CN1257866A - 环氧丙烯酸酯及其制备方法和用途 - Google Patents
环氧丙烯酸酯及其制备方法和用途 Download PDFInfo
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- CN1257866A CN1257866A CN99118524A CN99118524A CN1257866A CN 1257866 A CN1257866 A CN 1257866A CN 99118524 A CN99118524 A CN 99118524A CN 99118524 A CN99118524 A CN 99118524A CN 1257866 A CN1257866 A CN 1257866A
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- formula
- reaction
- epoxy acrylate
- epoxy
- acid
- 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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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 title claims description 42
- 238000000034 method Methods 0.000 title claims description 26
- 230000008569 process Effects 0.000 title description 16
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 125000005647 linker group Chemical group 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 150000002763 monocarboxylic acids Chemical class 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 abstract description 23
- 239000000203 mixture Substances 0.000 abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract description 3
- 239000004020 conductor Substances 0.000 abstract description 3
- 238000009472 formulation Methods 0.000 abstract description 3
- 239000012736 aqueous medium Substances 0.000 abstract description 2
- 229920005596 polymer binder Polymers 0.000 abstract 1
- 239000002491 polymer binding agent Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 65
- 239000007795 chemical reaction product Substances 0.000 description 41
- -1 carboxyl epoxy acrylate Chemical compound 0.000 description 34
- 238000004448 titration Methods 0.000 description 30
- 239000000243 solution Substances 0.000 description 27
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 23
- 239000002253 acid Substances 0.000 description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 22
- 239000007787 solid Substances 0.000 description 22
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 15
- 239000004922 lacquer Substances 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 125000003700 epoxy group Chemical group 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 11
- 238000005227 gel permeation chromatography Methods 0.000 description 11
- 150000002924 oxiranes Chemical group 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 10
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 9
- 229930003836 cresol Natural products 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 7
- 238000012937 correction Methods 0.000 description 7
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 206010034960 Photophobia Diseases 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 208000013469 light sensitivity Diseases 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- 229940110728 nitrogen / oxygen Drugs 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000004304 visual acuity Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NQBWNECTZUOWID-UHFFFAOYSA-N (E)-cinnamyl (E)-cinnamate Natural products C=1C=CC=CC=1C=CC(=O)OCC=CC1=CC=CC=C1 NQBWNECTZUOWID-UHFFFAOYSA-N 0.000 description 1
- OSQBFLZKVLCVGI-UHFFFAOYSA-N 1,2,3,4-tetrahydronaphthalene-1-carbonyl 1,2,3,4-tetrahydronaphthalene-1-carboxylate Chemical compound C1CCC2=CC=CC=C2C1C(=O)OC(=O)C1C2=CC=CC=C2CCC1 OSQBFLZKVLCVGI-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical group CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- QXBYUPMEYVDXIQ-UHFFFAOYSA-N 4-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical group CC1CCCC2C(=O)OC(=O)C12 QXBYUPMEYVDXIQ-UHFFFAOYSA-N 0.000 description 1
- OFXZNFPSUTXSRF-UHFFFAOYSA-N 5-ethyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(CC)CCC2C(=O)OC(=O)C12 OFXZNFPSUTXSRF-UHFFFAOYSA-N 0.000 description 1
- ZCSLAJZAESSSQF-UHFFFAOYSA-N 5-ethyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1=CC(CC)CC2C(=O)OC(=O)C12 ZCSLAJZAESSSQF-UHFFFAOYSA-N 0.000 description 1
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- NQBWNECTZUOWID-QSYVVUFSSA-N cinnamyl cinnamate Chemical compound C=1C=CC=CC=1\C=C/C(=O)OC\C=C\C1=CC=CC=C1 NQBWNECTZUOWID-QSYVVUFSSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IMHDGJOMLMDPJN-UHFFFAOYSA-N dihydroxybiphenyl Natural products OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 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
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 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
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 description 1
- 150000003755 zirconium compounds Chemical class 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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Abstract
本发明公开了式Ⅱ的新颖环氧环丙烯酸酯,它们的分子量较高,能化学交联,它们可应用于另外使用高聚合度聚合物胶粘剂的光致抗蚀剂配方中。这种光致抗蚀剂配方尤其适用于印刷电路板和印刷板材方面,并适用于含水介质、干燥后的配方几乎无粘性,并特别在导体上具有很好的边缘遮盖力。
Description
本发明涉及新颖的高分子量环氧丙烯酸酯及新颖的含多分子羧基环氧丙烯酸酯及它们的制备方法,还涉及所述丙烯酸酯在光致抗蚀剂配方中的应用以及所述配方的用途,具体地说涉及在印刷线路板和印刷板材方面的用途。
已知环氧丙烯酸酯生产量很多也广为使用,尤其是以组合物的形式用于光致抗蚀剂配方,如在GB2175908中采用了由不饱和多元酸酐同环氧丙烯酸酯与不饱和一元羧酸的反应产物所制得的树脂。
含环氧酚醛树脂与丙烯酸、环状羧酸酐的反应产物的阻焊抗蚀剂配方尤其在EP0273729中已公开。它们在碱性水介质中可显影,并具有良好的耐热性及光敏性。但是它耐化学品性不能令人满意。
EP0418011公开了用作阻焊剂掩膜的组合物,它们同样是基于环氧甲酚线型酚醛树脂与丙烯酸和环状二羧酸酐的反应产物,每当量环氧基用0.4至0.9当量的丙烯酸,以使最终产物在同一分子中同时含有酸和环氧基团。由此,使它在用于这些抗光蚀剂组合物时,这两种官能度间进行第二次热交联反应成为可能。但是,这里的问题除了来自产物的制备外(与酐反应有发生胶凝的危险),还有贮存的稳定性,因为含这种反应产物的配方即使在室温也有一定的反应活性。
所有这些提到的环氧丙烯酸酯很很通常是分子量较低。
已知由低分子量环氧树脂和环氧线型酚醛树脂制得的经光化学固化或热固化的环氧丙烯酸酯具有良好的热性能和机械性能以及良好的抗腐蚀性化学品侵蚀。但是,由这些体系得到的光致抗蚀剂膜在导体上的粘性的边缘遮盖性由于其颇低的分子量是不能令人满意的。所以在实际应用中常常需添加高度聚合的聚合物胶粘剂来避免这些缺点。这样的胶粘剂通常不含官能性的丙烯酸酯基团并且在光化学固化和热固化时不会同时发生反应,即它们是作为“惰性”组分结合到网状结构中,从而导致网状结构密度的稀释,这又尤其对所制得的光致抗蚀层的耐化学品性和电学性质产生不利的影响。此外,光敏性由于丙烯酸酯基团的“稀释”而降低。添加高度聚合的聚合物胶粘剂即使其固含量比较低也会使这些配方具有高粘度因此常导致涂敷时产生严重问题。
日本专利公开平04-294352公开了通过与不饱和一元羧酸反应接着与不饱和多元羧酸酐反应来改性环氧-线型酚醛树脂并将其应用于光敏水性配方中。
因此本发明的目的是提供没有上述缺点的丙烯酸酯。
本发明的目的已在通过在光致抗蚀剂配方中采用新颖环氧丙烯酸酯和新颖含羧基高分子量环氧丙烯酸酯的实施中达到,它们可以在没有或仅有较少量(<10%重量)的外加聚合物胶粘剂的情况下发挥作用。这类环氧丙烯酸酯可通过所谓“新式的”环氧树脂与通常是(甲基)丙烯酸反应而制得。
M是化学式为
或
的基团R1是-H或-CH3,R2-H、-CH3或苯基,R是C1-C4烷基或卤素,优选为CH3或Br,X是0-3的整数,优选为0或1,以及Y是如下式的连接基团或式中R3和R4各分别是不同的氢或C1-C4烷基,R3和R4也可以与连接的碳原子一起形成五元或六元烃环,连接基团Y的芳基可以是未被取代或为卤素或C1-C4烷基所取代。
X是-S-、-O-或SO2,以及
n是0-300的整数,优选为0至30,
如果连接基团Y的芳基是被取代的,那么适用的卤素取代基是氟基、氯基,优选为溴基;适用的C1-C4烷基取代基是直链或支链C1-C4烷基如甲基、乙基、正和异丙基、正、仲和叔丁基。
优选具有式II的环氧丙烯酸酯,式中R是-H(X=0)或-CH3,R1是-H或-CH3,R2是-H,X是0或1,n是0-30整数以及Y是式的连接基团,式中R3和R4是-H或C1-C4烷基,连接基团的芳基可以未被取代或为卤素或C1-C4烷基取代。
式II的新颖环氧丙烯酸酯可通过式I的新式环氧线型酚醛树脂与烯属不饱和一元羧酸反应来制得,如果需要可在高温下有催化剂及阻聚剂存在下进行反应。式中R、Y、n和x的规定同式II。
式I的新式环氧线型酚醛树脂是已知的(参看,尤其是JP专利公开平1-195056)并且是由式HO-Y-OH的双酚制得,式中Y的规定如上,按已知惯例,环氧线型酚醛树脂其双酚的摩尔量在环氧线型酚醛树脂中宜为每一环氧基团0.01至0.1mol。
式I的新式环氧线型酚醛树脂带有仲脂族羟基。
由式I的新式环氧线型酚醛树脂得到式II新颖环氧丙烯酸酯的反应按已知方法进行,合宜的方法是与烯属不饱和一元羧酸(式反应。适用的酸是巴豆酸、肉桂酸,优选为丙烯酸或甲基丙烯酸或它们的混合物,R1和R2的含义同上。
在反应中采用催化剂是优选的。具体适用的催化剂是金属盐(如铬化合物)、胺(如三乙胺或苄基二甲胺)还有铵盐(如苄基三甲基氯化铵)或三苯基膦和三苯基铋。
当式I的新式环氧线型酚醛树脂是固体状态时在反应中也可加入溶剂。但是溶剂对离析物必须是惰性的。适用的溶剂包括:酮类(如丙酮,甲乙酮、环己酮);酯类(如乙酸乙酯、乙酸丁酯、乙酸乙氧基乙酯或乙酸甲氧基丙酯)、醚类(如二甲氧基乙烷、二噁烷)、芳烃类(如甲苯、苯和二甲苯)以及两种或两种以上这些溶剂的混合物。
合宜的温度范围在80至140℃,与丙烯酸的反应优选在80°至120℃范围内进行,与甲基丙烯酸反应优选在80至140℃范围内进行。
在反应介质中可加入阻聚剂,适用的阻聚剂有氢醌、氢醌单甲醚及2,6-二-叔丁基-对-甲酚。
在反应介质中引入空气或氮/氧混合物是适宜的,因为前面提到的某些阻聚剂只在有氧的情况下才是有效的。根据烯属不饱和一元酸的用量,所得的式II环氧丙烯酸酯可以是完全被丙烯酸酯化或部分被丙烯酸酯化。一元羧酸相对于环氧基团的使用量可以是等摩尔量或少于等摩尔量。完全反应的环氧丙烯酸酯几乎不再含有环氧基团。
式II的新式环氧丙烯酸酯通常既不需要从反应介质中分离出来,也不需要加以纯化,得到的反应溶液可直接用于合成。
式II的部分及完全的反应产物含有来源于环氧基与烯属不饱和一元羧酸反应产生的脂族羟基,它们还可含有来源于离析物的羟基。
和R1、R2、R、n、x和Y如式II所规定,R5是去多元羧酸的环酐除去
酐基后的基,至少10mol%的基团A(如式II中)具有下述结构
优选的环氧丙烯酸酯式III相当于上述优选的环氧丙烯酸酯式II,式III中基团R1、R2、R、x、n和Y与式II给出的有关内容有相同的优选含义。
因为完全反应的环氧丙烯酸酯式II几乎不再含有环氧基,它们可以与多元羧酸的环酐反应。在该情况下,脂族羟基(式II)与环酐反应使环打开形成半酯。在该的应中,对每一反应的羟基,形成一个键合到树脂上的羧酸。该反应包括使式II的环氧丙烯酸酯在无或有催化剂和阻聚剂存在下于高温与环酐反应。式II化合物的OH基团是完全或部分被丙烯酸酯化,伴随有酐环的打开。所以式II的环氧丙烯酸酯不再含环氧基团是有利的,要不然会发生胶凝作用。该反应本质上是已知的。
适用的多元羧酸环酐通常包括琥珀酸酐、马来酸酐、戊二酸酐、四氢化邻苯二甲酸酐、衣康酸酐、邻苯二甲酸酐、六氢邻苯二甲酸酐、3-甲基和4-甲基六氢邻苯二甲酸酐、3-乙基和4-乙基六氢邻苯二甲酸酐、3-甲基-、3-乙基-、4-甲基和4-乙基四氢邻苯二甲酸酐以及1、2、4-苯三酸酐。
优选的酸酐是琥珀酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐及邻苯二甲酸酐。
适用的催化剂一般包括胺(如三乙胺、苄基二甲胺、吡啶或二甲氨基吡啶),或三苯膦或金属盐(如铬或锆化合物)。
根据需要,当式II的环氧丙烯酸酯是固态时,在反应介质中可加入溶剂。但是,该溶剂对环酐必须是惰性的,因此含羟基的溶剂是不适用的。与反应(与烯属不饱和一元羧酸的反应)有关的提及的溶剂可被采用,只要它们不含有能与酸酐起反应的官能团。
合宜的反应温度范围为60-140℃,适宜的阻聚剂通常是氢醌、氢醌单甲醚及2,6-二-叔-丁基-对-甲酚。
向反应介质引入干燥空气或氮/氧混合物是合宜的。在本发明的优选实施例中制得的式II环氧丙烯酸酯不需分离,可在同一反应器中与羧基进一步反应生成改性衍生物式III。
新颖的含羧基环氧丙烯酸酯式III通常是不需要分离和提纯的。按上所得的反应溶液可进一步用于合成反应。
由于分子中存在不饱和基团,式II环氧丙烯酸酯和式III含羧基的环氧丙烯酸酯是可热交联和可光化学交联的,因此它们可借助已知的方法以丙烯酸酯成分应用于光致抗蚀剂配方中供阻焊抗蚀剂或主抗蚀剂的制造,如瑞士专利申请2005/93-4(1993年7月2日提出申请,题目:“可光聚合的组合物”)中所公开的,其抗蚀剂层具有高的热、机械、电和化学性质。由此制备的抗蚀剂配方,具体说是应用于印刷线路板方面作为阻焊抗蚀剂或主抗蚀剂(蚀刻抗蚀剂或电镀抗蚀剂)和印刷板材方面。适用的显影剂是水性体系以及水-有机或有机体系。由于式III化合物中含的羧基,这些体系对于碱水溶液可显影的光致抗蚀剂的制备是特别适用的。
与配方中含聚合物胶粘剂的低分子量环氧丙烯酸酯相比较,令人惊奇的是含高分子量环氧丙烯酸酯的配方不需添加这类聚合物胶粘剂就能产生提高效果而不损失光敏性并且也不增加粘性。此外,作为阻焊抗蚀剂配方使用时将会改善对导体的边缘遮盖力。因为配方中没有采用其它的聚合物胶粘剂,由此产生涉及热、机械和电性能的另外一些优点,特别是由此配方制备的抗蚀剂组合物的耐化学品性能。新颖的环氧丙烯酸酯式II和含羧基的环氧丙烯酸酯式III具有较高的玻璃态转变温度。
用下述非限制性实施例对本发明加以说明。制备实施例新式的环氧甲酚线型酚醛树脂实施例1
将ECN1299(ex CIBA-GEIGY公司)环氧甲酚线性酚醛树脂4000.00g(18.58mol环氧基)装入反应器中并加热至100℃将其溶解于1780g乙酸甲氧基丙酯(MPA)中。然后将4.00g 5%四甲基氯化铵(TMAC)的乙醇溶液加入反应器中,搅拌反应混合物10分钟。使形成的清沏溶液的温度上升到130℃,然后加入165.78g(0.73mol双酚A。反应混合物在130℃反应,用滴定环氧基及用Brook-field粘度计(心轴#31)在25℃测定粘度的方法来跟踪反应进程(供测定粘度的试样用乙酸甲氧基丙酯稀释至固含量为50%)。起始值 环氧值=3.09mol/kg 粘度=141mPas反应时间1小时 环氧值=3.03mol/kg反应时间2.5小时 粘度=319mPas反应时间3.5小时 环氧值=2.85mol/kg反应时间5小时 粘度=474mPas反应时间6小时 环氧值=2.85mol/kg 粘度=571mPas
在130℃下反应6小时后中止反应(经第一个2小时反应后环氧值变化很小)。
反应产物的分析数据
固体含量(干重量): 68.4%
环氧值(滴定): 2.85mol/kg(溶液)
Brookfield粘度,25°,Sp#31: 571mPas(50%MPA溶液)
GPC(凝胶渗透色谱,
聚苯乙烯校正) Mw=16050;Mn=2059产物符合式I,其中Y是
x是1,R是甲基、n是0至6。新式的环氧甲酚线型酚醛树脂的环氧丙烯酸酯实施例2(实施例1,用100mol%丙烯酸反应)
在整个反应期间空气流由表层下面通入并加以充分的搅拌保证空气泡均匀地分布。空气应当是干净、干燥、无油。
将上述实施例1的反应产物5594.90g(配成63%乙酸甲氧基丙酯溶液;15.95mol环氧基),446.50g乙酸甲氧基丙酯及4.67g2,6-二-叔-丁基-对-甲酚装入反应器中加热至100℃,然后加入其余反应物,即1149.00g丙烯酸和9 3.50毫升Naosynchrominm5(由HARCROS-Darham Chemicals公司供应,Durham DH31QX.GB)(10%乙酸甲氧基丙酯溶液)。
混合物在105-110℃反应,反应开始是放热反应所以在反应开始后15分钟需要用水浴冷却。
反应约45分钟后,除去冷却浴并用油浴继续加热,用滴定酸含量的方法来跟踪反应进程。起始值 2.19mol/kg反应时间1小时 0.89mol/kg反应时间2小时 0.55mol/kg反应时间3小时 0.09mol/kg反应时间5小时 0.11mol/kg反应时间7.5小时 0.065mol/kg
反应7.5小时后中止反应,在温热下放出产物。
反应产物的分析数据
1.固体含量(干重量) 68%
2.环氧值(滴定): 0.05mol/kg
3.酸含量(滴定): 0.065mol/kg
4.Brookfield粘度,25°,Sp#31: 28100mPas(溶液用MPA
所用的装置由带有搅拌器、温度计、回流冷凝器以及一根空气入口管的5000ml反应器所组成。为了抑制丙烯酸酯的聚合作用,在反应过程中从表层下引入一股弱空气流。用恒温油浴加热,将实施例2的反应产物313.27g(0.73mol羟基)和147.14g乙酸甲氧基丙酯装入反应器中并加热到100℃。然后加入36.37g(0.36mol)琥珀酸酐和作为催化剂的1.25g吡啶。混合物在该温度下反应4小时。均相反应产物可不加提纯作进一步的利用。
反应产物的分析数据
1.固体含量: 51%
2.酸含量(滴定): 0.785mol/kg
3.粘度(Brookfield): 2890mPa.S,25℃
产物符合式III,其中x、Y及R如实施例1所规定,R1和R2是H,n是0-6以及A为50mol%的
基团和50mol%的H。实施例4
使用实施例3的装置,将341.18g(0.73mol OH基)实施例2的反应产物(固体含量=69.2%)和204g乙酸甲氧基丙酯装入反应器中并加热至105℃。然后加入72.33g(0.475mol)四氢邻苯二甲酸酐和1.55g作为催化剂的吡啶。混合物在110℃反应8小时。均匀的反应产物不需要提纯可作进一步使用。
反应产物的分析数据
1.固体含量 49.7%
2.酸含量(滴定) 0.82mol/kg产物与式III相符,其中x、Y、R1、R2和n如实施例3所规定,A为65mol%的
基团和35mol%的H。新式的环氧甲酚线性酚醛的树脂(根据式I)实施例5(含四溴双酚A的新式产物)
将2000.00g(9.29mol环氧基团)ECN 1299环氧甲酚线型酚醛树脂装入反应器中并加热至100℃使其溶解于940g乙酸甲氧基丙酯(MPA)中,然后加入2.00g 5%四甲基氯化铵(TMAC)乙醇溶液并搅拌10分钟。将清沏的溶液温度升到130℃并加入200.00g(0.36mol)四溴双酚A。混合物在130℃反应并用滴定环氧基团以及测定粘度的方法跟踪反应过程。在130℃反应6小时后中止反应。反应产物可直接应用于下一步骤中。
分析数据
1.固体含量(干重量); 71%
2.环氧值(滴定): 2.75mol/kg(溶液)
3.Brookfield粘度,25℃,Sp#31: 571mPaS(5%溶液)
4.GPC(聚苯乙烯校正): Mw=19492;Mn=
2126
实施例6〔含双(4-羟苯基)砜的新式产物〕
1400.00g ECN 1299
627.00g 乙酸甲氧基丙酯
1.40g 5%四甲基氯化铵乙醇溶液
63.42g 双(4-羟苯基)砜按照实施例5的过程在130℃反应6小时。所得到的反应产物分析数据如下:
1.环氧值(滴定): 2.88mol/kg(溶液)
2.GPC(聚苯乙烯校正): Mw=12863,Mn=1972实施例7〔含4,4′-二羟基联苯的新式产物〕
200.00g ECN1299
89.00g 乙酸甲氧基丙酯
0.20g 5%四甲基氯化铵乙醇溶液
6.74g 4,4′-二羟基联苯按照实施例5的过程在130℃反应6小时。所得到的反应产物分析数据如下:
1.环氧值(滴定) 2.82mol/kg(溶液)实施例8〔含双酚A的新式产物〕
1600.00g ECN1299
727.00g 乙酸甲氧基丙酯
1.60g 5%四甲基氯化铵乙醇溶液
92.40g 双酚A按照实施例5的过程在130℃反应6小时。所得到的反应产物分析数据如下:
1.固体含量(干重量); 67%
2.环氧值(滴定): 2.74mol/kg(溶液)
3.GPC(聚苯乙烯校正): Mw=25725;Mn=2257
新式的环氧甲酚线型酚醛树脂的环氧丙烯酸酯(根据式II)实施例9〔实施例5,与75mol%丙烯酸反应〕
在整个反应期间将空气流通入表层下,用有效的搅拌保证空气泡均匀地分布。空气应是干净、干燥和无油的。
将4646.30g实施例5的反应产物(70%乙酸甲氧基丙酯,12.36mol环氧值)、702.70g乙酸甲氧基丙酯和3.91g 2,6-二-叔-丁基-对-甲酚装入反应器中并加热至80℃。然后加入其余反应剂即667.90g丙烯酸和78.20mol Nuosynchromium5的10%稀溶液(10.00g工业产品+90.00g乙酸甲氧基丙酯)。混合物在105-110℃反应并用滴定酸含量跟踪反应进程。反应2.5小时后酸含量为0.00mol/kg,完成反应并在温热下放出产物。
分析数据
1.固体含量(干重量); 65.40%
2.环氧值(滴定): 0.60mol/kg
3.酸含量(滴定): 0.00mol/kg
4.Brookfield粘度,25℃,Sp#31: 675mPaS(50%溶液)
5.GPC(聚苯乙烯校正): Mw=25084;Mn=3004实施例10〔实施例5,与10mol%丙烯酸反应〕
按照实施例9所述的过程用下列组分进行反应:
500.00g 实施例5的稀释产物(57%乙酸甲氧基丙酯溶液,
1.12mol环氧基)
8.03g 丙烯酸
0.29g 2,6-二-叔-丁基-对-甲酚,以及
5.84ml 10%Nuosynchromium 5乙酸甲氧基丙酯溶液。
所得反应产物的分析数据如下:
1.固体含量(干重量); 57.40%
2.环氧值(滴定): 1.99mol/kg
3.酸含量(滴定): 0.05mol/kg
4.Brookfield粘度,25℃,Sp#31: 3510mPaS
5.GPC(聚苯乙烯校正): Mw=24113;Mn=2565实施例11〔实施例1,与65mol%丙烯酸反应〕
按照实施例9所述的过程用下列组进行反应:
900.00g 实施例1的反应产物(69%乙酸甲氧基丙酯溶液,
2.56mol/kg环氧基)
119.72g 丙烯酸
105.04g 乙酸甲氧基丙酯
0.74g 2,6-二-叔-丁基-对-甲酚,以及
14.81ml 10%Nuosynchromium 5乙酸甲氧基丙酯溶液。
反应产物的分析数据如下:
1.固体含量(干重量); 67.40%
2.环氧值(滴定): 0.81mol/kg
3.酸含量(滴定): 0.05mol/kg
4.Brookfield粘度,25℃,Sp#31: 43400mPaS
5.GPC(聚苯乙烯校正): Mw=27770;Mn=2815实施例12〔实施例8,与75mol%丙烯酸反应〕
按照实施例9所述的过程用下列组分进行反应:
200.00g 实施例8的反应产物(0.548mol环氧基)
29.61g 丙烯酸
31.32g 乙酸甲氧基丙酯
0.17g 2,6-二-叔-丁基-对-甲酚,以及
3.40ml 10%Nuosynchromium 5的乙酸甲氧基丙酯溶液,
反应产物的分析数据如下:
1.固体含量(干重量); 65.20%
2.环氧值(滴定): 0.51mol/kg
3.酸含量(滴定): 0.05mol/kg
4.GPC(聚苯乙烯校正): Mw=44949;Mn=2997
实施例13〔实施例6,与100mol%丙烯酸反应〕
按照实施例2所述的过程以下列组分反应8小时:
298.00g 实施例6的反应产物(0.854mol环氧基)
61.60g 丙烯酸
52.00g 乙酸甲氧基丙酯
0.27g 2,6-二-叔-丁基-对-甲酚,以及
5.42ml 10%Nuosynchromium 5的乙酸甲氧基丙酯溶液,
反应产物的分析数据如下:
1.环氧值(滴定): 0.03mol/kg
2.酸含量(滴定): 0.06mol/kg实施例14〔实施例7,与100mol%丙烯酸反应〕
按照实施例2所述的过程以下列组分反应8小时:
295.00g 实施例7的反应产物(0.83mol环氧基)
60.06g 丙烯酸
50.00g 乙酸甲氧基丙酯
0.36g 2,6-二-叔-丁基-对-甲酚,以及
5.34ml 10%Nuosynchromium 5的乙酸甲氧基丙酯溶液,
反应产物的分析数据如下:
1.环氧值(滴定): 0.06mol/kg
2.酸含量(滴定): 0.00mol/kg
新式的环氧甲酚线型酚醛树脂的含羧基丙烯酸酯(根据式III)实施例15〔实施例2,与70mol%琥珀酸酐反应〕
按照实施例3所述的过程以下列组分反应6小时:
434.50g 实施例2的反应产物(66%溶液,OH数=
2.1mol/kg,0.92mol OH基),
64.45g 琥珀酸酐,
41.38g 乙酸甲氧基丙酯,以及
1.76g 吡啶
反应产物的分析数据如下:
1.固体含量(干重量): 65.60%
2.酸含量(滴定): 1.31mol/kg实施例16〔实施例2,与80mol%四氢邻苯二甲酸酐反应,用4-
二甲氨基吡啶作催化剂〕
按照实施例3所述过程以下列组分反应7小时:
500.00g 实施例2的反应产物(1.04mol,OH基),
126.83g 四氢邻苯二甲酸酐,
276.83 乙酸甲氧基丙酯,以及
0.23g 4-二甲氨基吡啶
反应产物的分析数据如下:
1.固体含量(干重量): 48.40%
2.酸含量(滴定): 1.02mol/kg
3.Brookfield粘度,25℃,Sp#31: 2340mPaS实施例17〔实施例2,与65mol%邻苯二甲酸酐反应〕
按照实施例3所述过程以下列组分反应8小时:
328.80g 实施例2的反应产物(0.70mol,OH基),
67.86g 邻苯二甲酸酐,
194.77g 乙酸甲氧基丙酯
1.48g 吡啶
反应产物的分析数据如下:
1.固体含量(干重量): 43.90%
2.酸含量(滴定): 0.88mol/kg实施例18〔实施例13,与65mol%四氢邻苯二甲酸酐反应〕
按照实施例3所述的过程以下列组分反应6小时:
398.80g 实施例13的反应产物(0.85molOH基),
89.00g 四氢邻苯二甲酸酐,
190.00g 乙酸甲氧基丙酯,以及
1.68g 吡啶
反应产物的分析数据如下:
1.固体含量(干重量): 51.10%
2.酸含量(滴定): 0.95mol/kg实施例19〔实施例14,与65mol%四氢邻苯二甲酸酐反应〕
按照实施例3所述的过程以下列组分反应4.5小时:
400.00g 实施例14的反应产物(0.83molOH基),
86.76g 四氢邻苯二甲酸酐
211.20g 乙酸甲氧基丙酯
1.76g 吡啶
反应产物的分析数据如下:
1.固体含量(干重量): 46.00%
2.酸含量(滴定): 0.91mol/kg新式的环氧甲酚线性酚醛树脂的环氧甲基丙烯酸酯(根据式II)实施例20〔实施例1,与50mol%甲基丙烯酸反应〕
按照实施例9所述的过程以下列组分反应4小时:
300.00g 实施例1的反应产物(70%乙酸甲氧基丙酯溶液;
2.85mol/kg环氧基;相当0.855mol环氧基),
36.80g 甲基丙烯酸,
37.96g 乙酸甲氧基丙酯,
0.25g 2,6-二-叔-丁基-对-甲酚,以及
4.94ml 10%Nuosynchromium 5的乙酸甲氧基丙酯溶液。
反应产物的分析数据如下:
1.固体含量(干重量); 64.80%
2.环氧值(滴定): 1.10mol/kg
3.酸含量(滴定): 0.00mol/kg
4.Brookfield粘度,25℃,Sp#31: 27000mPaS
5.GPC(聚苯乙烯标定): Mw=28981;Mn=2809应用实施例一般过程:
所采用的涂布基材是清洗过的敷铜箔的电子用层压板或具有电路图形的加工好的印刷电路板。抗蚀剂配方通过将列于各实施例中的各组分经混合、溶解而制得,接着可任选地进行过滤。所有操作在保护性的黄色灯光下进行。
为了测试起见,可将各配方用金属绕丝涂布器涂布在印刷电路板上。对于大批量涂布可采用落帘式涂布法或辊涂法以及丝网印刷法。
干燥是在有循环空气流的干燥箱中进行。采用市售的涂有金属卤化物的5000W高压汞灯辐射光源进行曝光。显影是在市售的连续显影装置中进行。通过Stouffer灰梯尺和测定分辨力用梯尺曝光并根据显出的抗蚀剂影象来评估感光度和分辨力。配方1.1 含新颖的环氧丙烯酸酯
80.00g 实施例2的反应产物(50%乙酸甲氧基丙
酯溶液),
13.00g Sartomer 295(季戊四醇四丙烯酸酯),
3.00g Irgacure907(光引发剂CIBA AG,Basel),
1.50g Quantacure ITX(异丙基 噻吨酮,增感剂),
0.15g Qrasol兰GN(染料,由CIBA AG销售,Basel),配方1,2 对照实施例,含高聚合度的胶粘剂,不含新颖环氧丙烯酸酯:
133.33g Scripset550E溶液(30%乙酸甲氧基丙酯溶液,
聚合物胶粘剂,由Monsanto公司销售,苯
乙烯/马来酸共聚物),
13.00g Sartomer 295,
3.00g Irgacure 907,
1.50g Quantacure ITX,
0.15g Qrasol 兰 GN结果
配方1.1 | 配方1.2(对照) |
固含量 59%粘度25℃(Epprecht) 2200mPa.s干涂层厚 12μm干燥条件 5min 80℃曝光 150mJ/cm2显影 1%碳酸钠 35℃最后可见的灰梯尺级数 11 | 38.2%3000mPa.s12μm5min80℃150mJ/cm21%碳酸钠35℃2-3 |
含新颖环氧丙烯酸酯(实施例2)的配方1.1,尽管固含量要高得多但比配方1.2有较低的粘度。配方1.1的感光度(其影象的灰梯尺级数为11)远高于对照配方1.2(其影象的灰梯尺级数仅为2-3)的感光度。
Claims (6)
4.根据权利要求1的环氧丙烯酸酯,其中R1是-H或-CH3,R2是-H。
5.制备按照权利要求1的环氧丙烯酸酯的方法,该方法包括将新式的式I环氧线性酚醛树脂与烯属不饱和一元羧酸,在有或没有催化剂和阻聚剂存在的情况下于80℃-140℃进行反应,
其中R、Y、n和x按权利要求1所定义。
6.权利要求1的式II所示环氧丙烯酸酯用作光致抗蚀剂配方中的丙烯酸酯组分的用途。
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US20030219656A1 (en) * | 2002-04-11 | 2003-11-27 | Baughman Donald Richard | Waterborne printed circuit board coating compositions |
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US4359370A (en) * | 1980-11-24 | 1982-11-16 | Shell Oil Company | Curable epoxy-vinyl ester compositions |
JPS61243869A (ja) * | 1985-04-19 | 1986-10-30 | Taiyo Ink Seizo Kk | レジストインキ組成物 |
US4789620A (en) * | 1986-03-03 | 1988-12-06 | Mitsubishi Rayon Co. Ltd. | Liquid photosensitive resin composition containing carboxylated epoxy acrylates or methacrylates |
JPS63258975A (ja) * | 1986-12-26 | 1988-10-26 | Toshiba Corp | ソルダーレジストインキ組成物 |
JPH01195056A (ja) * | 1988-01-30 | 1989-08-04 | Toshiba Corp | 印字ヘッドの製造方法およびその製造用治具 |
GB8804044D0 (en) * | 1988-02-22 | 1988-03-23 | Coates Brothers Plc | Coating compositions |
JPH0372578A (ja) * | 1989-05-30 | 1991-03-27 | Kansai Paint Co Ltd | 缶内面用複層塗膜 |
JPH0359022A (ja) * | 1989-07-27 | 1991-03-14 | Nippon Chibagaigii Kk | 熱硬化性樹脂 |
GB2235925B (en) * | 1989-09-12 | 1992-09-30 | Sericol Group Ltd | Photocurable compositions |
US5157078A (en) * | 1990-05-25 | 1992-10-20 | The Glidden Company | Glycidyl-epoxy-acrylic copolymers |
US5218061A (en) * | 1990-09-17 | 1993-06-08 | Nippon Kayaku Kabushiki Kaisha | Partially post-glycidylated epoxy resin, epoxy resin composition and cured product thereof |
CA2055833C (en) * | 1990-11-20 | 2001-04-24 | Katsue Nishikawa | Preparation of unsaturated epoxy ester resin and carboxylated unsaturated epoxy ester resin and photosensitive composition comprising the same |
JP2988736B2 (ja) * | 1991-03-11 | 1999-12-13 | 株式会社アサヒ化学研究所 | 一液型感光性熱硬化性樹脂組成物 |
JPH04294352A (ja) * | 1991-03-22 | 1992-10-19 | Tamura Kaken Kk | 感光性水性樹脂組成物 |
JP3059022B2 (ja) | 1993-06-07 | 2000-07-04 | シャープ株式会社 | 動画像表示装置 |
-
1994
- 1994-06-15 TW TW083105379A patent/TW270123B/zh not_active IP Right Cessation
- 1994-06-23 DE DE59409454T patent/DE59409454D1/de not_active Expired - Lifetime
- 1994-06-23 EP EP94810376A patent/EP0632079B1/de not_active Expired - Lifetime
- 1994-06-23 AT AT94810376T patent/ATE194848T1/de active
- 1994-06-28 US US08/268,095 patent/US5576399A/en not_active Expired - Lifetime
- 1994-06-30 CA CA002127232A patent/CA2127232C/en not_active Expired - Fee Related
- 1994-07-01 KR KR1019940015947A patent/KR100305323B1/ko not_active IP Right Cessation
- 1994-07-01 CN CN94108126A patent/CN1052245C/zh not_active Expired - Fee Related
- 1994-07-04 JP JP17482494A patent/JP3451383B2/ja not_active Ceased
-
1996
- 1996-05-23 US US08/652,394 patent/US6479596B1/en not_active Expired - Fee Related
-
1999
- 1999-09-07 CN CNB991185242A patent/CN1133631C/zh not_active Expired - Fee Related
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2000
- 2000-10-23 HK HK00106718A patent/HK1029581A1/xx not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
US5576399A (en) | 1996-11-19 |
US6479596B1 (en) | 2002-11-12 |
EP0632079B1 (de) | 2000-07-19 |
CA2127232C (en) | 2006-11-21 |
JP3451383B2 (ja) | 2003-09-29 |
HK1029581A1 (en) | 2001-04-06 |
DE59409454D1 (de) | 2000-08-24 |
KR100305323B1 (ko) | 2001-11-22 |
CN1102838A (zh) | 1995-05-24 |
TW270123B (zh) | 1996-02-11 |
KR950003342A (ko) | 1995-02-16 |
EP0632079A1 (de) | 1995-01-04 |
CN1052245C (zh) | 2000-05-10 |
JPH0770280A (ja) | 1995-03-14 |
CA2127232A1 (en) | 1995-01-03 |
ATE194848T1 (de) | 2000-08-15 |
CN1133631C (zh) | 2004-01-07 |
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