JP6173130B2 - 鋳型用ウレタン硬化型有機粘結剤並びにこれを用いて得られる鋳物砂組成物及び鋳型 - Google Patents
鋳型用ウレタン硬化型有機粘結剤並びにこれを用いて得られる鋳物砂組成物及び鋳型 Download PDFInfo
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- JP6173130B2 JP6173130B2 JP2013178899A JP2013178899A JP6173130B2 JP 6173130 B2 JP6173130 B2 JP 6173130B2 JP 2013178899 A JP2013178899 A JP 2013178899A JP 2013178899 A JP2013178899 A JP 2013178899A JP 6173130 B2 JP6173130 B2 JP 6173130B2
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- Prior art keywords
- mold
- organic binder
- phenol resin
- urethane
- acid
- Prior art date
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- 239000011230 binding agent Substances 0.000 title claims description 58
- 239000004576 sand Substances 0.000 title claims description 58
- 239000000203 mixture Substances 0.000 title claims description 40
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims description 32
- 239000005011 phenolic resin Substances 0.000 claims description 56
- 229920001228 polyisocyanate Polymers 0.000 claims description 41
- 239000005056 polyisocyanate Substances 0.000 claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 37
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 23
- 238000000465 moulding Methods 0.000 claims description 18
- 150000007942 carboxylates Chemical class 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 9
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 61
- 239000000243 solution Substances 0.000 description 29
- 238000005266 casting Methods 0.000 description 18
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 13
- -1 aluminum alloys Chemical class 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
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- 150000002989 phenols Chemical class 0.000 description 7
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- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 6
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
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- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 3
- OAWAZQITIZDJRB-UHFFFAOYSA-N 2-chloro-2,2-difluoroacetic acid Chemical compound OC(=O)C(F)(F)Cl OAWAZQITIZDJRB-UHFFFAOYSA-N 0.000 description 2
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
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- 239000012298 atmosphere Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
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- 238000012999 compression bending Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- SIEILFNCEFEENQ-UHFFFAOYSA-N dibromoacetic acid Chemical compound OC(=O)C(Br)Br SIEILFNCEFEENQ-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 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
- 230000007613 environmental effect Effects 0.000 description 2
- XIRNKXNNONJFQO-UHFFFAOYSA-N ethyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC XIRNKXNNONJFQO-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
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- 125000005843 halogen group Chemical group 0.000 description 2
- 229910021331 inorganic silicon compound Inorganic materials 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 2
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
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- Mold Materials And Core Materials (AREA)
Description
コールドボックス造型機のサンドマガジン内に、混練直後の鋳物砂組成物を投入した後、この鋳物砂組成物を曲げ強度試験片造型用金型内に充填し、引き続いて、その金型内に、硬化触媒としてのトリエチルアミンを通気せしめることにより、幅:30mm×長さ:85mm×厚さ:10mmの曲げ強度試験片を作製した。なお、かかる試験片の作製に際しては、金型内への鋳物砂組成物の充填条件を、圧力:0.3MPaで3秒間とする一方、トリエチルアミンのガッシングとエアーパージ条件は、それぞれ、圧力:0.3MPaで10秒間とした。そして、得られた曲げ強度試験片を、造型後に直ちに用いて、或いは、常温常湿下にて2時間又は24時間放置した後に用いて、各試験片の曲げ強度(N/cm2 )を高千穂精機株式会社製小型圧縮曲げ試験機SC200Dにて測定した。かかる測定は、放置時間毎に2回ずつ実施し、その平均値を算出した。なお、下記表1の「1分後」の欄には、造型直後の試験片についての曲げ強度試験の結果(平均値)を示している。
コールドボックス造型機のサンドマガジン内に、混練直後の鋳物砂組成物を投入した後、この鋳物砂組成物を曲げ強度試験片造型用金型内に充填し、引き続いて、その金型内に、硬化触媒としてのトリエチルアミンを通気せしめることにより、幅:30mm×長さ:85mm×厚さ:10mmの曲げ強度試験片を作製した。なお、かかる試験片の作製に際しては、金型内への鋳物砂組成物の充填条件を、圧力:0.3MPaで3秒間とする一方、トリエチルアミンのガッシングとエアーパージ条件は、それぞれ、圧力:0.3MPaで10秒間とした。そして、得られた曲げ強度試験片を、エスペック株式会社製小型環境試験機SH220を用いて、25℃×95%RHの条件の下に2時間又は24時間、処理し、かかる処理後の試験片について、高千穂精機株式会社製小型圧縮曲げ試験機SC200Dにて曲げ強度(N/cm2 )を測定した。かかる測定は、放置時間毎に2回ずつ実施し、その平均値を算出した。
還流器、温度計及び撹拌機を備えた三つ口反応フラスコ内に、フェノールの100質量部、92質量%パラホルムアルデヒドの55.5質量部及び二価金属塩としてナフテン酸鉛の0.32質量部を仕込み、還流温度で90分間反応を行なった後、加熱濃縮して、水分含有率1%以下のベンジルエーテル型フェノール樹脂を得た。次いで、得られたフェノール樹脂を、極性有機溶剤(DBE)及び非極性有機溶剤(イプゾール150)を用いて溶解、希釈すると共に、そこに、フェノール樹脂溶液量の1.5質量%γ−グリシドキシプロピルトリメトキシシランを加えて、フェノール樹脂分が50質量%のフェノール樹脂溶液を調製した。
ポリイソシアネート化合物であるポリメリックMDIを、非極性有機溶剤(イプゾール150)を用いて溶解すると共に、そこに、ポリメリックMDI量の0.93質量%のフタル酸クロライドを加えて、ポリイソシアネート化合物が75質量%のポリイソシアネート溶液を調製した。
先ず、予め調製したフェノール樹脂溶液100質量部に対して、表1に記載のハロゲン化カルボン酸成分を各々、0.3質量部添加して、撹拌することにより、ハロゲン化カルボン酸成分を均一に混合した。次いで、ダルトン株式会社製品川式卓上ミキサー内に、予め25℃×60%RHの雰囲気下にて24時間放置させておいたフラタリー珪砂1000質量部と、フェノール樹脂溶液10質量部(フェノール樹脂成分の量:5質量部、ハロゲン化カルボン酸成分の量:0.03質量部)と、ポリイソシアネート溶液10質量部(ポリイソシアネート化合物の量:約7.5質量部)とを、それぞれ投入し、40秒間撹拌し、混練することにより、有機粘結剤にて被覆された鋳物砂組成物を調製した。そして、得られた鋳物砂組成物について、上記の試験法に従って、常湿環境下及び高湿環境下における各鋳型強度(N/cm2 )を測定し、得られた結果を、下記表1に示した。
先ず、予め調製したフェノール樹脂溶液100質量部に対して、トリフルオロ酢酸を各々、下記表1に示す割合において添加して、撹拌することにより、トリフルオロ酢酸を均一に混合した。次いで、ダルトン株式会社製品川式卓上ミキサー内に、予め25℃×60%RHの雰囲気下にて24時間放置させておいたフラタリー珪砂1000質量部と、フェノール樹脂溶液10質量部(フェノール樹脂成分の量:5質量部、トリフルオロ酢酸の量:0.001、0.005、0.01、0.05、0.1、0.2、0.3又は0.5質量部)と、ポリイソシアネート溶液10質量部(ポリイソシアネート化合物の量:約7.5質量部)とを、それぞれ投入し、40秒間撹拌し、混練することにより、有機粘結剤にて被覆された鋳物砂組成物を調製した。そして、得られた鋳物砂組成物について、上記の試験法に従って、常湿環境下及び高湿環境下における各鋳型強度(N/cm2 )を測定し、得られた結果を、下記表1に示した。
ハロゲン化カルボン酸成分を用いることなく、ハロゲン化カルボン酸成分を含まないフェノール樹脂溶液の5質量部を用いた以外は実施例1と同様にして、鋳物砂組成物を調製した。得られた鋳物砂組成物について、上記の試験法に従って、常湿環境下及び高湿環境下における各鋳型強度(N/cm2 )を測定し、得られた結果を、下記表1に示した。
Claims (4)
- ウレタン系鋳型の造型に用いられる鋳型用ウレタン硬化型有機粘結剤であって、フェノール樹脂及びポリイソシアネート化合物と共に、ハロゲン化カルボン酸、ハロゲン化カルボン酸無水物及びハロゲン化カルボン酸塩からなる群より選ばれる一種以上の化合物と、イソフタル酸クロリド及びリン系クロライドより選ばれる一種以上の添加剤とを含有することを特徴とする鋳型用ウレタン硬化型有機粘結剤。
- 有機溶剤を更に含有する請求項1に記載の鋳型用ウレタン硬化型有機粘結剤。
- 前記ハロゲン化カルボン酸塩がハロゲン化カルボン酸ナトリウムである請求項1又は請求項2に記載の鋳型用ウレタン硬化型有機粘結剤。
- 請求項1乃至請求項3の何れか1項に記載の鋳型用ウレタン硬化型有機粘結剤を、鋳物砂に被覆せしめてなる鋳物砂組成物。
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