JP2024089621A - Binder composition, sand composition, mold making kit and mold making method - Google Patents
Binder composition, sand composition, mold making kit and mold making method Download PDFInfo
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- JP2024089621A JP2024089621A JP2023172514A JP2023172514A JP2024089621A JP 2024089621 A JP2024089621 A JP 2024089621A JP 2023172514 A JP2023172514 A JP 2023172514A JP 2023172514 A JP2023172514 A JP 2023172514A JP 2024089621 A JP2024089621 A JP 2024089621A
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- mold
- binder composition
- sand
- mass
- composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 159
- 239000011230 binding agent Substances 0.000 title claims abstract description 96
- 239000004576 sand Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000005011 phenolic resin Substances 0.000 claims abstract description 59
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 50
- -1 amine compounds Chemical class 0.000 claims abstract description 45
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- 229920000768 polyamine Polymers 0.000 claims abstract description 8
- 150000003141 primary amines Chemical class 0.000 claims abstract description 7
- 150000003335 secondary amines Chemical class 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 150000002895 organic esters Chemical class 0.000 claims description 41
- 239000008187 granular material Substances 0.000 claims description 34
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- 238000005266 casting Methods 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 239000004848 polyfunctional curative Substances 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 125
- 238000003860 storage Methods 0.000 abstract description 15
- 239000000243 solution Substances 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 86
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 10
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- 239000002904 solvent Substances 0.000 description 10
- 229960001755 resorcinol Drugs 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
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- 238000012360 testing method Methods 0.000 description 8
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- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 230000009471 action Effects 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
- 230000007547 defect Effects 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000009970 fire resistant effect Effects 0.000 description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 3
- OTJFQRMIRKXXRS-UHFFFAOYSA-N (hydroxymethylamino)methanol Chemical compound OCNCO OTJFQRMIRKXXRS-UHFFFAOYSA-N 0.000 description 2
- BXJGUBZTZWCMEX-UHFFFAOYSA-N 2,3-dimethylbenzene-1,4-diol Chemical compound CC1=C(C)C(O)=CC=C1O BXJGUBZTZWCMEX-UHFFFAOYSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 2
- VTCDZPUMZAZMSB-UHFFFAOYSA-N 3,4,5-trimethoxyphenol Chemical compound COC1=CC(O)=CC(OC)=C1OC VTCDZPUMZAZMSB-UHFFFAOYSA-N 0.000 description 2
- FDQQNNZKEJIHMS-UHFFFAOYSA-N 3,4,5-trimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1C FDQQNNZKEJIHMS-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 2
- PGSWEKYNAOWQDF-UHFFFAOYSA-N 3-methylcatechol Chemical compound CC1=CC=CC(O)=C1O PGSWEKYNAOWQDF-UHFFFAOYSA-N 0.000 description 2
- VLJSLTNSFSOYQR-UHFFFAOYSA-N 3-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(O)=C1 VLJSLTNSFSOYQR-UHFFFAOYSA-N 0.000 description 2
- MPWGZBWDLMDIHO-UHFFFAOYSA-N 3-propylphenol Chemical compound CCCC1=CC=CC(O)=C1 MPWGZBWDLMDIHO-UHFFFAOYSA-N 0.000 description 2
- MBGGFXOXUIDRJD-UHFFFAOYSA-N 4-Butoxyphenol Chemical compound CCCCOC1=CC=C(O)C=C1 MBGGFXOXUIDRJD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- LKVFCSWBKOVHAH-UHFFFAOYSA-N 4-Ethoxyphenol Chemical compound CCOC1=CC=C(O)C=C1 LKVFCSWBKOVHAH-UHFFFAOYSA-N 0.000 description 2
- VGMJYYDKPUPTID-UHFFFAOYSA-N 4-ethylbenzene-1,3-diol Chemical compound CCC1=CC=C(O)C=C1O VGMJYYDKPUPTID-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 2
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- GHVHDYYKJYXFGU-UHFFFAOYSA-N Beta-Orcinol Chemical compound CC1=CC(O)=C(C)C(O)=C1 GHVHDYYKJYXFGU-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
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- XIIIHRLCKLSYNH-UHFFFAOYSA-N 4-Hexyloxyphenol Chemical compound CCCCCCOC1=CC=C(O)C=C1 XIIIHRLCKLSYNH-UHFFFAOYSA-N 0.000 description 1
- 239000004101 4-Hexylresorcinol Substances 0.000 description 1
- IJALWSVNUBBQRA-UHFFFAOYSA-N 4-Isopropyl-3-methylphenol Chemical compound CC(C)C1=CC=C(O)C=C1C IJALWSVNUBBQRA-UHFFFAOYSA-N 0.000 description 1
- ARIREUPIXAKDAY-UHFFFAOYSA-N 4-butylbenzaldehyde Chemical compound CCCCC1=CC=C(C=O)C=C1 ARIREUPIXAKDAY-UHFFFAOYSA-N 0.000 description 1
- SNBKPVVDUBFDEJ-UHFFFAOYSA-N 4-cyclopentylphenol Chemical compound C1=CC(O)=CC=C1C1CCCC1 SNBKPVVDUBFDEJ-UHFFFAOYSA-N 0.000 description 1
- WFJIVOKAWHGMBH-UHFFFAOYSA-N 4-hexylbenzene-1,3-diol Chemical compound CCCCCCC1=CC=C(O)C=C1O WFJIVOKAWHGMBH-UHFFFAOYSA-N 0.000 description 1
- 235000019360 4-hexylresorcinol Nutrition 0.000 description 1
- ZBCATMYQYDCTIZ-UHFFFAOYSA-N 4-methylcatechol Chemical compound CC1=CC=C(O)C(O)=C1 ZBCATMYQYDCTIZ-UHFFFAOYSA-N 0.000 description 1
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 1
- KIIIPQXXLVCCQP-UHFFFAOYSA-N 4-propoxyphenol Chemical compound CCCOC1=CC=C(O)C=C1 KIIIPQXXLVCCQP-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- 239000004348 Glyceryl diacetate Substances 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 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
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals 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
- 150000001413 amino acids Chemical class 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- UBXYXCRCOKCZIT-UHFFFAOYSA-N biphenyl-3-ol Chemical compound OC1=CC=CC(C=2C=CC=CC=2)=C1 UBXYXCRCOKCZIT-UHFFFAOYSA-N 0.000 description 1
- CRHLZRRTZDFDAJ-UHFFFAOYSA-N butoxymethanol Chemical compound CCCCOCO CRHLZRRTZDFDAJ-UHFFFAOYSA-N 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 235000019443 glyceryl diacetate Nutrition 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229960003258 hexylresorcinol Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VHWYCFISAQVCCP-UHFFFAOYSA-N methoxymethanol Chemical compound COCO VHWYCFISAQVCCP-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003110 molding sand Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NRZWYNLTFLDQQX-UHFFFAOYSA-N p-tert-Amylphenol Chemical compound CCC(C)(C)C1=CC=C(O)C=C1 NRZWYNLTFLDQQX-UHFFFAOYSA-N 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 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
- 229920001296 polysiloxane Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000004992 toluidines Chemical class 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
- 229940045136 urea Drugs 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 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
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Mold Materials And Core Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
【課題】鋳型強度を維持しつつ、ホルムアルデヒドの発生量を低減でき、保存安定性にも優れる粘結剤組成物、砂組成物、鋳型造型用キット及び鋳型の製造方法の提供。【解決手段】水溶性フェノール樹脂と、１級アミン、２級アミン及び多価アミンからなる群より選ばれる１種以上のアミン化合物（但し、尿素を除く。）と、を含み、前記水溶性フェノール樹脂の濃度４５質量％水溶液の２５℃におけるｐＨが１２以上である、粘結剤組成物。【選択図】なし[Problem] To provide a binder composition, a sand composition, a kit for mold making, and a method for manufacturing a mold that can reduce the amount of formaldehyde generated while maintaining mold strength and have excellent storage stability. [Solution] A binder composition containing a water-soluble phenolic resin and one or more amine compounds selected from the group consisting of primary amines, secondary amines, and polyamines (excluding urea), and in which the pH of an aqueous solution of the water-soluble phenolic resin with a concentration of 45% by mass at 25°C is 12 or higher. [Selected Figures] None
Description
本発明は、粘結剤組成物、砂組成物、鋳型造型用キット及び鋳型の製造方法に関する。 The present invention relates to a binder composition, a sand composition, a mold making kit, and a method for making a mold.
鋳型造型プロセスの１種に、アルカリフェノール樹脂を粘結剤として用いたアルカリフェノール樹脂プロセスがある。アルカリフェノール樹脂プロセスの代表的なものとして、珪砂等の耐火性粒状材料にアルカリフェノール樹脂と、硬化剤である有機エステルとを加えて混練して砂組成物（混練砂）とし、得られた砂組成物を木型、樹脂型、金型等（以下、これらを総称して「鋳型造型用型」ともいう。）に充填して造型し、アルカリフェノール樹脂を硬化させて耐火性粒状材料を粘結して固化させて鋳型（自硬性鋳型）とする方法（自硬性鋳型造型法）が知られている。また、耐火性粒状材料にアルカリフェノール樹脂を加えて砂組成物とし、得られた砂組成物を鋳型造型用型に充填して造型し、これに硬化剤である有機エステル又は炭酸ガスを通気してアルカリフェノール樹脂を硬化させて砂を粘結して固化させて鋳型（ガス硬化鋳型）とする方法（ガス硬化鋳型造型法）も知られている。 One type of casting process is the alkaline phenol resin process, which uses alkaline phenol resin as a binder. A representative alkaline phenol resin process is a process in which an alkaline phenol resin and an organic ester as a hardener are added to a refractory granular material such as silica sand, and the mixture is kneaded to form a sand composition (mixed sand), and the resulting sand composition is filled into a wooden mold, a resin mold, a metal mold, etc. (hereinafter, these are also collectively referred to as "casting molds") to form a mold, and the alkaline phenol resin is hardened to bind and solidify the refractory granular material to form a mold (self-hardening mold) (self-hardening casting mold forming method). Another known process is a process in which an alkaline phenol resin is added to a refractory granular material to form a sand composition, and the resulting sand composition is filled into a casting mold to form a mold, and the organic ester or carbon dioxide gas as a hardener is passed through the sand composition to harden the alkaline phenol resin, thereby binding and solidifying the sand to form a mold (gas-hardening casting mold) (gas-hardening casting mold forming method).
ところが、粘結剤の硬化時等にホルムアルデヒドが発生し、作業環境が悪化することがある。
従来、ホルムアルデヒドの発生量を低減する方法として、尿素やレゾルシン等のホルムアルデヒド捕捉剤を粘結剤に添加する方法が知られている。
例えば特許文献１には、レゾルシン等のフェノール化合物単量体と有機エステルとを含む硬化剤組成物と、耐火性粒状材料と、水溶性フェノール樹脂とを混練した混練砂を鋳型造型用型に充填して鋳型を製造する方法が開示されている。
However, formaldehyde is generated when the binder hardens, which can deteriorate the working environment.
Conventionally, a method for reducing the amount of formaldehyde generated has been known in which a formaldehyde scavenger such as urea or resorcin is added to a binder.
For example, Patent Document 1 discloses a method for producing a casting mold by filling a mold with mixed sand obtained by kneading a hardener composition containing a phenolic compound monomer such as resorcin and an organic ester, a fire-resistant granular material, and a water-soluble phenolic resin.
しかしながら、粘結剤に尿素を添加する場合、ホルムアルデヒドの発生量を十分に低減するためには、大量の尿素を添加する必要がある。その結果、粘結剤組成物中の尿素由来の窒素量が増えてしまい、鋳物欠陥が生じることがある。また、ホルムアルデヒド自体は架橋剤の役割を果たすため、尿素がホルムアルデヒドを捕捉すると架橋剤としての効果が得られにくくなるため、鋳型の強度が低下してしまう。 However, when urea is added to the binder, a large amount of urea must be added to sufficiently reduce the amount of formaldehyde generated. As a result, the amount of nitrogen derived from urea in the binder composition increases, which can cause casting defects. In addition, since formaldehyde itself acts as a cross-linking agent, if urea captures formaldehyde, it becomes difficult to obtain the effect as a cross-linking agent, which reduces the strength of the mold.
一方、レゾルシンはフェノール樹脂の１種であることから、ホルムアルデヒドを捕捉した状態で粘結剤の硬化に取り込まれるため、ホルムアルデヒドがレゾルシンに捕捉されても鋳型の強度を維持できる。
しかし、レゾルシンを配合した粘結剤組成物は増粘しやすく、保存安定性が低下しやすい。
On the other hand, since resorcin is a type of phenolic resin, it is incorporated into the hardening of the binder in a state in which it captures formaldehyde, so that the strength of the mold can be maintained even if formaldehyde is captured by resorcin.
However, a binder composition containing resorcinol is likely to thicken and its storage stability is likely to decrease.
本発明は、鋳型強度を維持しつつ、ホルムアルデヒドの発生量を低減でき、保存安定性にも優れる粘結剤組成物、砂組成物、鋳型造型用キット及び鋳型の製造方法を提供することを目的とする。 The present invention aims to provide a binder composition, a sand composition, a mold making kit, and a mold manufacturing method that can reduce the amount of formaldehyde generated while maintaining mold strength and have excellent storage stability.
本発明は、以下の態様を有する。
［１］ 水溶性フェノール樹脂と、
１級アミン、２級アミン及び多価アミンからなる群より選ばれる１種以上のアミン化合物（但し、尿素を除く。）と、
を含み、
前記水溶性フェノール樹脂の濃度４５質量％水溶液の２５℃におけるｐＨが１２以上である、粘結剤組成物。
［２］ 前記アミン化合物の含有量が窒素換算で、前記水溶性フェノール樹脂１００質量部に対して０．０５～０．５３質量部である、前記［１］の粘結剤組成物。
［３］ 前記［１］又は［２］の粘結剤組成物と、耐火性粒状材料とを含む、砂組成物。
［４］ 有機エステルをさらに含む、前記［３］の砂組成物。
［５］ 前記［１］又は［２］の粘結剤組成物と、耐火性粒状材料とを各々独立して有する、鋳型造型用キット。
［６］ 有機エステル及び炭酸ガスからなる群より選ばれる１種以上の硬化剤をさらに独立して有する、前記［５］の鋳型造型用キット。
［７］ 前記［４］の砂組成物を鋳型製造用の型に充填し、前記砂組成物に含まれる前記粘結剤組成物を硬化させる、鋳型の製造方法。
［８］ 前記［３］の砂組成物を鋳型製造用の型に充填し、有機エステル又は炭酸ガスを通気させて、前記砂組成物に含まれる前記粘結剤組成物を硬化させる、鋳型の製造方法。
The present invention has the following aspects.
[1] A water-soluble phenolic resin,
One or more amine compounds selected from the group consisting of primary amines, secondary amines, and polyamines (excluding urea);
Including,
The binder composition, wherein the pH of an aqueous solution of the water-soluble phenolic resin at a concentration of 45% by mass at 25° C. is 12 or more.
[2] The binder composition according to [1], wherein the content of the amine compound is 0.05 to 0.53 parts by mass, calculated as nitrogen, per 100 parts by mass of the water-soluble phenolic resin.
[3] A sand composition comprising the binder composition according to [1] or [2] above and a refractory granular material.
[4] The sand composition of [3], further comprising an organic ester.
[5] A mold-making kit comprising the binder composition according to [1] or [2] above and a refractory granular material, each of which is independently selected from the group consisting of refractory granular material and refractory granular material.
[6] The mold-making kit according to [5] above, further independently comprising one or more hardeners selected from the group consisting of organic esters and carbon dioxide gas.
[7] A method for producing a mold, comprising filling the sand composition according to [4] into a mold for producing a mold, and hardening the binder composition contained in the sand composition.
[8] A method for producing a mold, comprising filling the sand composition according to [3] into a mold for producing a mold, and passing an organic ester or carbon dioxide gas through the sand composition to harden the binder composition contained in the sand composition.
本発明によれば、鋳型強度を維持しつつ、ホルムアルデヒドの発生量を低減でき、保存安定性にも優れる粘結剤組成物、砂組成物、鋳型造型用キット及び鋳型の製造方法を提供できる。 The present invention provides a binder composition, a sand composition, a mold making kit, and a mold manufacturing method that can reduce the amount of formaldehyde generated while maintaining mold strength and have excellent storage stability.
以下では本発明を実施するための形態を詳細に説明するが、本発明は後述する実施の形態に限定されるものではなく、本発明の要旨を逸脱しない限り種々の変形が可能である。
本明細書及び特許請求の範囲において、「～」で表される数値範囲は、～の前後の数値を下限値及び上限値として含む数値範囲を意味する。
以下の明細書において、「鋳型」とは、本発明の粘結剤組成物、砂組成物又は鋳型造型用キットを用いて造型してなるものである。
The following describes in detail the forms for implementing the present invention, but the present invention is not limited to the embodiments described below, and various modifications are possible without departing from the gist of the present invention.
In this specification and claims, a numerical range expressed as "to" means a numerical range including the numerical values before and after "to" as the lower and upper limits.
In the following description, the term "mold" refers to a mold produced using the binder composition, the sand composition, or the mold-making kit of the present invention.
［粘結剤組成物］
以下、本発明の第一の態様の粘結剤組成物の一実施形態について説明する。
本実施形態の粘結剤組成物は、以下に示す水溶性フェノール樹脂とアミン化合物（但し、尿素を除く。）とを含む。
粘結剤組成物は、本発明の効果を損なわない範囲内であれば、必要に応じて、水溶性フェノール樹脂及びアミン化合物に加えて、これら以外の成分（以下、「任意成分」ともいう。）をさらに含んでいてもよい。
[Binding agent composition]
Hereinafter, one embodiment of the binder composition according to the first aspect of the present invention will be described.
The binder composition of the present embodiment contains the following water-soluble phenolic resin and amine compound (excluding urea).
The binder composition may further contain, in addition to the water-soluble phenolic resin and the amine compound, other components (hereinafter also referred to as "optional components") as necessary, so long as the effects of the present invention are not impaired.
＜水溶性フェノール樹脂＞
水溶性フェノール樹脂の２５℃におけるｐＨは１２以上であり、１２～１４が好ましく、１２～１３がより好ましくい。すなわち、本実施形態の粘結剤組成物に含まれる水溶性フェノール樹脂は、アルカリフェノール樹脂であるともいえる。
水溶性フェノール樹脂のｐＨは、水溶性フェノール樹脂を濃度が４５質量％となるように水に溶解して調製した水溶液のｐＨを測定温度２５℃で測定した値である。
<Water-soluble phenolic resin>
The pH of the water-soluble phenolic resin at 25° C. is 12 or more, preferably 12 to 14, and more preferably 12 to 13. In other words, the water-soluble phenolic resin contained in the binder composition of the present embodiment can be said to be an alkaline phenolic resin.
The pH of the water-soluble phenolic resin is a value measured at 25° C. of the pH of an aqueous solution prepared by dissolving the water-soluble phenolic resin in water to a concentration of 45% by mass.
水溶性フェノール樹脂は、アルカリ金属の水酸化物の存在下、常法により、フェノール類及びビスフェノール類からなる群より選ばれる１種以上（以下、「フェノール系化合物」という。）と、アルデヒド類とを水系で反応させることで得られる。
水溶性フェノール樹脂は、１種単独で用いてもよく、２種以上を併用してもよい。
The water-soluble phenolic resin can be obtained by reacting one or more compounds selected from the group consisting of phenols and bisphenols (hereinafter referred to as "phenolic compounds") with aldehydes in an aqueous system in the presence of an alkali metal hydroxide by a conventional method.
The water-soluble phenolic resin may be used alone or in combination of two or more kinds.
フェノール類としては、例えばフェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、２，３－キシレノール、３，５－キシレノール、ｍ－エチルフェノール、ｍ－プロピルフェノール、ｍ－ブチルフェノール、ｐ－ブチルフェノール、ｏ－ブチルフェノール、レゾルシノール、ハイドロキノン、カテコール、３－メトキシフェノール、４－メトキシフェノール、３－メチルカテコール、４－メチルカテコール、メチルハイドロキノン、２－メチルレゾルシノール、２，３－ジメチルハイドロキノン、２，５－ジメチルレゾルシノール、２－エトキシフェノール、４－エトキシフェノール、４－エチルレゾルシノール、３－エトキシ－４－メトキシフェノール、２－プロペニルフェノール、２－イソプロピルフェノール、３－イソプロピルフェノール、４－イソプロピルフェノール、３，４，５－トリメチルフェノール、２－イソプロポキシフェノール、４－ピロポキシフェノール、２－アリルフェノール、３，４，５－トリメトキシフェノール、４－イソプロピル－３－メチルフェノール、ピロガロール、フロログリシノール、１，２，４－ベンゼントリオール、５－イソプロピル－３－メチルフェノール、４－ブトキシフェノール、４－ｔ－ブチルカテコール、ｔ－ブチルハイドロキノン、４－ｔ－ペンチルフェノール、２－ｔ－ブチル－５－メチルフェノール、２－フェニルフェノール、３－フェニルフェノール、４－フェニルフェノール、３－フェノキシフェノール、４－フェノキシフェノール、４－へキシルオキシフェノール、４－ヘキサノイルレゾルシノール、３，５－ジイソプロピルカテコール、４－ヘキシルレゾルシノール、４－ヘプチルオキシフェノール、３，５－ジ－ｔ－ブチルフェノール、３，５－ジ－ｔ－ブチルカテコール、２，５－ジ－ｔ－ブチルハイドロキノン、ジ－ｓｅｃ－ブチルフェノール、４－クミルフェノール、ノニルフェノール、２－シクロペンチルフェノール、４－シクロペンチルフェノール、ビスフェノールＡ、ビスフェノールＦなどが挙げられる。
これらフェノール類は、１種単独で用いてもよく、２種以上を併用してもよい。
Examples of phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 3,5-xylenol, m-ethylphenol, m-propylphenol, m-butylphenol, p-butylphenol, o-butylphenol, resorcinol, hydroquinone, catechol, 3-methoxyphenol, 4-methoxyphenol, 3-methylcatechol, 4-methylcatechol, methylhydroquinone, 2-methylresorcinol, 2,3-dimethylhydroquinone, 2,5-dimethylresorcinol, 2-ethoxyphenol, 4-ethoxyphenol, 4-ethylresorcinol, 3-ethoxy-4-methoxyphenol, 2-propenylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 3,4,5-trimethylphenol, 2-isopropoxyphenol, 4-propoxyphenol, 2-allylphenol, and 3,4,5-trimethoxyphenol. phenol, 4-isopropyl-3-methylphenol, pyrogallol, phloroglucinol, 1,2,4-benzenetriol, 5-isopropyl-3-methylphenol, 4-butoxyphenol, 4-t-butylcatechol, t-butylhydroquinone, 4-t-pentylphenol, 2-t-butyl-5-methylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3-phenoxyphenol, 4-phenoxyphenol, 4-hexyloxyphenol, 4-hexanoylresorcinol, 3,5-diisopropylcatechol, 4-hexylresorcinol, 4-heptyloxyphenol, 3,5-di-t-butylphenol, 3,5-di-t-butylcatechol, 2,5-di-t-butylhydroquinone, di-sec-butylphenol, 4-cumylphenol, nonylphenol, 2-cyclopentylphenol, 4-cyclopentylphenol, bisphenol A, bisphenol F, and the like.
These phenols may be used alone or in combination of two or more.
ビスフェノール類としては、例えばビスフェノールＡ、ビスフェノールＦ、ビスフェノールＣ、ビスフェノールＳ、ビスフェノールＺなどが挙げられる。
これらビスフェノール類は、１種単独で用いてもよく、２種以上を併用してもよい。
Examples of bisphenols include bisphenol A, bisphenol F, bisphenol C, bisphenol S, and bisphenol Z.
These bisphenols may be used alone or in combination of two or more.
アルデヒド類としては、例えばホルムアルデヒド、トリオキサン、フルフラール、パラホルムアルデヒド、ベンズアルデヒド、メチルヘミホルマール、エチルへミホルマール、プロピルへミホルマール、サリチルアルデヒド、グリオキザール、ブチルヘミホルマール、フェニルへミホルマール、アセトアルデヒド、プロピルアルデヒド、フェニルアセトアルデヒド、α－フェニルプロピルアルデヒド、β－フェニルプロピルアルデヒド、ｏ－ヒドロキシベンズアルデヒド、ｍ－ヒドロキシベンズアルデヒド、ｐ－ヒドロキシベンズアルデヒド、ｏ－クロロベンズアルデヒド、ｏ－ニトロベンズアルデヒド、ｍ－ニトロベンズアルデヒド、ｐ－ニトロベンズアルデヒド、ｏ―メチルベンズアルデヒド、ｍ－メチルベンズアルデヒド、ｐ－メチルベンズアルデヒド、ｐ－エチルベンズアルデヒド、ｐ－ｎ－ブチルベンズアルデヒドなどが挙げられる。
これらアルデヒド類は、１種単独で用いてもよく、２種以上を併用してもよい。
Examples of aldehydes include formaldehyde, trioxane, furfural, paraformaldehyde, benzaldehyde, methylhemiformal, ethylhemiformal, propylhemiformal, salicylaldehyde, glyoxal, butylhemiformal, phenylhemiformal, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropyl Examples of the aldehyde include o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, and p-n-butylbenzaldehyde.
These aldehydes may be used alone or in combination of two or more.
フェノール系化合物としては、フェノール類及びビスフェノール類のいずれか一方を単独で用いてもよいし、フェノール類及びビスフェノール類を混合して用いてもよい。 As the phenol-based compound, either phenols or bisphenols may be used alone, or a mixture of phenols and bisphenols may be used.
アルカリ金属の水酸化物としては、例えば水酸化ナトリウム、水酸化カリウム、水酸化リチウムなどが挙げられる。これらの中でも、水酸化ナトリウム、水酸化カリウムが好ましい。
これらアルカリ金属の水酸化物は、１種単独で用いてもよく、２種以上を併用してもよい。
Examples of the hydroxide of an alkali metal include sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. Among these, sodium hydroxide and potassium hydroxide are preferred.
These alkali metal hydroxides may be used alone or in combination of two or more.
なお、フェノール系化合物とアルデヒド類とを反応させる際に、反応系中にアルデヒドと縮合可能なモノマー（例えば尿素、シクロヘキサノン、メラミン等）を加えてもよい。
また、得られたアルカリフェノール樹脂を水又は１価のアルコール類（例えばメタノール、エタノール、プロパノール等）で所望の濃度となるように希釈してもよい。
When the phenolic compound is reacted with the aldehyde, a monomer capable of condensing with the aldehyde (such as urea, cyclohexanone, melamine, etc.) may be added to the reaction system.
The resulting alkaline phenol resin may be diluted with water or a monohydric alcohol (e.g., methanol, ethanol, propanol, etc.) to a desired concentration.
水溶性フェノール樹脂は、水や有機溶剤等の溶剤を含んだ状態で用いることができる。
水溶性フェノール樹脂の総質量に対する水の含有量（水分量）については特に制限されないが、３０～８０質量％が好ましく、４０～７０質量％がより好ましい。水の含有量が３０質量％以上であれば、高粘性による混練ムラが起こりにくい。水の含有量が８０質量％以下であれば、強度の高い鋳型が得られやすい。
The water-soluble phenolic resin can be used in a state containing water or a solvent such as an organic solvent.
The water content (moisture content) relative to the total mass of the water-soluble phenolic resin is not particularly limited, but is preferably 30 to 80% by mass, more preferably 40 to 70% by mass. If the water content is 30% by mass or more, uneven kneading due to high viscosity is unlikely to occur. If the water content is 80% by mass or less, a mold with high strength is likely to be obtained.
水溶性フェノール樹脂の含有量は、粘結剤組成物の総質量に対して３５～６５質量％が好ましく、４０～６０質量％がより好ましく、４５～５０質量％がさらに好ましい。水溶性フェノール樹脂の含有量が上記下限値以上であれば、十分な粘結性が得られるとともに、粘結剤組成物の硬化速度が速まる。水溶性フェノール樹脂の含有量が上記上限値以下であれば、粘結剤組成物の粘度の上昇を抑制できる。加えて、鋳型の強度が向上する。
なお、本明細書において、「水溶性フェノール樹脂の含有量」は純分換算量である。すなわち、水溶性フェノール樹脂が溶剤を含む場合は、水溶性フェノール樹脂の全質量から溶剤の全含有量を除いた質量のことである。
The content of the water-soluble phenolic resin is preferably 35 to 65 mass %, more preferably 40 to 60 mass %, and even more preferably 45 to 50 mass %, based on the total mass of the binder composition. If the content of the water-soluble phenolic resin is equal to or greater than the lower limit, sufficient binding properties are obtained and the hardening speed of the binder composition is increased. If the content of the water-soluble phenolic resin is equal to or less than the upper limit, an increase in the viscosity of the binder composition can be suppressed. In addition, the strength of the mold is improved.
In this specification, the "content of the water-soluble phenolic resin" is a pure content. In other words, when the water-soluble phenolic resin contains a solvent, it is the mass obtained by subtracting the total content of the solvent from the total mass of the water-soluble phenolic resin.
＜アミン化合物＞
アミン化合物は、１級アミン、２級アミン及び多価アミンからなる群より選ばれる１種以上（但し、尿素を除く。）である。
これらアミン化合物は、１種単独で用いてもよく、２種以上を併用してもよい。
<Amine Compound>
The amine compound is at least one selected from the group consisting of primary amines, secondary amines and polyamines (excluding urea).
These amine compounds may be used alone or in combination of two or more.
１級アミンとしては、例えばモノメチルアミン、モノエチルアミン、モノプロピルアミン、モノメタノールアミン、モノエタノールアミン等の鎖状１級アミン；アニリン、トルイジン、フェニエチルアミン等の環状１級アミン；グリシン等のアミノ酸などが挙げられる。これらの中でも、モノエチルアミン、モノエタノールアミン、グリシンが好ましく、モノエタノールアミンがより好ましい。
これら１級アミンは、１種単独で用いてもよく、２種以上を併用してもよい。
Examples of the primary amine include linear primary amines such as monomethylamine, monoethylamine, monopropylamine, monomethanolamine, and monoethanolamine, cyclic primary amines such as aniline, toluidine, and phenylethylamine, and amino acids such as glycine. Among these, monoethylamine, monoethanolamine, and glycine are preferred, and monoethanolamine is more preferred.
These primary amines may be used alone or in combination of two or more.
２級アミンとしては、例えばジメチルアミン、ジエチルアミン、ジプロピルアミン、エチルメチルアミン、ジメタノールアミン、ジエタノールアミン等の鎖状２級アミン；ジフェニルアミン、ピリジン等の環状２級アミンなどが挙げられる。これらの中でも、ジメタノールアミンが好ましい。
これら２級アミンは、１種単独で用いてもよく、２種以上を併用してもよい。
Examples of the secondary amine include chain secondary amines such as dimethylamine, diethylamine, dipropylamine, ethylmethylamine, dimethanolamine, and diethanolamine, and cyclic secondary amines such as diphenylamine and pyridine. Among these, dimethanolamine is preferred.
These secondary amines may be used alone or in combination of two or more.
多価アミンとしては、例えばエチレンジアミン、ジエチルトリアミン等の鎖状多価アミン；ピペラジン、メラミン、ベンゾグアナミン等の環状多価アミンなどが挙げられる。これらの中でも、エチレンジアミン、ピペラジンが好ましい。
これら多価アミンは、１種単独で用いてもよく、２種以上を併用してもよい。
Examples of the polyamine include chain polyamines such as ethylenediamine and diethyltriamine, and cyclic polyamines such as piperazine, melamine and benzoguanamine. Among these, ethylenediamine and piperazine are preferred.
These polyamines may be used alone or in combination of two or more kinds.
アミン化合物の含有量は、水溶性フェノール樹脂１００質量部に対して０．１０質量部以上が好ましく、０．２０質量部以上がより好ましく、０．３０質量部以上がさらに好ましく、０．４０質量部以上が特に好ましい。また、アミン化合物の含有量は、水溶性フェノール樹脂１００質量部に対して１．１８質量部以下が好ましく、１．００質量部以下がより好ましく、０．７０質量部以下がさらに好ましく、０．５０質量部以下が特に好ましい。アミン化合物の含有量が上記下限値以上であれば、ホルムアルデヒドの発生量をより低減できる。アミン化合物の含有量が上記上限値以下であれば、鋳型の強度を良好に維持できる。
アミン化合物の含有量の前記の上限及び下限は任意に組み合わせることができる。例えば、アミン化合物の含有量は、水溶性フェノール樹脂１００質量部に対して、０．１０～１．１８質量部が好ましく、０．２０～１．００質量部がより好ましく、０．３０～０．７０質量部がさらに好ましく、０．４０～０．５０質量部が特に好ましい。
なお、本発明において、「水溶性フェノール樹脂１００質量部」は純分換算量である。
The content of the amine compound is preferably 0.10 parts by mass or more, more preferably 0.20 parts by mass or more, even more preferably 0.30 parts by mass or more, and particularly preferably 0.40 parts by mass or more, relative to 100 parts by mass of the water-soluble phenolic resin. The content of the amine compound is preferably 1.18 parts by mass or less, more preferably 1.00 parts by mass or less, even more preferably 0.70 parts by mass or less, and particularly preferably 0.50 parts by mass or less, relative to 100 parts by mass of the water-soluble phenolic resin. If the content of the amine compound is equal to or more than the lower limit, the amount of formaldehyde generated can be further reduced. If the content of the amine compound is equal to or less than the upper limit, the strength of the mold can be well maintained.
The upper and lower limits of the content of the amine compound can be arbitrarily combined. For example, the content of the amine compound is preferably 0.10 to 1.18 parts by mass, more preferably 0.20 to 1.00 parts by mass, further preferably 0.30 to 0.70 parts by mass, and particularly preferably 0.40 to 0.50 parts by mass, relative to 100 parts by mass of the water-soluble phenolic resin.
In the present invention, "100 parts by mass of the water-soluble phenolic resin" is the amount calculated as the pure content.
アミン化合物の含有量は窒素換算で、水溶性フェノール樹脂１００質量部に対して、０．０５質量部以上が好ましく、０．０６質量部以上がより好ましく、０．０７質量部以上がさらに好ましく、０．０９質量部が特に好ましい。また、アミン化合物の含有量は窒素換算で、水溶性フェノール樹脂１００質量部に対して、０．５３質量部以下が好ましく、０．４０質量部以下がより好ましく、０．３０質量部以下がさらに好ましく、０．２０質量部以下が特に好ましい。アミン化合物の含有量が上記下限値以上であれば、ホルムアルデヒドの発生量をより低減できる。アミン化合物の含有量が上記上限値以下であれば、鋳型の強度を良好に維持できる。
アミン化合物の含有量の前記の上限及び下限は任意に組み合わせることができる。例えば、アミン化合物の含有量は窒素換算で、水溶性フェノール樹脂１００質量部に対して、０．０５～０．５３質量部が好ましく、０．０６～０．４０質量部がより好ましく、０．０７～０．３０質量部がさらに好ましく、０．０９～０．２０質量部が特に好ましい。
The content of the amine compound is preferably 0.05 parts by mass or more, more preferably 0.06 parts by mass or more, even more preferably 0.07 parts by mass or more, and particularly preferably 0.09 parts by mass, relative to 100 parts by mass of the water-soluble phenolic resin, in terms of nitrogen. The content of the amine compound is preferably 0.53 parts by mass or less, more preferably 0.40 parts by mass or less, even more preferably 0.30 parts by mass or less, and particularly preferably 0.20 parts by mass or less, relative to 100 parts by mass of the water-soluble phenolic resin, in terms of nitrogen. If the content of the amine compound is equal to or more than the lower limit, the amount of formaldehyde generated can be further reduced. If the content of the amine compound is equal to or less than the upper limit, the strength of the mold can be well maintained.
The upper and lower limits of the content of the amine compound can be arbitrarily combined. For example, the content of the amine compound is preferably 0.05 to 0.53 parts by mass, more preferably 0.06 to 0.40 parts by mass, even more preferably 0.07 to 0.30 parts by mass, and particularly preferably 0.09 to 0.20 parts by mass, relative to 100 parts by mass of the water-soluble phenolic resin, calculated as nitrogen.
窒素換算でのアミン化合物の含有量は、水溶性フェノール樹脂１００質量部に対するアミン化合物の含有量と、アミン化合物の分子量及び１分子当たりの窒素原子数から、下記式（ｉ）に基づき求めることができる。
窒素換算でのアミン化合物の含有量＝（アミン化合物の含有量／アミン化合物の分子量）×１４．０×窒素原子数 ・・・（ｉ）
The content of the amine compound in terms of nitrogen can be calculated based on the content of the amine compound relative to 100 parts by mass of the water-soluble phenolic resin, the molecular weight of the amine compound, and the number of nitrogen atoms per molecule, according to the following formula (i).
Amine compound content in terms of nitrogen=(amine compound content/molecular weight of amine compound)×14.0×number of nitrogen atoms (i)
＜任意成分＞
任意成分としては、例えばシランカップリング剤；水、有機溶剤等の溶剤などが挙げられる。有機溶剤としては、例えばメタノールなどが挙げられる。
粘結剤組成物がシランカップリング剤を含んでいれば、鋳型の強度がさらに向上する。
シランカップリング剤としては、例えばＮ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、３－アミノプロピルトリエトキシシラン、３－（２－アミノエチル）アミノ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などが挙げられる。
<Optional ingredients>
Examples of the optional components include a silane coupling agent, water, and solvents such as organic solvents. Examples of the organic solvent include methanol.
If the binder composition contains a silane coupling agent, the strength of the mold is further improved.
Examples of the silane coupling agent include N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane.
粘結剤組成物は、本発明の効果を損なわない範囲内であれば、上述したアミン化合物以外のホルムアルデヒド捕捉剤（以下、「他のホルムアルデヒド捕捉剤」ともいう。）を含んでいてもよい。但し、本実施形態の粘結剤組成物は、他のホルムアルデヒド捕捉剤を含んでいなくても十分にホルムアルデヒドの発生量を低減できるので、他のホルムアルデヒド捕捉剤を含む必要がない。鋳型強度、鋳型の製造コスト、鋳物製品の品質等を考慮すると、粘結剤組成物は他のホルムアルデヒド捕捉剤を実質的に含まないことが好ましい。
ここで、「実質的に含まない」とは、意図せずして含有するものを除き、積極的に他のホルムアルデヒド捕捉剤を粘結剤組成物にしないことを意味する。
他のホルムアルデヒド捕捉剤としては、例えば尿素、レゾルシン、ピロガロールなどが挙げられる。
The binder composition may contain a formaldehyde scavenger other than the above-mentioned amine compound (hereinafter, also referred to as "other formaldehyde scavengers") within a range that does not impair the effects of the present invention. However, since the binder composition of the present embodiment can sufficiently reduce the amount of formaldehyde generated without containing other formaldehyde scavengers, it is not necessary to contain other formaldehyde scavengers. In consideration of mold strength, mold manufacturing costs, quality of cast products, and the like, it is preferable that the binder composition does not substantially contain other formaldehyde scavengers.
Here, the term "substantially free" means that, except for those unintentionally contained, other formaldehyde scavengers are not intentionally added to the binder composition.
Other formaldehyde scavengers include, for example, urea, resorcinol, pyrogallol, and the like.
＜製造方法＞
粘結剤組成物は、水溶性フェノール樹脂及びアミン化合物と、必要に応じて任意成分とを混合することで得られる。
なお、粘結剤組成物が任意成分を含む場合、予め水溶性フェノール樹脂に任意成分を添加しておいてもよい。
<Production Method>
The binder composition can be obtained by mixing a water-soluble phenolic resin and an amine compound, and, if necessary, any optional components.
When the binder composition contains an optional component, the optional component may be added in advance to the water-soluble phenolic resin.
＜作用効果＞
以上説明した本実施形態の粘結剤組成物は、上述したアミン化合物を含むので、粘結剤組成物の硬化時等にホルムアルデヒドが発生しても、発生したホルムアルデヒドを捕捉できる。これは、例えば以下の反応式に示すように、水溶性フェノール樹脂と、ホルムアルデヒドと、アミン化合物とが反応（マンニッヒ反応）することで、ホルムアルデヒドが反応生成物中に取り込まれることによるものと考えられる。なお、以下に示す反応式は、水溶性フェノール樹脂がアルカリレゾール樹脂であり、アミン化合物がモノエタノールアミンである場合の反応式である。
<Action and effect>
The binder composition of the present embodiment described above contains the above-mentioned amine compound, so even if formaldehyde is generated during curing of the binder composition, the generated formaldehyde can be captured. This is thought to be because, as shown in the following reaction formula, for example, the water-soluble phenolic resin, formaldehyde, and the amine compound react (Mannich reaction) to capture the formaldehyde in the reaction product. Note that the reaction formula shown below is a reaction formula for the case where the water-soluble phenolic resin is an alkali resol resin and the amine compound is monoethanolamine.
また、上述したように、ホルムアルデヒドは反応生成物中に取り込まれる。すなわち、ホルムアルデヒドを水溶性フェノール樹脂に取り込みつつ、硬化反応が進行するので、鋳型の強度を維持できる。
また、アミン化合物を含んだ粘結剤組成物は増粘しにくいので、保存安定性にも優れる。
加えて、アミン化合物はレゾルシンと比較して安価であることから、鋳型の製造コストを抑えることもできる。
As described above, the formaldehyde is incorporated into the reaction product. That is, the hardening reaction proceeds while the formaldehyde is being incorporated into the water-soluble phenolic resin, so that the strength of the mold can be maintained.
In addition, the binder composition containing the amine compound is less likely to thicken, and therefore has excellent storage stability.
In addition, since amine compounds are cheaper than resorcinol, the manufacturing cost of the mold can be reduced.
ところで、粘結剤組成物中の窒素原子含有量が多いと、得られる鋳型中の窒素原子含有量も増えることとなる。そのような鋳型を用いて鋳物を製造すると、ピンホールと呼ばれるガス欠陥（鋳物欠陥）を誘発することがある。
しかし、本実施形態の粘結剤組成物であれば、少量のアミン化合物でもホルムアルデヒドの発生量を十分に低減できるので、必要以上にアミン化合物を配合する必要がない。アミン化合物の含有量が少量であるほど、粘結剤組成物中の窒素原子含有量を減らすことができ、最終的な鋳物製品のガス欠陥を抑制できる。
However, if the binder composition contains a large amount of nitrogen atoms, the resulting mold will also contain a large amount of nitrogen atoms. If such a mold is used to produce a casting, a gas defect (casting defect) called a pinhole may be induced.
However, in the binder composition of the present embodiment, even a small amount of the amine compound can sufficiently reduce the amount of formaldehyde generated, so there is no need to mix an amine compound more than necessary. The smaller the content of the amine compound, the more the nitrogen atom content in the binder composition can be reduced, and the more gas defects in the final cast product can be suppressed.
［砂組成物］
以下、本発明の第二の態様の砂組成物の一実施形態について説明する。
本実施形態の砂組成物は、上述した本発明の第一の態様の粘結剤組成物と、耐火性粒状材料とを含む。
砂組成物は、有機エステルをさらに含んでいてもよい。
砂組成物は、本発明の効果を損なわない範囲内であれば、必要に応じて、粘結剤組成物、耐火性粒状材料及び有機エステルに加えて、これら以外の成分（以下、「任意成分」ともいう。）をさらに含んでいてもよい。
Sand Composition
Hereinafter, one embodiment of the sand composition according to the second aspect of the present invention will be described.
The sand composition of this embodiment comprises the binder composition of the first aspect of the invention described above and a refractory granular material.
The sand composition may further comprise an organic ester.
The sand composition may contain, in addition to the binder composition, the refractory granular material and the organic ester, further components other than these (hereinafter also referred to as "optional components"), as necessary, within a range that does not impair the effects of the present invention.
＜耐火性粒状材料＞
耐火性粒状材料としては、珪砂、クロマイト砂、ジルコン砂、オリビン砂、非晶質シリカ、アルミナ砂、ムライト砂等の天然砂；人工砂などの従来公知のものを使用できる。また、使用済みの耐火性粒状材料を回収したもの（回収砂）や再生処理したもの（再生砂）なども使用できる。製造コストの観点では天然砂が好ましく、その中でも珪砂がより好ましい。熱により膨張しにくい観点では人工砂が好ましい。製造コストと耐熱性とのバランスを考慮し、天然砂と人工砂とを混合して用いてもよい。
これら耐火性粒状材料は、１種単独で用いてもよく、２種以上を併用してもよい。
<Fire-resistant granular material>
As the refractory granular material, conventionally known materials such as natural sands, such as silica sand, chromite sand, zircon sand, olivine sand, amorphous silica, alumina sand, and mullite sand, and artificial sand can be used. In addition, used refractory granular materials that have been recovered (recovered sand) or regenerated (regenerated sand) can also be used. From the viewpoint of production costs, natural sand is preferred, and among them, silica sand is more preferred. Artificial sand is preferred from the viewpoint of resistance to expansion due to heat. Taking into consideration the balance between production costs and heat resistance, natural sand and artificial sand may be mixed and used.
These refractory granular materials may be used alone or in combination of two or more.
耐火性粒状材料の平均粒子径は５０～６００μｍが好ましく、１００～５５０μｍがより好ましく、２００～５００μｍがさらに好ましい。耐火性粒状材料の平均粒子径が上記下限値以上であれば、強度の高い鋳型が得られる。耐火性粒状材料の平均粒子径が上記上限値以下であれば、鋳型を用いて鋳造される鋳物の表面性に優れる。
耐火性粒状材料の平均粒子径は、動的光散乱法により測定した耐火性粒状材料の体積分布基準での累積頻度５０％に相当する粒子径（メジアン径）である。
The average particle size of the refractory granular material is preferably 50 to 600 μm, more preferably 100 to 550 μm, and even more preferably 200 to 500 μm. If the average particle size of the refractory granular material is equal to or greater than the lower limit, a mold with high strength can be obtained. If the average particle size of the refractory granular material is equal to or less than the upper limit, the surface quality of the casting cast using the mold is excellent.
The average particle size of the refractory granular material is a particle size (median size) corresponding to a cumulative frequency of 50% on a volume distribution basis of the refractory granular material measured by dynamic light scattering.
＜粘結剤組成物＞
粘結剤組成物の含有量は、耐火性粒状材料１００質量部に対して、０．５～３．０質量部が好ましく、０．８～２．０質量部がより好ましく、１．０～１．５質量部がさらに好ましい。粘結剤組成物の含有量が上記下限値以上であれば、強度がより高い鋳型が得られやすい。粘結剤組成物の含有量が上記上限値以下であれば、混練ムラが起きにくい。
なお、本明細書において、「粘結剤組成物の含有量」は純分換算量である。すなわち、粘結剤組成物が溶剤を含む場合は、粘結剤組成物の全質量から溶剤の全含有量を除いた質量のことである。
<Binding agent composition>
The content of the binder composition is preferably 0.5 to 3.0 parts by mass, more preferably 0.8 to 2.0 parts by mass, and even more preferably 1.0 to 1.5 parts by mass, based on 100 parts by mass of the refractory granular material. If the content of the binder composition is equal to or greater than the above lower limit, a mold having higher strength is likely to be obtained. If the content of the binder composition is equal to or less than the above upper limit, uneven kneading is unlikely to occur.
In this specification, the "content of the binder composition" is a pure content. In other words, when the binder composition contains a solvent, it is the mass obtained by subtracting the total content of the solvent from the total mass of the binder composition.
＜有機エステル＞
本実施形態の砂組成物に含まれる有機エステルは、液状である。
液状の有機エステルとしては、アルカリフェノール樹脂の硬化剤として用いられているものを使用することができ、例えばギ酸メチル、ギ酸エチル、プロピレンカーボネート、モノアセチン、ジアセチン、トリアセチン、エチレングリコールモノアセテート、エチレングリコールジアセテート、γ－ブチロラクトン、プロピオラクトン、ε－カプロラクトンなどが挙げられる。
これら液状の有機エステルは、１種単独で用いてもよく、２種以上を併用してもよい。
<Organic ester>
The organic ester contained in the sand composition of the present embodiment is in liquid form.
As the liquid organic ester, those used as curing agents for alkaline phenol resins can be used, such as methyl formate, ethyl formate, propylene carbonate, monoacetin, diacetin, triacetin, ethylene glycol monoacetate, ethylene glycol diacetate, γ-butyrolactone, propiolactone, and ε-caprolactone.
These liquid organic esters may be used alone or in combination of two or more.
有機エステルの含有量は、耐火性粒状材料１００質量部に対して、０．１～０．６質量部が好ましく、０．１６～０．４質量部がより好ましく、０．２～０．３質量部がさらに好ましい。有機エステルの含有量が上記下限値以上であれば、粘結剤組成物を十分に硬化させることができる。有機エステルの含有量が上記上限値以下であれば、過剰含有による注湯時のガスの発生量を抑制できる。 The content of the organic ester is preferably 0.1 to 0.6 parts by mass, more preferably 0.16 to 0.4 parts by mass, and even more preferably 0.2 to 0.3 parts by mass, per 100 parts by mass of the refractory granular material. If the content of the organic ester is equal to or greater than the lower limit, the binder composition can be sufficiently hardened. If the content of the organic ester is equal to or less than the upper limit, the amount of gas generated during pouring due to excessive content can be suppressed.
＜任意成分＞
任意成分としては、本発明の第一の態様の粘結剤組成物の説明において先に例示した任意成分が挙げられる。
砂組成物は、本発明の効果を損なわない範囲内であれば、他のホルムアルデヒド捕捉剤を含んでいてもよい。但し、砂組成物に含まれる粘結剤組成物は、他のホルムアルデヒド捕捉剤を含んでいなくても十分にホルムアルデヒドの発生量を低減できるので、砂組成物は他のホルムアルデヒド捕捉剤を含む必要がない。鋳型強度、鋳型の製造コスト、鋳物製品の品質等を考慮すると、砂組成物は他のホルムアルデヒド捕捉剤を実質的に含まないことが好ましい。
<Optional ingredients>
Examples of the optional components include the optional components exemplified above in the description of the binder composition according to the first embodiment of the present invention.
The sand composition may contain other formaldehyde scavengers as long as the effects of the present invention are not impaired. However, since the binder composition contained in the sand composition can sufficiently reduce the amount of formaldehyde generated without containing other formaldehyde scavengers, the sand composition does not need to contain other formaldehyde scavengers. Considering the mold strength, the manufacturing cost of the mold, the quality of the cast product, etc., it is preferable that the sand composition does not substantially contain other formaldehyde scavengers.
＜製造方法＞
砂組成物は、耐火性粒状材料及び粘結剤組成物と、必要に応じて有機エステル及び任意成分の１つ以上とを混合することで得られる。
なお、砂組成物が有機エステルを含む場合、耐火性粒状材料と有機エステルとを混合して混合物を得た後に、得られた混合物に粘結剤組成物と、必要に応じて任意成分とを加えて、さらに混合することが好ましい。
<Production Method>
The sand composition is obtained by mixing the refractory granular material and the binder composition, optionally with the organic ester and one or more of the optional ingredients.
In addition, when the sand composition contains an organic ester, it is preferable to mix the refractory granular material and the organic ester to obtain a mixture, and then add the binder composition and, if necessary, optional components to the obtained mixture and further mix them.
＜作用効果＞
以上説明した本実施形態の砂組成物は、上述した本発明の第一の態様の粘結剤組成物を含むので、ホルムアルデヒドの発生量を低減できる。また、本実施形態の砂組成物を用いれば、実用的な強度の鋳型を製造できる。
<Action and effect>
The sand composition of the present embodiment described above contains the binder composition of the first aspect of the present invention, and therefore can reduce the amount of formaldehyde generated. Furthermore, by using the sand composition of the present embodiment, a mold with practical strength can be manufactured.
［鋳型造型用キット］
以下、本発明の第三の態様の鋳型造型用キットの一実施形態について説明する。
本実施形態の鋳型造型用キットは、耐火性粒状材料と、上述した本発明の第一の態様の粘結剤組成物とを各々独立して有する。
鋳型造型用キットは、以下に示す硬化剤をさらに独立して有していてもよい。
ここで、「独立して有する」とは、各々の成分が互いに混合、接触しない状態で存在していることを意味する。各成分は、鋳型造型用キットを使用するときに初めて混合、接触される。
鋳型造型用キットとしては、例えば各成分を別々に収容した容器の集合体であってもよい。
[Mold making kit]
Hereinafter, one embodiment of the mold making kit according to the third aspect of the present invention will be described.
The mold making kit of this embodiment independently contains a refractory granular material and the binder composition of the first aspect of the present invention described above.
The mold making kit may further independently contain a hardener as described below.
Here, "independently possessed" means that each component is present without being mixed or in contact with each other. Each component is first mixed or in contact with each other when the mold making kit is used.
The mold making kit may be, for example, a collection of containers each containing a separate component.
鋳型造型用キットに含まれる耐火性粒状材料としては、本発明の第二の態様の砂組成物の説明において先に例示した耐火性粒状材料が挙げられる。 The refractory granular material contained in the foundry mold making kit includes the refractory granular materials exemplified above in the description of the sand composition of the second embodiment of the present invention.
鋳型造型用キットに含まれる硬化剤は、有機エステル及び炭酸ガスからなる群より選ばれる１種である。
鋳型造型用キットに含まれる有機エステルは、液状又はガス状である。
液状の有機エステルとしては、本発明の第二の態様の砂組成物の説明において先に例示した液状の有機エステルが挙げられる。
ガス状の有機エステルとしては、液状の有機エステルをガス化したものが挙げられる。
中でも、ギ酸メチルをガス化したギ酸メチルガス、ギ酸エチルをガス化したギ酸エチルガスが好ましい。
これらガス状の有機エステルは、１種単独で用いてもよく、２種以上を併用してもよい。
The hardener contained in the mold making kit is one selected from the group consisting of organic esters and carbon dioxide gas.
The organic ester contained in the mold making kit may be in liquid or gaseous form.
Examples of the liquid organic ester include the liquid organic esters exemplified above in the explanation of the sand composition according to the second embodiment of the present invention.
The gaseous organic ester may be a gasified liquid organic ester.
Among these, methyl formate gas obtained by gasifying methyl formate and ethyl formate gas obtained by gasifying ethyl formate are preferable.
These gaseous organic esters may be used alone or in combination of two or more.
鋳型造型用キットが、各成分を別々に収容した容器の集合体である場合、耐火性粒状材料を収容した容器及び粘結剤組成物を収容した容器の少なくとも一方には、任意成分が含まれていてもよい。なお、これら容器には、他のホルムアルデヒド捕捉剤を実質的に含まないことが好ましい。
任意成分としては、本発明の第一の態様の粘結剤組成物の説明において先に例示した任意成分が挙げられる。
When the mold making kit is a collection of containers each containing a component separately, at least one of the container containing the refractory granular material and the container containing the binder composition may contain optional components, and preferably these containers are substantially free of other formaldehyde scavengers.
Examples of the optional components include the optional components exemplified above in the description of the binder composition according to the first embodiment of the present invention.
［鋳型の製造方法］
本発明の第四の態様の鋳型の製造方法は、自硬性鋳型造型法により鋳型を製造する方法である。
本発明の第五の態様の鋳型の製造方法は、ガス硬化鋳型造型法により鋳型を製造する方法である。
[Method of manufacturing the mold]
The method for producing a mold according to the fourth embodiment of the present invention is a method for producing a mold by a self-hardening mold making method.
The fifth aspect of the method for producing a casting mold of the present invention is a method for producing a casting mold by a gas hardening casting molding method.
本発明の第四の態様の鋳型の製造方法では、本発明の第二の態様の砂組成物のうち有機エステルを含むものを鋳型製造用の型（鋳型造型用型）に充填し、砂組成物に含まれる有機エステルの硬化作用により粘結剤組成物を硬化させて、鋳型を製造する。
また、本発明の第三の態様の鋳型造型用キットを用いて鋳型を製造してもよい。その場合は、耐火性粒状材料と、本発明の第一の態様の粘結剤組成物と、液状の有機エステルと、必要に応じて任意成分とを混合して砂組成物とし、得られた砂組成物を鋳型造型用型に充填すればよい。本発明の第三の態様の鋳型造型用キットが液状の有機エステルを独立して有する場合、その鋳型造型用キットを構成する有機エステルを用いて砂組成物を調製すればよい。
In the method for producing a casting mold of the fourth aspect of the present invention, the sand composition of the second aspect of the present invention containing an organic ester is filled into a mold for producing a casting mold (mold for casting), and the binder composition is hardened by the hardening action of the organic ester contained in the sand composition to produce the mold.
A mold may be manufactured using the mold-making kit of the third aspect of the present invention. In this case, a refractory granular material, the binder composition of the first aspect of the present invention, a liquid organic ester, and optional components as necessary are mixed to prepare a sand composition, and the obtained sand composition is filled into a mold for mold-making. When the mold-making kit of the third aspect of the present invention independently contains a liquid organic ester, the organic ester constituting the mold-making kit may be used to prepare a sand composition.
本発明の第五の態様の鋳型の製造方法では、本発明の第二の態様の砂組成物のうち有機エステルを含まないものを鋳型造型用型に充填し、有機エステル又は炭酸ガスを通気させて、有機エステル又は炭酸ガスの硬化作用により砂組成物に含まれる粘結剤組成物を硬化させて、鋳型を製造する。
また、本発明の第三の態様の鋳型造型用キットを用いて鋳型を製造してもよい。その場合は、耐火性粒状材料と、本発明の第一の態様の粘結剤組成物と、必要に応じて任意成分とを混合して砂組成物とし、得られた砂組成物を鋳型造型用型に充填すればよい。本発明の第三の態様の鋳型造型用キットがガス状の有機エステル又は炭酸ガスを独立して有する場合は、その鋳型造型用キットを構成する有機エステル又は炭酸ガスを用いて、鋳型造型用型中の砂組成物に通気させてもよい。
In the method for producing a casting mold of the fifth aspect of the present invention, the sand composition of the second aspect of the present invention that does not contain an organic ester is filled into a foundry molding mold, and an organic ester or carbon dioxide gas is passed through to harden the binder composition contained in the sand composition by the hardening action of the organic ester or carbon dioxide gas, thereby producing a casting mold.
A mold may be manufactured using the mold-making kit of the third aspect of the present invention. In this case, a refractory granular material, the binder composition of the first aspect of the present invention, and optional components, if necessary, are mixed to form a sand composition, and the resulting sand composition is filled into a mold for mold-making. When the mold-making kit of the third aspect of the present invention independently contains a gaseous organic ester or carbon dioxide gas, the organic ester or carbon dioxide gas constituting the mold-making kit may be used to aerate the sand composition in the mold for mold-making.
有機エステル又は炭酸ガスの通気流量は１分間あたり５～３０Ｌが好ましく、１０～２０Ｌがより好ましい。通気流量が上記下限値以上であれば、粘結剤組成物が十分に硬化する。通気流量が上記上限値以下であれば、鋳型の常温強度を良好に維持できる。
有機エステル又は炭酸ガスを通気させる時間（通気時間）は、３０～１８０秒が好ましく、６０～１８０秒がより好ましい。通気時間が上記下限値以上であれば、粘結剤組成物が十分に硬化するが、上記上限値を超えても粘結剤組成物の硬化は頭打ちとなるため、コストを高めるだけである。
The flow rate of the organic ester or carbon dioxide gas is preferably 5 to 30 L per minute, more preferably 10 to 20 L per minute. If the flow rate is equal to or higher than the lower limit, the binder composition is sufficiently cured. If the flow rate is equal to or lower than the upper limit, the room temperature strength of the mold can be well maintained.
The time for aerating the organic ester or carbon dioxide gas (aeration time) is preferably 30 to 180 seconds, more preferably 60 to 180 seconds. If the aeration time is equal to or more than the lower limit, the binder composition is sufficiently cured, but if the aeration time exceeds the upper limit, the curing of the binder composition reaches a plateau, which simply increases the cost.
以上説明した本実施形態の鋳型の製造方法によれば、耐火性粒状材料と本発明の第一の態様の粘結剤組成物とを含む砂組成物を用いているので、鋳型の強度を維持しつつ、ホルムアルデヒドの発生量を低減できる。 The mold manufacturing method of this embodiment described above uses a sand composition containing a refractory granular material and the binder composition of the first aspect of the present invention, so that the amount of formaldehyde generated can be reduced while maintaining the strength of the mold.
以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。各例で用いた材料を以下に示す。また、各種測定方法は以下の通りである。
なお、以下の各例において「部」、「％」「ｐｐｍ」は、それぞれ、特に限定のない場合は「質量部」、「質量％」、「質量ｐｐｍ」を示す。
実施例３～９は参考例である。
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these. The materials used in each example are shown below. Various measurement methods are also as follows.
In the following examples, unless otherwise specified, "parts", "%" and "ppm" respectively represent "parts by mass", "% by mass" and "ppm by mass".
Examples 3 to 9 are for reference only.
［測定・評価方法］
＜ホルムアルデヒドの発生量の測定＞
１Ｌのポリエチレン製の容器に、混練直後の砂組成物３０．０ｇを入れ、温度２０℃、湿度５０％の条件で１時間保存した。保存後の容器中に発生したホルムアルデヒド量を北川式ガス検知管により測定した。
[Measurement and evaluation method]
<Measurement of the amount of formaldehyde generated>
30.0 g of the sand composition immediately after kneading was placed in a 1 L polyethylene container and stored for 1 hour under conditions of a temperature of 20° C. and a humidity of 50%. The amount of formaldehyde generated in the container after storage was measured using a Kitagawa gas detector.
＜圧縮強度の測定＞
試験片の圧縮強度は、ＪＩＳ Ｚ ２６０１の鋳物砂の試験方法に準じて、卓上抗圧力試験機（高千穂機械株式会社製）を用いて測定した。
<Measurement of Compressive Strength>
The compressive strength of the test pieces was measured using a bench-top compression tester (manufactured by Takachiho Kikai Co., Ltd.) in accordance with the testing method for molding sand of JIS Z 2601.
＜保存安定性の評価＞
１Ｌのポリエチレン製の容器に、調製直後の粘結剤組成物１ｋｇを入れ、温度３５℃、湿度５０％の条件で１５日間保存した。保存前と保存後の粘結剤組成物のそれぞれについて、Ｅ型粘度計（東機産業株式会社製、製品名「ＶＩＳＣＯＭＥＴＥＲ ＴＶ－２５」）を使用して、２５℃における粘度を測定した。保存前の粘結剤組成物の粘度に対する、保存後の粘結剤組成物の粘度上昇を求め、以下の評価基準にて粘結剤組成物の保存安定性を評価した。
〇：粘度上昇が１．２倍未満である。
×：粘度上昇が１．２倍以上である。
<Evaluation of storage stability>
1 kg of the binder composition immediately after preparation was placed in a 1 L polyethylene container and stored for 15 days under conditions of a temperature of 35° C. and a humidity of 50%. The viscosity of each of the binder compositions before and after storage was measured at 25° C. using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name "VISCOMETER TV-25"). The increase in viscosity of the binder composition after storage relative to the viscosity of the binder composition before storage was determined, and the storage stability of the binder composition was evaluated according to the following evaluation criteria.
Good: The viscosity increase is less than 1.2 times.
×: Viscosity increase is 1.2 times or more.
＜窒素原子含有量の算出＞
粘結剤組成物の調製に用いた各種成分の配合量、添加剤の分子量及び１分子当たりの窒素原子数から、下記式（ii）に基づき粘結剤組成物中の窒素原子含有量を算出した。なお、窒素原子含有量は、粘結剤組成物の総質量に対する量（ｐｐｍ）である。
粘結剤組成物中の窒素原子含有量＝１００×１０，０００×｛（添加剤の配合量／添加剤の分子量）×窒素原子の原子量（１４．０）｝×窒素原子数／（水溶性フェノール樹脂と添加剤と水の配合量の合計） ・・・（ii）
<Calculation of Nitrogen Atom Content>
The nitrogen atom content in the binder composition was calculated based on the amounts of the various components used in the preparation of the binder composition, the molecular weight of the additive, and the number of nitrogen atoms per molecule according to the following formula (ii). The nitrogen atom content is the amount (ppm) relative to the total mass of the binder composition.
Nitrogen atom content in binder composition=100×10,000×{(amount of additive mixed/molecular weight of additive)×atomic weight of nitrogen atom (14.0)}×number of nitrogen atoms/(total amount of water-soluble phenolic resin, additive, and water mixed) (ii)
［水溶性フェノール樹脂の合成］
撹拌機、温度計、アリーン冷却管、滴下ロートを付けた３Ｌの４つ口フラスコに、フェノール３６４．９ｇ（３．６９ｍｏｌ)、５０％ホルマリン４２０．３ｇ（７．００ｍｏｌ）、炭酸亜鉛１．７３ｇ（０．０１４ｍｏｌ）、イオン交換水１３８．８ｇを投入し、４８％水酸化ナトリウム水溶液１０４．１ｇをさらに投入した。
次いで、４つ口フラスコにマントルヒーターを取り付け、内温が９０℃になるまで昇温した後、９０℃にて２時間保持した。次いで、イオン交換水２１９．６ｇを投入し、撹拌により均一混合させた後、４８％水酸化ナトリウム水溶液６９．４ｇと、４８％水酸化カリウム水溶液１３８．８ｇとを液温が４５℃以下となる滴下速度にて順次投入した。次いで、シランカップリング剤として３－グリシドキシプロピルトリエトキシシラン（信越化学工業株式会社製、商品名「信越シリコーンＭＢＥ－４０３」）１０．４ｇを投入した後、さらにイオン交換水２８．７ｇを投入し、水溶性フェノール樹脂であるアルカリレゾール樹脂１４８７．６ｇを得た。
得られた水溶性フェノール樹脂の純分が４５％になるようにイオン交換水に溶解して水溶液を調製した。得られた水溶液の２５℃におけるｐＨを測定したところ、１２．５であった。
[Synthesis of water-soluble phenolic resin]
Into a 3 L four-neck flask equipped with a stirrer, a thermometer, an Allen condenser, and a dropping funnel, 364.9 g (3.69 mol) of phenol, 420.3 g (7.00 mol) of 50% formalin, 1.73 g (0.014 mol) of zinc carbonate, and 138.8 g of ion-exchanged water were added, and 104.1 g of a 48% aqueous sodium hydroxide solution was further added.
Next, a mantle heater was attached to the four-neck flask, and the internal temperature was raised to 90°C, and then the mixture was maintained at 90°C for 2 hours. Next, 219.6g of ion-exchanged water was added, and the mixture was mixed uniformly by stirring. Then, 69.4g of 48% aqueous sodium hydroxide solution and 138.8g of 48% aqueous potassium hydroxide solution were added in sequence at a drop rate such that the liquid temperature was 45°C or less. Next, 10.4g of 3-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "Shin-Etsu Silicone MBE-403") was added as a silane coupling agent, and then 28.7g of ion-exchanged water was added to obtain 1487.6g of an alkali resol resin, which is a water-soluble phenolic resin.
The water-soluble phenolic resin was dissolved in ion-exchanged water to prepare an aqueous solution having a purity of 45%. The pH of the aqueous solution at 25° C. was measured and found to be 12.5.
［実施例１～９、比較例１～５］
＜粘結剤組成物の調製＞
表１～３に示す配合組成に従って、水溶性フェノール樹脂と、添加剤と、粘結剤組成物中の水溶性フェノール樹脂の含有量が４５％となるのに必要なイオン交換水とを２０℃で均一になるまで混合し、粘結剤組成物を得た。なお、表中の水溶性フェノール樹脂の配合量は、純分換算での量である。また、表中の溶剤の配合量は、粘結剤組成物に含まれる溶剤の合計量である。溶剤には、粘結剤組成物の調製の際に用いたイオン交換水に加えて、水溶性フェノール樹脂の合成に用いた原料から持ち込まれる溶剤が含まれる。
得られた粘結剤組成物中の窒素原子含有量を求めた。
また、実施例２及び比較例２、４で得られた粘結剤組成物については、保存安定性を評価した。結果を表１、３に示す。
[Examples 1 to 9, Comparative Examples 1 to 5]
<Preparation of Binder Composition>
According to the formulations shown in Tables 1 to 3, the water-soluble phenolic resin, the additives, and the ion-exchanged water necessary to make the content of the water-soluble phenolic resin in the binder composition 45% were mixed at 20°C until uniform, to obtain a binder composition. The amount of the water-soluble phenolic resin in the tables is the amount converted into a pure content. The amount of the solvent in the tables is the total amount of the solvent contained in the binder composition. The solvent includes the ion-exchanged water used in the preparation of the binder composition, as well as the solvent carried over from the raw materials used in the synthesis of the water-soluble phenolic resin.
The nitrogen atom content in the resulting binder composition was determined.
The binder compositions obtained in Example 2 and Comparative Examples 2 and 4 were evaluated for storage stability. The results are shown in Tables 1 and 3.
＜砂組成物の調製＞
表１～３に示す配合組成に従って、耐火性粒状材料と、有機エステルとしてアルカリフェノール樹脂用硬化剤（群栄化学工業株式会社製、アルファシステム硬化剤「ＡＨ－５３０」、トリアセチン及びエチレングリコールジアセテートの混合物）とを品川式万能撹拌機（株式会社品川工業所製、製品名「ＭＩＸＥＲ」）に投入し、６０秒間混練した。次いで、表１～３に示す配合組成に従って、粘結剤組成物をさらに投入し、６０秒間混練して砂組成物（混練砂）を得た。なお、表中の配合量は、純分換算での量である。
得られた砂組成物を用いて、ホルムアルデヒドの発生量を測定した。結果を表１～３に示す。
なお、耐火性粒状材料としては、天然砂又は人工砂を用いた。
天然砂としては、珪砂（三菱商事建材株式会社製、商品名「フリーマントル新砂」）若しくは珪砂（再生砂）を用いた。
人工砂としては、アルサンド（伊藤機工株式会社製、「アルサンド＃１０００」）を用いた。
Preparation of Sand Composition
According to the formulations shown in Tables 1 to 3, the fire-resistant granular material and an organic ester curing agent for alkaline phenolic resin (Alpha System Curing Agent "AH-530" manufactured by Gun-ei Chemical Industry Co., Ltd., a mixture of triacetin and ethylene glycol diacetate) were charged into a Shinagawa universal mixer (manufactured by Shinagawa Kogyosho Co., Ltd., product name "MIXER") and mixed for 60 seconds. Next, according to the formulations shown in Tables 1 to 3, a binder composition was further charged and mixed for 60 seconds to obtain a sand composition (mixed sand). The amounts in the tables are calculated as pure contents.
The amount of formaldehyde generated from the resulting sand composition was measured, and the results are shown in Tables 1 to 3.
As the refractory granular material, natural sand or artificial sand was used.
As the natural sand, silica sand (manufactured by Mitsubishi Corporation Construction Materials Co., Ltd., product name "Fremantle New Sand") or silica sand (recycled sand) was used.
As the artificial sand, Alsand (manufactured by Ito Kiko Co., Ltd., "Alsand #1000") was used.
＜試験片の作製＞
砂組成物を直ちに温度２０℃、湿度５０％の条件下、直径５０ｍｍ、深さ５０ｍｍの円柱状の型が複数形成された木型に充填して、粘結剤組成物を硬化させ、混練開始から１時間経過した後に木型から試験片を取り出した。
混練開始から１時間、２時間、３時間及び２４時間経過後の試験片の圧縮強度を測定した。結果を表１～３に示す。
<Preparation of test specimen>
The sand composition was immediately filled into a wooden mold in which a plurality of cylindrical shapes of 50 mm in diameter and 50 mm in depth were formed under conditions of a temperature of 20° C. and a humidity of 50%, and the binder composition was allowed to harden. After 1 hour had passed from the start of kneading, a test piece was taken out of the wooden mold.
The compressive strength of the test pieces was measured 1 hour, 2 hours, 3 hours and 24 hours after the start of kneading. The results are shown in Tables 1 to 3.
表１～３から明らかなように、各実施例で得られた粘結剤組成物は、ホルムアルデヒドの発生量を低減できた。これら粘結剤組成物を用いて作製した試験片は圧縮強度が高かった。また、実施例２で得られた粘結剤組成物は保存安定性に優れていた。なお、残りの実施例で得られた粘結剤組成物についても、実施例２と同様の保存安定性を有している。
一方、添加剤を用いていない比較例１の場合、ホルムアルデヒドが発生しやすかった。
添加剤として尿素を用いた比較例２の場合、実施例４、６と同程度のホルムアルデヒドの発生量の低減効果を得るためには、実施例４、６で用いた添加剤（モノエチルアミン又はピペラジン）の４倍量の尿素が必要であった。また、比較例２で得られた試験片は、実施例４、６で得られた試験片よりも圧縮強度が低かった。
比較例３の場合、実施例８で用いた添加剤（モノエタノールアミン）の４倍量の尿素を用いたにも関わらず、ホルムアルデヒドが発生しやすかった。
添加剤としてレゾルシンを含む比較例４で得られた粘結剤組成物は、保存安定性に劣っていた。
添加剤として３級アミンを用いた比較例５の場合、ホルムアルデヒドが発生しやすかった。
As is clear from Tables 1 to 3, the binder compositions obtained in each Example were able to reduce the amount of formaldehyde generated. The test pieces prepared using these binder compositions had high compressive strength. In addition, the binder composition obtained in Example 2 had excellent storage stability. The binder compositions obtained in the remaining Examples also had the same storage stability as Example 2.
On the other hand, in the case of Comparative Example 1 in which no additive was used, formaldehyde was easily generated.
In the case of Comparative Example 2, in which urea was used as an additive, in order to obtain the same degree of reduction in the amount of formaldehyde generated as in Examples 4 and 6, four times the amount of urea was required as the additive (monoethylamine or piperazine) used in Examples 4 and 6. In addition, the test pieces obtained in Comparative Example 2 had lower compressive strength than the test pieces obtained in Examples 4 and 6.
In the case of Comparative Example 3, even though four times the amount of urea was used as the additive (monoethanolamine) used in Example 8, formaldehyde was easily generated.
The binder composition obtained in Comparative Example 4, which contained resorcin as an additive, had poor storage stability.
In the case of Comparative Example 5 in which a tertiary amine was used as the additive, formaldehyde was easily generated.
以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。各例で用いた材料を以下に示す。また、各種測定方法は以下の通りである。
なお、以下の各例において「部」、「％」「ｐｐｍ」は、それぞれ、特に限定のない場合は「質量部」、「質量％」、「質量ｐｐｍ」を示す。
実施例２～９は参考例である。
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these. The materials used in each example are shown below. Various measurement methods are also as follows.
In the following examples, unless otherwise specified, "parts", "%" and "ppm" respectively represent "parts by mass", "% by mass" and "ppm by mass".
Examples 2 to 9 are for reference only.
Claims (8)
１級アミン、２級アミン及び多価アミンからなる群より選ばれる１種以上のアミン化合物（但し、尿素を除く。）と、
を含み、
前記水溶性フェノール樹脂の濃度４５質量％水溶液の２５℃におけるｐＨが１２以上である、粘結剤組成物。 A water-soluble phenolic resin,
One or more amine compounds selected from the group consisting of primary amines, secondary amines, and polyamines (excluding urea);
Including,
The binder composition, wherein the pH of an aqueous solution of the water-soluble phenolic resin at a concentration of 45% by mass at 25° C. is 12 or more.
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