JPS6116213B2 - - Google Patents
Info
- Publication number
- JPS6116213B2 JPS6116213B2 JP13953080A JP13953080A JPS6116213B2 JP S6116213 B2 JPS6116213 B2 JP S6116213B2 JP 13953080 A JP13953080 A JP 13953080A JP 13953080 A JP13953080 A JP 13953080A JP S6116213 B2 JPS6116213 B2 JP S6116213B2
- Authority
- JP
- Japan
- Prior art keywords
- sand
- component
- mold
- polyol
- group
- 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.)
- Expired
Links
- 239000004576 sand Substances 0.000 claims description 67
- -1 polyol compound Chemical class 0.000 claims description 46
- 229920005862 polyol Polymers 0.000 claims description 43
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 36
- 238000005266 casting Methods 0.000 claims description 27
- 239000011230 binding agent Substances 0.000 claims description 25
- 239000005056 polyisocyanate Substances 0.000 claims description 20
- 229920001228 polyisocyanate Polymers 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 150000003077 polyols Chemical group 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 229910001234 light alloy Inorganic materials 0.000 claims description 10
- 229930185605 Bisphenol Natural products 0.000 claims description 9
- 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 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 76
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- 239000000203 mixture Substances 0.000 description 26
- 239000000047 product Substances 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 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 11
- 239000003110 molding sand Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000005011 phenolic resin Substances 0.000 description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229920001568 phenolic resin Polymers 0.000 description 8
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005056 compaction Methods 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 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 5
- 229920002866 paraformaldehyde Polymers 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000011134 resol-type phenolic resin Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 3
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 3
- AQIIVEISJBBUCR-UHFFFAOYSA-N 4-(3-phenylpropyl)pyridine Chemical compound C=1C=NC=CC=1CCCC1=CC=CC=C1 AQIIVEISJBBUCR-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical group C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000007849 furan resin Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- UUNMKKRWFDYYKW-UHFFFAOYSA-N 2,2-dimethylpentane-3,3-diamine Chemical compound CCC(N)(N)C(C)(C)C UUNMKKRWFDYYKW-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- OVOUKWFJRHALDD-UHFFFAOYSA-N 2-[2-(2-acetyloxyethoxy)ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOC(C)=O OVOUKWFJRHALDD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KOPGXQBFEROLEQ-UHFFFAOYSA-N benzhydrylbenzene;isocyanic acid Chemical compound N=C=O.C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 KOPGXQBFEROLEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- MYHDUJKDRGLQBN-UHFFFAOYSA-N ethyl 2-morpholin-4-ylpropanoate Chemical compound CCOC(=O)C(C)N1CCOCC1 MYHDUJKDRGLQBN-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- XJRAOMZCVTUHFI-UHFFFAOYSA-N isocyanic acid;methane Chemical compound C.N=C=O.N=C=O XJRAOMZCVTUHFI-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Mold Materials And Core Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
本発明はアルミニウム等の軽合金鋳物製品の製
造方法に関するものである。本発明の方法に従え
ば自硬性及びコールドボツクス法で優れた造型性
を示し、外観が美麗な鋳物製品を得ることができ
るとともに、鋳物製品取出後の砂落しが容易であ
る。
鋳物工業において、砂型を製造する為の鋳物砂
用バインダー組成物は非常に有用である。
従来、鋳物用砂型の製造に使用されるバインダ
ー(結合材)には、無機系および有機系のものが
あるが、アルミニウム鋳物用砂型の製造に用いる
バインダーとしてはいずれも一長一短があり、充
分に満足しうるものは見出されていない。
無機系バインダーを用いる鋳物用砂型の製造法
としては、水ガラスを表面に付着させた砂で砂型
をつくり、これに炭酸ガスを吹き込み硬化させる
方法が代表的である。
この方法は、砂型へ鉄湯やアルミニウム湯を流
入し、鋳物を造型した後、それを取出す場合、砂
型の崩壊性が悪く、著しく作業性が低下する問題
がある。
また、鋳物砂の再利用ができず。アルカリ公害
が問題となるので、その投棄場所がないこと、鋳
込時にガス欠陥を生じ、美麗な鋳物表面を得にく
いことなどの問題点を有する。
有機系バインダーを用いる鋳物用砂型の製造法
としては、フラン樹脂やフエノール樹脂などを用
いる方法がある。
しかしながら、フラン樹脂やレゾール型のフエ
ノール樹脂をパラトルエンスルホン酸やリン酸等
の強酸で硬化させて砂型をつくつた場合には、残
存する酸により鋳物表面が腐食したり、硬化速度
が気温により大きく変動したりする問題がある。
また、次式(I)で示すベンジルエーテル基ま
たはメチロール基をを有するフエノール樹脂と有
機イソシアネート化合物を反応させて鋳物砂を硬
化させて砂型を製造する方法も知られている(特
公昭45―32820号、同48―25431号、同特開昭53―
128526号公報)。
〔式中、RはH又はフエノール性水酸基に対
し、メタ位置のフエノール置換基、mとnの和は
少くとも2でmとnの比は少なくとも1、XはH
又はメチロール基の末端基を示し、該メチロール
対水素末端基のモル比は少なくとも1である〕。
このバインダーを用いて得た砂型を用いて1200
℃以上の高温の鋳鉄を鋳込む場合、上記式()
で示されるフエノール樹脂は耐熱性に富み、か
つ、フエノール樹脂は炭化しやすいので上記の
1200℃以上という鋳込温度においても鋳型の鉄湯
と接する部分の鋳物砂がフエノール樹脂の炭化物
で結合されるため美麗な鋳肌の鋳物を得ることが
できるとともに、使用した鋳物砂も前記高温にフ
エノール樹脂が晒れ、美化が進む故に崩壊し易く
なつており、鋳物砂が再使用できる利点がある。
しかし、このバインダーをアルミニウム等の
760℃以下で鋳込む軽合金の鋳型の鋳物砂用バイ
ンダーとして用いる場合、使用した鋳物砂の崩壊
性が悪いという欠点がある(特開昭56―4621号公
報参照)。
これは、同一体積の鋳物を得る場合、鉄はアル
ミニウムと比較して比重が約2.5倍であるととも
に、溶湯温度も1200℃以上と高く、砂型に対する
熱容量が非常に大きくなる。それ故、注湯終了後
迄、かかる熱容量に耐えうる強度がバインダーに
要求される。
しかも、熱容量が大きいことは逆に冷却時間も
長くかかるのでその間にフエノール樹脂の炭化も
進み、鋳物砂の崩壊性が容易となる。
しかし、このバインダーを軽合金鋳造型の鋳物
砂のバインダーに用いた場合、熱容量が鉄湯と比
較してかなり低いことおよび溶湯の冷却時間も短
いことから、炭化の進み具合は少なく、鋳物砂は
強固に結合しているため、崩壊性が悪いと推定さ
れる。
更に、レゾール型フエノール樹脂又はベンジリ
ツクエーテル型フエノール樹脂とポリイソシアネ
ートとγピコリン等の塩基性触媒とからなる自硬
性バインダーも公知である。(特開昭53―128526
号)。該公報の実施例にはレゾール型フエノール
樹脂をバインダー成分とする実施例の記載はない
が、フエノールとパラフオルムとから得られるレ
ゾール型フエノール樹脂はポリイソシアネートと
の相溶性が悪く、得られる砂型の強度が弱い〔つ
き固め強度(1日経過後)の抗圧力は約10〜15
Kg/cm2Gである〕とともに、鋳物砂の崩壊性も悪
い欠点がある。
この鋳造後の鋳物砂の崩壊性を良好とするため
に、フエノール樹脂にかえて、
〔式中、R1,R2は各々H、CH3又はC2H5であ
り、R3はC2H4又はC3H9であり、m+n=1
〜20である〕
で示されるポリエーテル・ポリオール類を用い、
このポリエーテル・ポリオール類とポリイソシア
ネートおよびアミン系ポリオール(反応型硬化触
媒)を含有するバインダーを用いる鋳造法が提案
された(特開昭54―103734号、同54―107427
号)。
このバインダーを用いた鋳型の鋳物砂の崩壊性
は極めて容易であるが、崩壊性がよすぎるため大
物鋳物では鋳込時に砂が流されて鋳肌が荒れると
か、鋳型が軟化し、変形する問題がある。又、ア
ミン含有ポリオールの比率を増やすと著しく可使
時間が短かくなり、逆に、アミン含有ポリオール
比率を減少すると硬化の速度が低下し、抜型する
のに著しく時間がかかる問題がある。このため耐
熱性をあげるために、バインダー成分に更にコロ
イダル、水ガラス等の増強材を配合する必要があ
るが、この場合は、砂の再使用が困難となる。
また、このバインダーはポリオールが脂肪属系
の1級又は2級酸基であること及び触媒となりう
る三級窒素をもつポリオールであるため室温でも
イソシアネート基と短時間に反応するため可使時
間が短い。それ故に、アミン等の硬化触媒をガス
を用いて砂型内に吹き込んで硬化させるコールド
ボツクス法には利用できない。
本発明者は、ビスフエノール類にメチロール基
を導入することにより得られるポリオールは可使
時間が長いばかりでなく、ポリイソシアネートが
フエノール性水酸基の他にメチロール基とも反応
して三次元構造をとることにより砂型の強度も向
上し、しかも崩壊性も良好で、かつ、適度は耐熱
性をもつため、砂が流され鋳肌が荒れる問題もな
く、、鋳型の軟化変形もないことを見い出し、本
発明に到達した。
即ち、本発明は、
(a) 有機ポリイソシアネート化合物
(b) ビスフエノール類とホルムアルデヒドとを反
応させて得られるメチロール基を有する次式
()で示されるポリオールを主成分とするポ
リオール化合物
〔式中、Rは−CH2−または
The present invention relates to a method for manufacturing light alloy casting products such as aluminum. According to the method of the present invention, it is possible to obtain a cast product that exhibits excellent self-hardening properties and moldability using the cold box method, and has a beautiful appearance, and it is easy to remove sand after taking out the cast product. Binder compositions for foundry sand for making sand molds are very useful in the foundry industry. Conventionally, there are inorganic and organic binders used in the production of foundry sand molds, but each type of binder used in the production of aluminum foundry sand molds has advantages and disadvantages and is fully satisfactory. Nothing that can be done has been found. A typical method for producing foundry sand molds using an inorganic binder is to make a sand mold with water glass adhered to the surface, and then harden it by blowing carbon dioxide gas into it. This method has a problem in that when iron or aluminum hot water is poured into a sand mold to form a casting and then taken out, the sand mold has poor collapsibility and workability is significantly reduced. Also, the foundry sand cannot be reused. Since alkali pollution is a problem, there are problems such as there is no place to dump it, gas defects occur during casting, and it is difficult to obtain a beautiful casting surface. Examples of methods for manufacturing foundry sand molds using organic binders include methods using furan resins, phenol resins, and the like. However, if a sand mold is made by curing furan resin or resol type phenolic resin with strong acids such as para-toluene sulfonic acid or phosphoric acid, the remaining acid may corrode the surface of the casting, or the curing speed may increase depending on the temperature. There is a problem with fluctuations. Also known is a method of manufacturing a sand mold by curing foundry sand by reacting a phenol resin having a benzyl ether group or a methylol group represented by the following formula (I) with an organic isocyanate compound (Japanese Patent Publication No. 45-32820 No. 48-25431, Japanese Unexamined Patent Publication No. 1983-
Publication No. 128526). [In the formula, R is H or a phenol substituent at the meta position to the phenolic hydroxyl group, the sum of m and n is at least 2, the ratio of m and n is at least 1, and X is H
or methylol end groups, the molar ratio of methylol to hydrogen end groups being at least 1]. 1200 using a sand mold obtained using this binder
When casting cast iron at a high temperature of ℃ or higher, the above formula ()
The phenolic resin represented by is highly heat resistant, and since phenolic resin is easily carbonized, the above
Even at casting temperatures of 1200°C or higher, the molding sand in the part of the mold that comes into contact with the iron molten metal is bound by the carbide of phenolic resin, making it possible to obtain castings with beautiful casting surfaces, and the molding sand used also remains at the above-mentioned high temperature. As the phenolic resin is exposed and beautified, it becomes more easily disintegrated, and the foundry sand has the advantage of being reusable. However, this binder can be used with aluminum etc.
When used as a binder for molding sand in molds of light alloys cast at temperatures below 760°C, there is a drawback that the molding sand used has poor collapsibility (see JP-A-56-4621). This is because, when producing castings of the same volume, iron has a specific gravity approximately 2.5 times that of aluminum, and the temperature of the molten metal is as high as 1200°C or higher, resulting in a very large heat capacity for the sand mold. Therefore, the binder is required to have the strength to withstand such heat capacity until the end of pouring. Moreover, since the large heat capacity conversely requires a long cooling time, the carbonization of the phenolic resin progresses during that time, and the foundry sand becomes easily disintegrated. However, when this binder is used as a binder for molding sand for light alloy casting molds, the heat capacity is considerably lower than that of iron molten metal, and the cooling time of the molten metal is also short, so the progress of carbonization is small and the foundry sand is It is presumed that it has poor disintegration properties because it is strongly bonded. Further, a self-hardening binder comprising a resol type phenolic resin or a benzyl ether type phenolic resin, a polyisocyanate, and a basic catalyst such as γ picoline is also known. (Unexamined Japanese Patent Publication No. 53-128526
issue). Although the examples in this publication do not include examples in which a resol type phenolic resin is used as a binder component, the resol type phenolic resin obtained from phenol and paraform has poor compatibility with polyisocyanate, and the strength of the resulting sand mold is poor. is weak [the resistance pressure of compaction strength (after 1 day) is about 10 to 15
Kg/cm 2 G] and the disintegrability of the foundry sand is also poor. In order to improve the disintegrability of the foundry sand after casting, instead of using phenolic resin, [In the formula, R 1 and R 2 are each H, CH 3 or C 2 H 5 , R 3 is C 2 H 4 or C 3 H 9 , m + n = 1
~20] Using polyether polyols shown in
A casting method using a binder containing these polyether polyols, polyisocyanate, and amine polyol (reactive curing catalyst) was proposed (Japanese Patent Application Laid-open Nos. 103734-1982 and 107427-1982).
issue). The disintegration of molding sand in molds using this binder is extremely easy, but because the disintegration is so good, problems with large castings include sand being washed away during casting, resulting in rough casting surfaces, and softening and deformation of molds. There is. In addition, increasing the proportion of the amine-containing polyol significantly shortens the pot life, and conversely, decreasing the proportion of the amine-containing polyol reduces the curing speed, resulting in the problem that it takes a considerable amount of time to demold. Therefore, in order to increase the heat resistance, it is necessary to further add reinforcing materials such as colloidal and water glass to the binder component, but in this case, it becomes difficult to reuse the sand. In addition, this binder has a short pot life because the polyol is an aliphatic primary or secondary acid group and has tertiary nitrogen that can act as a catalyst, so it reacts with isocyanate groups in a short time even at room temperature. . Therefore, it cannot be used in the cold box method, in which a curing catalyst such as amine is blown into a sand mold using a gas to cure it. The present inventor has discovered that polyols obtained by introducing methylol groups into bisphenols not only have a long pot life, but also that polyisocyanates react with methylol groups in addition to phenolic hydroxyl groups to form a three-dimensional structure. It was discovered that the strength of the sand mold is improved, the disintegration property is good, and it has a moderate heat resistance, so there is no problem of sand being washed away and the casting surface becomes rough, and there is no softening and deformation of the mold. reached. That is, the present invention provides a polyol compound whose main component is (a) an organic polyisocyanate compound (b) a polyol represented by the following formula () having a methylol group obtained by reacting bisphenols with formaldehyde. [In the formula, R is -CH 2 - or
【式】であ
り、Xは−Hまたは−CH2OH基であつて、少く
ともXの一つは−CH2OH基である〕
上記(a)成分および(b)成分とからなる鋳物砂用
バインダーを硬化触媒の存在下に硬化させて鋳
物砂を固めて得た砂型に、アルミニウム等の軽
合金湯を流入して鋳物を製造することを特徴と
する軽合金鋳物製品の製造方法を提供するもの
である(但し、(a)成分と(b)成分の配合割合は、
(b)成分のポリオール化合物のヒドロキシル基1
当量当り、(a)成分のイソシアネート基が0.3〜
3当量の割合である)。
本発明の実施に用いるバインダー組成物は、硬
化物の強度が大きいこと、硬化速度が速にこと、
鋳込後の鋳物を取出す際の砂型の崩壊性が良いこ
となどの特長があり、鋳鉄、鋳鋼用にも使えるが
特にアルミニウムなどの軽合金鋳物用のバインダ
ー組成物として適している。
本発明に用いる(a)成分の有機ポリイソシアネー
ト化合物は、ポリウレタン用原料として一般に広
く用いられている有機ポリイソシアネート化合物
より適宜選択して用いることができ、ジ或いはト
リイソシアネートが好ましい。
適当な有機ポリイソシアネート化合物として
は、ヘキサメチレンジイソシアネートのような脂
肪族イソシアネート;4,4′―ジシクロヘキシル
メタンジイソシアネート、イソホロンジイソシア
ネート等の脂環式イソシアネート;2,4および
2,6トリレンジイソシアネート、ジフエニルメ
タンジイソシアネート、トリフエニルメタンイソ
シアネート、1,5ナフタリンジイソシアネー
ト、ポリメチレンポリフエニレンイソシアネー
ト、クロロフエニレン―2,4―ジイソシアネー
ト等の芳香族ポリイソシアネート;キシリレンジ
イソシアネートおよびそのメチル誘導体などがあ
げられる。
これらの中でも、芳香族ポリイソシアネートが
好ましく、特に、ジフエニルメタンジイソシアネ
ート、トリフエニルメタントリイソシアネートお
よびこれらの混合物を用いることが好ましい。
これらの有機ポリイソシアネート化合物は、ト
ルエン、キシレン、エチルベンゼン、ジエチルベ
ンゼン、キユメン、ジイソプロピルベンゼン、エ
チルベンゼン製造時の副生重質油、キユメン製造
時の副生重質油などの芳香族炭化水素に溶解して
用いてもよい。
有機ポリイソシアネート化合物と反応させるこ
とによりポリウレタンを生成せしめ、鋳物砂を硬
化せしめるために用いる(b)成分のポリオール化合
物は、ビスフエノール類とホルムアルデヒドとを
反応させて得られる前式()で示されるポリオ
ールを主成分とするポリオール化合物である。
ビスフエノール類としては、ビスフエノールA
または、ビスフエノールFをあげることができ
る。ホルムアルデヒド源としては、ホルマリン水
溶液、ホルムアルデヒドとアルコールのヘミアセ
タール化物、パラホルムアルデヒド、トリオキサ
ン等が使用できる。
ビスフエノール類とホルムアルデヒドとの反応
は、通常、ナフテン酸亜鉛、ナフテン酸鉛等の金
属塩触媒或いは水酸化ナトリウム等のアルカリ触
媒の存在下、常温ないし150℃、好ましくは、60
℃ないし120℃で行なわれる。
反応温度がこれより高いと、ビスフエノール類
に付加したメチロール基間の脱水縮合によるメチ
レンエーテル結合の生成或いは脱水縮合及び脱ホ
ルムアルデヒド縮合によるメチレン結合の生成等
により、縮合物が更に高分子量化するので好まし
くない。
ビスフエノール類とホルムアルデヒドとモル比
は、化学量論的には、1:1〜4、好ましくは、
1:1〜2が適当であるが、実際には、適宜、ホ
ルムアルデヒドの量をその理論量より少なく又は
多くして反応を行なうことができる。
得られるポリオール化合物は、ビスフエノール
類にメチロール基が付加した前記()式で示さ
れる構造のもの、が主成分となるが、一部縮合し
て、ベンゼン核が4個或いは6個有するものを生
成する。
上記ポリオール化合物は、通常、シクロヘキサ
ノン、エチルセロソルブアセテート、エチレング
リコールジアセテート、トリエチレングリコール
ジアセテート等の極性溶媒に、或いは、これら極
性溶媒と前述した有機ポリイソシアネート化合物
を溶解する為に用いられるものと同様な芳香族炭
化水素との混合溶媒に溶解して用いられる。
(b)成分以外の他のポリオール化合物を併用する
ことももちろん可能である。
アルミニウムなどの軽合金鋳物用には、本願の
バインダー組成物は充分な耐熱性を有するが、注
湯の耐熱性を増加させる為に、ノポラツク型フエ
ノール樹脂、レゾール型フエノール樹脂、ベンジ
リツクエーテル型フエノール樹脂等のオリゴマー
を添加することもできる。
(b)成分以外の他のポリオール化合物を併用しな
い場合には、(a)成分の(b)成分に対する配合量は、
(b)成分のヒドロキシル基1当量に対し、(a)成分の
イソシアネート基が0.3〜3当量、好ましくは0.6
〜1.5当量となるように配合するのが適当であ
る。
なお、(b)成分と他のポリオール化合物とを併用
する場合には、(b)成分と他のポリオール化合物の
合計のヒドロキシル基量1に対して、(a)成分のイ
ソシアネート基が0.3〜3、好ましくは0.6〜1.5と
なるように配合するのが適当ぜある。
(a)成分と(b)成分及び必要に応じて用いられる他
のポリオール化合物は、鋳物砂100重量部に対
し、0.5〜5重量部の割合で配合される。
鋳物砂は、鋳物用に用いられる砂類或いは無機
粉体類であれば何でもよく、その粒度、種類等に
ついては適宜選択して用いうる。
このバインダーは鋳物砂と混合して用いられ
る。バインダー組成物と混合した鋳物砂により、
常温で、砂型を造型する場合、砂型の強度発現を
速める為に、触媒を添加して迅速硬化を行うこと
ができる。この硬化触媒としては、ナフテン酸コ
バルト、オクチル酸錫、ジブチル錫ジラウレート
等の金属塩及びN―エチレンモルフオリン、4―
フエニルブロピルピリジン、モルフオリノプロピ
オン酸エチル、テトラメチルジアミノプロパン、
トリエチレンジアミン等の第3級アミンなどが使
用できる。
その使用量は、(a)成分と(b)成分を含むポリオー
ル化合物との和100重量部に対して、5重量部以
下が適当である。
また、鋳物砂とバインダー組成物とを均一に混
合し、型に充填後、室温で、アミンを含むガスと
接触させて、急速硬化させることにより、砂型を
造型する場合には、触媒となるアミンとしては、
第3級アミンが好ましく、特に、トリメチルアミ
ン、トリエチルアミン、ジメチルエタノールアミ
ン、N―エチルモルフオリン等が好ましい。
これらの第3級アミンは、窒素或いは空気など
の不活性ガスをキヤリヤーガスとして用い、通常
約5容量%以下の濃度で、型内に導入される。
このようにして硬化させて固めた砂型より模型
を抜き出し、ついで砂型の空洞内にアルミニウム
等の軽合金湯を流し込み、冷却し、鋳造製品を取
り出すことにより本発明は実施される。
次に、実施例により、本発明を更に具体的に説
明する。
なお、実施例及び参考例中の「部」及び「%」
は、重量基準である。
参考例1:ポリオール化合物の製造例
ビスフエノールA228.3g(1mo)、パラホルム
アルデヒド60g、エチレングリコールジアセテー
ト230g、ナフテン酸鉛3.0gを1の4つ口フラス
コに入れ、撹拌しながら、110℃で3時間反応さ
せた。減圧下で未反応のホルムアルデヒドを除去
し、常温に冷却した。生成物はGPC、IR及び
NMRの分析結果からメチロー基を有するビスフ
エノールA誘導体が主成分であるポリオール化合
物混合物()であつた。
参考例2:ポリオール化合物の製造例
ビスフエノールA228.3g(1mo)、パラホルム
アルデヒド42.4g、エチレングリコールジアセテ
ート228.4g、ナフテン酸鉛1.0gを1の4つ口フ
ラスコに入れ、撹拌しながら、100℃で4時間反
応させた。減圧下で未反応のホルムアルデヒド及
び水を除去し常温に冷却した。生成物はGRC、
IR及びNMRの分析結果から、メチロール基を有
するビスフエノールA誘導体が主成分であるポリ
オール化合物の混合物であつた。このポリオール
化合物の混合物85部ヘキシレン15部を添加し均一
に混合してポリオール化合物の溶液()を得
た。
参考例3:ポリオール化合物の製造例
ビスフエノールF200.3g(1mo)、パラホルム
アルデヒド39.1g、3―メトキシ酢酸ブチル
225.4g、ナフテン酸鉛1.0gを1の4つ口フラス
コに入れ、撹拌しながら100℃で5時間反応させ
た後、冷却した。
生成物はGPC、IR及びNMRの分析結果からメ
チロール基を有するビスフエノールF誘導体が主
成分であるポリオール化合物の混合物であつた。
このポリオール化合物の混合物85部へジイソプロ
ピルベンゼン15部を添加し均一に混合してポリオ
ール化合物の溶液()を得た。
実施例 1
あやらぎ珪砂6号100部に参考例1で得られた
ポリオール化合物()の溶液0.95部、N―エチ
ルモルフオリンの10%エチルセロソブルブアセテ
ート溶液0.10部を添加し均一に混合した。次にポ
リメリツクポリイソシアネート((ジフエニルメ
タンジイソシアネートとトリフエニルメタントリ
イソシアネートの混合物)の66%ジイソプロピル
ベンゼン溶液1.05部を添加し均一に混合後、直径
5cm、高さ13cmの円筒状金型内へ深さ5cmとなる
ように入れ、標準つき固め試験機でつき固めて試
験片を作成し、一定時間毎にサンプルの抗圧力を
測定した。結果を下表に示す。[Formula], X is -H or -CH 2 OH group, and at least one of X is -CH 2 OH group] Foundry sand consisting of the above components (a) and (b) Provided is a method for producing a light alloy casting product, characterized in that casting is produced by pouring a light alloy molten metal such as aluminum into a sand mold obtained by hardening molding sand by hardening a binder for molding in the presence of a curing catalyst. (However, the blending ratio of component (a) and component (b) is
(b) Hydroxyl group 1 of polyol compound as component
Per equivalent, the isocyanate group of component (a) is 0.3 to
3 equivalents). The binder composition used in carrying out the present invention has high strength of the cured product, fast curing speed,
It has features such as good disintegration of the sand mold when removing the casting after casting, and although it can be used for cast iron and cast steel, it is especially suitable as a binder composition for light alloy castings such as aluminum. The organic polyisocyanate compound as component (a) used in the present invention can be appropriately selected from organic polyisocyanate compounds generally widely used as raw materials for polyurethane, and di- or triisocyanates are preferred. Suitable organic polyisocyanate compounds include aliphatic isocyanates such as hexamethylene diisocyanate; cycloaliphatic isocyanates such as 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate; 2,4 and 2,6 tolylene diisocyanate, diphenyl Aromatic polyisocyanates such as methane diisocyanate, triphenylmethane isocyanate, 1,5 naphthalene diisocyanate, polymethylene polyphenylene isocyanate, and chlorophenylene-2,4-diisocyanate; xylylene diisocyanate and its methyl derivatives. Among these, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate, triphenylmethane triisocyanate, and mixtures thereof are particularly preferred. These organic polyisocyanate compounds are dissolved in aromatic hydrocarbons such as toluene, xylene, ethylbenzene, diethylbenzene, kyumene, diisopropylbenzene, by-product heavy oil during ethylbenzene production, and by-product heavy oil during kyumene production. May be used. The polyol compound of component (b) used to produce polyurethane and harden foundry sand by reacting with an organic polyisocyanate compound is a polyol compound represented by the preceding formula () obtained by reacting bisphenols with formaldehyde. It is a polyol compound whose main component is polyol. As bisphenols, bisphenol A
Alternatively, bisphenol F can be mentioned. As the formaldehyde source, an aqueous formalin solution, a hemiacetal of formaldehyde and alcohol, paraformaldehyde, trioxane, etc. can be used. The reaction between bisphenols and formaldehyde is usually carried out at room temperature to 150°C, preferably at 60°C, in the presence of a metal salt catalyst such as zinc naphthenate or lead naphthenate, or an alkali catalyst such as sodium hydroxide.
It is carried out at between 120°C and 120°C. If the reaction temperature is higher than this, the molecular weight of the condensate will further increase due to the formation of methylene ether bonds due to dehydration condensation between methylol groups added to bisphenols, or the generation of methylene bonds due to dehydration condensation and formaldehyde condensation. Undesirable. The molar ratio of bisphenols to formaldehyde is stoichiometrically 1:1 to 4, preferably
A ratio of 1:1 to 2 is suitable, but in practice, the reaction can be carried out using a smaller or larger amount of formaldehyde than the theoretical amount, as appropriate. The main component of the resulting polyol compound is a structure represented by the above formula (2), in which a methylol group is added to a bisphenol, but it is partially condensed to contain a compound having 4 or 6 benzene nuclei. generate. The above polyol compounds are usually used in polar solvents such as cyclohexanone, ethyl cellosolve acetate, ethylene glycol diacetate, triethylene glycol diacetate, etc., or in order to dissolve these polar solvents and the above-mentioned organic polyisocyanate compounds. It is used by dissolving it in a mixed solvent with a similar aromatic hydrocarbon. Of course, it is also possible to use other polyol compounds in addition to component (b). The binder composition of the present application has sufficient heat resistance for castings of light alloys such as aluminum, but in order to increase the heat resistance of pouring, noporak type phenolic resin, resol type phenolic resin, and benzyl ether type phenol are used. Oligomers such as resins can also be added. When other polyol compounds other than component (b) are not used together, the amount of component (a) to component (b) is as follows:
The amount of isocyanate group in component (a) is 0.3 to 3 equivalents, preferably 0.6 equivalent to 1 equivalent of hydroxyl group in component (b).
It is appropriate to mix it so that it becomes ~1.5 equivalent. In addition, when using component (b) and other polyol compounds together, the amount of isocyanate groups in component (a) is 0.3 to 3 per 1 of the total hydroxyl group amount of component (b) and other polyol compounds. , preferably 0.6 to 1.5. Components (a) and (b) and other polyol compounds used as necessary are blended in a proportion of 0.5 to 5 parts by weight based on 100 parts by weight of foundry sand. The foundry sand may be any sand or inorganic powder used for foundries, and its particle size, type, etc. can be selected as appropriate. This binder is used in combination with foundry sand. Foundry sand mixed with binder composition
When molding a sand mold at room temperature, a catalyst can be added to quickly harden the sand mold in order to accelerate the strength development of the sand mold. This curing catalyst includes metal salts such as cobalt naphthenate, tin octylate, dibutyltin dilaurate, N-ethylene morpholin, 4-
Phenylpropylpyridine, ethyl morpholinopropionate, tetramethyldiaminopropane,
Tertiary amines such as triethylenediamine can be used. The amount used is suitably 5 parts by weight or less per 100 parts by weight of the total of the polyol compound containing component (a) and component (b). In addition, when molding a sand mold by uniformly mixing foundry sand and a binder composition, filling a mold, and then bringing the mixture into contact with an amine-containing gas at room temperature for rapid curing, amines as catalysts can be used. as,
Tertiary amines are preferred, and trimethylamine, triethylamine, dimethylethanolamine, N-ethylmorpholine and the like are particularly preferred. These tertiary amines are introduced into the mold using an inert gas such as nitrogen or air as a carrier gas, usually at a concentration of about 5% by volume or less. The present invention is carried out by extracting the model from the sand mold that has been hardened and hardened in this way, then pouring a light alloy such as aluminum into the cavity of the sand mold, cooling it, and then taking out the cast product. Next, the present invention will be explained in more detail with reference to Examples. In addition, "part" and "%" in Examples and Reference Examples
is based on weight. Reference Example 1: Example of producing a polyol compound 228.3 g (1 mo) of bisphenol A, 60 g of paraformaldehyde, 230 g of ethylene glycol diacetate, and 3.0 g of lead naphthenate were placed in a four-necked flask (No. 1) and heated at 110°C while stirring. The reaction was allowed to proceed for 3 hours. Unreacted formaldehyde was removed under reduced pressure, and the mixture was cooled to room temperature. The product is GPC, IR and
From the results of NMR analysis, it was found to be a polyol compound mixture (2) whose main component was a bisphenol A derivative having a methylo group. Reference Example 2: Example of producing a polyol compound 228.3 g (1 mo) of bisphenol A, 42.4 g of paraformaldehyde, 228.4 g of ethylene glycol diacetate, and 1.0 g of lead naphthenate were placed in a four-necked flask, and while stirring, The reaction was carried out at ℃ for 4 hours. Unreacted formaldehyde and water were removed under reduced pressure, and the mixture was cooled to room temperature. The product is GRC,
According to the results of IR and NMR analysis, it was a mixture of polyol compounds whose main component was a bisphenol A derivative having a methylol group. 85 parts of this polyol compound mixture and 15 parts of hexylene were added and mixed uniformly to obtain a polyol compound solution (). Reference example 3: Production example of polyol compound Bisphenol F 200.3g (1mo), paraformaldehyde 39.1g, 3-methoxybutyl acetate
225.4 g of lead naphthenate and 1.0 g of lead naphthenate were placed in a four-necked flask (No. 1), reacted with stirring at 100° C. for 5 hours, and then cooled. The product was a mixture of polyol compounds whose main component was a bisphenol F derivative having a methylol group, based on the results of GPC, IR, and NMR analyses.
15 parts of diisopropylbenzene was added to 85 parts of this polyol compound mixture and mixed uniformly to obtain a polyol compound solution (2). Example 1 To 100 parts of Ayaragi Silica Sand No. 6, 0.95 part of the solution of the polyol compound () obtained in Reference Example 1 and 0.10 part of a 10% ethyl cellosoluble acetate solution of N-ethylmorpholine were added and mixed uniformly. did. Next, 1.05 parts of a 66% diisopropylbenzene solution of polymeric polyisocyanate ((a mixture of diphenylmethane diisocyanate and triphenylmethane triisocyanate)) was added, mixed uniformly, and placed into a cylindrical mold with a diameter of 5 cm and a height of 13 cm. The sample was placed at a depth of 5 cm and compacted using a standard compaction tester to prepare a test piece, and the counter pressure of the sample was measured at regular intervals.The results are shown in the table below.
【表】
また同一の鋳物砂組成物で、カークーラーケー
ス用の鋳型を作成した。15分後に型抜きし、3時
間後に760℃の溶解したアルミニウムを鋳込ん
だ。冷却後の鋳物製品とりだし時の外型及び中子
の崩壊性は良好であり、鋳物表面の美麗な製品が
得られた。
実施例 2
あやらぎ珪砂6号100部に参考例1で得られた
ポリオール化合物()の溶液0.95部を添加し、
均一に混合した後、ポリメリツクポリイソシアネ
ートの66%ジイソプロピルベンゼン溶液1.05部を
添加し、均一に混合した。このようにして調製さ
れた鋳物砂組成物で、カークーラーケース用の鋳
型を作成し、窒素を吹き込み気化させたトリエチ
ルアミンを30秒通過させて硬化させた。これに
760℃の溶解したアルミニウムを鋳込んだ。冷却
後の鋳物製品とりだし時の砂型の崩壊性、特に中
子の崩壊性は良好であり、鋳物表面の美麗な製品
が得られた。
また、同一の鋳物砂組成物調製後、直ちに直径
5cm、高さ13cmの円筒状金型へ入れ、標準つき固
め試験機で5cm高さとなるようつき固めた後、ト
リエチルアミンを含有する窒素ガスを10秒通し硬
化させた。鋳物砂テストピースを金型よりとりだ
した直後の、その抗圧力は33.9Kg/cm2、1時間放
置後の抗圧力は50.2Kg/cm2であつた。
更に、鋳物砂組成物を調整後、30分経過した後
に上記円筒状金型へ入れ、つき固めた後、同様に
してトリエチルアミンガスで硬化した得た鋳物砂
テストピースを金型よりとり出した直後の抗圧力
は31.4Kg/cm2であり、1時間放置後のそれは49.8
Kg/cm2であつた。
比較例 1
あやらぎ珪砂6号100部に、ビスフエノールA
の酸化プロピレン2モル付加物30.7部、エチレン
ジアミンの酸化プロピレン4モル付加物13.5部、
芳香族溶剤(ハイゾール:日本石油化学(株)製品)
54.2部からなるポリオール溶液の1.33部を均一に
混合した。次に、ポリメリツクイソシアネート
0.67部を添加し、均一に混合後、これをただちに
直径5cm、高さ13cmの円筒状金型内へ深さ5cmと
なるように入れ、標準つき固め試験機でつき固め
鋳型を作成し、窒素を吹き込み気化させたトリエ
チルアミンを30秒通過させて硬化させた。
鋳物砂テストピースを金型よりとり出した直後
の抗圧力は4.9Kg/cm2(但し、砂型の変形あり)、
1時間放置後の抗圧力は30.1Kg/cm2であつた。
また、珪砂、上記のポリオール溶液、ポリメリツ
クイソシアネートを混合後、30分経過した後に型
内に入れ、つき固め、窒素を吹き込み気化させた
トリエチルアミンのガス体を吹き込んだ際の砂型
の抗圧力は0Kg/cm2であり、1時間後のそれも0
Kg/cm2であつた。
実施例 3
フーカーサンド(オーストラリア産の珪砂)
100部に参考例2で得られたポリオール化合物の
溶液()0.95部、4―フエニルプロピルビリジ
ンの30%3―メトキシ酢酸ブチル溶液0.10部を添
加し均一に混合した。次に、ポリメリツクポリイ
ソシアネート(実施例1と同じ)の75%ジイソプ
ロピルベンゼン溶液1.0部を添加し均一に混合
後、実施例1と同様の方法で試験片の作成及びそ
れらの抗圧力を測定した。結果を次表に示す。[Table] A mold for a car cooler case was also created using the same foundry sand composition. The mold was removed after 15 minutes, and molten aluminum at 760°C was cast after 3 hours. The disintegration of the outer mold and core when the cast product was taken out after cooling was good, and a product with a beautiful cast surface was obtained. Example 2 0.95 parts of the solution of the polyol compound () obtained in Reference Example 1 was added to 100 parts of Ayaragi Silica Sand No. 6,
After uniformly mixing, 1.05 parts of a 66% diisopropylbenzene solution of polymeric polyisocyanate was added and uniformly mixed. A mold for a car cooler case was made using the foundry sand composition thus prepared, and triethylamine, which had been vaporized by blowing nitrogen, was passed through it for 30 seconds to harden it. to this
Molten aluminum was cast at 760℃. The disintegration properties of the sand mold, especially the disintegration properties of the core, when the cast product was taken out after cooling were good, and a product with a beautiful casting surface was obtained. In addition, after preparing the same foundry sand composition, it was immediately put into a cylindrical mold with a diameter of 5 cm and a height of 13 cm, and after being compacted to a height of 5 cm using a standard compaction tester, nitrogen gas containing triethylamine was added to the mold for 10 minutes. It was cured for seconds. Immediately after the molding sand test piece was taken out from the mold, its counter pressure was 33.9 Kg/cm 2 , and after being left for 1 hour, its counter pressure was 50.2 Kg/cm 2 . Furthermore, after 30 minutes had elapsed after adjusting the foundry sand composition, it was put into the cylindrical mold and compacted, and then immediately after the foundry sand test piece obtained, which had been similarly hardened with triethylamine gas, was taken out from the mold. The counter pressure is 31.4Kg/ cm2 , and after leaving for 1 hour it is 49.8
It was Kg/ cm2 . Comparative Example 1 Bisphenol A to 100 parts of Ayaragi Silica Sand No. 6
30.7 parts of a 2 mole adduct of propylene oxide, 13.5 parts of a 4 mole adduct of propylene oxide of ethylenediamine,
Aromatic solvent (Hysol: Nippon Petrochemical Co., Ltd. product)
1.33 parts of a polyol solution consisting of 54.2 parts were mixed homogeneously. Next, polymeric isocyanate
After adding 0.67 parts and mixing uniformly, this was immediately placed into a cylindrical mold with a diameter of 5 cm and a height of 13 cm to a depth of 5 cm, a tamping mold was created using a standard tamping tester, and nitrogen was added. Triethylamine, which had been blown in and vaporized, was passed through the solution for 30 seconds to cure it. Immediately after taking the molding sand test piece out of the mold, the counter pressure was 4.9Kg/cm 2 (however, the sand mold was deformed).
The counter pressure after standing for 1 hour was 30.1 Kg/cm 2 . In addition, after 30 minutes had elapsed after mixing silica sand, the above polyol solution, and polymeric isocyanate, they were placed in a mold, compacted, and nitrogen was blown into the mold to blow a vaporized triethylamine gas into the sand mold.The anti-pressure of the sand mold was 0 kg. /cm 2 and after 1 hour it is also 0
It was Kg/ cm2 . Example 3 Hookah sand (silica sand from Australia)
To 100 parts, 0.95 part of the solution of the polyol compound obtained in Reference Example 2 () and 0.10 part of a 30% 3-methoxybutyl acetate solution of 4-phenylpropyl pyridine were added and mixed uniformly. Next, 1.0 part of a 75% diisopropylbenzene solution of polymeric polyisocyanate (same as in Example 1) was added and mixed uniformly, and test pieces were prepared in the same manner as in Example 1 and their anti-pressure was measured. . The results are shown in the table below.
【表】
また、同一の鋳物砂組成で、実施例1と同様に
カークーラーケース用の鋳型を作成し、溶解した
アルミニウムを鋳込み、、鋳物製品を製作したと
ころ、実施例と同様なきわめて良好は鋳型の外型
及び中子の崩壊性を示した。
実施例 4
参考例2で得られたポリオール化合物の溶液
1.0部、ポリメリツクポリイソシアネートの74%
ジイソプロピルベンゼン溶液1.0部を用いた他
は、実施例2と同様に調製された鋳物組成物を用
い、、カークーラーケース用の鋳型を作成し、窒
素を吹き込み気化させたトリエチルアミンを30秒
通過させて硬化させた。これに760℃の溶解した
アルミニウムを鋳込んだ。冷却後の鋳物製品とり
だし時の砂型の崩壊性、特に中子の崩壊性は極め
て良好であり、鋳物製品表面も美麗であつた。
また、同一の鋳物砂組成物を直径5cm、高さ13
cmの円筒状金型へ入れ、標準つき固め試験機で5
cm高さとなるようにつき固めた後、トリエチルア
ミンを含有する窒素ガスを10秒通し硬化させた。
鋳物砂テストピースを金型よりとりだした直後
の、その抗圧力は35.5Kg/cm2、1時間後の抗圧力
は54.6Kg/cm2であつた。
実施例 5
あらやぎ珪砂120部に、ポリメリツクポリイソ
シアネート(実施例1と同じ)の75%ジイソプロ
ピルベンゼン溶液1.0部を添加し、均一に混合し
た。次に、参考例3で得られたポリオール化合物
の溶液()0.95部、4―フエニルプロピルピリ
ジンの30%3―メトキシ酢酸ブチル溶液0.10部を
添加し均一に混合した後、実施例1と同様の方法
で試験片の作成及びそれらの抗圧力を測定した。
結果を次表に示す。[Table] In addition, a mold for a car cooler case was made in the same manner as in Example 1 using the same foundry sand composition, and molten aluminum was cast into it to produce a cast product. The disintegration properties of the outer mold and core of the mold were shown. Example 4 Solution of polyol compound obtained in Reference Example 2
1.0 part, 74% of polymeric polyisocyanate
A mold for a car cooler case was made using a foundry composition prepared in the same manner as in Example 2, except that 1.0 part of diisopropylbenzene solution was used, and triethylamine, which had been vaporized by blowing nitrogen, was passed through it for 30 seconds. hardened. Molten aluminum at 760°C was cast into this. The disintegrability of the sand mold, especially the disintegration of the core, when the cast product was taken out after cooling was extremely good, and the surface of the cast product was also beautiful. In addition, the same foundry sand composition was made with a diameter of 5 cm and a height of 13 cm.
5 cm into a cylindrical mold and run on a standard compaction tester.
After hardening to a height of cm, nitrogen gas containing triethylamine was passed through for 10 seconds to harden.
Immediately after the molding sand test piece was taken out from the mold, its resistance pressure was 35.5Kg/cm 2 , and its resistance pressure 1 hour later was 54.6Kg/cm 2 . Example 5 1.0 part of a 75% diisopropylbenzene solution of polymeric polyisocyanate (same as in Example 1) was added to 120 parts of Arayagi silica sand and mixed uniformly. Next, 0.95 parts of the polyol compound solution obtained in Reference Example 3 () and 0.10 parts of a 30% 3-methoxybutyl acetate solution of 4-phenylpropylpyridine were added and mixed uniformly, followed by the same procedure as in Example 1. Test pieces were prepared and their resistance pressures were measured using the method described above.
The results are shown in the table below.
【表】
また、同一の鋳物砂組成で実施例1と同様にカ
ークーラーケース用鋳型を作成し、溶解したアル
ミニウム(760℃)を鋳込み、鋳物製品を製作し
たところ、実施例と同様なきわめて良好な鋳型の
外型及び中子の崩壊性を示した。
実施例 6
参考例3で得られたポリオール化合物の溶液
()0.8部、ポリメリツクポリイソシアネートの
74%ジイソプロピルベ溶液0.8部を用いた他は、
実施例2と同様に調整された鋳物組成物を用い、
カークーラーケース用の鋳型を作成し、窒素を吹
き込み気化させたトリエチルアミンを30秒通過さ
せて硬化さてた。これに760℃に溶解したアルミ
ニウムを鋳込んだ。
冷却後の鋳物製品の崩壊性は極めて良好であ
り、鋳物製品表面も美麗であつた。
また、同一の鋳物砂組成物を直径5cm、高さ13
cmの円筒状金型へ入れ、標準つき固め試験機で5
cm高さとなるようつき固めた後、トリエチルアミ
ンを含有する窒素ガスを10秒通して硬化させた。
鋳物砂テストピースを金型よりとりだした直後
の、その抗圧力は3.6Kg/cm2、1時間の抗圧力は
54.6Kg/cm2であつた。[Table] In addition, a mold for a car cooler case was made in the same manner as in Example 1 using the same foundry sand composition, and molten aluminum (760°C) was cast into it to produce a cast product. The disintegration properties of the outer mold and core of the mold were shown. Example 6 0.8 parts of the solution of the polyol compound obtained in Reference Example 3 () and 0.8 parts of the solution of the polymeric polyisocyanate
Other than using 0.8 part of 74% diisopropyl bene solution,
Using a casting composition prepared in the same manner as in Example 2,
A mold for a car cooler case was made, and the mold was cured by blowing nitrogen into it and passing vaporized triethylamine through it for 30 seconds. Aluminum molten at 760°C was cast into this. The disintegration properties of the cast product after cooling were extremely good, and the surface of the cast product was also beautiful. In addition, the same foundry sand composition was made with a diameter of 5 cm and a height of 13 cm.
5 cm into a cylindrical mold and run on a standard compaction tester.
After compacting to a height of cm, nitrogen gas containing triethylamine was passed through for 10 seconds to harden.
Immediately after taking the molding sand test piece out of the mold, its resistance pressure was 3.6Kg/cm 2 , and the resistance pressure for 1 hour was
It was 54.6Kg/ cm2 .
Claims (1)
応させて得られるメチロール基を有する次式で
示されるポリオールを主成分とするポリオール
化合物 〔式中、Rは−CH2−または【式】であ り、Xは−Hまたは−CH2OH基であつて、少く
ともXの一つは−CH2OH基である〕 上記(a)成分および(b)成分とからなる鋳物砂用
バインダーを硬化触媒の存在下に硬化させて鋳
物砂を固めて得た砂型に、軽合金湯を流入して
鋳物を製造することを特徴とするアルミニウム
等軽合金鋳物製品の製造方法。 但し、(a)成分と(b)成分の配合割合は、(b)成分
のポリオール化合物のヒドロキシル基1当量当
り、(a)成分のイソシアネート基が0.3〜3当量
の割合である。[Scope of Claims] 1 (a) an organic polyisocyanate compound (b) a polyol compound whose main component is a polyol represented by the following formula having a methylol group obtained by reacting bisphenols with formaldehyde [In the formula, R is -CH 2 - or [Formula], X is -H or -CH 2 OH group, and at least one of X is -CH 2 OH group] (a) above Aluminum, characterized in that a casting is produced by pouring a light alloy molten metal into a sand mold obtained by hardening a foundry sand binder consisting of a component and (b) component in the presence of a curing catalyst and hardening the foundry sand. A method for producing light alloy casting products. However, the blending ratio of component (a) and component (b) is such that the isocyanate group of component (a) is 0.3 to 3 equivalents per 1 equivalent of hydroxyl group of the polyol compound of component (b).
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13953080A JPS5764435A (en) | 1980-10-06 | 1980-10-06 | Binder composition for molding sand |
GB8129764A GB2088886B (en) | 1980-10-06 | 1981-10-02 | Binder composition for foundry molds or cores |
US06/308,236 US4352914A (en) | 1980-10-06 | 1981-10-02 | Binder composition for foundry sand molds and cores |
DE19813139484 DE3139484A1 (en) | 1980-10-06 | 1981-10-03 | BINDING COMPOSITION FOR FOUNDRY SAND AND CORE SAND |
FR8118796A FR2491363B1 (en) | 1980-10-06 | 1981-10-06 | BINDER COMPOSITION FOR MOLDS AND FOUNDRY CORES IN SAND |
CA000387393A CA1176785A (en) | 1980-10-06 | 1981-10-06 | Binder composition for foundry sand molds and cores |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13953080A JPS5764435A (en) | 1980-10-06 | 1980-10-06 | Binder composition for molding sand |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5764435A JPS5764435A (en) | 1982-04-19 |
JPS6116213B2 true JPS6116213B2 (en) | 1986-04-28 |
Family
ID=15247422
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13953080A Granted JPS5764435A (en) | 1980-10-06 | 1980-10-06 | Binder composition for molding sand |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5764435A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01122439U (en) * | 1988-02-10 | 1989-08-21 | ||
JPH042556U (en) * | 1990-04-24 | 1992-01-10 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5973144A (en) * | 1982-10-20 | 1984-04-25 | Mitsubishi Petrochem Co Ltd | Casting mold and composition for forming core |
NL8601829A (en) * | 1986-07-14 | 1988-02-01 | Philips Nv | PLASTIC COMPOSITION, SUBSTRATE MATERIAL FOR PRINTED WIRING PANELS AND METHOD FOR MANUFACTURING A PLASTIC COMPOSITION. |
-
1980
- 1980-10-06 JP JP13953080A patent/JPS5764435A/en active Granted
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01122439U (en) * | 1988-02-10 | 1989-08-21 | ||
JPH042556U (en) * | 1990-04-24 | 1992-01-10 |
Also Published As
Publication number | Publication date |
---|---|
JPS5764435A (en) | 1982-04-19 |
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