obtained by mixing the binder composition and the curing agent composition constituting the kit for molding a mold according to any one of <1> to <23>, and refractory particles.
<26> A method for producing a mold, comprising filling the mold composition for mold production according to <24> or <25> into a mold for mold production, and curing the mold composition.
<27> Manufacture of a mold having a mixing step of mixing a binder composition and a curing agent composition constituting the mold making kit according to any one of <1> to <23>, and refractory particles. Method.
<28> After the mixing step mixes the binder composition and the curing agent composition to produce a mold molding composition, the mold molding composition and the refractory particles are mixed; Alternatively, the step of adding and mixing the binder composition, the curing agent composition, and the refractory particles is preferable, and the step of mixing the binder composition, the curing agent composition, and the refractory particles. More preferable method for producing a mold according to <27>.
<29> The ratio of the refractory particles, the binder composition and the curing agent composition is 0.5 parts by mass or more with respect to 100 parts by mass of the refractory particles. Preferably, 3.0 parts by mass or less is preferable, 1.5 parts by mass or less is more preferable, and with respect to 100 parts by mass of the refractory particles, the curing agent composition is preferably 0.07 parts by mass or more, More than mass part is more preferable, 2.0 mass part or less is preferable, 1.0 mass part or less is more preferable, The said binder composition is 0.5-3. 0 parts by mass is preferable, 0.5 to 1.5 parts by mass is more preferable, the curing agent composition is preferably 0.07 to 2.0 parts by mass, and more preferably 0.40 to 1.0 parts by mass < The manufacturing method of the casting_mold | template as described in 27> or <28>.
<30> Use of the kit according to any one of <1> to <23> for producing a mold.
以下、本発明を具体的に示す実施例等について説明する。 Examples and the like specifically showing the present invention will be described below.
＜評価方法＞
〔粘結剤組成物のフルフリルアルコール含有量〕
ガスクロマトグラフィーにて測定を行った。（フルフリルアルコールで検量線を作成）
測定条件：
・内部標準溶液：１，６−ヘキサンジオール
・カラム：ＰＥＧ−２０Ｍ Ｃｈｒｏｍｏｓｏｒｂ ＷＡＷ ＤＭＣＳ ６０／８０ｍｅｓ・ｈ（ジーエルサイエンス社製）
・カラム温度：８０〜２００℃（８℃／ｍｉｎ）
・インジェクション温度：２１０℃
・検出器温度：２５０℃
・キャリアーガス：５０ｍＬ／ｍｉｎ（Ｈｅ）
<Evaluation method>
[Furfuryl alcohol content of the binder composition]
Measurement was performed by gas chromatography. (Create a calibration curve with furfuryl alcohol)
Measurement condition:
Internal standard solution: 1,6-hexanediol Column: PEG-20M Chromosorb WAW DMCS 60 / 80mes / h (manufactured by GL Sciences Inc.)
Column temperature: 80 to 200 ° C. (8 ° C./min)
・ Injection temperature: 210 ℃
-Detector temperature: 250 ° C
Carrier gas: 50 mL / min (He)
〔粘度〕
実施例３３の硬化剤組成物及び比較例９の粘結剤組成物それぞれについて、調製直後、及び３５℃で１ヶ月間保管後に、Ｅ型粘度計（東京計器社製）を用いて２５℃における粘度を測定した。
〔viscosity〕
About each of the curing agent composition of Example 33 and the binder composition of Comparative Example 9, immediately after preparation and after storage at 35 ° C. for 1 month, using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 25 ° C. The viscosity was measured.
＜実施例等＞
〔縮合物１の製造〕
三ツ口フラスコに３７％ホルムアルデヒド液１００質量部と、エチレン尿素を１０６質量部と、尿素を２５質量部とを混合し、１００℃で３時間反応させ、縮合物１を得た。縮合物１の組成は、尿素・エチレン尿素共縮合樹脂６６質量％、水３４質量％であった。
<Examples>
[Production of Condensate 1]
In a three-necked flask, 100 parts by mass of 37% formaldehyde solution, 106 parts by mass of ethylene urea, and 25 parts by mass of urea were mixed and reacted at 100 ° C. for 3 hours to obtain a condensate 1. The composition of the condensate 1 was 66% by mass of urea / ethylene urea cocondensation resin and 34% by mass of water.
〔縮合物２の製造〕
三ツ口フラスコにフルフリルアルコール１００質量部とパラホルムアルデヒド３５質量部と尿素１３質量部とを混合し、２５％水酸化ナトリウム水溶液でｐＨ９に調整し、１００℃に昇温後、同温度で１時間反応させた後、３７％塩酸でｐＨ４．５に調整し、更に１００℃で１時間反応させた。その後、２５％水酸化ナトリウム水溶液でｐＨ７に調整し、尿素５質量部を添加して、１００℃で３０分反応させ、反応物１を得た。未反応のフルフリルアルコールを上記分析方法で求め、未反応フルフリルアルコール除いた部分を縮合物２とした。縮合物２の組成は、尿素変性フラン樹脂８９質量％、水１１質量％であった。
[Production of condensate 2]
In a three-necked flask, 100 parts by weight of furfuryl alcohol, 35 parts by weight of paraformaldehyde and 13 parts by weight of urea are mixed, adjusted to pH 9 with a 25% aqueous sodium hydroxide solution, heated to 100 ° C., and reacted at the same temperature for 1 hour. Then, the pH was adjusted to 4.5 with 37% hydrochloric acid, and the mixture was further reacted at 100 ° C. for 1 hour. Then, it adjusted to pH 7 with 25% sodium hydroxide aqueous solution, 5 mass parts of urea was added, and it was made to react at 100 degreeC for 30 minutes, and the reaction material 1 was obtained. Unreacted furfuryl alcohol was determined by the above analysis method, and the portion excluding unreacted furfuryl alcohol was designated as condensate 2. The composition of the condensate 2 was 89 mass% urea-modified furan resin and 11 mass% water.
〔硬化剤組成物の製造〕
表１、表３に示すカルボン酸（２，６−ジヒドロキシ安息香酸、シュウ酸、マレイン酸）、芳香族ヒドロキシ化合物（レゾルシン、ピロガロール）、メタノールをそれぞれ所定の質量比率で混合し、実施例及び比較例の硬化剤組成物を製造した。
[Manufacture of curing agent composition]
Carboxylic acid (2,6-dihydroxybenzoic acid, oxalic acid, maleic acid), aromatic hydroxy compound (resorcin, pyrogallol), and methanol shown in Table 1 and Table 3 are mixed at a predetermined mass ratio, and Examples and Comparison An example curing agent composition was prepared.
〔粘結剤組成物の製造〕
表１、表３に示すＦＦＡ、ＦＬ、ＨＭＦ、添加剤（縮合物１、縮合物２、尿素）及びシランカップリング剤を所定の質量比率で混合し、実施例及び比較例の粘結剤組成物を製造した。「ＦＦＡ」はフルフリルアルコール、「ＦＬ」はフルフラール、「ＨＭＦ」は５−ヒドロキシメチルフルフラール、「シランカップリング剤」は３‐グリシドキシプロピルメチルジメトキシシランを意味する。
(Production of binder composition)
FFA, FL, HMF, additives (condensate 1, condensate 2, urea) and silane coupling agent shown in Tables 1 and 3 are mixed at a predetermined mass ratio, and binder compositions of Examples and Comparative Examples are mixed. The thing was manufactured. “FFA” means furfuryl alcohol, “FL” means furfural, “HMF” means 5-hydroxymethylfurfural, and “silane coupling agent” means 3-glycidoxypropylmethyldimethoxysilane.
〔鋳型造型用砂組成物の製造〕
２５℃、５５％ＲＨの条件下で、珪砂（フリーマントル）新砂１００質量部に対し、表１、表３に示す硬化剤組成物を添加して混合し、次いで表１、表３に示す粘結剤組成物１．０質量部を添加し、これらを混合して鋳型造型用砂組成物を得た。
[Manufacture of sand composition for mold making]
Under the conditions of 25 ° C. and 55% RH, 100 parts by mass of silica sand (free mantle) fresh sand was added and mixed with the hardener compositions shown in Tables 1 and 3, and then the viscosity shown in Tables 1 and 3 was added. 1.0 part by weight of the binder composition was added and mixed to obtain a sand composition for mold making.
＜試験例＞
混練直後の鋳型造型用砂組成物を直径５０ｍｍ、高さ５０ｍｍの円柱形状のテストピース枠に充填し、３時間経過した時に抜型を行い、充填から２４時間後に、ＪＩＳ Ｚ ２６０１に記載された方法で、圧縮強度（ＭＰａ）を測定した。「２４時間後の圧縮強度」とし、数値が高いほど鋳型強度に優れる。結果を表１〜４に示す。なお、表２は表１で表される粘結剤組成物、及び硬化剤組成物それぞれにおける配合割合を、鋳型造型用組成物中の配合割合に換算したものであり、表４は表３で表される粘結剤組成物、及び硬化剤組成物それぞれにおける配合割合を、鋳型造型用組成物中の配合割合に換算したものである。また、表５はレゾルシンを粘結剤成分として用いた場合と硬化剤成分として用いた場合の試験結果を示す。表５で表される結果から、レゾルシンを硬化剤として用いた場合には、粘度増加が起こらず、取扱いしやすいことがわかる。
<Test example>
A method described in JIS Z 2601 after filling the sand mold molding composition immediately after kneading into a cylindrical test piece frame having a diameter of 50 mm and a height of 50 mm, and removing the mold when 3 hours have passed. Then, the compressive strength (MPa) was measured. “Compressive strength after 24 hours”, the higher the value, the better the mold strength. The results are shown in Tables 1-4. Table 2 shows the compounding ratio in each of the binder composition and the curing agent composition represented in Table 1 converted to the compounding ratio in the mold making composition, and Table 4 shows in Table 3. The blending ratio in each of the binder composition and the curing agent composition represented is converted to the blending ratio in the mold making composition. Table 5 shows the test results when resorcin is used as a binder component and as a curing agent component. From the results shown in Table 5, it can be seen that when resorcin is used as a curing agent, the viscosity does not increase and it is easy to handle.
Claims (7)
前記粘結剤組成物が、フランアルデヒド化合物を含有し、
前記硬化剤組成物が、ピロガロール、及びレゾルシンからなる群より選ばれる少なくとも１種以上である芳香族ヒドロキシ化合物、及び２，６−ジヒドロキシ安息香酸、シュウ酸、及びマレイン酸からなる群より選ばれる少なくとも１種以上であるカルボン酸を含有する鋳型造型用キット。 A mold making kit for producing a mold composition, comprising a binder composition and a curing agent composition,
The binder composition contains a furanaldehyde compound,
The curing agent composition is at least one selected from the group consisting of pyrogallol and at least one aromatic hydroxy compound selected from the group consisting of resorcin, and 2,6-dihydroxybenzoic acid, oxalic acid, and maleic acid A mold making kit containing at least one carboxylic acid.
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