WO1998038248A1 - Procede pour enduire des corps moules avec des masses ou des solutions de resine de polyester - Google Patents
Procede pour enduire des corps moules avec des masses ou des solutions de resine de polyester Download PDFInfo
- Publication number
- WO1998038248A1 WO1998038248A1 PCT/EP1998/001024 EP9801024W WO9838248A1 WO 1998038248 A1 WO1998038248 A1 WO 1998038248A1 EP 9801024 W EP9801024 W EP 9801024W WO 9838248 A1 WO9838248 A1 WO 9838248A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyester resin
- resin compositions
- solutions
- compounds
- coating
- Prior art date
Links
- 239000004645 polyester resin Substances 0.000 title claims abstract description 68
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 67
- 150000001875 compounds Chemical class 0.000 title claims abstract description 43
- 238000000576 coating method Methods 0.000 title claims abstract description 21
- 239000011248 coating agent Substances 0.000 title claims abstract description 18
- 238000000465 moulding Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 31
- 230000008569 process Effects 0.000 title claims description 12
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 60
- 229920000728 polyester Polymers 0.000 claims description 24
- 238000001723 curing Methods 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 125000000746 allylic group Chemical group 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000012876 carrier material Substances 0.000 claims description 3
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 3
- 229940018557 citraconic acid Drugs 0.000 claims description 3
- 239000008199 coating composition Substances 0.000 claims description 3
- 239000000615 nonconductor Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000000016 photochemical curing Methods 0.000 claims description 2
- 238000001029 thermal curing Methods 0.000 claims description 2
- 239000002966 varnish Substances 0.000 claims description 2
- -1 acryl Chemical group 0.000 abstract description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 2
- 239000012212 insulator Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 229920002554 vinyl polymer Chemical group 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 239000002253 acid Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 10
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 229920001451 polypropylene glycol Polymers 0.000 description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 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 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920006337 unsaturated polyester resin Polymers 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 3
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 150000002689 maleic acids Chemical class 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 150000003022 phthalic acids Chemical class 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical group OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- OGFRUZNFTUBONW-UHFFFAOYSA-N 4,4-bis(hydroxymethyl)cyclohexane-1,1-diol Chemical compound C(O)C1(CCC(CC1)(O)O)CO OGFRUZNFTUBONW-UHFFFAOYSA-N 0.000 description 1
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000004426 flaxseed Nutrition 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000011521 glass Substances 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
- 239000004615 ingredient Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
- C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
Definitions
- the invention relates to methods for coating moldings with polyester resin compositions or solutions and the use of polyester resin compositions or solutions as impregnating, casting and coating compositions or impregnating lacquers.
- Polyester resin compounds are widely used for coating moldings, in particular electronic or electrotechnical components, such as wires or coils.
- Unsaturated polyesters are generally used in the form of a solution in a copolymerizable monomer, usually styrene. After the moldings or components have been coated with the polyester resin compositions, they are cured by copolymerization with the monomers, in particular styrene.
- DE-A-32 30 924 describes processes for the preparation of unsaturated polyester resins based on maleic anhydride as the unsaturated acid component, the polyesters obtained having been reacted with dicyclopentadiene and the esterification in the presence of N-hydroxyalkyl imides of monounsaturated cycloaliphatic 1, 2-dicarboxylic acids is carried out.
- the polyesters are dissolved in styrene.
- EP-B-0 118 786 and EP-B-0 260 688 describe processes for the production of moldings from unsaturated polyester resins, esters based on maleic anhydride as unsaturated acid and reacted with dicyclopentadiene being dissolved in styrene and subjected to a two-stage curing process Can be hardened using two different radical formers.
- DE-A-1 570 273 and DE-A-1 720 323 describe unsaturated polyesters which have cyclic imide groups. These polyesters are also used as a solution in styrene.
- polyesters When the above-described polyesters are used as impregnating resins in copolymerizable monomers, such as acrylates, allyl phthalate, styrene, ⁇ -methylstyrene or methyltoluene or vinyltoluene, these monomers are partially released when the mixtures are used for coating. In known applications of impregnating agents with these substances, mass losses of approximately 20 to 30% occur. These considerable amounts have to be removed from the workplace, since the monomers are often harmful to health and irritating to the skin and thus pose a health risk to those working with these substances. The extracted amounts of monomer are usually disposed of in exhaust air incineration plants, which can lead to undesirable emissions. In addition, the substances lost in this way represent a considerable economic loss.
- copolymerizable monomers such as acrylates, allyl phthalate, styrene, ⁇ -methylstyrene or methyltoluene or vinyltoluene
- the object of the present invention is to provide a method for coating shaped articles by soaking in, casting with or coating with polyester resin compositions or solutions, which avoids these disadvantages.
- this object is achieved by a process for coating moldings by soaking in, casting with or coating with polyester resin compositions or solutions which are essentially free of acrylic, allylic or vinylically unsaturated monomers and contain unsaturated polyesters,
- unsaturated polyesters or polyester resins can also be cured essentially without the use of the acrylic, allylic or vinylically unsaturated monomers previously considered to be absolutely necessary.
- solvents can also be dispensed with.
- the masses are also essentially free of solvents.
- the expression “essentially” means that there are no amounts of acrylic, allylic or vinylically unsaturated monomers or, if appropriate, solvents which substantially change the properties of the polyester resin compositions or solutions.
- the amount of acrylic, allylic or vinylically unsaturated monomers is preferably at most 30, particularly preferably at most 10, in particular at most 5% by weight, based on the total weight of the polyester resin compositions.
- the polyester resin compositions are particularly preferably completely free of acrylic, allylic or vinylically unsaturated monomers.
- solvent here means those solvents or diluents which do not undergo any chemical reactions with the rest of the polyester resin compositions, particularly during curing. These are compounds that escape or remain in the polyester resin compositions during or after curing without forming chemical bonds with the polymer structure.
- Monomers or oligomeric compounds which carry functional groups which allow their reaction in the curing of the polyester resin are not included under the term "solvent".
- the molded articles coated by the process according to the invention are preferably electronic or electrotechnical components or carrier materials for electrical insulators, in particular flat electrical insulators.
- Examples of such shaped bodies or components are wires and winding goods, such as coils, motor windings, transformer windings, or corresponding components based on foils and other components.
- Carrier materials for flat insulating materials such as glass silk, mica tapes and other absorbent substances, as well as combinations thereof, can be used as insulators, the hardening of these substances in the B state possibly being interrupted in order to obtain curable prepregs. The hardening is stopped when the prepregs have solidified to such an extent that they are detackified and can be stacked or wound.
- the polyester resin compositions or solutions used according to the invention are impregnation, casting or coating solutions or compositions.
- the method according to the invention for coating shaped articles includes the generally known methods of dip impregnation, trickling technology, the dip roller method, the flooding method and the encapsulation for impregnating windings. If appropriate, these methods can be supported by applying reduced pressure and / or pressure. Suitable methods are known to the person skilled in the art.
- the polyester resin compositions or solutions used according to the invention can be heated in the coating process in order to lower the viscosity and to facilitate their use.
- the polyester resin compositions or solutions used according to the invention can be processed on known, not or only slightly modified plants.
- polyester resin compositions or solutions used according to the invention contain unsaturated polyesters.
- These polyester resins can be built up by known processes for the production of polyesters, generally by polycondensation of polyfunctional hydroxyl compounds with polyfunctional acids or their anhydrides at higher temperatures. It is often advantageous to start from the esters of such substances and to obtain the polyesters by transesterification at higher temperatures, since in some cases such transesterifications are easier and faster than the direct esterification. Multi-functional amines can also be used. The use of monofunctional feedstocks is also possible, for example to regulate the molecular weight. According to the invention, all known polyester resins can be used, provided they contain at least partially unsaturated polyesters.
- polyesters examples of basic building blocks from which the polyesters can be built are:
- amide and imide structures is described for example in DE-A-1 570 273 and DE-A-1 720 323.
- Such polyester amides or polyester imides are used, for example, when there are special requirements with regard to heat resistance.
- the polyesters used according to the invention can be unsaturated overall.
- the double bonds are preferably provided by unsaturated dicarboxylic acids or their anhydrides, such as fumaric acid, maleic acid, itaconic acid, citraconic acid or their anhydrides or mixtures thereof.
- unsaturated polyesters are based on these acids as unsaturated compounds.
- the polyester resin compositions used can additionally contain saturated polyesters.
- Saturated polyesters have no C-C double bonds or triple bonds.
- Aromatic unsaturation and the double bond in the 5-ring of the structures of the formulas (I) and (II) are not regarded as double bonds since they do not participate in a polymerization.
- saturated acids in such polyesters are phthalic acids in the different isomeric forms.
- the polyester resin compositions preferably contain not more than 50, particularly preferably not more than 20% by weight of saturated polyesters, based on the total weight of the polyester resin compositions.
- the polyester resin compositions or solutions preferably contain compounds which have structures of the formula (I)
- n has a value from 0 to 10.
- N can have an integer value, but it can also be an average.
- N preferably has a value from 0 to 7, particularly preferably 0 to 5, in particular 0 to 3.
- Preferred examples of n are 0, 1, 2.
- the structures of the formula (I) are based on cyclopentadiene (CPD) or dicyclopentadiene (DCPD) . Methods for producing these structures are known, for example from M.C. Kloetzel; Org. Reactions 4 1 to 59 (1948) or W.M. Carmody; Ind. Eng. Chem. 30 245 to 251 (1938).
- the structures can have an oxygen atom on the free valence.
- polyester resin compositions or solutions preferably contain compounds which have structures of the formula (II)
- n has a value from 0 to 10. All possible isomeric structures can be present on the ethylenic double bond. The preferred ranges for n are as indicated above.
- the structures of the formula (II) can be prepared by reacting maleic acid or maleic anhydride and water with dicyclopentadiene. Simply substituted maleic acids are obtained, which thus have a free acid function. These compounds can be in the form of the free acid.
- the structures of the formula (II) are preferably in the form of esterification products. The esterification can take place with monofunctional alcohols and / or polyfunctional alcohols and / or alkoxylation products thereof and / or polyether polyols and / or polyester polyols.
- polyether polyols or polyester polyols of polyethylene oxide, polypropylene oxide, polytetrahydrofuran and / or polycaprolactone examples of preferred alcohols are neopentyl glycol, propylene glycol, dimethylol, cyclohexanediol, 1,6-hexanediol, trimethylolpropane, diethylene glycol monoethyl ether and ethoxylation products or propoxylation products thereof.
- an ethoxylation product of one mole of trimethylolpropane and 20 moles of ethylene oxide can be used.
- alkylating agent and the degree of alkoxylation also allow properties of the end products, such as hardness, hydrophilicity and elasticity, to be controlled.
- Such polyols can also be only partially esterified with structures of the formula (II), the remaining hydroxyl groups either remaining free or esterified or etherified with other compounds or reacted with other compounds which are reactive with hydroxyl groups.
- isocyanates or epoxides can be used, as can natural oils containing hydroxyl groups, such as castor oil.
- Preferred products are obtained by reacting equal molar parts of dicyclopentadiene and maleic anhydride in the presence of water and then reacting the products with polyols, the number of OH groups in the polyols corresponding to the number of free acid functions of the substituted maleic acid.
- Particularly preferred alcohols are 1,6-hexanediol, trimethylolpropane with 20 EO (ethylene oxide) and diethylene glycol monoethyl ether.
- the structures of the general formula (II) or (I) can also be present in the form of amide or amine bonds in the corresponding compounds. These compounds can be produced, for example, by reaction with mono- and polyvalent amines.
- reaction products can be salt-like adducts, but amides are preferred.
- examples are the reaction products of amino-functional polyethylene oxides, polypropylene oxides or diene oils.
- Dihydrodicyclopentadienol which corresponds to the structure of formula (I), with a hydroxyl group on the free valence, is commercially available.
- ester structures can also be introduced by esterifying mono- or polycarboxylic acids or carboxylic acid functions of the polyester with this alcohol.
- the compounds containing structures of the formulas (I) and (II) are preferably oligomeric or monomeric compounds, which are in particular liquids.
- Cyclopentadiene can be grafted onto the double bonds of the unsaturated polyesters used according to the invention, whereby endomethylene tetrahydrophthalic acid structures are obtained. This is particularly the case when maleic acid or fumaric acid is used.
- Polyesters which do not have any of these structures are preferably used. They are preferably mixed with the monomeric or oligomeric compounds described above and thus form the polyester resin compositions or used in the process according to the invention -Solutions.
- the viscosity of the polyester resin compositions used can be changed via the amount of the monomeric or oligomeric compounds added in order to obtain a suitable viscosity.
- the polyester resin compositions or solutions preferably contain 60 to 5, particularly preferably 30 to 10% by weight of compounds which have the structures of the formulas (I) and / or (II).
- the polyester resin compositions or solutions used according to the invention are thermally and / or photochemically cured after impregnation, casting or coating and, if appropriate, removal of the solvent.
- the polyester resin compositions preferably contain compounds or functional groups which can be activated thermally and / or photochemically in order to trigger crosslinking or radical polymerization.
- the initiators can be chemically bound to the polyesters or can be present as free compounds in the polyester resin compositions. Examples of initiators which can be activated thermally are those compounds which form free radicals when heated. Known radical formers are peroxides, azo compounds, azides and CC-labile compounds.
- the polyester resin compositions according to the invention have a high UV in the presence of UV initiators of the ⁇ -splitter type (Norrish type 1) or the H donor / acceptor systems (Norrish type 2). Sensitivity to.
- a preferred way of introducing H-acceptor groups is to use condensable phenone compounds, such as hydroxy- or bishydroxybenzophenone, in the polycondensation of the polyester resins.
- the photo initiators are activated with actinic radiation, preferably UV radiation.
- Other suitable photoinitiators have xanthone, thioxanthone and / or the above phenon structures.
- the photoinitiator is preferably hydroxybenzophenone, which is condensed into the polyester.
- the curing can take place in one or more steps. For example, curing can be carried out first with actinic radiation and then or simultaneously or simultaneously with peroxides or C-C-labile substances. Partial hardening can also be carried out, for example up to the B state, which is followed by complete hardening at a later point in time. Suitable initiators and curing processes are listed in the documents described at the outset.
- the polyester resin compositions or solutions are preferably first cured with UV light on the surface and then cured using heat-activatable initiators with heating. Also of importance is a method in which the polyester resin compositions or solutions, for example in electrical windings, are first cured inside the components by heat, the heat being generated by the flow of an electrical current through the component, and then optionally with UV - Light to be post-cured on the surface. Any combination and order of the above methods can be used for curing.
- the softening temperature of the polyester resin compositions or solutions used according to the invention can be achieved by mixing different polyesters can be set. Monomeric or oligomeric compounds which have structures of the formulas (I) / (II) are also preferably added.
- the softening temperature and the melt viscosity can be adjusted to the desired value by appropriate mixing.
- These compounds can therefore be referred to as "reactive thinners" without having the disadvantages of the known ethylenically unsaturated compounds such as styrene.
- the polyester resin compositions are preferably liquid at 20 ° C. or have softening ranges according to DIN 53180 of below 130 ° C., preferably below 90 ° C., particularly preferably below 40 ° C. They preferably have a viscosity of less than 100,000 mPas at 100 ° C, particularly preferably less than 30,000 mPas at 75 ° C, in particular less than 5,000 mPas at 50 ° C. They are preferably viscosity-stable for at least 24 hours at a temperature at which they have a viscosity of at most 10,000 mPas, particularly preferably at most 2,000 mPas. These advantageous values can be set in particular by using the above monomeric and oligomeric compounds.
- polyester resin compositions which can be used without known unsaturated monomers, such as styrene , Vinyl toluene, ⁇ -methyl styrene, allyl esters, (meth) acrylic esters can be processed in liquid form.
- unsaturated monomers such as styrene , Vinyl toluene, ⁇ -methyl styrene, allyl esters, (meth) acrylic esters can be processed in liquid form.
- unsaturated monomers such as styrene , Vinyl toluene, ⁇ -methyl styrene, allyl esters, (meth) acrylic esters can be processed in liquid form.
- acrylic, allylic or vinylically unsaturated monomers in small amounts, for example in order to formulate low-viscosity, low-styrene polyester resin compositions or solutions.
- low-styrene polyester resin compounds or solutions can be formulated that comply with legal limits for styrene concentrations or emissions
- polyester resin compositions can be adapted accordingly.
- the chain length of the polyols or polycarboxylic acids can be varied, for example.
- polyester resins built up with hexanediol or adipic acid are more flexible than polyester resins based on phthalic acid and ethylene glycol.
- polyfunctional compounds which produce branches in the polyester molecules is known.
- Known compounds are trimellitic acid or trimethylolpropane.
- the polyester resin compositions or solutions can be prepared by any method.
- the compounds which regulate the reactivity and viscosity in particular compounds which have structures of the formulas (I) and (II), are preferably prepared separately and then mixed with the polyesters and any other compounds used. It is also possible in many cases to produce the substances regulating the reactivity and viscosity in situ in polyester production by appropriately adjusting the stoichiometric ratios.
- polyester resin compositions or solutions used according to the invention can also have other ingredients customary for polyester resins, such as Catalysts, coloring compounds, pigments, fillers and other auxiliaries.
- polyester resin compositions or solutions used according to the invention can be used as impregnating, potting or coating compositions or solutions for coating moldings, i.e. as impregnating resins or impregnating lacquers.
- Appropriate impregnation, casting or coating processes are known to the person skilled in the art.
- 358 g of neopentyl glycol and 75 g of propylene glycol are heated to 140 ° C. under nitrogen and 356 g of isophthalic acid are added in portions.
- the mixture is heated to 180 ° C. in 2 hours while distilling off the condensate water and then cooled to 100 ° C.
- 209 g Ma Linseed anhydride added, and the mixture is heated to 200 ° C in 2 hours, a reduced pressure being applied in the last 30 minutes.
- the resulting melt is poured onto aluminum foil and solidifies to a resin with an acid number of 17.
- the flask contents are cooled to 70 ° C. and 715.0 g (6.05 mol) 1,6-hexanediol, 4.0 g dibutyltin dilaurate (DBTL) and 0.5 g hydroquinone are added.
- the mixture is then rapidly heated to 120 ° C. under a gentle stream of nitrogen and the temperature is gradually raised to 190 ° C. in the course of 6 hours, during which condensation water is distilled off.
- a soft resin with an acid number of 24 and viscosities of 3650 mPas at 50 ° C and 944 mPas at 75 ° C is obtained.
- TP 200 is an ethoxylation product from one mole of trimethylolpropane and 20 moles of ethylene oxide) (corresponding to 5.5 mole equivalent of OH), 3.00 g of dibutyltin dilaurate (DBTL) and 0.3 g of hydroquinone were added. It is rapidly heated to 120 ° C under a gentle stream of nitrogen, and then the temperature is gradually raised to 190 ° C in 6 hours. The water of condensation is distilled off. A viscous, liquid resin with an acid number of 21 and viscosities of 9340 mPas at 25 ° C. and 1560 mPas at 75 ° C. is obtained.
- DBTL dibutyltin dilaurate
- the flask contents are cooled to 70 ° C and then with 683.4 g (5.1 mol) of diethylene glycol monoethyl ether, 4.0 g of dibutyltin dilaurate (DBTL) and 0.5 g Hydroquinone added. It is quickly heated to 120 ° C. under a gentle stream of nitrogen and then to a temperature of 190 ° C. in 6 hours. The water of condensation is distilled off. A low-viscosity substance with an acid number of 32 and viscosities of 290 mPas at 25 ° C. and 34 mPas at 50 ° C. is obtained.
- DBTL dibutyltin dilaurate
- sheet metal lids are filled with the polyester resin masses in approximately 20 mm thick layers and annealed at 150 ° C for 2 hours in a forced air oven. After cooling, hard, crack-free, light brown resin blocks result.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Organic Insulating Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53728598A JP2001513830A (ja) | 1997-02-25 | 1998-02-23 | ポリエステル樹脂組成物または溶液により成形体を被覆する方法 |
| BR9807614-0A BR9807614A (pt) | 1997-02-25 | 1998-02-23 | Processo para revestir artigos conformados, e, uso de resinas de poliéster ou soluções |
| CA002282412A CA2282412A1 (fr) | 1997-02-25 | 1998-02-23 | Procede pour enduire des corps moules avec des masses ou des solutions de resine de polyester |
| EP98912371A EP0963413A1 (fr) | 1997-02-25 | 1998-02-23 | Procede pour enduire des corps moules avec des masses ou des solutions de resine de polyester |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19707492.8 | 1997-02-25 | ||
| DE1997107492 DE19707492A1 (de) | 1997-02-25 | 1997-02-25 | Verfahren zum Beschichten von Formkörpern mit Polyesterharzmassen oder -lösungen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1998038248A1 true WO1998038248A1 (fr) | 1998-09-03 |
Family
ID=7821407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1998/001024 WO1998038248A1 (fr) | 1997-02-25 | 1998-02-23 | Procede pour enduire des corps moules avec des masses ou des solutions de resine de polyester |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0963413A1 (fr) |
| JP (1) | JP2001513830A (fr) |
| BR (1) | BR9807614A (fr) |
| CA (1) | CA2282412A1 (fr) |
| DE (1) | DE19707492A1 (fr) |
| WO (1) | WO1998038248A1 (fr) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19711410A1 (de) | 1997-03-19 | 1998-09-24 | Beck & Co Ag Dr | Tränk-, Verguß- und Überzugsmassen für elektrotechnische und/oder elektronische Bauteile sowie für Trägermaterialien für flächige Isolierstoffe |
| US20110160341A1 (en) | 2009-12-30 | 2011-06-30 | E. I. Du Pont De Nemours And Company | Composition for fixing wound items |
| DE102012109803A1 (de) | 2012-06-21 | 2013-12-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Hochzähe Werkstoffe auf Basis ungesättigter Polyester |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU42334A1 (fr) * | 1961-09-11 | 1962-11-12 | ||
| FR2183053A1 (fr) * | 1972-04-29 | 1973-12-14 | Bayer Ag | |
| JPS5539243B2 (fr) * | 1977-12-28 | 1980-10-09 | ||
| US4261872A (en) * | 1977-03-28 | 1981-04-14 | Rohm And Haas Company | Autoxidizable compositions |
| EP0134513A1 (fr) * | 1983-07-19 | 1985-03-20 | Herberts Gesellschaft mit beschränkter Haftung | Masses d'imprégnation et procédé d'isolation d'enroulements électriques |
| DD257945A3 (de) * | 1981-08-14 | 1988-07-06 | Werner Freitag | Autooxydierbare bindemittelkombinationen fuer luft- und forcierttrocknende ueberzugsmittel |
| US4801629A (en) * | 1987-09-28 | 1989-01-31 | Eastman Kodak Company | Heat-curable compositions comprising a mixture of bis(2-hydroxyethyl)dicyclopentadiene-containing polyesters and unsaturated polyesters |
| EP0325154A2 (fr) * | 1988-01-20 | 1989-07-26 | BASF Aktiengesellschaft | Résines de polyester insaturé à faible teneur en styrène |
| EP0368083A2 (fr) * | 1988-11-08 | 1990-05-16 | Bayer Ag | Procédé pour la préparation de revêtements |
| EP0522400A2 (fr) * | 1991-07-10 | 1993-01-13 | Bayer Ag | Esters insaturés, procédé pour leur préparation et leur utilisation |
| JPH08109322A (ja) * | 1994-10-13 | 1996-04-30 | Hitachi Chem Co Ltd | 電気絶縁用樹脂組成物および電気絶縁処理されたトランスの製造法 |
| DE19600149A1 (de) * | 1996-01-04 | 1997-07-10 | Beck & Co Ag Dr | Tränk-, Verguß- und Überzugsmassen |
-
1997
- 1997-02-25 DE DE1997107492 patent/DE19707492A1/de not_active Withdrawn
-
1998
- 1998-02-23 EP EP98912371A patent/EP0963413A1/fr not_active Withdrawn
- 1998-02-23 WO PCT/EP1998/001024 patent/WO1998038248A1/fr not_active Application Discontinuation
- 1998-02-23 JP JP53728598A patent/JP2001513830A/ja active Pending
- 1998-02-23 CA CA002282412A patent/CA2282412A1/fr not_active Abandoned
- 1998-02-23 BR BR9807614-0A patent/BR9807614A/pt not_active Application Discontinuation
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU42334A1 (fr) * | 1961-09-11 | 1962-11-12 | ||
| FR2183053A1 (fr) * | 1972-04-29 | 1973-12-14 | Bayer Ag | |
| US4261872A (en) * | 1977-03-28 | 1981-04-14 | Rohm And Haas Company | Autoxidizable compositions |
| JPS5539243B2 (fr) * | 1977-12-28 | 1980-10-09 | ||
| DD257945A3 (de) * | 1981-08-14 | 1988-07-06 | Werner Freitag | Autooxydierbare bindemittelkombinationen fuer luft- und forcierttrocknende ueberzugsmittel |
| EP0134513A1 (fr) * | 1983-07-19 | 1985-03-20 | Herberts Gesellschaft mit beschränkter Haftung | Masses d'imprégnation et procédé d'isolation d'enroulements électriques |
| US4801629A (en) * | 1987-09-28 | 1989-01-31 | Eastman Kodak Company | Heat-curable compositions comprising a mixture of bis(2-hydroxyethyl)dicyclopentadiene-containing polyesters and unsaturated polyesters |
| EP0325154A2 (fr) * | 1988-01-20 | 1989-07-26 | BASF Aktiengesellschaft | Résines de polyester insaturé à faible teneur en styrène |
| EP0368083A2 (fr) * | 1988-11-08 | 1990-05-16 | Bayer Ag | Procédé pour la préparation de revêtements |
| EP0522400A2 (fr) * | 1991-07-10 | 1993-01-13 | Bayer Ag | Esters insaturés, procédé pour leur préparation et leur utilisation |
| JPH08109322A (ja) * | 1994-10-13 | 1996-04-30 | Hitachi Chem Co Ltd | 電気絶縁用樹脂組成物および電気絶縁処理されたトランスの製造法 |
| DE19600149A1 (de) * | 1996-01-04 | 1997-07-10 | Beck & Co Ag Dr | Tränk-, Verguß- und Überzugsmassen |
Non-Patent Citations (2)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 94, no. 14, 6 April 1981, Columbus, Ohio, US; abstract no. 104337, XP002070335 * |
| DATABASE WPI Section Ch Week 9627, Derwent World Patents Index; Class A13, AN 96-263908, XP002070336 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0963413A1 (fr) | 1999-12-15 |
| DE19707492A1 (de) | 1998-08-27 |
| CA2282412A1 (fr) | 1998-09-03 |
| BR9807614A (pt) | 2000-02-22 |
| JP2001513830A (ja) | 2001-09-04 |
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