JP2017030009A - Binder composition for molding casting mold - Google Patents
Binder composition for molding casting mold Download PDFInfo
- Publication number
- JP2017030009A JP2017030009A JP2015151496A JP2015151496A JP2017030009A JP 2017030009 A JP2017030009 A JP 2017030009A JP 2015151496 A JP2015151496 A JP 2015151496A JP 2015151496 A JP2015151496 A JP 2015151496A JP 2017030009 A JP2017030009 A JP 2017030009A
- Authority
- JP
- Japan
- Prior art keywords
- mold
- mass
- composition
- binder composition
- preferable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 190
- 239000011230 binding agent Substances 0.000 title claims abstract description 120
- 238000000465 moulding Methods 0.000 title claims abstract description 12
- 238000005266 casting Methods 0.000 title abstract description 17
- -1 furan aldehyde compound Chemical class 0.000 claims abstract description 51
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 71
- 239000004202 carbamide Substances 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- AKEUNCKRJATALU-UHFFFAOYSA-N 2,6-dihydroxybenzoic acid Chemical compound OC(=O)C1=C(O)C=CC=C1O AKEUNCKRJATALU-UHFFFAOYSA-N 0.000 claims description 10
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 10
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 7
- 239000012965 benzophenone Substances 0.000 claims description 7
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 5
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 5
- 150000001732 carboxylic acid derivatives 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
- 238000002156 mixing Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 abstract 2
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Natural products OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 69
- 229920005989 resin Polymers 0.000 description 26
- 239000011347 resin Substances 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 150000001299 aldehydes Chemical class 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- 239000004576 sand Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229910052815 sulfur oxide Inorganic materials 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000009833 condensation Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 229920001864 tannin Polymers 0.000 description 6
- 239000001648 tannin Substances 0.000 description 6
- 235000018553 tannin Nutrition 0.000 description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007849 furan resin Substances 0.000 description 5
- 229960001755 resorcinol Drugs 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 5
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 4
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-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 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
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 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
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-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
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-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
- 238000007696 Kjeldahl method Methods 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- FFSAXUULYPJSKH-UHFFFAOYSA-N butyrophenone Chemical compound CCCC(=O)C1=CC=CC=C1 FFSAXUULYPJSKH-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229920002770 condensed tannin Polymers 0.000 description 2
- SHQSVMDWKBRBGB-UHFFFAOYSA-N cyclobutanone Chemical compound O=C1CCC1 SHQSVMDWKBRBGB-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 2
- 238000007865 diluting Methods 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
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- JPTOCTSNXXKSSN-UHFFFAOYSA-N methylheptenone Chemical compound CCCC=CC(=O)CC JPTOCTSNXXKSSN-UHFFFAOYSA-N 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 2
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 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
- XKGLSKVNOSHTAD-UHFFFAOYSA-N valerophenone Chemical compound CCCCC(=O)C1=CC=CC=C1 XKGLSKVNOSHTAD-UHFFFAOYSA-N 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 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
- CHZLVSBMXZSPNN-UHFFFAOYSA-N 2,4-dimethylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C(C)=C1 CHZLVSBMXZSPNN-UHFFFAOYSA-N 0.000 description 1
- NKRNKUWYXIABEN-UHFFFAOYSA-N 2,5-bis(ethoxymethyl)furan Chemical compound CCOCC1=CC=C(COCC)O1 NKRNKUWYXIABEN-UHFFFAOYSA-N 0.000 description 1
- DZEPFNDOOWFEKN-UHFFFAOYSA-N 2,5-bis(methoxymethyl)furan Chemical compound COCC1=CC=C(COC)O1 DZEPFNDOOWFEKN-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
- ZUAURMBNZUCEAF-UHFFFAOYSA-N 2-(2-phenoxyethoxy)ethanol Chemical compound OCCOCCOC1=CC=CC=C1 ZUAURMBNZUCEAF-UHFFFAOYSA-N 0.000 description 1
- PSZORLXATPJPGW-UHFFFAOYSA-N 2-(ethoxymethyl)-5-(methoxymethyl)furan Chemical compound CCOCC1=CC=C(COC)O1 PSZORLXATPJPGW-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
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
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- 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 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
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 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
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- PWKAMVGLPNBYPI-UHFFFAOYSA-N [5-(ethoxymethyl)furan-2-yl]methanol Chemical compound CCOCC1=CC=C(CO)O1 PWKAMVGLPNBYPI-UHFFFAOYSA-N 0.000 description 1
- JOFDQONITRMYMX-UHFFFAOYSA-N [5-(methoxymethyl)furan-2-yl]methanol Chemical compound COCC1=CC=C(CO)O1 JOFDQONITRMYMX-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- PMZXXNPJQYDFJX-UHFFFAOYSA-N acetonitrile;2,2,2-trifluoroacetic acid Chemical compound CC#N.OC(=O)C(F)(F)F PMZXXNPJQYDFJX-UHFFFAOYSA-N 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
- 229940114055 beta-resorcylic acid Drugs 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229940013361 cresol Drugs 0.000 description 1
- 238000004132 cross linking Methods 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
- 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
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 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
- 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
- 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
- MTZWHHIREPJPTG-UHFFFAOYSA-N phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 description 1
- 229930193351 phorone Natural products 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 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
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallyl group Chemical group C1(=C(C(=CC=C1)O)O)O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 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
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-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
- 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
Abstract
Description
本発明は、鋳型造型用粘結剤組成物に関する。 The present invention relates to a binder composition for mold making.
一般に、酸硬化性自硬性鋳型は、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。得られた鋳型は、機械鋳物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使用される。 In general, an acid-curable self-hardening mold is composed of a binder composition for mold making containing an acid-curable resin in refractory particles such as silica sand, and a curing agent composition containing a sulfonic acid, sulfuric acid, phosphoric acid, etc. And kneading these, the obtained kneaded sand is filled into a mold such as a wooden mold, and the acid curable resin is cured to produce. Furan resin, phenol resin, etc. are used for acid curable resin. Furan resin is furfuryl alcohol, furfuryl alcohol / urea formaldehyde resin, furfuryl alcohol / formaldehyde resin, furfuryl alcohol / phenol / formaldehyde. Resins and other known modified furan resins are used. The obtained mold is used when casting a casting such as a machine casting part, a construction machine part, or an automobile part.
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課題として、鋳型の強度を向上させることが挙げられる。また、もう一つの重要な課題として、鋳型の可撓性が挙げられる。例えば、複雑な形状の鋳型を造型した際に、鋳型の可撓性が高ければ、抜型時に鋳型の肉厚が薄い部分に応力が集中することに起因する鋳型割れを防ぐことができる。鋳型割れは、手直しすることで補えない場合、再度鋳型を製造する必要があり、生産性を大きく悪化させる要因の一つである（例えば、特許文献１）。 Improving the strength of the mold is an important issue when casting a mold or casting a desired casting using the mold. Another important issue is the flexibility of the mold. For example, when a mold having a complicated shape is formed, if the mold has high flexibility, it is possible to prevent mold cracks caused by stress concentration at a portion where the thickness of the mold is thin at the time of mold removal. Mold cracking is one of the factors that greatly deteriorates productivity because it is necessary to remanufacture the mold if it cannot be compensated by reworking (for example, Patent Document 1).
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その他の重要な項目として、鋳造時の作業環境の改善が挙げられる。酸硬化性自硬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（例えば、特許文献２）。 Moreover, improvement of the working environment at the time of casting is mentioned as another important item when casting a desired casting using a casting_mold | template or a casting_mold | template. Since acid-curable self-hardening molds use acids containing sulfur atoms such as organic sulfonic acid and sulfuric acid as curing agents, SOx such as sulfur dioxide and other pyrolysis gases such as sulfur dioxide at the time of casting have an effect on the working environment. There is a risk of worsening. Therefore, it is desired to suppress the generation of SOx (for example, Patent Document 2).
しかしながら、ＳＯｘ等の有害物質や有害ガスの発生の抑制を目的とする従来の技術では、十分な鋳型の強度及び鋳型の可撓性が得られないことがあり、鋳型の生産性が低下することがあった。 However, the conventional technology for the purpose of suppressing the generation of harmful substances and harmful gases such as SOx may not provide sufficient mold strength and mold flexibility, resulting in lower mold productivity. was there.
本発明は、ＳＯｘ等の有害物質や有害ガスの発生を抑制しながら鋳型の強度が高く、鋳型の可撓性を向上させることができる鋳型造型用粘結剤組成物を提供する。 The present invention provides a binder composition for mold making, which has high mold strength and can improve mold flexibility while suppressing generation of harmful substances such as SOx and harmful gases.
本発明の鋳型造型用粘結剤組成物は、フランアルデヒド化合物、及び下記一般式（１）で表されるケトン化合物を３〜１５質量％含有する。
Ｒ１−ＣＯ−Ｒ２ （１）
（前記一般式（１）において、Ｒ１、Ｒ２はそれぞれ炭素数１〜６の炭化水素基であり、Ｒ１とＲ２が環を形成する場合はＲ１とＲ２の炭素数の合計が３〜６の炭化水素基である。）
The binder composition for mold making of the present invention contains 3 to 15% by mass of a furanaldehyde compound and a ketone compound represented by the following general formula (1).
R 1 —CO—R 2 (1)
(In the general formula (1), R 1 and R 2 are each a hydrocarbon group having 1 to 6 carbon atoms, and when R 1 and R 2 form a ring, the total number of carbon atoms of R 1 and R 2 Is a hydrocarbon group of 3 to 6.)
本発明によれば、ＳＯｘ等の有害物質や有害ガスの発生を抑制しながら鋳型の強度が高く、鋳型の可撓性を向上させることができる鋳型造型用粘結剤組成物を提供することができる。 According to the present invention, it is possible to provide a binder composition for mold making capable of improving the flexibility of a mold while suppressing the generation of harmful substances such as SOx and harmful gases while increasing the strength of the mold. it can.
＜鋳型造型用粘結剤組成物＞
本実施形態の鋳型造型用粘結剤組成物（以下、単に粘結剤組成物ともいう）は、フランアルデヒド化合物、及び下記一般式（１）で表されるケトン化合物を３〜１５質量％含有する。
Ｒ１−ＣＯ−Ｒ２ （１）
（前記一般式（１）において、Ｒ１、Ｒ２はそれぞれ炭素数１〜６の炭化水素基であり、Ｒ１とＲ２が環を形成する場合はＲ１とＲ２の炭素数の合計が３〜６の炭化水素基である）。当該粘結剤組成物によれば、ＳＯｘ等の有害物質や有害ガスの発生を抑制しながら鋳型の強度が高く、鋳型の可撓性を向上させることができる。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。
<Binder composition for mold making>
The binder composition for mold making according to this embodiment (hereinafter also simply referred to as a binder composition) contains 3 to 15% by mass of a furanaldehyde compound and a ketone compound represented by the following general formula (1). To do.
R 1 —CO—R 2 (1)
(In the general formula (1), R 1 and R 2 are each a hydrocarbon group having 1 to 6 carbon atoms, and when R 1 and R 2 form a ring, the total number of carbon atoms of R 1 and R 2 Is a hydrocarbon group of 3-6). According to the binder composition, the strength of the mold is high while suppressing the generation of harmful substances such as SOx and harmful gas, and the flexibility of the mold can be improved. The reason for such an effect is not clear, but is considered as follows.
フランアルデヒド化合物を含有する樹脂に対し、特定構造のケトン化合物を添加すると当該ケトン化合物が可塑剤として働き、三次元網目構造中のソフトセグメントが増大するため、脆さが改善されることで、鋳型の可撓性が向上し、鋳型の強度を向上させることができると考えられる。 When a ketone compound with a specific structure is added to a resin containing a furanaldehyde compound, the ketone compound functions as a plasticizer, and soft segments in the three-dimensional network structure increase. It is considered that the flexibility of the mold can be improved and the strength of the mold can be improved.
〔フランアルデヒド化合物〕
前記粘結剤組成物は、ＳＯｘ等の有害物質や有害ガスの発生を抑制する観点、及び鋳型の強度向上の観点から、フランアルデヒド化合物を含有する。前記フランアルデヒド化合物は、フラン環を有するアルデヒドであり、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種以上が例示できる。これらの中でも、鋳型の強度向上の観点から、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種以上が好ましく、フルフラールがより好ましい。
[Furanaldehyde compound]
The binder composition contains a furanaldehyde compound from the viewpoint of suppressing the generation of harmful substances such as SOx and harmful gases, and improving the strength of the mold. The furanaldehyde compound is an aldehyde having a furan ring, and can be exemplified by at least one selected from the group consisting of furfural, 5-hydroxymethylfurfural, and 5-acetoxymethylfurfural. Among these, from the viewpoint of improving the strength of the template, at least one selected from the group consisting of furfural and 5-hydroxymethylfurfural is preferable, and furfural is more preferable.
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、鋳型の強度向上の観点から、１０質量％以上が好ましく、２０質量％以上がより好ましい。前記粘結剤組成物中のフランアルデヒド化合物の含有量は、同様の観点から、８５質量％以下が好ましく、８０質量％以下がより好ましく、７５質量％以下が更に好ましい。また、前記粘結剤組成物中のフランアルデヒド化合物の含有量は、同様の観点から、１０〜８５質量％が好ましく、２０〜８０質量％がより好ましく、２０〜７５質量％が更に好ましい。 The content of the furanaldehyde compound in the binder composition is preferably 10% by mass or more, and more preferably 20% by mass or more from the viewpoint of improving the strength of the mold. From the same viewpoint, the content of the furanaldehyde compound in the binder composition is preferably 85% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less. Moreover, 10-85 mass% is preferable from the same viewpoint, as for content of the furanaldehyde compound in the said binder composition, 20-80 mass% is more preferable, and 20-75 mass% is still more preferable.
〔ケトン化合物〕
前記粘結剤組成物は、鋳型の強度向上の観点、及び鋳型の可撓性向上の観点から、前記一般式（１）で表されるケトン化合物を含有する。前記一般式（１）において、Ｒ１、Ｒ２がそれぞれ炭化水素基である場合、Ｒ１、Ｒ２の炭素数は、鋳型の強度向上の観点、及び鋳型の可撓性向上の観点から、それぞれ１以上が好ましく、２以上がより好ましく、３以上が更に好ましい。Ｒ１、Ｒ２がそれぞれ炭化水素基である場合、Ｒ１、Ｒ２の炭素数は、同様の観点から、それぞれ６以下が好ましい。また、Ｒ１、Ｒ２がそれぞれ炭化水素基である場合、Ｒ１、Ｒ２の炭素数は、同様の観点から、それぞれ１〜６が好ましく、２〜６がより好ましく、３〜６が更に好ましい。
[Ketone compound]
The binder composition contains a ketone compound represented by the general formula (1) from the viewpoint of improving the strength of the mold and improving the flexibility of the mold. In the general formula (1), when R 1 and R 2 are each a hydrocarbon group, the number of carbon atoms of R 1 and R 2 is from the viewpoint of improving the strength of the mold and from the viewpoint of improving the flexibility of the mold. Each is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. When R 1 and R 2 are each a hydrocarbon group, the number of carbon atoms of R 1 and R 2 is preferably 6 or less from the same viewpoint. Further, when R 1, R 2 are each a hydrocarbon group, R 1, the number of carbon atoms of R 2, from the same viewpoint, 1-6 each preferably, more preferably 2 to 6, 3 to 6 further preferable.
前記一般式（１）において、Ｒ１とＲ２が環を形成する場合、Ｒ１とＲ２の炭素数の合計は、鋳型の強度向上の観点、及び鋳型の可撓性向上の観点から、３以上が好ましく、４以上がより好ましく、５以上が更に好ましい。Ｒ１とＲ２が環を形成する場合、Ｒ１とＲ２の炭素数の合計は、同様の観点から、６以下が好ましい。また、Ｒ１とＲ２が環を形成する場合、Ｒ１とＲ２の炭素数の合計は、同様の観点から、３〜６が好ましく、４〜６がより好ましく、５又は６が更に好ましい。 In the general formula (1), when R 1 and R 2 form a ring, the total number of carbon atoms of R 1 and R 2 is from the viewpoint of improving the strength of the mold and from the viewpoint of improving the flexibility of the mold. 3 or more are preferable, 4 or more are more preferable, and 5 or more are still more preferable. When R 1 and R 2 form a ring, the total number of carbon atoms of R 1 and R 2 is preferably 6 or less from the same viewpoint. Further, when R 1 and R 2 form a ring, the total number of carbon atoms of R 1 and R 2, from the same viewpoint, 3-6, more preferably 4-6, more preferably 5 or 6 .
前記ケトン化合物は、鋳型の強度向上の観点、及び鋳型の可撓性向上の観点から、アセトン、メチルエチルケトン、メチルプロピルケトン、イソプロピルメチルケトン、ブチルメチルケトン、イソブチルメチルケトン、ピナコロン、ジエチルケトン、ジプロピルケトン、ジイソプロピルケトン、メシチルオキシド、メチルヘプテノン、シクロブタノン、シクロペンタノン、シクロヘキサノン、ホロン、イソホロン、アセトフェノン、プロピオフェノン、ブチロフェノン、バレロフェノン、及びベンゾフェノン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、アセトフェノン、ベンゾフェノン、及びシクロヘキサノ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く、ベンゾフェノンが更に好ましい。 The ketone compound is acetone, methyl ethyl ketone, methyl propyl ketone, isopropyl methyl ketone, butyl methyl ketone, isobutyl methyl ketone, pinacolone, diethyl ketone, dipropyl from the viewpoint of improving the strength of the template and the flexibility of the template. Preferably, at least one selected from the group consisting of ketone, diisopropyl ketone, mesityl oxide, methyl heptenone, cyclobutanone, cyclopentanone, cyclohexanone, phorone, isophorone, acetophenone, propiophenone, butyrophenone, valerophenone, and benzophenone, acetophenone, At least one selected from the group consisting of benzophenone and cyclohexanone is more preferable, and benzophenone is still more preferable.
前記粘結剤組成物中の前記ケトン化合物の含有量は、鋳型の強度向上の観点、及び鋳型の可撓性向上の観点から、３質量％以上が好ましく、４質量％以上がより好ましく、５質量％以上が更に好ましい。前記粘結剤組成物中の前記ケトン化合物の含有量は、同様の観点から、１５質量％以下が好ましく、１２質量％以下がより好ましく、１０質量％以下が更に好ましい。また、前記粘結剤組成物中の前記ケトン化合物の含有量は、同様の観点から、３〜１５質量％が好ましく、４〜１２質量％がより好ましく、５〜１０質量％が更に好ましい。 The content of the ketone compound in the binder composition is preferably 3% by mass or more, more preferably 4% by mass or more, from the viewpoint of improving the strength of the mold and the flexibility of the mold. More preferably, it is more than mass%. From the same viewpoint, the content of the ketone compound in the binder composition is preferably 15% by mass or less, more preferably 12% by mass or less, and still more preferably 10% by mass or less. Moreover, 3-15 mass% is preferable from the same viewpoint, as for content of the said ketone compound in the said binder composition, 4-12 mass% is more preferable, and 5-10 mass% is still more preferable.
前記粘結剤組成物中における、前記フランアルデヒド化合物の含有量に対する前記ケトン化合物の含有量の比（フランアルデヒド化合物の含有量／ケトン化合物の含有量）は、鋳型の強度向上の観点、及び鋳型の可撓性向上の観点から、３以上が好ましく、５以上がより好ましく、７以上が更に好ましい。前記粘結剤組成物中における、前記フランアルデヒド化合物の含有量に対する前記ケトン化合物の含有量の比は、同様の観点から、３０以下が好ましく、２３以下がより好ましく、１４以下が更に好ましい。また、前記粘結剤組成物中における、前記フランアルデヒド化合物の含有量に対する前記ケトン化合物の含有量の比は、同様の観点から、３〜３０が好ましく、５〜２３がより好ましく、７〜１４が更に好ましい。 The ratio of the content of the ketone compound to the content of the furanaldehyde compound in the binder composition (the content of the furanaldehyde compound / the content of the ketone compound) depends on the viewpoint of improving the strength of the template and the template. From the viewpoint of improving flexibility, 3 or more is preferable, 5 or more is more preferable, and 7 or more is more preferable. From the same viewpoint, the ratio of the content of the ketone compound to the content of the furanaldehyde compound in the binder composition is preferably 30 or less, more preferably 23 or less, and still more preferably 14 or less. Moreover, from the same viewpoint, the ratio of the content of the ketone compound to the content of the furanaldehyde compound in the binder composition is preferably 3-30, more preferably 5-23, and 7-14. Is more preferable.
〔その他の成分〕
［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、鋳型の強度向上の観点、及び鋳型の可撓性向上の観点から、フルフリルアルコール、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）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。
[Other ingredients]
[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 strength of the mold and improving the flexibility of the mold, one or more selected from furfuryl alcohol, a condensate of urea, ethylene urea and aldehyde (urea / ethylene urea co-condensation resin) As well as these cocondensates, it is preferred to use. 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.
前記アルデヒド類としては、ホルムアルデヒド、アセトアルデヒド、グリオキザール、フルフラール、テレフタルアルデヒド等が挙げられ、これらのうち１種以上を適宜使用できる。鋳型の強度向上の観点からは、ホルムアルデヒドが好ましい。 Examples of the aldehydes include formaldehyde, acetaldehyde, glyoxal, furfural, terephthalaldehyde, and the like, and one or more of these can be used as appropriate. Formaldehyde is preferable from the viewpoint of improving the strength of the mold.
前記粘結剤組成物中の前記酸硬化性樹脂の含有量は、鋳型の強度向上の観点、及び鋳型の可撓性向上の観点から、１質量％以上が好ましく、１０質量％以上がより好ましく、１５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、６０質量％以下がより好ましく、３０質量％以下が更に好ましい。また、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、１〜９０質量％が好ましく、１０〜６０質量％がより好ましく、１５〜３０質量％が更に好ましい。 The content of the acid curable resin in the binder composition is preferably 1% by mass or more, more preferably 10% by mass or more from the viewpoint of improving the strength of the mold and improving the flexibility of the mold. 15% by mass or more is more preferable. From the same viewpoint, the content of the acid curable resin in the binder composition is preferably 90% by mass or less, more preferably 60% by mass or less, and still more preferably 30% by mass or less. Moreover, 1-90 mass% is preferable from the same viewpoint, as for content of the said acid curable resin in the said binder composition, 10-60 mass% is more preferable, 15-30 mass% is still more preferable. .
〔尿素〕
前記粘結剤組成物は、鋳型の強度向上の観点、及び鋳型の可撓性向上の観点から、尿素を含んでもよい。
〔urea〕
The binder composition may contain urea from the viewpoint of improving the strength of the mold and the flexibility of the mold.
前記尿素とは、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。前記粘結剤組成物中の前記尿素の含有量は、鋳型の強度向上の観点、及び鋳型の可撓性向上の観点から、０．５質量％以上が好ましく、１．０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前記尿素の含有量は、硬化速度を向上させ、鋳型の強度を向上させ、ホルムアルデヒド濃度を低減させる観点から、１０質量％以下が好ましく、６．０質量％以下がより好ましく４．５質量％以下が更に好ましい。 The urea is urea that has not undergone a condensation reaction with formaldehyde, furfuryl alcohol, or the like, and may remain as an unreacted component or may be added separately. The content of the urea in the binder composition is preferably 0.5% by mass or more, more preferably 1.0% by mass or more from the viewpoint of improving the strength of the mold and improving the flexibility of the mold. Preferably, 1.5 mass% or more is more preferable. The content of the urea in the binder composition is preferably 10% by mass or less, and preferably 6.0% by mass or less from the viewpoint of improving the curing rate, improving the strength of the mold, and reducing the formaldehyde concentration. More preferred is 4.5% by mass or less.
なお、粘結剤組成物中の尿素は、以下のようなＬＣ／ＭＳ分析操作により測定することができる。サンプルの調製は、アセトン／水＝５０／５０の混合溶液で１００倍希釈し、さらに移動相で１００倍希釈する。
＜ＬＣ／ＭＳ分析条件＞
カラム：Ｕｎｉｓｏｎ ＵＫ−Ａｍｉｎｏ ＨＴ
移動相：０．１％ ＴＦＡ アセトニトリル／水＝９５／５
流量：０．２ｍＬ／ｍｉｎ
カラム温度：４０℃
ＭＳ：ＳＩＭ ｍ／ｚ：６１．０ ［Ｍ＋Ｈ］＋
Urea in the binder composition can be measured by the following LC / MS analysis operation. The sample is prepared by diluting 100 times with a mixed solution of acetone / water = 50/50 and further diluting 100 times with a mobile phase.
<LC / MS analysis conditions>
Column: Unison UK-Amino HT
Mobile phase: 0.1% TFA acetonitrile / water = 95/5
Flow rate: 0.2mL / min
Column temperature: 40 ° C
MS: SIM m / z: 61.0 [M + H] +
アミノ基を有する化合物（例えば尿素など）から得られる粘結剤組成物では、当該アミノ基が樹脂成分と架橋結合を形成すると考えられ、得られる鋳型の可撓性に好ましい影響を与えることが推測される。アミノ基の含有量は窒素含有量（質量％）で見積もることが出来る。鋳型の強度向上の観点、及び鋳型の可撓性向上の観点から、前記粘結剤組成物中の窒素含有量は、０．５質量％以上が好ましく、１．０質量％以上がより好ましく、１．５質量％以上が更に好ましく、１．８質量％以上がより更に好ましい。また、前記粘結剤組成物中の窒素含有量は、同様の観点から、４．０質量％以下が好ましく、３．８質量％以下がより好ましく、３．７質量％以下が更に好ましく、３．６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窒素含有量は、同様の観点から、０．５〜４．０質量％が好ましく、１．０〜３．８質量％がより好ましく、１．５〜３．７質量％が更に好ましく、１．８〜３．６質量％がより更に好ましい。前記粘結剤組成物中の窒素含有量を前記範囲内に調整するには、前記粘結剤組成物中の窒素含有化合物の含有量を調整すればよい。窒素含有化合物としては、尿素、メラミン、尿素とアルデヒド類の縮合物、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、尿素樹脂及び尿素変性樹脂等が好ましい。前記粘結剤組成物中の窒素含有量は、ケルダール法により定量することが出来る。更には、尿素、尿素樹脂、フルフリルアルコール・尿素樹脂（尿素変性樹脂）、及びフルフリルアルコール・尿素ホルムアルデヒド樹脂由来の窒素含有量は、尿素由来のカルボニル基（Ｃ＝Ｏ基）を１３Ｃ−ＮＭＲで定量することで求めることも出来る。 In a binder composition obtained from a compound having an amino group (for example, urea, etc.), it is considered that the amino group forms a cross-linking bond with the resin component and has a favorable influence on the flexibility of the obtained template. Is done. The amino group content can be estimated by the nitrogen content (% by mass). From the viewpoint of improving the strength of the mold and the viewpoint of improving the flexibility of the mold, the nitrogen content in the binder composition is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, 1.5 mass% or more is still more preferable, and 1.8 mass% or more is still more preferable. In addition, the nitrogen content in the binder composition is preferably 4.0% by mass or less, more preferably 3.8% by mass or less, still more preferably 3.7% by mass or less, from the same viewpoint. More preferably, it is 6 mass% or less. Moreover, from the same viewpoint, the nitrogen content in the binder composition is preferably 0.5 to 4.0% by mass, more preferably 1.0 to 3.8% by mass, and 1.5 to 3%. 0.7 mass% is still more preferable, and 1.8-3.6 mass% is still more preferable. In order to adjust the nitrogen content in the binder composition within the above range, the content of the nitrogen-containing compound in the binder composition may be adjusted. Nitrogen-containing compounds include urea, melamine, condensate of urea and aldehydes, condensate of urea, ethylene urea and aldehydes (urea / ethylene urea co-condensation resin), condensate of melamine and aldehydes, urea resin and urea A modified resin or the like is preferable. The nitrogen content in the binder composition can be quantified by the Kjeldahl method. Furthermore, nitrogen content derived from urea, urea resin, furfuryl alcohol / urea resin (urea modified resin), and furfuryl alcohol / urea formaldehyde resin is 13C-NMR for carbonyl group (C═O group) derived from urea. It can also be determined by quantifying with.
〔硬化促進剤〕
前記粘結剤組成物中には、鋳型の硬化速度向上の観点から、硬化促進剤が含まれていてもよい。硬化促進剤としては、鋳型の硬化速度向上の観点、及び鋳型の強度向上の観点から、下記一般式（２）で表される化合物（以下、硬化促進剤（１）という）、フェノール誘導体、芳香族ジアルデヒド、及びタンニン類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 curing rate of the mold. Examples of the curing accelerator include a compound represented by the following general formula (2) (hereinafter referred to as a curing accelerator (1)), a phenol derivative, and a fragrance from the viewpoint of improving the mold curing rate and the mold strength. One or more selected from the group consisting of group dialdehydes and tannins is preferred.
前記粘結剤組成物中の前記硬化促進剤の含有量は、鋳型の硬化速度向上の観点から、０．５質量％以上であることが好ましく、１質量％以上であることがより好ましく、２質量％以上であることが更に好ましい。前記粘結剤組成物中の前記硬化促進剤の含有量は、硬化促進剤の粘結剤組成物への溶解性の観点から、５０質量％以下であることが好ましく、４０質量％以下であることがより好ましく、３０質量％以下であることが更に好ましい。 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, from the viewpoint of improving the curing rate of the mold. More preferably, it is at least mass%. From the viewpoint of solubility of the curing accelerator in the binder composition, the content of the curing accelerator in the binder composition is preferably 50% by mass or less, and 40% by mass or less. It is more preferable, and it is still more preferable that it is 30 mass% or less.
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、鋳型の硬化速度向上の観点から、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 curing rate of the mold.
前記フェノール誘導体としては、例えばレゾルシン、クレゾール、ヒドロキノン、フロログルシノール、メチレンビスフェノール等が挙げられる。なかでも、鋳型の硬化速度向上の観点から、レゾルシンが好ましい。前記粘結剤組成物中の前記フェノール誘導体の含有量は、フェノール誘導体の粘結剤組成物への溶解性の観点、鋳型の硬化速度向上の観点から、１〜２５質量％が好ましく、２〜１５質量％がより好ましく、３〜１０質量％が更に好ましい。なかでも、レゾルシンを用いる場合は、前記粘結剤組成物中のレゾルシンの含有量は、レゾルシンの粘結剤組成物への溶解性の観点から、１〜１０質量％が好ましく、２〜７質量％がより好ましく、３〜６質量％が更に好ましい。 Examples of the phenol derivative include resorcin, cresol, hydroquinone, phloroglucinol, and methylene bisphenol. Of these, resorcin is preferable from the viewpoint of improving the curing rate of the mold. The content of the phenol derivative in the binder composition is preferably 1 to 25% by mass from the viewpoint of solubility of the phenol derivative in the binder composition and from the viewpoint of improving the curing rate of the mold. 15 mass% is more preferable, and 3-10 mass% is still more preferable. Among these, when resorcin is used, the content of resorcin in the binder composition is preferably 1 to 10% by mass, preferably 2 to 7% by mass from the viewpoint of the solubility of resorcin in the binder composition. % Is more preferable, and 3-6 mass% is still more preferable.
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。鋳型の硬化速度向上の観点から、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。前記粘結剤組成物中の芳香族ジアルデヒドの含有量は、芳香族ジアルデヒドを粘結剤組成物に十分に溶解させる観点、及び芳香族ジアルデヒド自体の臭気を抑制する観点から、０．１〜１５質量％が好ましく、０．５〜１０質量％がより好ましく、１〜５質量％が更に好ましい。 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 curing rate, terephthalaldehyde and terephthalaldehyde derivatives are preferred, and terephthalaldehyde is more preferred. The content of the aromatic dialdehyde in the binder composition is from the viewpoint of sufficiently dissolving the aromatic dialdehyde in the binder composition and from the viewpoint of suppressing the odor of the aromatic dialdehyde itself. 1-15 mass% is preferable, 0.5-10 mass% is more preferable, 1-5 mass% is still more preferable.
タンニン類としては、縮合タンニンや加水分解型タンニンが挙げられる。これら縮合タンニンや加水分解型タンニンの例としては、ピロガロール骨格やレゾルシン骨格を持つタンニンが挙げられる。また、これらタンニン類を含有する樹皮抽出物や植物由来の葉、実、種、植物に寄生した虫こぶ等の天然物からの抽出物を添加しても構わない。 Examples of tannins include condensed tannins and hydrolyzed tannins. Examples of these condensed tannins and hydrolyzed tannins include tannins having a pyrogallol skeleton and a resorcin skeleton. Moreover, you may add the extract from natural products, such as a leaf bark extract containing these tannins, and a leaf derived from a plant, a fruit, a seed | species, and a worm hump parasitic on a plant.
〔水〕
前記粘結剤組成物中には、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。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、前記粘結剤組成物の水の含有量は０．５質量％以上が好ましく、１質量％以上がより好ましく、３質量％以上が更に好ましい。ただし、硬化反応速度を維持する観点から、前記粘結剤組成物の水の含有量は３０質量％以下が好ましく、２５質量％以下がより好ましい。また、前記粘結剤組成物の水の含有量は、前記粘結剤組成物を取扱いやすい粘度に調整する観点、及び硬化反応速度を維持する観点から、０．５〜３０質量％が好ましく、１〜２５質量％がより好ましく、３〜２５質量％が更に好ましい。
〔water〕
The binder composition may 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. Moreover, water may be further added for the purpose of adjusting the binder composition to a viscosity that is easy to handle. When water is further added for the purpose of adjusting the binder composition to an easy-to-handle viscosity, the water content of the binder composition is preferably 0.5% by mass or more, more preferably 1% by mass or more. 3 mass% or more is still more preferable. However, from the viewpoint of maintaining the curing reaction rate, the water content of the binder composition is preferably 30% by mass or less, and more preferably 25% by mass or less. The water content of the binder composition is preferably 0.5 to 30% by mass from the viewpoint of adjusting the binder composition to a viscosity that is easy to handle and maintaining the curing reaction rate. 1-25 mass% is more preferable, and 3-25 mass% is still more preferable.
前記粘結剤組成物中には、シランカップリング剤が含まれていてもよい。例えば、前記粘結剤組成物中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、３−アミノプロピルトリエ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メチルジメトキシシラン、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る。アミノシランの中でも、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が好ましい。エポキシシランの中でも、３−グリシドキシプロピルメチルジメトキシシランが好ましい。シランカップリング剤の前記粘結剤組成物中の含有量は、鋳型の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。シランカップリング剤の前記粘結剤組成物中の含有量は、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。 A silane coupling agent may be contained in the binder composition. For example, it is preferable that the binder composition contains a silane coupling agent because the 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-aminopropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Epoxy silanes such as glycidoxypropylmethyldiethoxysilane and 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 aminosilane and epoxysilane. Among aminosilanes, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane is preferable. Of the epoxy silanes, 3-glycidoxypropylmethyldimethoxysilane is preferred. 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 strength of the mold. 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.
＜鋳型造型用組成物＞
本実施形態の鋳型造型用組成物は、前記鋳型造型用粘結剤組成物、及び当該鋳型造型用粘結剤組成物を硬化させる硬化剤組成物を含有する。
<Mold molding composition>
The mold making composition of the present embodiment contains the mold making binder composition and a curing agent composition for curing the mold making binder composition.
前記硬化剤組成物は、前記粘結剤組成物を硬化させるものである。当該硬化剤組成物としては、ｏ−ヒドロキシ安息香酸、ｍ−ヒドロキシ安息香酸、ｐ−ヒドロキシ安息香酸、２，４−ジヒドロキシ安息香酸、２，６−ジヒドロキシ安息香酸、３，５−ジヒドロキシ安息香酸等のカルボン酸、キシレンスルホン酸（特に、ｍ−キシレンスルホン酸）やトルエンスルホン酸（特に、ｐ−トルエンスルホン酸）、メタンスルホン酸等のスルホン酸系化合物、リン酸、酸性リン酸エステル等のリン酸系化合物、硫酸等を含む酸性水溶液など、従来公知のものを１種以上使用できる。ただし、スルホン酸や硫酸などの硫黄を含む酸を含有する硬化剤組成物を使用した場合、鋳造時にＳＯｘガスが発生するため、硬化剤組成物中の硫黄を含む酸の含有量は、６０質量％以下が好ましく、３０質量％以下がより好ましく、１０質量％以下が更に好ましく、１質量％以下がより更に好ましく、実質的に０％がより更に好ましい。係る場合、鋳造時のＳＯｘガスの発生量をゼロにすることができる。ＳＯｘガスを抑制しながら鋳型の強度向上の観点から、前記硬化剤組成物はカルボン酸が好ましく、当該カルボン酸の中でも２，６−ジヒドロキシ安息香酸が好ましい。 The said hardening | curing agent composition hardens the said binder composition. Examples of the curing agent composition include o-hydroxybenzoic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid and the like. Carboxylic acids, xylene sulfonic acid (especially m-xylene sulfonic acid), toluene sulfonic acid (especially p-toluene sulfonic acid), sulfonic acid compounds such as methane sulfonic acid, phosphorus such as phosphoric acid and acidic phosphate One or more conventionally known compounds such as acidic aqueous solutions containing acidic compounds and sulfuric acid can be used. However, when a curing agent composition containing an acid containing sulfur such as sulfonic acid or sulfuric acid is used, SOx gas is generated during casting. Therefore, the content of the acid containing sulfur in the curing agent composition is 60 mass. % Or less, more preferably 30% by mass or less, still more preferably 10% by mass or less, still more preferably 1% by mass or less, and still more preferably 0%. In such a case, the amount of SOx gas generated during casting can be reduced to zero. From the viewpoint of improving the strength of the mold while suppressing SOx gas, the curing agent composition is preferably a carboxylic acid, and among these carboxylic acids, 2,6-dihydroxybenzoic acid is preferable.
前記硬化剤組成物は、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、鋳型の強度向上の観点から、アルコール類、エーテルアルコール類が好ましく、エーテルアルコール類がより好ましい。前記溶剤を含有させると、前記硬化剤組成物中の水分量が低減されるため、鋳型の強度が更に向上する。前記溶剤の硬化剤組成物中の含有量は、鋳型の強度向上の観点から、５〜８０質量％が好ましく、１０〜７０質量％がより好ましい。また、前記硬化剤組成物の粘度を低減させる観点からは、メタノールやエタノールを含有させることが好ましい。 The curing agent composition may contain one or more solvents selected from the group consisting of alcohols, ether alcohols, and esters. Among these, from the viewpoint of improving the strength of the template, alcohols and ether alcohols are preferable, and ether alcohols are more preferable. When the solvent is contained, the amount of water in the curing agent composition is reduced, so that the strength of the mold is further improved. 5-80 mass% is preferable from a viewpoint of the intensity | strength improvement of a casting_mold | template, and, as for content in the hardening | curing agent composition of the said solvent, 10-70 mass% is more preferable. Moreover, it is preferable to contain methanol and ethanol from a viewpoint of reducing the viscosity of the said hardening | curing agent composition.
鋳型の強度向上の観点から、前記アルコール類としては、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、前記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、前記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 the strength of the mold, the alcohols are preferably propanol, butanol, pentanol, hexanol, heptanol, octanol, benzyl alcohol, and the ether alcohols include ethylene glycol monoethyl ether, ethylene glycol monobutyl 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 the esters include butyl acetate, butyl benzoate, ethylene glycol monobutyl ether Acetate, diethylene glycol monobutyl ether Seteto is preferable.
更に、前記粘結剤組成物と前記硬化剤組成物の質量比は、鋳型の硬化速度向上の観点及び鋳型の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、前記硬化剤組成物２０質量部以上が好ましく、３０質量部以上がより好ましい。前記粘結剤組成物と前記硬化剤組成物の質量比は、経済性の観点及び鋳物品質向上の観点から、前記粘結剤組成物１００質量部に対して、前記硬化剤組成物１００質量部以下が好ましく、９０質量部以下がより好ましい。 Furthermore, the mass ratio of the binder composition to the curing agent composition is such that the curing with respect to 100 parts by mass of the binder composition from the viewpoint of improving the curing rate of the mold and the strength of the mold. The agent composition is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more. The mass ratio of the binder composition to the curing agent composition is 100 parts by mass of the curing agent composition with respect to 100 parts by mass of the binder composition from the viewpoints of economy and improved casting quality. The following is preferable, and 90 parts by mass or less is more preferable.
＜鋳型用組成物＞
本実施形態の鋳型用組成物は、前記鋳型造型用粘結剤組成物、前記硬化剤組成物、及び耐火性粒子を含有する。
<Composition for mold>
The mold composition of the present embodiment contains the mold-forming binder composition, the curing agent composition, and refractory particles.
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。 As the refractory particles, conventionally known ones such as silica sand, chromite sand, zircon sand, olivine sand, alumina sand, mullite sand, synthetic mullite sand, etc. can be used. Recycled ones can also be used.
前記鋳型用組成物において、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適宜設定できるが、鋳型の硬化速度向上の観点及び鋳型の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、１．５質量部以下が好ましい。鋳型の硬化速度向上の観点及び鋳型の強度向上の観点から、前記耐火性粒子１００質量部に対して、前記硬化剤組成物は０．０７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、１．０質量部以下が好ましい。 In the mold composition, the ratio of the refractory particles, the binder composition, and the curing agent composition can be appropriately set, but from the viewpoint of improving the mold curing speed and the 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, and from the viewpoint of economic efficiency and improvement in casting quality, 1 part of the refractory particles is 1 part. .5 parts by mass or less is preferable. From the viewpoint of improving the curing rate of the mold and the strength of the mold, the curing agent composition is preferably 0.07 parts by mass or more with respect to 100 parts by mass of the refractory particles. In view of the above, 1.0 part by mass or less is preferable with respect to 100 parts by mass of the refractory particles.
前記鋳型用組成物を硬化させることによって鋳型を製造することができる。本実施形態の鋳型の製造方法において、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、前記耐火性粒子と前記鋳型造型用粘結剤組成物と、前記硬化剤組成物とを混合して前記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。 A mold can be produced by curing the mold composition. In the mold manufacturing method of the present embodiment, the mold can be manufactured using the conventional mold manufacturing process as it is. As a preferred method for producing a mold, a mixing step of obtaining the mold composition by mixing the refractory particles, the mold forming binder composition, and the curing agent composition, and the mold composition, Examples of the method for producing a mold include a curing step of filling a mold and curing the mold composition.
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＞フランアルデヒド化合物、及び下記一般式（１）で表されるケトン化合物を３〜１５質量％含有する鋳型造型用粘結剤組成物。
Ｒ１−ＣＯ−Ｒ２ （１）
（前記一般式（１）において、Ｒ１、Ｒ２はそれぞれ炭素数１〜６の炭化水素基であり、Ｒ１とＲ２が環を形成する場合はＲ１とＲ２の炭素数の合計が３〜６の炭化水素基である。）
＜２＞前記フランアルデヒド化合物が、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粘結剤組成物。
＜３＞前記鋳型造型用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が、１０質量％以上が好ましく、２０質量％以上がより好ましく、８５質量％以下が好ましく、８０質量％以下がより好ましく、７５質量％以下が更に好ましく、１０〜８５質量％が好ましく、２０〜８０質量％がより好ましく、２０〜７５質量％が更に好ましい＜１＞又は＜２＞に記載の鋳型造型用粘結剤組成物。
＜４＞前記一般式（１）において、Ｒ１、Ｒ２がそれぞれ炭化水素基である場合、Ｒ１、Ｒ２の炭素数が、それぞれ１以上が好ましく、２以上がより好ましく、３以上が更に好ましく、６以下が好ましく、１〜６が好ましく、２〜６がより好ましく、３〜６が更に好ましい＜１＞〜＜３＞いずれかに記載の鋳型造型用粘結剤組成物。
＜５＞前記一般式（１）において、Ｒ１とＲ２が環を形成する場合、Ｒ１とＲ２の炭素数の合計が、３以上が好ましく、４以上がより好ましく、５以上が更に好ましく、６以下が好ましく、３〜６が好ましく、４〜６がより好ましく、５又は６が更に好ましい＜１＞〜＜４＞いずれかに記載の鋳型造型用粘結剤組成物。
＜６＞前記ケトン化合物が、アセトン、メチルエチルケトン、メチルプロピルケトン、イソプロピルメチルケトン、ブチルメチルケトン、イソブチルメチルケトン、ピナコロン、ジエチルケトン、ジプロピルケトン、ジイソプロピルケトン、メシチルオキシド、メチルヘプテノン、シクロブタノン、シクロペンタノン、シクロヘキサノン、ホロン、イソホロン、アセトフェノン、プロピオフェノン、ブチロフェノン、バレロフェノン、及びベンゾフェノン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、アセトフェノン、ベンゾフェノン、及びシクロヘキサノ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く、ベンゾフェノンが更に好ましい＜１＞〜＜５＞いずれかに記載の鋳型造型用粘結剤組成物。
＜７＞前記鋳型造型用粘結剤組成物中の前記ケトン化合物の含有量が、３質量％以上が好ましく、４質量％以上がより好ましく、５質量％以上が更に好ましく、１５質量％以下が好ましく、１２質量％以下がより好ましく、１０質量％以下が更に好ましく、３〜１５質量％が好ましく、４〜１２質量％がより好ましく、５〜１０質量％が更に好ましい＜１＞〜＜６＞いずれかに記載の鋳型造型用粘結剤組成物。
＜８＞前記鋳型造型用粘結剤組成物中における、前記フランアルデヒド化合物の含有量に対する前記ケトン化合物の含有量の比（フランアルデヒド化合物の含有量／ケトン化合物の含有量）が、３以上が好ましく、５以上がより好ましく、７以上が更に好ましく、３０以下が好ましく、２３以下がより好ましく、１４以下が更に好ましく、３〜３０が好ましく、５〜２３がより好ましく、７〜１４が更に好ましい＜１＞〜＜７＞いずれかに記載の鋳型造型用粘結剤組成物。
＜９＞更に、酸硬化性樹脂を含むのが好ましい＜１＞〜＜８＞いずれかに記載の鋳型造型用粘結剤組成物。
＜１０＞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からなる群、並びに当該群から選ばれる２種以上の共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、フルフリルアルコール、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）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＜９＞に記載の鋳型造型用粘結剤組成物。
＜１１＞前記鋳型造型用粘結剤組成物中の前記酸硬化性樹脂の含有量が、１質量％以上が好ましく、１０質量％以上がより好ましく、１５質量％以上が更に好ましく、９０質量％以下が好ましく、６０質量％以下がより好ましく、３０質量％以下が更に好ましく、１〜９０質量％が好ましく、１０〜６０質量％がより好ましく、１５〜３０質量％がより好ましい＜９＞又は＜１０＞に記載の鋳型造型用粘結剤組成物。
＜１２＞更に、尿素を含むのが好ましい＜１＞〜＜１１＞いずれかに記載の鋳型造型用粘結剤組成物。
＜１３＞前記鋳型造型用粘結剤組成物中の前記尿素の含有量が、０．５質量％以上が好ましく、１．０質量％以上がより好ましく、１．５質量％以上が更に好ましく、１０質量％以下が好ましく、６．０質量％以下がより好ましく４．５質量％以下が更に好ましい＜１２＞に記載の鋳型造型用粘結剤組成物。
＜１４＞前記鋳型造型用粘結剤組成物中の窒素含有量が、０．５質量％以上が好ましく、１．０質量％以上がより好ましく、１．５質量％以上が更に好ましく、１．８質量％以上がより更に好ましく、４．０質量％以下が好ましく、３．８質量％以下がより好ましく、３．７質量％以下が更に好ましく、３．６質量％以下がより更に好ましく、０．５〜４．０質量％が好ましく、１．０〜３．８質量％がより好ましく、１．５〜３．７質量％が更に好ましく、１．８〜３．６質量％がより更に好ましい＜１＞〜＜１３＞いずれかに記載の鋳型造型用粘結剤組成物。
＜１５＞更に、シランカップリング剤を含むのが好ましい＜１＞〜＜１４＞いずれかに記載の鋳型造型用粘結剤組成物。
＜１６＞前記シランカップリング剤の前記鋳型造型用粘結剤組成物中の含有量が、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％以下がより好ましい＜１＞〜＜１５＞いずれかに記載の鋳型造型用粘結剤組成物。
＜１７＞＜１＞〜＜１６＞いずれかに記載の鋳型造型用粘結剤組成物、及び前記鋳型造型用粘結剤組成物を硬化させる硬化剤組成物を含有する鋳型造型用組成物。
＜１８＞前記硬化剤組成物中の硫黄を含む酸の含有量が、６０質量％以下が好ましく、３０質量％以下がより好ましく、１０質量％以下が更に好ましく、１質量％以下がより更に好ましく、実質的に０％がより更に好ましい＜１７＞に記載の鋳型造型用組成物。
＜１９＞前記硬化剤組成物が、カルボン酸が好ましい＜１７＞又は＜１８＞に記載の鋳型造型用組成物。
＜２０＞前記硬化剤組成物が、２，６−ジヒドロキシ安息香酸が好ましい＜１７＞〜＜１９＞いずれかに記載の鋳型造型用組成物。
＜２１＞前記鋳型造型用粘結剤組成物と前記硬化剤組成物の質量比が、前記粘結剤組成物１００質量部に対して、前記硬化剤組成物２０質量部以上が好ましく、３０質量部以上がより好ましく、１００質量部以下が好ましく、９０質量部以下がより好ましい＜１７＞〜＜２０＞いずれかに記載の鋳型造型用組成物。
＜２２＞＜１＞〜＜１６＞いずれかに記載の鋳型造型用粘結剤組成物、前記鋳型造型用粘結剤組成物を硬化させる硬化剤組成物、及び耐火性粒子を含有する鋳型用組成物。
＜２３＞前記硬化剤組成物が、＜１７＞〜＜２１＞いずれかに記載の鋳型造型用組成物に含有される硬化剤組成物である＜２２＞に記載の鋳型用組成物。
＜２４＞前記耐火性粒子１００質量部に対して、前記鋳型造型用粘結剤組成物が０．５質量部以上が好ましく、１．５質量部以下が好ましい＜２２＞又は＜２３＞に記載の鋳型用組成物。
＜２５＞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、１．０質量部以下が好ましい＜２２＞〜＜２４＞いずれかに記載の鋳型用組成物。
＜２６＞耐火性粒子と＜１＞〜＜１６＞いずれかに記載の鋳型造型用粘結剤組成物と当該鋳型造型用粘結剤組成物を硬化させる硬化剤組成物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。
＜２７＞前記硬化剤組成物が、＜１７＞〜＜２１＞いずれかに記載の鋳型造型用組成物に含有される硬化剤組成物である＜２６＞に記載の鋳型の製造方法。
＜２８＞前記＜１＞〜＜１６＞いずれかに記載の組成物の鋳型造型用粘結剤組成物としての使用。
<1> A binder composition for mold making containing 3 to 15% by mass of a furanaldehyde compound and a ketone compound represented by the following general formula (1).
R 1 —CO—R 2 (1)
(In the general formula (1), R 1 and R 2 are each a hydrocarbon group having 1 to 6 carbon atoms, and when R 1 and R 2 form a ring, the total number of carbon atoms of R 1 and R 2 Is a hydrocarbon group of 3 to 6.)
<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 binder composition for mold making 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 for mold making is preferably 10% by mass or more, more preferably 20% by mass or more, preferably 85% by mass or less, and preferably 80% by mass or less. More preferably, 75% by mass or less is more preferable, 10 to 85% by mass is preferable, 20 to 80% by mass is more preferable, and 20 to 75% by mass is further preferable. <1> or <2> Binder composition.
<4> In the general formula (1), when R 1 and R 2 are each a hydrocarbon group, the number of carbon atoms of R 1 and R 2 is preferably 1 or more, more preferably 2 or more, and more preferably 3 or more. More preferably, 6 or less are preferable, 1-6 are preferable, 2-6 are more preferable, and 3-6 are more preferable <1>-<3> The binder composition for mold making in any one of <1>-<3>.
<5> In the general formula (1), when R 1 and R 2 form a ring, the total number of carbon atoms of R 1 and R 2 is preferably 3 or more, more preferably 4 or more, and further more preferably 5 or more. Preferably, 6 or less are preferable, 3-6 are preferable, 4-6 are more preferable, and 5 or 6 is still more preferable <1>-<4> Binder composition for mold making in any one.
<6> The ketone compound is acetone, methyl ethyl ketone, methyl propyl ketone, isopropyl methyl ketone, butyl methyl ketone, isobutyl methyl ketone, pinacolone, diethyl ketone, dipropyl ketone, diisopropyl ketone, mesityl oxide, methyl heptenone, cyclobutanone, cyclopenta Preferably, at least one selected from the group consisting of non, cyclohexanone, holon, isophorone, acetophenone, propiophenone, butyrophenone, valerophenone, and benzophenone, and at least one selected from the group consisting of acetophenone, benzophenone, and cyclohexanone. More preferably, the binder composition for mold making according to any one of <1> to <5>, more preferably benzophenone.
<7> The content of the ketone compound in the binder composition for mold making is preferably 3% by mass or more, more preferably 4% by mass or more, further preferably 5% by mass or more, and 15% by mass or less. Preferably, 12 mass% or less is more preferable, 10 mass% or less is more preferable, 3-15 mass% is preferable, 4-12 mass% is more preferable, 5-10 mass% is still more preferable <1>-<6>. The binder composition for mold making according to any one of the above.
<8> The ratio of the content of the ketone compound to the content of the furanaldehyde compound in the binder composition for mold making (content of furanaldehyde compound / content of ketone compound) is 3 or more. Preferably, 5 or more is more preferable, 7 or more is more preferable, 30 or less is preferable, 23 or less is more preferable, 14 or less is more preferable, 3-30 are preferable, 5-23 are more preferable, and 7-14 are still more preferable The binder composition for mold making according to any one of <1> to <7>.
<9> The binder composition for mold making according to any one of <1> to <8>, which preferably further comprises an acid curable resin.
<10> 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 And a condensate of ethyleneurea and aldehydes (urea / ethyleneurea co-condensation resin), a condensate of melamine and aldehydes, and a condensate of urea and aldehydes, and two or more kinds selected from the group At least one selected from the group consisting of condensates is preferable, and one or more selected from furfuryl alcohol, condensates of urea, ethylene urea and aldehydes (urea / ethylene urea co-condensation resin), and their co-condensation The mold forming binder composition according to <9>, wherein a product is more preferable, and furfuryl alcohol is more preferable.
<11> The content of the acid curable resin in the binder composition for mold making is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and 90% by mass. The following is preferable, 60 mass% or less is more preferable, 30 mass% or less is further preferable, 1-90 mass% is preferable, 10-60 mass% is more preferable, 15-30 mass% is more preferable <9> or <10>. Binder composition for mold making according to 10>.
<12> The binder composition for mold making according to any one of <1> to <11>, which preferably further contains urea.
<13> The content of the urea in the binder composition for mold making is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and further preferably 1.5% by mass or more. The binder composition for mold making according to <12>, preferably 10% by mass or less, more preferably 6.0% by mass or less, and further preferably 4.5% by mass or less.
<14> The nitrogen content in the binder composition for mold making is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, still more preferably 1.5% by mass or more. 8 mass% or more is still more preferable, 4.0 mass% or less is preferable, 3.8 mass% or less is more preferable, 3.7 mass% or less is more preferable, 3.6 mass% or less is more preferable, 0 0.5-4.0 mass% is preferable, 1.0-3.8 mass% is more preferable, 1.5-3.7 mass% is still more preferable, 1.8-3.6 mass% is still more preferable. <1>-<13> The binder composition for mold making as described in any one of the above.
<15> The binder composition for mold making according to any one of <1> to <14>, which preferably further includes a silane coupling agent.
<16> The content of the silane coupling agent in the binder composition for mold making is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 5% by mass or less, The binder composition for mold making according to any one of <1> to <15>, more preferably 4% by mass or less.
<17> A mold-forming composition comprising the mold-forming binder composition according to any one of <1> to <16> and a curing agent composition for curing the mold-molding binder composition.
<18> The content of the acid containing sulfur in the curing agent composition is preferably 60% by mass or less, more preferably 30% by mass or less, still more preferably 10% by mass or less, and still more preferably 1% by mass or less. <18> The mold molding composition according to <17>, wherein substantially 0% is even more preferable.
<19> The mold molding composition according to <17> or <18>, wherein the curing agent composition is preferably a carboxylic acid.
<20> The mold molding composition according to any one of <17> to <19>, wherein the curing agent composition is preferably 2,6-dihydroxybenzoic acid.
<21> The mass ratio of the mold forming binder composition to 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. The composition for mold making according to any one of <17> to <20>, more preferably at least 100 parts, more preferably at most 100 parts, more preferably at most 90 parts by weight.
<22> Binder composition for mold making according to any one of <1> to <16>, a curing agent composition for curing the binder composition for mold making, and a mold containing refractory particles Composition.
<23> The mold composition according to <22>, wherein the curing agent composition is a curing agent composition contained in the mold molding composition according to any one of <17> to <21>.
<24> The binder composition for mold making is preferably 0.5 parts by mass or more and preferably 1.5 parts by mass or less with respect to 100 parts by mass of the refractory particles. <22> or <23> A mold composition.
<25> The mold according to any one of <22> to <24>, in which the curing agent composition is preferably 0.07 parts by mass or more and preferably 1.0 parts by mass or less with respect to 100 parts by mass of the refractory particles. Composition.
<26> A refractory particle, a binder for mold making according to any one of <1> to <16>, and a curing agent composition for curing the binder composition for mold making, and a mold. The manufacturing method of a casting_mold | template which has a hardening process which packs the said composition for casting_mold | templates in a formwork, and hardens the said composition for casting_mold | templates which obtains the composition for use.
<27> The method for producing a mold according to <26>, wherein the curing agent composition is a curing agent composition contained in the composition for molding a mold according to any one of <17> to <21>.
<28> Use of the composition according to any one of <1> to <16> as a binder composition for mold making.
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.
＜原料の製造＞
〔縮合物１（尿素・エチレン尿素共縮合樹脂）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。
<Manufacture of raw materials>
[Production of condensate 1 (urea / ethylene urea co-condensation resin)]
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.
＜実施例１〜７、比較例１〜３＞
〔粘結剤組成物の製造〕
表１に示すフランアルデヒド化合物、フルフリルアルコール、酸硬化性樹脂、尿素、ケトン化合物、及びシランカップリング剤をそれぞれ所定の質量比率で混合し、実施例１〜７、及び比較例１〜３の粘結剤組成物を製造した。なお、表１中、「ＦＬ」はフルフラール、「ＦＦＡ」はフルフリルアルコールを意味する。また、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（商品名：ＫＢＭ-４０２、信越化学工業株式会社製）を用いた。
<Examples 1-7, Comparative Examples 1-3>
(Production of binder composition)
The furanaldehyde compound, furfuryl alcohol, acid curable resin, urea, ketone compound, and silane coupling agent shown in Table 1 were mixed at a predetermined mass ratio, and Examples 1 to 7 and Comparative Examples 1 to 3 were mixed. A binder composition was produced. In Table 1, “FL” means furfural and “FFA” means furfuryl alcohol. As the silane coupling agent, 3-glycidoxypropylmethyldimethoxysilane (trade name: KBM-402, manufactured by Shin-Etsu Chemical Co., Ltd.) was used.
〔粘結剤組成物中の窒素含有量〕
ＪＩＳ Ｍ ８８１３に示されるケルダール法にて測定を行った。粘結剤組成物中の窒素含有量は比較例、実施例ともに全て１．８質量％であった。
[Nitrogen content in binder composition]
Measurement was performed by the Kjeldahl method shown in JIS M 8813. The nitrogen content in the binder composition was 1.8% by mass in both Comparative Examples and Examples.
〔鋳型用組成物〕
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に示す硬化剤組成物０．７質量部を添加し、次いで表１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用組成物（混練砂）を得た。なお、表１中、２，６−ＤＨＢは２，６−ジヒドロキシ安息香酸を意味する。
[Mold composition]
Under the conditions of 25 ° C. and 55% RH, 0.7 parts by mass of the hardener composition shown in Table 1 is added to 100 parts by mass of fresh sand (free mantle), and then the binder composition shown in Table 1 1.0 part by mass was added, and these were mixed to obtain a mold composition (kneaded sand). In Table 1, 2,6-DHB means 2,6-dihydroxybenzoic acid.
＜試験例＞
〔試験例１：鋳型の強度〕
２５℃、５５％ＲＨの条件下で、混練した直後の混練砂を直径５０ｍｍ、高さ５０ｍｍの円柱形状のテストピース枠に充填し、同条件下で１時間経過したときに抜型を行い、ＪＩＳ Ｚ ２６０１に記載された方法で、テストピースの圧縮強度（ＭＰａ）を測定し、「１時間後強度」とした。「１時間後強度」の数値が高いものほど、硬化速度が速いことを示す。また、別途同様に作製し１時間後に抜型したテストピースは、充填から２４時間後にＪＩＳ Ｚ ２６０１に記載された方法で、テストピースの圧縮強度（ＭＰａ）を測定し、「２４時間後強度」とした。「２４時間後の圧縮強度」が高いものほど、鋳型強度が高いことを示す。得られた結果を表１に示す。
<Test example>
[Test Example 1: Mold strength]
Under the conditions of 25 ° C. and 55% RH, the kneaded sand immediately after kneading is filled into a cylindrical test piece frame having a diameter of 50 mm and a height of 50 mm. The compressive strength (MPa) of the test piece was measured by the method described in Z 2601 and was defined as “strength after 1 hour”. A higher numerical value of “strength after 1 hour” indicates a faster curing rate. In addition, a test piece that was prepared in the same manner and was cut out after 1 hour was measured for the compressive strength (MPa) of the test piece by the method described in JIS Z 2601 24 hours after filling. did. The higher the “compression strength after 24 hours”, the higher the mold strength. The obtained results are shown in Table 1.
〔試験例２：鋳型の可撓性〕
２５℃、５５％ＲＨの条件下で、混練した直後の混練砂を直径５０ｍｍ、高さ５０ｍｍの円柱形状のテストピース枠に充填し、同条件下で所定時間放置した後に抜型を行い、ＪＩＳ Ｚ ２６０１に記載された方法で、テストピースの圧縮強度（ＭＰａ）を測定し、得られた測定値が放置後はじめて１．０ＭＰａに到達したときの充填直後からの放置時間を抜型時間とした。
[Test Example 2: Mold flexibility]
Under the conditions of 25 ° C. and 55% RH, the kneaded sand immediately after kneading is filled into a columnar test piece frame having a diameter of 50 mm and a height of 50 mm, left to stand for a predetermined time under the same conditions, and then removed from the mold. The compressive strength (MPa) of the test piece was measured by the method described in 2601, and the leaving time immediately after filling when the obtained measured value reached 1.0 MPa for the first time after standing was defined as the mold release time.
２５℃、５５％ＲＨの条件下で、混練した直後の混練砂を長さ１８０ｍｍ、幅２３ｍｍ、厚み２３ｍｍの直方体状のテストピース枠に充填し、同条件下で放置し、上述した抜型時間経過時に抜型した後、ＪＩＳ Ｋ ７１７１に基づいて、荷重速度１０ｍｍ／ｍｉｎ、支点間距離１２０ｍｍでテストピースが破断するまでの変位（ｍｍ）を測定した。当該変位が大きいほど鋳型の可撓性が高いことを示す。得られた結果を表１に示す。 Under the conditions of 25 ° C. and 55% RH, the kneaded sand immediately after kneading is filled in a rectangular parallelepiped test piece frame having a length of 180 mm, a width of 23 mm, and a thickness of 23 mm, and left to stand under the same conditions. After sometimes removing the mold, the displacement (mm) until the test piece broke at a load speed of 10 mm / min and a distance between fulcrums of 120 mm was measured based on JIS K 7171. The larger the displacement, the higher the flexibility of the mold. The obtained results are shown in Table 1.
Claims (9)
Ｒ１−ＣＯ−Ｒ２ （１）
（前記一般式（１）において、Ｒ１、Ｒ２はそれぞれ炭素数１〜６の炭化水素基であり、Ｒ１とＲ２が環を形成する場合はＲ１とＲ２の炭素数の合計が３〜６の炭化水素基である。） A binder composition for mold making containing 3 to 15% by mass of a furanaldehyde compound and a ketone compound represented by the following general formula (1).
R 1 —CO—R 2 (1)
(In the general formula (1), R 1 and R 2 are each a hydrocarbon group having 1 to 6 carbon atoms, and when R 1 and R 2 form a ring, the total number of carbon atoms of R 1 and R 2 Is a hydrocarbon group of 3 to 6.)
5. A mold composition comprising a mixture of refractory particles, the mold forming binder composition according to any one of claims 1 to 4, and a mold forming binder curing agent composition. A mold manufacturing method comprising a mixing step of obtaining a product, and a curing step of filling the mold composition in a mold and curing the mold composition.
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