JPS636330B2 - - Google Patents
Info
- Publication number
- JPS636330B2 JPS636330B2 JP54129049A JP12904979A JPS636330B2 JP S636330 B2 JPS636330 B2 JP S636330B2 JP 54129049 A JP54129049 A JP 54129049A JP 12904979 A JP12904979 A JP 12904979A JP S636330 B2 JPS636330 B2 JP S636330B2
- Authority
- JP
- Japan
- Prior art keywords
- mold release
- release agent
- mold
- phosphonic acid
- salt
- 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
- 239000006082 mold release agent Substances 0.000 claims description 22
- -1 perfluorononenyl group Chemical group 0.000 claims description 9
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000008378 aryl ethers Chemical class 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000008043 acidic salts Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- IIRVGTWONXBBAW-UHFFFAOYSA-M disodium;dioxido(oxo)phosphanium Chemical compound [Na+].[Na+].[O-][P+]([O-])=O IIRVGTWONXBBAW-UHFFFAOYSA-M 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- SLGOCMATMKJJCE-UHFFFAOYSA-N 1,1,1,2-tetrachloro-2,2-difluoroethane Chemical compound FC(F)(Cl)C(Cl)(Cl)Cl SLGOCMATMKJJCE-UHFFFAOYSA-N 0.000 description 1
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-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
- 239000005060 rubber Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
Landscapes
- Moulds For Moulding Plastics Or The Like (AREA)
- Lubricants (AREA)
Description
本発明は離型剤、就中、パーフルオロアルケニ
ルアリールエーテルのホスホン酸誘導体の酸性塩
を含有する離型剤に関する。
従来、合成樹脂、ゴム等の高分子物質（発泡体
を含む）、セメント、セラミツク等の成形にはシ
リコーンオイル、鉱物油、パラフインワツクス、
各種脂肪酸誘導体、グリコール類、タルク、マイ
カ等が離型剤として用いられてきた。特にシリコ
ーンオイルは離型性に優れているため最も普遍的
に使用されている離型剤の一つであるが、ウレタ
ン、エポキシ、ポリイミド樹脂のように極性が大
きく接着性の強い物質の離型剤としては不充分で
あり、しかも一般的な用途としても離型性能の保
持力は必らずしも十分でなく、成型の都度モール
ドに離型剤を塗布する必要がある。
以上の欠点を改良する方法として、シリコーン
オイルにシリカ、マイカ等の微粉やその他適当な
添加剤を用いて離型剤被膜の強度を高めたり、シ
リコーンオイルの粘度をあげる等の手段が講じら
れているが、その場合でも離型剤使用量を比較的
多くしなければならないため、離型剤の成形体へ
の移行を招き、成形体の割れ、成形体表面の汚
れ、成形体の後処理、例えば塗装や接着が困難ま
たは不可能となる場合がある。
一方、本発明者らは先にパーフルオロアルケニ
ルアリールエーテルのホスホン酸誘導体が界面活
性剤として有用であることを見出し、その際、そ
の化合物が優れた離型性能を有することを確認し
た（特開昭52−52188号）。しかしながらこのパー
フルオロアルケニルアリールエーテルのホスホン
酸またはその中性塩は前記従来の離型剤に比べ比
較的高い性能が認められながら価格的な面で使用
量が制限されるため、実用的にはより優れた性能
が要請されていた。
本発明者らはこの要請に対処すべく、種々の置
換基の導入、中和剤の種類の検討、配合剤の検討
を繰返すうち、中和剤の量を調整し酸性塩の状態
にすると未中和物および中性塩では達成し得ない
ように優れた効果が得られることを見出し、本発
明を完成した。
即ち本発明は、一般式〔〕：
（式中、Rfはヘキサフルオロプロペンオリゴマ
ー残基を示し、Arは置換基を有することもある
芳香族残基を示し、ｌは１〜３の数を示し、ｎは
１または２の数を示す）
で表わされるホスホン酸１モルを0.7〜1.3当量の
アルカリで中和した酸性塩を必須成分とする離型
剤に関する。
一般式〔〕においてRfはヘキサフルオロプ
ロペンオリゴマー残基、好ましくは２〜４量体残
基を示し、Arは置換基を有することもある芳香
族残基、例えばフエニル基、ナフチル基およびこ
れらの残基に置換基、例えばアルキル基、アリー
ル基、アシル基、アルコキシ基、ハロゲン等が結
合した残基等を示し、ｌは１〜３の数を示し、ｎ
は１または２の数を示す。
具体的な塩残基は、例えば、ナトリウム、カリ
ウム等のアルカリ金属、マグネシウム、カルシウ
ム、ストロンチウム、バリウム等のアルカリ土類
金属、亜鉛、鉛、アルミニウム、カドニウム、ジ
ルコニウム、錫、銅、ニツケル、鉄、クロム等の
金属、アンモニア、メチル、エチル、イソプロピ
ル、ｎ−プロピル、ｎ−ブチル、イソブチル、２
−エチルヘキシル、ラウリル、ステアリル等のア
ルキル基を有する一級、二級、三級アミン類、ア
ルカノールアミン類、シクロヘキシルアミン、ア
ニリン、ピリジン、モリホリン、ピペラジン等の
異項環式アミン類、エチレンジアミン等の多価ア
ミン類であつてもよい。更にこれらアミン類にエ
チレンオキシド鎖が付いていてもかまわない。中
和剤として特に好ましいのは亜鉛、ジルコニウム
（例えばジルコニル塩）等である。
本発明で使用される上記ホスホン酸の酸性塩は
一般に次のような方法で合成し得る。まず(1)ヘキ
サフルオロプロペンオリゴマーとヒドロキシル基
を少くとも一以上有する芳香族化合物と反応させ
パーフルオロアルケニルアリールエーテルを製造
する。(2)該アリールエーテルとモノハロまたはジ
ハロエーテル類と反応させるか、あるいはホルム
アルデヒドもしくはその重合体をハロゲン化水素
の存在下に反応させるか、あるいはまた該アリー
ルエーテルがアルキル置換基を有するときはその
アルキル基をラジカル触媒の存在下にハロゲン化
することにより、パーフルオロアルケニルハロア
ルキルアリールエーテルを製造する。(3)得られる
ハロアルキルアリールエーテルと亜りん酸トリア
ルキルエステルとを反応させ、ホスホン酸ジアル
キル誘導体を得、これを加水分解し、所望により
これを適宜の塩基で半中和して目的化合物を得
る。アルカル金属塩はナトリウム塩の複分解法を
用いてもよい。
中和に用いるアルカリの量は必らずしも完全半
中和でなくともよく、ホスホン酸１モルに対し、
0.7〜1.3当量のアルカリを用いると好結果が得ら
れる。
本発明離型剤は必要に応じて上記ホスホン酸塩
のほかに界面活性剤、シリコーンオイル（エマル
シヨン等も含む）、フツ素化油、シリカ粉末、ポ
リテトラフルオロエチレン粉末、フツ化黒鉛粉
末、メチルセルロース、ポリビニルアルコール、
酢酸ビニル樹脂等を含有してもよい。
本発明離型剤は少なくとも上記ホスホン酸塩を
一種以上併用し、これらを水や有機溶剤は溶解若
しくは分散（グリース状も含む）させることによ
り製造される。
有機溶媒としては、メタノール、エタノール、
プロパノール、イソプルピルアルコール等のアル
コール類、アセトン、メチルエチルケトン、メチ
ルイソブチルケトン等のケトン類、エチルエーテ
ル、イソプロピルエーテル、ジオキサン、テトラ
ヒドロフラン等のエーテル類、酢酸エチル、酢酸
ブチル等のエステル類、メチルセロソルブ、エチ
ルセロソルブ、メチルカービトール、エチルカー
ビトール等の多価アルコール誘導体、四塩化炭
素、塩化メチレン、塩化エチレン、トリクロロエ
チレン、パークロロエチレン、トリクロロエタ
ン、トリクロロフルオロメタン、テトラクロロジ
フルオロエタン、トリクロロトリフルオロエタン
等のハロゲン化炭化水素類などが挙げられる。こ
れら有機溶媒は単独あるいは併用もしくは水との
併用により用いることができる。
本発明離型剤の媒体中における濃度（不揮発
分）は離型剤の使用目的によつて異なり、１回の
離型だけを目的とする場合は通常0.1w／ｗ％以
下で十分であるが、一度の離型剤塗布で特に離型
持続性を長期間要求する場合には通常0.5〜
20w／ｗ％、好ましくは１〜10w／ｗ％が適当で
ある。
本発明において離型の対象とする成型物の原材
料としては、例えばポリウレタン、クロロプレン
ゴム、ポリカーボネート、フツ素ゴム、エポキシ
樹脂、フエノール樹脂、ポリイミド樹脂、塩化ビ
ニール樹脂等の合成樹脂若しくは合成ゴム、天然
樹脂若しくは天然ゴム等があげられる。
本発明離型剤を用いて特に有効な金型は金属の
金型である。特に工具鋼、ステンレス、クロムメ
ツキ鋼、アルミニウム、等に用いて好ましい結果
が得られる。これはホスホン酸酸性塩の未中和酸
残基が金属表面と化学的に結合しパーフルオロア
ルケニル残基を金属表面の外に向つて配向するた
めと考えられる。
本発明離型剤を型に塗布するには通常公知の方
法を用いれば良く、例えば離型剤を型に浸漬、吹
付、刷毛塗り等により、或いはエアゾール化して
噴射したり、布に浸み込ませて塗り付けることに
より塗布して、媒体を蒸発除去すればよい。
以下、実施例をあげて本発明を説明する。
実施例１〜９および比較例１〜12
ウレタンエラストマーに対する離型性評価：
(1) 離型剤処方：
式：
で示されるホスホン酸の酸性塩を溶媒に分散ま
たは溶解し離型剤（ホスホン酸塩２％）を調製
した。これを以下に述べる金型に塗布した。ホ
スホン酸の塩の種類、溶剤の種類を表−１に示
す。
(2) 金型およびフツク：
金型：直径45mm、深さ45mm、アルミニウム製
カツプ。
フツク：直径30mm鉄製円盤に先端をかぎ状に
曲げた長さ73mmの棒を取りつけたもの（成型体
引き抜き用に使用）。
(3) 供試成形材料および成形条件：
コロネートＣ−4090（日本ポリウレタン工業
製ポリエーテルプレポリマー：NCO含量4.2
％）100重量部を85℃に加熱し、10mmHgで脱泡
する。別にイハラキユアミンMT（イハラケミ
カル工業(株)製メチレンビスオルソクロロアニリ
ン）12.7重量部を120℃で加熱溶融する。
気泡を巻き込まないよう両者を撹拌混合す
る。
一方、離型剤を塗布した前記金型を70〜80℃
に予熱し、これに上記混合物10ｇを注入し、フ
ツクを立てた後120℃で一時間一次硬化する。
硬化後、フツクをバネ秤を用いて引張り、成
型物を金型から脱型するに要する荷重を測定す
る。離型した金型に更に成形材料を注入し同じ
操作を繰返し、離型しなくなるまでの回数を数
える。
試験結果を表−１に示す。
The present invention relates to a mold release agent, in particular a mold release agent containing an acid salt of a phosphonic acid derivative of a perfluoroalkenyl aryl ether. Conventionally, silicone oil, mineral oil, paraffin wax,
Various fatty acid derivatives, glycols, talc, mica, etc. have been used as mold release agents. In particular, silicone oil is one of the most commonly used mold release agents due to its excellent mold release properties, but it can also be used to release materials with high polarity and strong adhesive properties such as urethane, epoxy, and polyimide resins. It is insufficient as an agent, and even for general use, the retention of mold release performance is not necessarily sufficient, and it is necessary to apply a mold release agent to the mold each time molding is performed. As a method to improve the above-mentioned drawbacks, measures have been taken such as increasing the strength of the release agent film by adding fine powder such as silica or mica or other suitable additives to silicone oil, and increasing the viscosity of silicone oil. However, even in that case, the amount of mold release agent used must be relatively large, which may lead to migration of the mold release agent into the molded product, resulting in cracking of the molded product, dirt on the surface of the molded product, post-treatment of the molded product, For example, painting or gluing may be difficult or impossible. On the other hand, the present inventors previously discovered that a phosphonic acid derivative of perfluoroalkenyl arylether is useful as a surfactant, and at that time confirmed that the compound had excellent mold release performance (Unexamined Japanese Patent Publication No. (Sho 52-52188). However, although this perfluoroalkenyl aryl ether phosphonic acid or its neutral salt has been recognized to have relatively high performance compared to the conventional mold release agents, its usage is limited due to price, so it is less practical. Excellent performance was required. In order to meet this demand, the present inventors repeatedly introduced various substituents, examined the types of neutralizing agents, and examined compounding agents. The present invention was completed based on the discovery that superior effects that cannot be achieved with neutralized products and neutral salts can be obtained. That is, the present invention is based on the general formula []: (In the formula, R f represents a hexafluoropropene oligomer residue, Ar represents an aromatic residue that may have a substituent, l represents a number of 1 to 3, and n represents a number of 1 or 2. This invention relates to a mold release agent whose essential component is an acid salt obtained by neutralizing 1 mole of phosphonic acid represented by the following formula with 0.7 to 1.3 equivalents of alkali. In the general formula [], R f represents a hexafluoropropene oligomer residue, preferably a dimer to tetramer residue, and Ar represents an aromatic residue that may have a substituent, such as a phenyl group, a naphthyl group, and the like. Represents a residue to which a substituent such as an alkyl group, aryl group, acyl group, alkoxy group, halogen, etc. is bonded, l represents a number from 1 to 3, and n
indicates the number 1 or 2. Specific salt residues include, for example, alkali metals such as sodium and potassium, alkaline earth metals such as magnesium, calcium, strontium, and barium, zinc, lead, aluminum, cadmium, zirconium, tin, copper, nickel, iron, Metals such as chromium, ammonia, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, 2
- Primary, secondary, and tertiary amines with alkyl groups such as ethylhexyl, lauryl, and stearyl, alkanolamines, heterocyclic amines such as cyclohexylamine, aniline, pyridine, morpholine, and piperazine, and polyvalent amines such as ethylenediamine. It may also be an amine. Furthermore, an ethylene oxide chain may be attached to these amines. Particularly preferred neutralizing agents are zinc, zirconium (eg, zirconyl salt), and the like. The acidic salt of the phosphonic acid used in the present invention can generally be synthesized by the following method. First, (1) a hexafluoropropene oligomer is reacted with an aromatic compound having at least one hydroxyl group to produce perfluoroalkenyl aryl ether. (2) Reacting the aryl ether with a monohalo or dihalo ether, or reacting formaldehyde or a polymer thereof in the presence of hydrogen halide, or, when the aryl ether has an alkyl substituent, the alkyl group. A perfluoroalkenyl haloalkylaryl ether is produced by halogenating the compound in the presence of a radical catalyst. (3) The obtained haloalkylaryl ether and phosphorous acid trialkyl ester are reacted to obtain a dialkyl phosphonate derivative, which is hydrolyzed and, if desired, semi-neutralized with an appropriate base to obtain the target compound. . For the alkali metal salt, a double decomposition method of sodium salt may be used. The amount of alkali used for neutralization does not necessarily have to be completely half-neutralized;
Good results are obtained using 0.7 to 1.3 equivalents of alkali. In addition to the above-mentioned phosphonate, the mold release agent of the present invention may optionally include surfactants, silicone oil (including emulsions, etc.), fluorinated oil, silica powder, polytetrafluoroethylene powder, fluorinated graphite powder, and methyl cellulose. , polyvinyl alcohol,
It may also contain vinyl acetate resin or the like. The mold release agent of the present invention is produced by using at least one or more of the above phosphonates in combination and dissolving or dispersing them (including in the form of a grease) in water or an organic solvent. Examples of organic solvents include methanol, ethanol,
Alcohols such as propanol and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as ethyl ether, isopropyl ether, dioxane and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; methyl cellosolve; Polyhydric alcohol derivatives such as ethyl cellosolve, methyl carbitol, ethyl carbitol, etc., halogens such as carbon tetrachloride, methylene chloride, ethylene chloride, trichloroethylene, perchloroethylene, trichloroethane, trichlorofluoromethane, tetrachlorodifluoroethane, trichlorotrifluoroethane, etc. Examples include carbonated hydrocarbons. These organic solvents can be used alone, in combination, or in combination with water. The concentration (non-volatile content) of the mold release agent of the present invention in the medium varies depending on the purpose of the mold release agent, and if the purpose is only one mold release, 0.1 w/w% or less is usually sufficient. , usually from 0.5 to 0.5 when long-term release persistence is required with one application of mold release agent.
A suitable amount is 20 w/w%, preferably 1 to 10 w/w%. In the present invention, raw materials for molded products to be released from molds include, for example, synthetic resins or synthetic rubbers such as polyurethane, chloroprene rubber, polycarbonate, fluorocarbon rubber, epoxy resins, phenol resins, polyimide resins, and vinyl chloride resins, and natural resins. Alternatively, natural rubber etc. can be mentioned. Molds for which the mold release agent of the present invention is particularly effective are metal molds. Particularly favorable results can be obtained when used on tool steel, stainless steel, chrome-plated steel, aluminum, etc. This is considered to be because the unneutralized acid residues of the phosphonic acid salt chemically bond to the metal surface and orient the perfluoroalkenyl residues toward the outside of the metal surface. The mold release agent of the present invention may be applied to a mold by a commonly known method, such as by dipping the mold with the mold release agent, spraying it, brushing it, etc., spraying it as an aerosol, or soaking it into cloth. It can be applied by dipping and smearing, and the medium can be removed by evaporation. The present invention will be explained below with reference to Examples. Examples 1 to 9 and Comparative Examples 1 to 12 Evaluation of mold release properties for urethane elastomers: (1) Release agent formulation: Formula: A mold release agent (phosphonic acid salt 2%) was prepared by dispersing or dissolving the acidic salt of phosphonic acid shown in the following in a solvent. This was applied to the mold described below. Table 1 shows the types of phosphonic acid salts and solvents. (2) Mold and hook: Mold: diameter 45mm, depth 45mm, aluminum cup. Hook: A 73mm long rod with a hook-shaped tip attached to a 30mm diameter iron disk (used for pulling out molded objects). (3) Test molding material and molding conditions: Coronate C-4090 (polyether prepolymer manufactured by Nippon Polyurethane Industries: NCO content 4.2
%) 100 parts by weight is heated to 85℃ and degassed at 10mmHg. Separately, 12.7 parts by weight of Iharakyuamine MT (methylene bis-orthochloroaniline manufactured by Ihara Chemical Industries, Ltd.) was heated and melted at 120°C. Stir and mix both to avoid creating air bubbles. Meanwhile, heat the mold coated with a mold release agent to 70-80℃.
10g of the above mixture was poured into it, a hook was put up, and the mixture was first cured at 120°C for one hour. After curing, the hook is pulled using a spring scale to measure the load required to release the molded product from the mold. Inject more molding material into the mold that has been released, repeat the same operation, and count the number of times until the mold no longer releases. The test results are shown in Table-1.
【表】【table】
【表】
実施例10〜14および比較例13〜20
エポキシ樹脂の離型試験：
トランスフア成型機（レイボルト機工社製）の
金型（肉厚２〜３mm、直径116mmの円盤状灰皿成
型用金型）に表−２に示す処方の離型剤（ホスホ
ン酸類として式：
を使用）を155℃に加熱した後塗布し、これにエ
ポハードPE300M（安達新産業(株)社製成形用エポ
キシ樹脂）57ｇを投入し、速かに加熱圧縮成形す
る（成形温度155℃。成形圧力200Kg／cm2、成形時
間２分）。成形物は５秒間エアジエツト冷却（コ
ンプレツサー圧1.75Kg／cm2）と１時間バキユーム
リフト（コンプレツサー圧1.75Kg／cm2）操作を繰
返し、離型するまでの冷却回数を測定する。結果
を表−２に示す。[Table] Examples 10 to 14 and Comparative Examples 13 to 20 Mold release test of epoxy resin: Mold of a transfer molding machine (manufactured by Raybolt Kiko Co., Ltd.) (metal for forming a disc-shaped ashtray with a wall thickness of 2 to 3 mm and a diameter of 116 mm) mold release agent with the formulation shown in Table 2 (as a phosphonic acid): 57g of Epohard PE300M (molding epoxy resin manufactured by Adachi Shinsangyo Co., Ltd.) is added to this, and quickly heated and compression molded (molding temperature 155℃. Molding (pressure 200Kg/cm 2 , molding time 2 minutes). The molded product was repeatedly cooled by air jet for 5 seconds (compressor pressure 1.75 Kg/cm 2 ) and vacuum lifted for 1 hour (compressor pressure 1.75 Kg/cm 2 ), and the number of cooling operations until it was released from the mold was measured. The results are shown in Table-2.
Claims (1)
ー残基を示し、Arは置換基を有することもある
芳香族残基を示し、ｌは１〜３の数を示し、ｎは
１または２の数を示す） で表わされるホスホン酸１モルを0.7〜1.3当量の
アルカリで中和した酸性塩を必須成分とする離型
剤。 ２ Rfがパーフルオロノネニル基を示す第１項
記載の離型剤。[Claims] 1 General formula []: (In the formula, R f represents a hexafluoropropene oligomer residue, Ar represents an aromatic residue that may have a substituent, l represents a number of 1 to 3, and n represents a number of 1 or 2. A mold release agent whose essential component is an acid salt obtained by neutralizing 1 mole of phosphonic acid represented by the following formula with 0.7 to 1.3 equivalents of alkali. 2. The mold release agent according to item 1, wherein R f represents a perfluorononenyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12904979A JPS5653193A (en) | 1979-10-05 | 1979-10-05 | Fluorine type release agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12904979A JPS5653193A (en) | 1979-10-05 | 1979-10-05 | Fluorine type release agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5653193A JPS5653193A (en) | 1981-05-12 |
| JPS636330B2 true JPS636330B2 (en) | 1988-02-09 |
Family
ID=14999814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12904979A Granted JPS5653193A (en) | 1979-10-05 | 1979-10-05 | Fluorine type release agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5653193A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004531617A (en) | 2001-06-18 | 2004-10-14 | ハネウェル・インターナショナル・インコーポレーテッド | Fluorine-containing compounds and polymers derived therefrom |
| JP2017177401A (en) * | 2016-03-29 | 2017-10-05 | 三菱マテリアル電子化成株式会社 | Liquid composition for mold release |
| JP7333278B2 (en) * | 2020-01-10 | 2023-08-24 | 三菱マテリアル電子化成株式会社 | Release liquid composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5252188A (en) * | 1975-10-24 | 1977-04-26 | Shinnitsutou Kagaku Kk | F-cont. surfactants |
-
1979
- 1979-10-05 JP JP12904979A patent/JPS5653193A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5252188A (en) * | 1975-10-24 | 1977-04-26 | Shinnitsutou Kagaku Kk | F-cont. surfactants |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5653193A (en) | 1981-05-12 |
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