JP5464212B2 - グラフト共重合体およびそれを有効成分とする離型剤 - Google Patents
グラフト共重合体およびそれを有効成分とする離型剤 Download PDFInfo
- Publication number
- JP5464212B2 JP5464212B2 JP2011518486A JP2011518486A JP5464212B2 JP 5464212 B2 JP5464212 B2 JP 5464212B2 JP 2011518486 A JP2011518486 A JP 2011518486A JP 2011518486 A JP2011518486 A JP 2011518486A JP 5464212 B2 JP5464212 B2 JP 5464212B2
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- JP
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- Prior art keywords
- graft copolymer
- release agent
- mold
- mold release
- reaction
- 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.)
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- 229920000578 graft copolymer Polymers 0.000 title claims description 29
- 239000004480 active ingredient Substances 0.000 title claims description 10
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 72
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000006082 mold release agent Substances 0.000 claims description 15
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 11
- 150000005215 alkyl ethers Chemical class 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000012736 aqueous medium Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 238000004581 coalescence Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 19
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 18
- 150000007514 bases Chemical class 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- -1 phosphate ester Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000003125 aqueous solvent Substances 0.000 description 4
- 231100000693 bioaccumulation Toxicity 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000003444 phase transfer catalyst Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PVCVRLMCLUQGBT-UHFFFAOYSA-N (1-tert-butylcyclohexyl) (1-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical group C1CCCCC1(C(C)(C)C)OC(=O)OOC(=O)OC1(C(C)(C)C)CCCCC1 PVCVRLMCLUQGBT-UHFFFAOYSA-N 0.000 description 1
- UAQDAWVXKDXJST-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,6,6,7,7,8,8,9,9,10,10-nonadecafluoro-12-iodododecane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)CC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCI UAQDAWVXKDXJST-UHFFFAOYSA-N 0.000 description 1
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PDCBZHHORLHNCZ-UHFFFAOYSA-N 1,4-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(C(F)(F)F)C=C1 PDCBZHHORLHNCZ-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical group CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- QDFXRVAOBHEBGJ-UHFFFAOYSA-N 3-(cyclononen-1-yl)-4,5,6,7,8,9-hexahydro-1h-diazonine Chemical compound C1CCCCCCC=C1C1=NNCCCCCC1 QDFXRVAOBHEBGJ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 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
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- QWVBGCWRHHXMRM-UHFFFAOYSA-N hexadecoxycarbonyloxy hexadecyl carbonate Chemical group CCCCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCCCC QWVBGCWRHHXMRM-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical class OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
- B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2096/00—Use of specified macromolecular materials not provided for in a single one of main groups B29K2001/00 - B29K2095/00, as moulding material
- B29K2096/02—Graft polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
CF3(CF2)7CH2CH2P(O)(OC2H5)2
が、この種の用途に好んで使用されている(特許文献4〜7参照)。
CnF2n+1(CH2CF2)a(CF2CF2)bCH=CH2
(ここで、nは1〜6の整数であり、aは1〜4の整数、bは1〜3の整数である)で表わされるポリフルオロ-1-アルケンをグラフト共重合させたグラフト共重合体ならびにそれを有効成分とする離型剤が提供される。
(1) すぐれた造膜性を有し、複雑な形状の成形品に対しても均一な塗膜を形成させることができる。
(2) 金型面に対する造膜性による金型面への密着性にすぐれているため、離型性能および離型寿命の著しい向上が図られる。
(3) 約0.1重量%程度の低濃度の希釈でもすぐれた離型性および持続性が発揮されるため、離型剤による型汚れが低減される。
(4) 離型剤の成形品への移行性が小さいため、成形後の成形品の品質に悪影響を及ぼすことが少なく、成形品の寸法精度が向上する。
(5) 成形品の電気接点不良という問題もなく、二次加工性にもすぐれている。
R1O-(RO)p+q-R2
RO:炭素数2〜6の直鎖状または分岐状オキシアルキレン基
R1、R2:それぞれ独立に水素原子、炭素数1〜20のアルキル基また
はアラルキル基
p+q:オキシアルキレン基の重合数(1〜50)
で表わされる化合物が用いられる。
CnF2n+1(CH2CF2)a(CF2CF2)bCH=CH2 〔I〕
は、一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)I 〔II〕
で表わされるポリフルオロアルキルアイオダイドに塩基性化合物を反応させ、末端脱HI化反応させることにより、生成物〔I〕として製造される。
CF3(CF2)(CH2CF2)(CF2CF2)I
CF3(CF2)(CH2CF2)(CF2CF2)2I
CF3(CF2)(CH2CF2)(CF2CF2)3I
CF3(CF2)2(CH2CF2)(CF2CF2)I
CF3(CF2)2(CH2CF2)(CF2CF2)2I
CF3(CF2)2(CH2CF2)(CF2CF2)3I
CF3(CF2)3(CH2CF2)(CF2CF2)I
CF3(CF2)3(CH2CF2)(CF2CF2)2I
CF3(CF2)3(CH2CF2)(CF2CF2)3I
R1O-(RO)p+q-R2
が用いられた場合、その生成物は、一般式
で示され、pはグラフト共重合されないオキシアルキレン基の数であり、またqはグラフト共重合されたオキシアルキレン基の数であって、p+qは一般に1〜50、好ましくは10〜50である。
(1) 攪拌機および温度計を備えた容量1200mlのオートクレーブに、
CF3(CF2)3(CH2CF2)(CF2CF2)2I (99GC%)
603g(0.99モル)およびジ第3ブチルパーオキサイド7gを仕込み、真空ポンプでオートクレーブを脱気した。内温を80℃迄加熱したところで、エチレンを逐次的に導入し、内圧を0.5MPaとした。内圧が0.2MPa迄下がったら、再びエチレンを導入して0.5MPaとし、これをくり返した。内温を80〜115℃に保ちながら、約3時間かけてエチレン41g(1.45モル)を導入した。内温50℃以下で内容物を回収し、
CF3(CF2)3(CH2CF2)(CF2CF2)2(CH2CH2)I (98GC%)
すなわち
C4F9CH2(CF2)5CH2CH2I
637g(収率98.8%)を得た。
生成物A:3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-ノナデカフ
ルオロ-1-ドデセン
CF3CF2CF2CF2CH2CF2CF2CF2CF2CF2CH=CH2
1H-NMR;δ=2.90(2H:-CH 2-)、5.79(1H:-CF2-CH=)、5.97(2H:=CH 2)
19F-NMR;δ=-82.02(3F:CF 3-)、-113.04(4F:-CF 2CH2-)、-114.79(2F:
-CF 2CH=)、-121.9〜-128.2(10F:-CF 2-)
攪拌機、還流装置および温度計を備えた容量300mlの反応容器内に、ポリエチレングリコールモノメチルエーテル(Mn 2012、p+q:約45、融点48℃)200g(0.10モル)を仕込み、70℃に加温した後、30分間窒素ガス置換を行った。その後、145℃迄昇温し、ジ第3ブチルパーオキサイド1.25gを添加して5分間攪拌した後、ポリフルオロ-1-アルケンA 56g(0.11モル)を2時間かけて滴下し、その温度で24時間反応させた。
1H-NMR;δ=1.74(2H:-CF2CH2CH 2-)、2.25(2H:-CF2CH 2CH2-)、2.9(2H:
-CF2CH 2CF2-)、3.25(3H:-OCH 3)、3.2〜3.7(179H:
-OCH 2CH 2O-、-OCH 2CH-)
19F-NMR;δ=-82.0(3F:CF 3-)、-113.1(4F:-CF 2CH2CF 2-)、-114.5(2F:
-CF2CF 2CH2CH2-)、-121.9〜-127.0(10F:-CF 2-)
実施例1において、ポリアルキレングリコール系化合物〔PAG〕の種類および仕込量が種々に変更され、またポリフルオロ-1-アルケン〔PFA〕の種類および仕込量も種々に変更され、グラフト共重合体II〜VIIを得た。
ポリアルキレングリコール系化合物〔PAG〕:R1O-(RO)p+q-R2
a:HO(CH2CH2O)p+qCH3 p+q:約45
b:HO(CH2CH2O)p+qCH3 p+q:約20
c:HO(CH2CH2O)p+qH p+q:約20
d:CH3O(CH2CH2O)p+qCH3 p+q:約45
e:HO〔CH2CH(CH3)O〕p+qCH3 p+q:約14
f:HO〔CH2CH(CH3)O〕p+q(CH2)3CH3 p+q:約14
RO:オキシアルキレン基
R′O:グラフト共重合のためオキシアルキレン基から水素原子1
個が除去された基
表1
実施例
1 2 3 4 5 6 7
〔PAG〕
種類 a b a c d e f
仕込量 (g) 200 90 200 88 200 83 87
〃 (モル) 0.10 0.10 0.10 0.10 0.10 0.10 0.10
〔PFA〕
種類 A B E C A D A
仕込量 (g) 56 90 34 168 56 90 112
〃 (モル) 0.11 0.22 0.11 0.33 0.11 0.22 0.22
〔生成物〕
種類 I II III IV V VI VII
p 44 18 44 17 44 12 12
q 1 2 1 3 1 2 2
回収量 (g) 235 165 225 238 247 160 180
収率 (%) 92 92 96 93 96 92 90
F含量 (%) 15 34 9 45 14 35 40
実施例1で得られたグラフト共重合体I 0.5重量部をイオン交換水99.5重量部に添加し、離型剤水溶液を調製した。この離型剤水溶液を用いて、次のような2種類の測定方法で離型性の評価を行うと、金型離型性評価では6Nであり、離型寿命評価は10回であった。一方、この離型剤水溶液を塗布しないで、金型離型性および離型寿命を評価したが、成形品が金型から剥がれず、測定不能であり、したがって離型寿命は0という結果があった。
80℃に加熱されたポリウレタンプレポリマー(日本ポリウレタン製品コロネートC-4090)100重量部と加熱溶融されたメチレンビス-o-クロロアニリン硬化剤(イハラケミカル製品イハラキュアミンMT)12.8重量部とを、気泡を巻き込まないようにしながら攪拌混合し、この混合物を80℃に予熱された上記離型剤水溶液スプレー塗布アルミニウム製金型(直径45mm、深さ50mm)内に注入する。金型空間部中央に、硬化した成形品を取出すためのフックを立てておき、120℃で1時間加熱硬化させた後、フックを引張って成形品を金型から取出す。この際の離型荷重を金型離型性とした。また、このようにして金型離型性を求めた後、1回の離型剤水溶液塗布で、50N以下の離型荷重条件下で、何回迄離型が可能であったかを測定し、金型寿命とした。
実施例8の離型剤水溶液の調製に際し、グラフト共重合体Iの代りに、それぞれグラフト共重合体II〜VIIが用いられた。
実施例8の離型剤溶液の調製に際し、イオン交換水99.5重量部の内14.5重量部をメタノールで置換し、離型剤水性溶液を調製して用いた。
実施例8の離型剤溶液の調製に際し、イオン交換水99.5重量部の代りに、1,4-ビス(トリフルオロメチル)ベンゼン86重量部およびイソプロパノール13.5重量部が用いられ、離型剤有機溶媒溶液を調製して用いた。
表2
実施例 グラフト共重合体 金型離型性(N) 離型寿命(回)
8 I 6.0 10
9 II 5.0 15
10 III 10.0 7
11 IV 4.0 16
12 V 6.2 11
13 VI 5.2 14
14 VII 5.0 11
15 I 6.1 12
16 I 6.2 10
Claims (6)
- ポリアルキレングリコールまたはそのアルキルエーテルに、一般式
CnF2n+1(CH2CF2)a(CF2CF2)bCH=CH2
(ここで、nは1〜6の整数であり、aは1〜4の整数、bは1〜3の整数である)で表わされるポリフルオロ-1-アルケンをグラフト共重合させたグラフト共重合体。 - 幹重合体となるポリマーとして、一般式
R1O-(RO)p+q-R2
(ここで、ROは炭素数2〜6の直鎖状または分岐状オキシアルキレン基であり、R1、R2はそれぞれ独立に水素原子、炭素数1〜20のアルキル基またはアラルキル基であり、p+qはオキシアルキレン基の数であって、1〜50の整数である)で表わされるポリアルキレングリコールまたはそのアルキルエーテルが用いられ、生成物が一般式
(ここで、RO、R1、R2、nは前記定義と同じであり、R′Oはグラフト共重合されたオキシアルキレン基であり、pはグラフト共重合されないオキシアルキレン基の数、qはグラフト共重合されたオキシアルキレン基の数である)で表わされる請求項1記載のグラフト共重合体。 - グラフト共重合体中のフッ素含有率が3〜70重量%である請求項1記載のグラフト共重合体。
- 請求項1、2または3記載のグラフト共重合体を有効成分とする離型剤。
- 水、水性媒体または有機溶媒の溶液または分散液として調製された請求項4記載の離型剤。
- 成形用金型に塗布されて用いられる請求項5記載の離型剤。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07246624A (ja) * | 1994-03-11 | 1995-09-26 | N O K Kluber Kk | 離型剤 |
WO2009151109A1 (ja) * | 2008-06-13 | 2009-12-17 | ユニマテック株式会社 | ポリフルオロアルカジエン混合物およびその製造法 |
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Publication number | Priority date | Publication date | Assignee | Title |
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JPS5239587A (en) | 1975-09-25 | 1977-03-26 | Daikin Ind Ltd | Mold releasing agent |
JPS5236588A (en) | 1975-09-18 | 1977-03-19 | Daikin Ind Ltd | Release agent |
JPS55133490A (en) | 1979-04-03 | 1980-10-17 | Daikin Ind Ltd | Fluorine-containing composition and its use |
JPS58180597A (ja) | 1982-04-19 | 1983-10-22 | Nippon Mektron Ltd | 離型剤 |
JPS59166596A (ja) | 1983-03-14 | 1984-09-19 | Nippon Mektron Ltd | 離型剤 |
JPS60190309A (ja) | 1984-03-12 | 1985-09-27 | Nippon Mektron Ltd | 離型剤 |
JPS60193615A (ja) | 1984-03-16 | 1985-10-02 | Nippon Mektron Ltd | 離型剤 |
ATE79857T1 (de) * | 1987-06-29 | 1992-09-15 | Mitsui Petrochemical Ind | Fluor enthaltende mono- oder polyalkylenglykole und verfahren zu deren herstellung. |
JPH0623759A (ja) * | 1992-07-03 | 1994-02-01 | Sanyo Chem Ind Ltd | 塗布型離型剤 |
CN101885666B (zh) | 2006-03-10 | 2013-07-24 | 优迈特株式会社 | 多氟烷基碘化物及其制造方法 |
US8197586B2 (en) * | 2009-03-13 | 2012-06-12 | Unimatec Co., Ltd. | Polyfluoroalkylphosphonic acid, method for producing the same and mold-releasing agent comprising the same as active ingredient |
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JPH07246624A (ja) * | 1994-03-11 | 1995-09-26 | N O K Kluber Kk | 離型剤 |
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WO2009151110A1 (ja) * | 2008-06-13 | 2009-12-17 | ユニマテック株式会社 | ポリフルオロ-1-アルケンおよびその製造法 |
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