NO141804B - PHOTOPOLYMERIZABLE PREPARATION. - Google Patents
PHOTOPOLYMERIZABLE PREPARATION. Download PDFInfo
- Publication number
- NO141804B NO141804B NO177/72A NO17772A NO141804B NO 141804 B NO141804 B NO 141804B NO 177/72 A NO177/72 A NO 177/72A NO 17772 A NO17772 A NO 17772A NO 141804 B NO141804 B NO 141804B
- Authority
- NO
- Norway
- Prior art keywords
- composition according
- binder
- monomer
- weight
- carbon atoms
- Prior art date
Links
- 238000002360 preparation method Methods 0.000 title claims description 25
- 239000000178 monomer Substances 0.000 claims description 22
- -1 acrylate ester Chemical class 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 238000012644 addition polymerization Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 5
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 5
- 239000012965 benzophenone Substances 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 claims 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 2
- OYKPJMYWPYIXGG-UHFFFAOYSA-N 2,2-dimethylbutane;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(C)(C)C OYKPJMYWPYIXGG-UHFFFAOYSA-N 0.000 claims 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims 1
- 125000005395 methacrylic acid group Chemical group 0.000 claims 1
- 239000000243 solution Substances 0.000 description 22
- 239000010410 layer Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 230000005855 radiation Effects 0.000 description 11
- 239000012670 alkaline solution Substances 0.000 description 9
- 238000005530 etching Methods 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229920006267 polyester film Polymers 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000000873 masking effect Effects 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- BATOPAZDIZEVQF-MQQKCMAXSA-N (E,E)-2,4-hexadienal Chemical compound C\C=C\C=C\C=O BATOPAZDIZEVQF-MQQKCMAXSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical group OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical class CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000004053 quinones Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- BATOPAZDIZEVQF-UHFFFAOYSA-N sorbic aldehyde Natural products CC=CC=CC=O BATOPAZDIZEVQF-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- LGPAKRMZNPYPMG-UHFFFAOYSA-N (3-hydroxy-2-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OC(CO)COC(=O)C=C LGPAKRMZNPYPMG-UHFFFAOYSA-N 0.000 description 1
- VSKCCZIUZNTICH-ZPYUXNTASA-N (e)-but-2-enoic acid;ethenyl acetate Chemical compound C\C=C\C(O)=O.CC(=O)OC=C VSKCCZIUZNTICH-ZPYUXNTASA-N 0.000 description 1
- AAFCVNRTKWSHAI-MKWAYWHRSA-N (z)-4-butoxy-4-oxobut-2-enoic acid;styrene Chemical compound C=CC1=CC=CC=C1.CCCCOC(=O)\C=C/C(O)=O AAFCVNRTKWSHAI-MKWAYWHRSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- XHXSXTIIDBZEKB-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octamethylanthracene-9,10-dione Chemical compound CC1=C(C)C(C)=C2C(=O)C3=C(C)C(C)=C(C)C(C)=C3C(=O)C2=C1C XHXSXTIIDBZEKB-UHFFFAOYSA-N 0.000 description 1
- AZESNEXPGASJRZ-UHFFFAOYSA-N 1,2,3,4-tetrahydrobenzo[a]anthracene-7,12-dione Chemical compound C1CCCC2=CC=C3C(=O)C4=CC=CC=C4C(=O)C3=C21 AZESNEXPGASJRZ-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- DVFAVJDEPNXAME-UHFFFAOYSA-N 1,4-dimethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(C)=CC=C2C DVFAVJDEPNXAME-UHFFFAOYSA-N 0.000 description 1
- KFQPRNVTVMCYEH-UHFFFAOYSA-N 1-amino-3-(4-methoxyphenoxy)propan-2-ol Chemical compound COC1=CC=C(OCC(O)CN)C=C1 KFQPRNVTVMCYEH-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- YAOJJEJGPZRYJF-UHFFFAOYSA-N 1-ethenoxyhexane Chemical class CCCCCCOC=C YAOJJEJGPZRYJF-UHFFFAOYSA-N 0.000 description 1
- WVOVXOXRXQFTAS-UHFFFAOYSA-N 1-methyl-7-propan-2-ylphenanthrene-9,10-dione Chemical compound C1=CC=C2C3=CC=C(C(C)C)C=C3C(=O)C(=O)C2=C1C WVOVXOXRXQFTAS-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
- SVPKNMBRVBMTLB-UHFFFAOYSA-N 2,3-dichloronaphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C(Cl)=C(Cl)C(=O)C2=C1 SVPKNMBRVBMTLB-UHFFFAOYSA-N 0.000 description 1
- LZWVPGJPVCYAOC-UHFFFAOYSA-N 2,3-diphenylanthracene-9,10-dione Chemical compound C=1C=CC=CC=1C=1C=C2C(=O)C3=CC=CC=C3C(=O)C2=CC=1C1=CC=CC=C1 LZWVPGJPVCYAOC-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- YQZHOBBQNFBTJE-UHFFFAOYSA-N 2-chloro-3-methylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=C(C)C(Cl)=C2 YQZHOBBQNFBTJE-UHFFFAOYSA-N 0.000 description 1
- FPKCTSIVDAWGFA-UHFFFAOYSA-N 2-chloroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3C(=O)C2=C1 FPKCTSIVDAWGFA-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- CKKQLOUBFINSIB-UHFFFAOYSA-N 2-hydroxy-1,2,2-triphenylethanone Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C(=O)C1=CC=CC=C1 CKKQLOUBFINSIB-UHFFFAOYSA-N 0.000 description 1
- RZCDMINQJLGWEP-UHFFFAOYSA-N 2-hydroxy-1,2-diphenylpent-4-en-1-one Chemical compound C=1C=CC=CC=1C(CC=C)(O)C(=O)C1=CC=CC=C1 RZCDMINQJLGWEP-UHFFFAOYSA-N 0.000 description 1
- DIVXVZXROTWKIH-UHFFFAOYSA-N 2-hydroxy-1,2-diphenylpropan-1-one Chemical compound C=1C=CC=CC=1C(O)(C)C(=O)C1=CC=CC=C1 DIVXVZXROTWKIH-UHFFFAOYSA-N 0.000 description 1
- TURITJIWSQEMDB-UHFFFAOYSA-N 2-methyl-n-[(2-methylprop-2-enoylamino)methyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCNC(=O)C(C)=C TURITJIWSQEMDB-UHFFFAOYSA-N 0.000 description 1
- UFFYQSOLZWNGSO-UHFFFAOYSA-N 2-methyl-n-[3-[1-[3-(2-methylprop-2-enoylamino)propoxy]ethoxy]propyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCCCOC(C)OCCCNC(=O)C(C)=C UFFYQSOLZWNGSO-UHFFFAOYSA-N 0.000 description 1
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 description 1
- NTZCFGZBDDCNHI-UHFFFAOYSA-N 2-phenylanthracene-9,10-dione Chemical compound C=1C=C2C(=O)C3=CC=CC=C3C(=O)C2=CC=1C1=CC=CC=C1 NTZCFGZBDDCNHI-UHFFFAOYSA-N 0.000 description 1
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- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- CZIRZNRQHFVCDZ-UHFFFAOYSA-L titan yellow Chemical compound [Na+].[Na+].C1=C(C)C(S([O-])(=O)=O)=C2SC(C3=CC=C(C=C3)/N=N/NC3=CC=C(C=C3)C3=NC4=CC=C(C(=C4S3)S([O-])(=O)=O)C)=NC2=C1 CZIRZNRQHFVCDZ-UHFFFAOYSA-L 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical class [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Chemical class CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
- H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/12—Using specific substances
- H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax or thiol
- H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
- H05K3/064—Photoresists
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Polymerisation Methods In General (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Foreliggende oppfinnelse angår et nytt og forbedret fotpolymeriserbart preparat. Mer spesielt angår foreliggende oppfinnelse et lyssensitivt preparat som lett kan fremkalles The present invention relates to a new and improved foot polymerizable preparation. More particularly, the present invention relates to a light-sensitive preparation which can be easily developed
ved hjelp av en alkalisk vandig oppløsning slik at de gir et produkt som er brukbart til trykkplater og fotoresister. by means of an alkaline aqueous solution so that they give a product which is usable for printing plates and photoresists.
Disse preparater er spesielt brukbare ved fremstilling av trykte kretser på grunn av at de derav dannede resister er overlegne vanlige plateringsoppløsninger. These preparations are particularly useful in the production of printed circuits due to the fact that the resists formed therefrom are superior to ordinary plating solutions.
Ønsket om tilgjengelige lyssensitive preparater som kan fremkalles uten behovet for de vanlige organiske oppløsnings - midler, er lenge erkjent. Organiske oppløsningsmidler er kost-bare, farlige med henblikk på toksisitet og brennbarhet, og de forurenser luft og vann. The desire for available light-sensitive preparations that can be developed without the need for the usual organic solvents has long been recognized. Organic solvents are expensive, dangerous in terms of toxicity and flammability, and they pollute air and water.
Fordelene ved slike vandige systemer ble bemerket så langt tilbake som i 1956 i US-patent nr. 2.760.86 3; imidlertid ble det ikke beskrevet noe spesielt preparat, og det er nær-liggende å anta at søkeren ikke var i stand til å finne et til-fredsstillende preparat. Andre referanser til slike vannoppløse-lige preparater er nevnt i US-patent'nr. 2.927.022 og US-patent nr. 2.893.868. Hvilken fordel preparatene ifølge disse patenter enn kunne ha, ser det ut til at slike preparater, i den grad de kunne fremkalles med vandige alkaliske oppløsninger, enten ikke var tilstrekkelig uoppløselige i de eksponerte andeler, eller de var offer for angrep av de vanlige platerings- og etseopp-løsninger der fotoresistene ble brukt i en trykket krets. The advantages of such aqueous systems were noted as far back as 1956 in US Patent No. 2,760,863; however, no particular preparation was described, and it is reasonable to assume that the applicant was unable to find a satisfactory preparation. Other references to such water-soluble preparations are mentioned in US patent no. 2,927,022 and US Patent No. 2,893,868. Whatever advantage the preparations according to these patents may have, it appears that such preparations, in so far as they could be developed with aqueous alkaline solutions, were either not sufficiently insoluble in the exposed portions, or they were victims of attack by the ordinary plating- and etching solutions where the photoresists were used in a printed circuit.
Ifølge oppfinnelsen er det nå oppdaget at det kan frem-stilles fotopolymeriserbare preparater som kan fremkalles med vandige alkaliske oppløsninger, og der de eksponerte andeler har fremragende motstand overfor alkaliske oppløsninger, inkludert de alkaliske etseoppløsninger og alkaliske plateringsopp-løsninger som hyppig benyttes i fremstillingen av trykte kretser og kjemisk fremstilte deler. According to the invention, it has now been discovered that it is possible to produce photopolymerizable preparations which can be developed with aqueous alkaline solutions, and where the exposed parts have excellent resistance to alkaline solutions, including the alkaline etching solutions and alkaline plating solutions which are frequently used in the production of printed circuits and chemically manufactured parts.
Foreliggende oppfinnelse angår et fotopolymeriserbart preparat som inneholder The present invention relates to a photopolymerizable preparation which contains
a) et addisjonspolymeriserbart materiale, a) an addition polymerizable material,
b) et fotoaktiverbart initieringssystem for addisjonspolymerisering, b) a photoactivatable initiation system for addition polymerization,
c) en termisk addisjonspolymeriseringsinhibitor og c) a thermal addition polymerization inhibitor and
d) et polymert bindemiddel, d) a polymeric binder,
samt eventuelt opp til 1 vekt-% av et triazol, og preparatet er and optionally up to 1% by weight of a triazole, and the preparation is
karakterisert ved at det addisjonspolymeriserbare materiale a) characterized in that the addition polymerizable material a)
i det vesentlige består av 10-60 vektdeler av en eller flere ikke-gassformige forbindelser med et kokepunkt over 100°C ved atmosfærisk trykk.og inneholdende minst to etyleniske terminal-grupper; at det fotoaktiverbare initieringssystem for addisjonspolymerisering b) består av 0,001-10 vektdeler av et system som virker ved dannelse av frie radikaler, at inhibitoren c) anvendes i en mengde av 0,0 01-5 vektdeler og at det polymere bindemiddel essentially consists of 10-60 parts by weight of one or more non-gaseous compounds with a boiling point above 100°C at atmospheric pressure and containing at least two terminal ethylenic groups; that the photoactivatable initiation system for addition polymerization b) consists of 0.001-10 parts by weight of a system that works by forming free radicals, that the inhibitor c) is used in an amount of 0.001-5 parts by weight and that the polymeric binder
d) utgjøres av 40-90 vektdeler av et fordannet makromolekylært bindemiddel som er en polymer av et første monomermateriale som d) consists of 40-90 parts by weight of a formed macromolecular binder which is a polymer of a first monomer material which
inneholder en eller flere ikke-sure vinylforbindelser valgt blant de med formelen contains one or more non-acidic vinyl compounds selected from those of the formula
eller or
der R er hydrogen, en alkylgruppe med 1-6 karbonatomer eller et halogenatom, og der X er hydrogen og Y er OOCR^, OR^, OCR^, where R is hydrogen, an alkyl group with 1-6 carbon atoms or a halogen atom, and where X is hydrogen and Y is OOCR^, OR^, OCR^,
COOR , CN, CH=CH2, COOR , CN, CH=CH2,
eller Cl, eller X er metyl og Y er COOR1, CN, CH=CH2, eller or Cl, or X is methyl and Y is COOR1, CN, CH=CH2, or
eller både X og Y er Cl; og der R, er en alkylgruppe med 1-12 karbonatomer, en fenylgruppe eller en benzylgruppe, og R^ og R^ er like eller forskjellige og er hydrogen, en alkylgruppe med 1-12 karbonatomer eller en benzylgruppe; og et andre monomermateriale som i det vesentlige består av en eller flere alfa, beta-umettede karboksylholdige monomerer med 3-15 karbonatomer; der forholdet mellom det første og det andre monomermateriale er tilstrekkelig til å gjøre bindemidlet oppløselig i en 2%-ig vandig oppløsning av trinatriumfosfat. or both X and Y are Cl; and where R 1 is an alkyl group of 1-12 carbon atoms, a phenyl group or a benzyl group, and R 1 and R 2 are the same or different and are hydrogen, an alkyl group of 1-12 carbon atoms or a benzyl group; and a second monomer material consisting essentially of one or more alpha, beta-unsaturated carboxyl-containing monomers of 3-15 carbon atoms; where the ratio between the first and the second monomer material is sufficient to make the binder soluble in a 2% aqueous solution of trisodium phosphate.
Fordelene ifølge oppfinnelsen oppnås ved å velge et forfremstilt, forenelig makromolekylært polymerbindemiddel som er en kopolymer av (1) en styrentype- eller en ikke-sur vinylmonomer og (2) en umettet karboksylholdig monomer. Bruken av preparatet som heri definert, eliminerer helt behovet for organiske oppløsningsmidler og gir en motstand med høy motstands-dyktighet overfor oppløsningsmidler. The advantages of the invention are achieved by selecting a preformed, compatible macromolecular polymer binder which is a copolymer of (1) a styrene type or a non-acidic vinyl monomer and (2) an unsaturated carboxylic monomer. The use of the preparation as defined herein completely eliminates the need for organic solvents and provides a resistance with high resistance to solvents.
Preparatene kan også inneholde egnede fargestoffer og pigmenter og andre additiver, slik som myknere og adhesjonspro-motorer, slik disse kan være nødvendige for å forbedre de fysikalske og kjemiske egenskaper i det fotopolymeriserbare preparat. The preparations may also contain suitable dyes and pigments and other additives, such as plasticizers and adhesion promoters, as these may be necessary to improve the physical and chemical properties of the photopolymerizable preparation.
Den etylenisk umettede forbindelse må inneholde minst The ethylenically unsaturated compound must contain at least
to endestående etyleniske grupper (CH2=CC), ha et kokepunkt på over 100°C ved atmosfærisk trykk og være i stand til å danne en høy polymer ved en fri-radikal fotoinitiert kjedefremmende addisjonspolymerisering. Slike forbindelser er beskrevet i US-patent nr. 2.760.863. two terminal ethylenic groups (CH2=CC), have a boiling point above 100°C at atmospheric pressure and be capable of forming a high polymer by a free-radical photoinitiated chain-promoting addition polymerization. Such compounds are described in US Patent No. 2,760,863.
Egnede forbindelser som kan benyttes alene eller i kombinasjon, omfatter et alkylen- eller et polyalkylenglykol-diakrylat fremstilt fra alkylenglykolene, med fra 2 til 15 karbonatomer eller polyalkyleneterglykoler med 1-10 eterbindinger. Suitable compounds which can be used alone or in combination include an alkylene or a polyalkylene glycol diacrylate prepared from the alkylene glycols, with from 2 to 15 carbon atoms or polyalkylene ether glycols with 1-10 ether linkages.
På grunn av deres vanligvis hurtigere uoppløseliggjør-ing ved eksponering, antagelig på grunn av en relativt hurtig etablering av en polymer nettverkstruktur, representerer de forbindelser en overlegen klasse addisjonspolymeriserbare be-standdeler med lav molekylvekt som har flere addisjonspolymeriserbare etyleniske bindinger, spesielt når disse foreligger som endestående bindinger, og spesielt hvor minst én og helst de fleste av disse bindingene er konjugert med et dobbeltbundet karbon, inkludert karbon som er dobbeltbundet til karbon og til slike heteroatomer som nitrogen, oksygen og svovel. De stoffer er overlegne hvori de etylenisk umettede grupper, spesielt vinylidengruppene, er konjugert med ester- eller amidstrukturer. Because of their generally more rapid insolubilization upon exposure, presumably due to relatively rapid establishment of a polymeric network structure, those compounds represent a superior class of low molecular weight addition polymerizable compounds having multiple addition polymerizable ethylenic linkages, especially when present as terminal bonds, and in particular where at least one and preferably most of these bonds are conjugated to a double-bonded carbon, including carbon double-bonded to carbon and to such heteroatoms as nitrogen, oxygen and sulfur. Those substances are superior in which the ethylenically unsaturated groups, especially the vinylidene groups, are conjugated with ester or amide structures.
De følgende spesielle forbindelser er videre illustrerende for denne klasse: umettede estere av polyoler, spesielt slike estere av metylenkarboksylsyrene, f.eks. etylendiakrylat; dietylen-glykoldiakrylat; glyceroldiakrylat; glyceroltriakrylat; etylen-dimetakrylat; 1,3-propylendimetakrylat; 1,2,4-butantrioltrimet-akrylat ; 1,4-benzendioldimetakrylat; pentaerytritoltetrametakry-lat; 1,3-propandioldiakrylat; 1,5-pentandioldimetakrylat; bis-akrylåtene og metakrylåtene av polyetylenglykoler med molekylvekt på 200-500 o.l.; umettede amider, spesielt de av metylenkarboksylsyrene, og spesielt de av alfa, omega-diaminer og oksygenavbrutte omega-diaminer, slik som metylenbisakrylamid; metylenbismetakrylamid; 1,6-heksametylenbisakrylamid; dietylen-triamintrismetakrylamid; bis-(metakrylamidopropoksy)-etan; B-metakrylamidoetylmetakrylat; N-.(B-hydroksyetyl) -oksyetyl) -akryl-amid; vinylestere slik som divinylsuccinat, divinyladipat, divinyl-ftalat, divinyltereftalat, divinylbenzen-1,3-disulfonat og divinylbutan-1,4-disulfonat; og umettede aldehyder, slik som sorbaldehyd (heksadienal). The following particular compounds are further illustrative of this class: unsaturated esters of polyols, especially such esters of the methylene carboxylic acids, e.g. ethylene diacrylate; diethylene glycol diacrylate; glycerol diacrylate; glycerol triacrylate; ethylene dimethacrylate; 1,3-propylene dimethacrylate; 1,2,4-butanetriol trimethacrylate; 1,4-benzenediol dimethacrylate; pentaerythritol tetramethacrylate; 1,3-propanediol diacrylate; 1,5-pentanediol dimethacrylate; the bis-acrylates and methacrylates of polyethylene glycols with a molecular weight of 200-500 o.l.; unsaturated amides, especially those of the methylene carboxylic acids, and especially those of alpha, omega-diamines and oxygen-interrupted omega-diamines, such as methylene bisacrylamide; methylenebismethacrylamide; 1,6-hexamethylenebisacrylamide; diethylene triamine trismethacrylamide; bis-(methacrylamidopropoxy)ethane; B-methacrylamidoethyl methacrylate; N-(B-hydroxyethyl)-oxyethyl)-acrylamide; vinyl esters such as divinyl succinate, divinyl adipate, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate and divinylbutane-1,4-disulfonate; and unsaturated aldehydes, such as sorbaldehyde (hexadienal).
De foretrukne monomere forbindelser er di- eller poly-funksjonelle, men monofunksjonelle monomerer kan også benyttes. Mengden tilsatt monomer varierer med det spesielle termoplast-iske monomer. The preferred monomeric compounds are di- or poly-functional, but monofunctional monomers can also be used. The amount of added monomer varies with the particular thermoplastic monomer.
Styrentypebestanddelen av det polymere bindemiddel kan The styrene-type component of the polymeric binder may
ha den generelle formel: have the general formula:
der R betyr hydrogen eller en alkylgruppe med fra 1 til 6 karbonatomer eller en halogengruppe. Benzenringen kan være ringsubstituert med fra 1 til 5 andre funksjonelle grupper, where R means hydrogen or an alkyl group with from 1 to 6 carbon atoms or a halogen group. The benzene ring can be ring substituted with from 1 to 5 other functional groups,
slik som hitro, alkoksy, acyl, karboksyl, sulfo, hydroksyl such as hitro, alkoxy, acyl, carboxyl, sulfo, hydroxyl
eller halogengrupper. Helst er substituenten en enkel alkylgruppe slik som en metyl eller t-butylgruppe. Mest foretrukket av disse forbindelser er styren, alfa-metylstyren, para-metylstyren og para-t-butylstyren. or halogen groups. Preferably, the substituent is a single alkyl group such as a methyl or t-butyl group. Most preferred of these compounds are styrene, alpha-methylstyrene, para-methylstyrene and para-t-butylstyrene.
Den ikke-sure vinylmonomerbestanddel av det polymere bindemiddel har den generelle formel: The non-acidic vinyl monomer component of the polymeric binder has the general formula:
der X er hydrogen og Y er OOCP^, OR^, OCR^ COOR^ CN, CH2=CH2, where X is hydrogen and Y is OOCP^, OR^, OCR^ COOR^ CN, CH2=CH2,
CNR3R4 eller Cl, eller X er metyl og Y er COOR^ CN, CH2=CH2, CNR3R4 or Cl, or X is methyl and Y is COOR^ CN, CH2=CH2,
eller CNR^R^; eller både X og Y er Cl; og hvor R, er en alkylgruppe med fra 1 til 12 karbonatomer eller fenylgruppe eller en benzylgruppe, og R^ og R4 er like eller forskjellige og er hydrogen, en alkylgruppe med fra 1 til 12 karbonatomer eller en benzylgruppe. or CNR^R^; or both X and Y are Cl; and where R 1 is an alkyl group of from 1 to 12 carbon atoms or phenyl group or a benzyl group, and R 1 and R 4 are the same or different and are hydrogen, an alkyl group of 1 to 12 carbon atoms or a benzyl group.
Eksempler på disse vinylmonomerer er vinylacetat, vinyl-butyrat, vinylbenzoat, vinylklorid, vinylidenklorid, metylmeta-krylat og metylakrylat, akrylonitril og metakrylonitril, met-akrylamid og alkylsubstituerte akrylamider, vinylmetylketon, vinylpropylketon, vinylmetyleter, vinyletyleter og vinylheksyl-eter. Examples of these vinyl monomers are vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl chloride, vinylidene chloride, methyl methacrylate and methyl acrylate, acrylonitrile and methacrylonitrile, meth-acrylamide and alkyl-substituted acrylamides, vinyl methyl ketone, vinyl propyl ketone, vinyl methyl ether, vinyl ethyl ether and vinyl hexyl ether.
Den andre komonomer kan være en eller flere umettede karboksylholdige monomerer med fra 3 til 15 karbonatomer, helst fra 3 til 6. De meste foretrukne forbindelser er akrylsyre og metakrylsyre. Andre syrer som kan benyttes, er kanelsyre, kro-tonsyre, sorbinsyre, itakonsyre, propargylsyre, maleinsyre og fumarsyre, eller de tilsvarende halvestere eller, hvis mulig, det tilsvarende anhydrid. The second comonomer may be one or more unsaturated carboxylic monomers having from 3 to 15 carbon atoms, preferably from 3 to 6. The most preferred compounds are acrylic acid and methacrylic acid. Other acids that can be used are cinnamic acid, crotonic acid, sorbic acid, itaconic acid, propargylic acid, maleic acid and fumaric acid, or the corresponding half-esters or, if possible, the corresponding anhydride.
Forholdet mellom styren eller vinylbestanddel og den sure komonomer velges slik at kopolymeren er oppløselig i det vandige alkaliske medium. Hvis mengden av styren eller vinylmonomer er for høy, ville den ikke-eksponerte andel ikke være tilstrekkelig oppløslig; hvis på den annen side mengden styren eller vinylmonomer er for lav, vil det eksponerte område være klebrig, svellet eller oppløst i den vandige alkaliske oppløsning. Som et hensiktsmessig kriterium, bør bindemiddelkopolymeren være slik at en 40%-ig oppløsning i ketoner eller alkoholer har en viskositet på fra 100-50.000 centipoise. The ratio between the styrene or vinyl component and the acidic comonomer is chosen so that the copolymer is soluble in the aqueous alkaline medium. If the amount of styrene or vinyl monomer is too high, the unexposed portion would not be sufficiently soluble; if, on the other hand, the amount of styrene or vinyl monomer is too low, the exposed area will be sticky, swollen or dissolved in the aqueous alkaline solution. As a convenient criterion, the binder copolymer should be such that a 40% solution in ketones or alcohols has a viscosity of from 100-50,000 centipoise.
Representative komonomerforhold er 70:30 til 85:15 for styrenakrylsyre eller metakrylsyre; 35:65 til 70:30 for styren-monobutylmaleat og 70:30 til 95:5 for vinylacetatkrotonsyre. Polymeriseringsgraden for bindemiddelkopolymeren er slik at bindemidlet danner en ikke-klebrig kontinuerlig film etter eksponering og fremkalling. Vanligvis er molekylvekten fra 1000 til 500.000. Områdene for kopolymerforholdene og for polymeriseringsgraden for det spesielle bindemiddel kan lett undersøkes ved å prøve oppløseligheten i den fortynnede alkaliske oppløsning for representative polymerer. Disse representerer en molekylvekt på fra omkring 1000 til 500.000. Representative comonomer ratios are 70:30 to 85:15 for styrene acrylic acid or methacrylic acid; 35:65 to 70:30 for styrene monobutyl maleate and 70:30 to 95:5 for vinyl acetate crotonic acid. The degree of polymerization of the binder copolymer is such that the binder forms a non-tacky continuous film after exposure and development. Usually the molecular weight is from 1000 to 500,000. The ranges of the copolymer ratios and of the degree of polymerization for the particular binder can be easily investigated by testing the solubility in the dilute alkaline solution of representative polymers. These represent a molecular weight of from about 1,000 to 500,000.
Som ovenfor nevnt, er dekkmidlene ifølge oppfinnelsen motstandsdyktige overfor vanlige pletterings og etseoppløsninger. Mest overraskende er motstandsevnen overfor kobberpyrofosfat As mentioned above, the cover agents according to the invention are resistant to common plating and etching solutions. Most surprising is the resistance to copper pyrophosphate
som brukes ved mønsterplettering og som har en ekstremt høy alkalitet. Andre oppløsninger som ikke påvirker dekkmidlene, omfatter jern(Ill)klorid, ammoniumpersulfat og krom-svovelsyre. which is used in pattern plating and which has an extremely high alkalinity. Other solutions that do not affect the covering agents include ferric chloride, ammonium persulfate and chromic sulfuric acid.
Fotoinitiatorene som benyttes i preparatene, er helst The photoinitiators used in the preparations are preferably
de som aktiveres av aktinisk lys og som er termisk uaktive ved 185°C eller lavere. Disse omfatter substituerte eller ikke-substituerte polynukleære kinoner, 9,10-antrakinon; 1-klorantrakinon, 2-klorantrakinon, 2-metylantrakinon; 2-etylantrakinon; 2-tert.-butylantrakinon; oktametylantrakinon; 1,4-naftokinon; 9,10-fenantrenkinon; 1,2-benzantrakinon; 2,3-benzantrakinon; 2-metyl-1,4-naftokinon; 2,3-diklornaftokinon; 1,4-dimetylantrakinon; 2.3- dimetylantrakinon; 2-fenylantrakinon; 2,3-difenylantrakinon; natriumsaltet av antrakinon-alfa-sulfonsyre; 3-klor-2-metylantrakinon; retenkinon; 7,8,9,10-tetrahydronaftacenkinon; 1,2, 3.4- tetrahydrobenz(a)antracen-7,12-dion. those which are activated by actinic light and which are thermally inactive at 185°C or below. These include substituted or unsubstituted polynuclear quinones, 9,10-anthraquinone; 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone; 2-ethylanthraquinone; 2-tert-butylanthraquinone; octamethylanthraquinone; 1,4-naphthoquinone; 9,10-phenanthrenequinone; 1,2-benzanthraquinone; 2,3-benzanthraquinone; 2-methyl-1,4-naphthoquinone; 2,3-dichloronaphthoquinone; 1,4-dimethylanthraquinone; 2.3-Dimethylanthraquinone; 2-phenylanthraquinone; 2,3-diphenylanthraquinone; the sodium salt of anthraquinone-alpha-sulfonic acid; 3-chloro-2-methylanthraquinone; retenquinone; 7,8,9,10-tetrahydronaphthacenequinone; 1,2,3,4-tetrahydrobenz(a)anthracene-7,12-dione.
De følgende fotoinitiatorer, beskrevet i US-patent nr. 2.760.863, av hvilke noen kan være termisk aktive ved tempera-turer ned til 85°C, kan det også brukes: vicinale ketaldonyl-forbindelser slik som diacetyl og benzil; alfa-ketaldonylalko-holer slik som benzoin og pivaloin; acyloineter, f.eks. benzo-inmetyl og etyletere; og alfa-hydrokarbonsubstituerte aromatiske acyloiner slik som alfa-metylbenzoin; alfa-allylbenzoin; og alfa-fenylbenzoin. The following photoinitiators, described in US Patent No. 2,760,863, some of which may be thermally active at temperatures down to 85°C, may also be used: vicinal ketaldonyl compounds such as diacetyl and benzyl; alpha-ketaldonyl alcohols such as benzoin and pivaloin; acyloin ethers, e.g. benzoinmethyl and ethyl ethers; and alpha-hydrocarbon substituted aromatic acyloins such as alpha-methylbenzoin; alpha-allylbenzoin; and alpha-phenylbenzoin.
Sølvpersulfat er også brukbar som en fri-radikaldannende initiator som kan aktiveres ved aktinisk stråling. Spesielle aromatiske ketoner, f.eks- benzofenon og 4,4<1->bis-dialkylamino-benzofenoner er også brukbare. Silver persulphate is also useful as a free-radical-forming initiator that can be activated by actinic radiation. Special aromatic ketones, eg benzophenone and 4,4<1->bis-dialkylamino-benzophenones are also usable.
Termiske polymeriseringsinhibitorer er også tilstede i preparatene. Disse omfatter p-metoksyfenol, hydrokinon og alkyl og arylsubstituerte hydrokinoner og kinoner, tert.-butylkatekol, pyrrogallol, kobberresinat, naftylaminer, beta-naftol, kobber(I)-klorid, 2,6-di-tert.-butyl-p-kresol, 2,2-metylen-bis-(4-etyl-6-t-butylfenol), fenotiazin, pyridin, nitrobenzen, dinitrobenzen, p-tolukinon, kloranil, arylfosfitter og arylalkylfosfitter. Thermal polymerization inhibitors are also present in the preparations. These include p-methoxyphenol, hydroquinone and alkyl and aryl substituted hydroquinones and quinones, tert-butylcatechol, pyrrogallol, copper resinate, naphthylamines, beta-naphthol, copper(I) chloride, 2,6-di-tert-butyl-p- cresol, 2,2-methylene-bis-(4-ethyl-6-t-butylphenol), phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluquinone, chloranil, aryl phosphites and aryl alkyl phosphites.
Hvis ønskelig kan preparatene inneholde fargestoffer og pigmenter. Egnede fargestoffer må kunne anvendes sammen med de fotosensitive preparater og ikke påvirke disse preparaters fotosensitivitet i vesentlig grad. Følgende spesielle forbindelser er illustrerende: "Fuchsine" (fargeindeks nr. 42510); "Auramin Base" (fargeindeks nr. 4100B); "Calcocid Green S" If desired, the preparations may contain dyes and pigments. Suitable dyes must be able to be used together with the photosensitive preparations and not affect the photosensitivity of these preparations to a significant extent. The following special compounds are illustrative: "Fuchsine" (Color Index No. 42510); "Auramin Base" (color index No. 4100B); "Calcocide Green S"
(fargeindeks nr. 44090); "Para Magenta" (fargeindeks nr. 42500); "Tryparosan" (fargeindeks 42505); "New Magenta" (fargeindeks 42520); "Acid Violet RRH" (fargeindeks 42425); "Red Violet 5RS" (color index no. 44090); "Para Magenta" (color index no. 42500); "Tryparosan" (color index 42505); "New Magenta" (color index 42520); "Acid Violet RRH" (color index 42425); "Red Violet 5RS"
(fargeindeks 42690); "Nile Blue 2B" (fargeindeks 51185); "New Methylene Blue GG" (fargeindeks 51195); "Basic Blue 20" (fargeindeks 42585); "Iodone Green"(fargeindeks 42556) ; "Night Green B" (color index 42690); "Nile Blue 2B" (color index 51185); "New Methylene Blue GG" (color index 51195); "Basic Blue 20" (color index 42585); "Iodone Green"(color index 42556) ; "Night Green B"
(fargeindeks 42115); "Direct Yellow 9" (fargeindeks 19540); "Acid Yellow 17" (fargeindeks 18965); "Acid Yellow 29" (fargeindeks 18900); "Tartrazine" (fargeindeks 19140); "Supramine Yellow G" (fargeindeks 193O0); Buffalo Black 10B" (fargeindeks nr. 27790); "Naphtalene Black 12"R" (fargeindeks nr. 20350); "Fast Black L" (fargeindeks nr. 51215); "Ethyl Violet" (fargeindeks nr. 42600) ; "Pontacyl Wool Blue BL" (fargeindeks nr. 50315); "Pontacyl Wood Blue GL" (fargeindeks nr. 523201. INxutimerne fra den andre utgave av Fargeindeksen) . (color index 42115); "Direct Yellow 9" (color index 19540); "Acid Yellow 17" (color index 18965); "Acid Yellow 29" (color index 18900); "Tartrazine" (color index 19140); "Supramine Yellow G" (color index 193O0); Buffalo Black 10B" (Color Index No. 27790); "Naphthalene Black 12"R" (Color Index No. 20350); "Fast Black L" (color index no. 51215); "Ethyl Violet" (color index No. 42600) ; "Pontacyl Wool Blue BL" (Colour Index No. 50315); "Pontacyl Wood Blue GL" (color index no. 523201. INxutimers from the second edition of the Color Index) .
De fotopolymeriserbare elementer eksponeres til en The photopolymerizable elements are exposed to a
kilde for aktinisk stråling. Dette kan skje gjennom et halv-tonebilde eller en prosesstransparent, f.eks. en prosessnega-tiv eller -positiv, en stensil eller en maske. Eksponeringen kan også sitje gjennom et negativt eller et positivt bilde med kontinuerlig tone. Eksponeringen kan skje ved kontakt- eller projeksjonsmetoden, med eller uten et dekkark over det fotopolymeriserbare sjikt, eller ved projisering ved bruk av et dekkark. Disse fremgangsmåter er alle vel kjent for fagmannen. source of actinic radiation. This can be done through a half-tone image or a process transparency, e.g. a process negative or positive, a stencil or a mask. The exposure can also be through a negative or a positive image with continuous tone. The exposure can take place by the contact or projection method, with or without a cover sheet over the photopolymerizable layer, or by projection using a cover sheet. These methods are all well known to those skilled in the art.
Da fri-radikaldannende addisjonspolymeriseringsinitia-torer som kan aktiveres ved aktinisk stråling, vanligvis viser den maksimale følsomhet i det ultrafiolette område, bør strål-ingskilden gi en effektiv mengde av denne stråling. Både punkt-strålingskilder og brede strålingskilder er virksomme. Slike kilder omfatter karbonbuer, kvikksølvdampbuer, fluoriserende lamper med fosfor som utstråler ultrafiolett stråling, argon-glødelamper, elektroniske lynlysenheter og fotografiske belys-ningslamper. Av disse er kvikksølvdampbuene, spesielt "høyfjells-soler", mest egnet. Under spesielle omstendigheter kan det være fordelaktig å eksponere med synlig lys, ved bruk av en fotoinitiator som er følsom i det synlige område av spektret, f.eks. 9,10-fenantrenkinon. I slike tilfelle må strålings-kilden gi en effektiv mengde synlig stråling. Mange av de ovenfor angitte strålingskilder gir den ønskede mengde synlig lys. Since free-radical-forming addition polymerization initiators which can be activated by actinic radiation usually show the maximum sensitivity in the ultraviolet region, the radiation source should provide an effective amount of this radiation. Both point radiation sources and broad radiation sources are effective. Such sources include carbon arcs, mercury vapor arcs, fluorescent lamps with phosphors emitting ultraviolet radiation, argon incandescent lamps, electronic flash units and photographic lighting lamps. Of these, the mercury vapor arcs, especially "mountain solar", are most suitable. Under special circumstances, it may be advantageous to expose with visible light, using a photoinitiator that is sensitive in the visible region of the spectrum, e.g. 9,10-phenanthrenequinone. In such cases, the radiation source must provide an effective amount of visible radiation. Many of the radiation sources listed above provide the desired amount of visible light.
De fotopolymeriserbare preparater kan fremkalles etter eksponering, f.eks. ved behandling med spraystråler, med skylling eller vasking ved agitert neddypping til oppnåelse av de ønskede bilder med vandige baser, dvs. vandige oppløsninger av vannoppløselige baser i konsentrasjoner vanligvis i området fra 0,01-10 vekt-%. The photopolymerizable preparations can be developed after exposure, e.g. by treatment with spray jets, with rinsing or washing by agitated immersion to obtain the desired images with aqueous bases, i.e. aqueous solutions of water-soluble bases in concentrations usually in the range from 0.01-10% by weight.
Egnede baser for fremkallingen omfatter alkalimetall-hydroksyder, f.eks. litium; natrium- og kaliumhydroksyd; de basisk reagerende alkalimetallsalter av svake syrer, f.eks. litium-, natrium- og kaliumkarbonater og -bikarbonater; aminer med en baseioniseringskonstant større enn omkring lx 10 ^, f.eks. primære aminer slik som benzyl-, butyl- og allylaminer; sekundære aminer, f.eks. dimetylamin og benzylmetylamin; Suitable bases for the development include alkali metal hydroxides, e.g. lithium; sodium and potassium hydroxide; the basic reacting alkali metal salts of weak acids, e.g. lithium, sodium and potassium carbonates and bicarbonates; amines with a base ionization constant greater than about lx 10 ^, e.g. primary amines such as benzyl, butyl and allyl amines; secondary amines, e.g. dimethylamine and benzylmethylamine;
tertiære aminer, f.eks. trimetylamin og trietylamin; primære, sekundære og tertiære hydroksyaminer, f.eks. propanol-, dieta-nol- og trietanolaminer, og 2-amino-2-hydroksymetyl-l,3-propan-diol; cykliske aminer, f.eks. morfolin, piperidin, piperazin og pyridin; polyaminer slik som hydrazin, etylen og heksametyi-enaminer; vannoppløselige basiske salter, f.eks. karbonater og bikarbonater av de ovenfor nevnte aminer; ammoniumhydroksyd og tetrasubstituerte ammoniumhydroksyder,. f.eks. tetrametyl-, tetraetyl-, trimetylbenzyl- og trimetylfenylammoniumhydroksyder, sulfoniumhydroksyder, f.eks. trimetyl-, dietylmetyl-, dimetyl- tertiary amines, e.g. trimethylamine and triethylamine; primary, secondary and tertiary hydroxyamines, e.g. propanol, diethanol and triethanolamines, and 2-amino-2-hydroxymethyl-1,3-propanediol; cyclic amines, e.g. morpholine, piperidine, piperazine and pyridine; polyamines such as hydrazine, ethylene and hexamethylenamines; water-soluble basic salts, e.g. carbonates and bicarbonates of the above-mentioned amines; ammonium hydroxide and tetrasubstituted ammonium hydroxides. e.g. tetramethyl, tetraethyl, trimethylbenzyl and trimethylphenylammonium hydroxides, sulfonium hydroxides, e.g. trimethyl-, diethylmethyl-, dimethyl-
benzylsulfoniumhydroksyder og de basiske oppløselige salter derav, f.eks. karbonatene, bikarbonatene og sulfidene; alkalimetall-fosfater og -pyrofosfater, f.eks. natrium- og kaliumtrifosfater og natrium- og kaliumpyrofosfater; tetra-substituert (helst ute-lukkende alkyl) fosfonium-, arsonium- og stiboniumhydroksyd, f.eks. tetrametylfosfoniumhydroksyd. benzylsulfonium hydroxides and the basic soluble salts thereof, e.g. the carbonates, bicarbonates and sulphides; alkali metal phosphates and pyrophosphates, e.g. sodium and potassium triphosphates and sodium and potassium pyrophosphates; tetra-substituted (preferably all-alkyl) phosphonium, arsonium and stibonium hydroxide, e.g. tetramethylphosphonium hydroxide.
De fotopolymeriserte preparater kan vanligvis fjernes The photopolymerized preparations can usually be removed
ved neddypping i oppvarmede vandige oppløsninger av sterke alkalier eller, hvis ønskelig, i kommersielt oppnåelige fjern-ingspreparater, vel kjent i teknikkens stand. by immersion in heated aqueous solutions of strong alkalis or, if desired, in commercially available removal preparations, well known in the art.
For videre å illustrere oppfinnelsen henvendes oppmerk-somheten på de følgende eksempler. To further illustrate the invention, attention is drawn to the following examples.
Eksempel 1 Example 1
Den følgende oppløsning ble belagt på en 0,025 mm tykk polyesterfilm og tørket i luft. Tørrtykkelsen av det følsomme sjikt var omkring 0,025 mm. Det tørkede sjikt ble dekket med en 0,025 mm tykk polyetylenfilm. The following solution was coated on a 0.025 mm thick polyester film and dried in air. The dry thickness of the sensitive layer was about 0.025 mm. The dried layer was covered with a 0.025 mm thick polyethylene film.
Et stykke kobberbelagt, epoksyfiberglass ble renset A piece of copper-clad, epoxy fiberglass was cleaned
ved skrubbing med et slipemiddel, pussing og grundig skylling i vann. Den ble deretter gitt en 20 sekunders neddypping i en fortynnet HCl-oppløsning (2 volumdeler vann + 1 volumdel konsen-tert HC1), en andre skylling med vann og deretter tørket med luftstråler. by scrubbing with an abrasive, sanding and thorough rinsing in water. It was then given a 20 second immersion in a dilute HCl solution (2 volumes of water + 1 volume of concentrated HCl), a second rinse with water and then dried with air jets.
Polyetylendekkfilmen ble fjernet fra en del av det polymeriserbare element. Det blottede dekkmiddelbelegg med polyesterbæreren ble laminert på det rene kobber med overflaten av det polymeriserbare sjikt i kontakt med kobberoverflaten. The polyethylene cover film was removed from a portion of the polymerizable element. The exposed masking agent coating with the polyester carrier was laminated onto the pure copper with the surface of the polymerizable layer in contact with the copper surface.
Lamineringen ble utført ved hjelp av gummikledde valser som arbeidet ved 120°C med et trykk på 535,7 g/lineær cm i gapet The lamination was carried out using rubber coated rollers operating at 120°C with a pressure of 535.7 g/linear cm in the gap
og med en hastighet på 0,6 m/min. Den resulterende følsomgjorte kobberkledte plate kunne, hvis nødvendig, lagres for senere bruk slik den var beskyttet av polyesterfilmen. I dette tilfelle ble den eksponert til lys gjennom et høykontrast transparent bilde and at a speed of 0.6 m/min. The resulting sensitized copper clad plate could, if necessary, be stored for later use as it was protected by the polyester film. In this case, it was exposed to light through a high-contrast transparent image
hvori det ledende mønster viste seg som transparente områder på en lys ugjennomskinnelig bakgrunn. Eksponeringen ble utført ved å anbringe den følsomgjorte kobberbelagte plate (med polyesterfilmen fremdeles intakt) og transparenten i en fotografisk trykkramme. Eksponeringen skjedde i et tidsrom på 45 sekunder til en 400 watts 50 ampere's kvikksølvdamplampe i en avstand på 0,3 meter. Polyetylentereftalatbærefilmen ble trukket av og det eksponerte dekkmiddelsjiktet fremkalt ved agitering av platen i et kar som inneholdt 2% natriumkarbonat i vann i 3^ min, fulgt av vannskyIling. Den resulterende plate hadde et farget dekk-sjiktmønster fra de klare områder av eksponeringstransparenten. in which the conductive pattern appeared as transparent areas on a light opaque background. The exposure was made by placing the sensitized copper-clad plate (with the polyester film still intact) and the transparency in a photographic print frame. The exposure was for a period of 45 seconds to a 400 watt 50 amp mercury vapor lamp at a distance of 0.3 meters. The polyethylene terephthalate carrier film was peeled off and the exposed coating layer developed by agitating the plate in a vessel containing 2% sodium carbonate in water for 3 min, followed by water rinsing. The resulting plate had a colored cover layer pattern from the clear areas of the exposure transparency.
Platen ble nå etset méd en 45° Baume-oppløsning av jern(III)klorid, deretter skylt og tørket. Dekkmidlet ble fjernet fra det gjenværende kobber ved dypping i to min i en 3%-ig oppløsning av natriumhydroksyd i vann av 70°C. Resultatet var en trykket kretsplate av høy kvalitet. The plate was now etched with a 45° Baume solution of ferric chloride, then rinsed and dried. The masking agent was removed from the remaining copper by dipping for two minutes in a 3% solution of sodium hydroxide in water at 70°C. The result was a high-quality printed circuit board.
Eksempel 2 Example 2
Den følgende oppløsning ble belagt på 0,025 mm tykt polyesterfilm og ble tillatt å tørke under omgivelsesbetingelser i 30 min. The following solution was coated on 0.025 mm thick polyester film and allowed to dry under ambient conditions for 30 min.
Tørrtykkelsen av det følsomgjorte sjikt var omkring 0T033 mm. Det belagte stoff ble deretter laminert på en renset kobberbelagt plate slik som i eks. 1. Eksponeringen skjedde gjennom en transparent som hadde et ugjennomskinnelig mønster av et kjent areal i 1^ min med en eksponeringsenhet slik som beskrevet i eks. 1. Polyesterbærefilmen ble trukket av og det eksponerte dekkmiddelsjikt fremkalt ved agitering av platen i et kar som inneholdt 2% trinatriumfosfat i vann i 2 min, fulgt av vannskylling. The dry thickness of the sensitized layer was about 0.033 mm. The coated fabric was then laminated onto a cleaned copper-coated plate as in ex. 1. The exposure took place through a transparent which had an opaque pattern of a known area for 1^ min with an exposure unit as described in ex. 1. The polyester carrier film was peeled off and the exposed masking agent layer developed by agitating the plate in a vessel containing 2% trisodium phosphate in water for 2 min, followed by a water rinse.
Overflaten av det eksponerte kobber ble videre renset etter utvikling ved dypping av platen i et 20%-ig ammoniumper-sulfatbad i 30 sekunder, rikelig vasking med vann, dypping i 30 sekunder i en 20%-ig oppløsning av HC1 i vann, skylling med vann og deretter tørking av platene i luftstrømmer. Denne rensede plate ble deretter plettert i 45 min ved 322,8 ampere pr. m<2>The surface of the exposed copper was further cleaned after development by dipping the plate in a 20% ammonium persulfate bath for 30 seconds, washing copiously with water, dipping for 30 seconds in a 20% solution of HC1 in water, rinsing with water and then drying the plates in air currents. This cleaned plate was then plated for 45 min at 322.8 amps per m<2>
i et kobberpyrofosfat-pletteringsbad av 55°C. in a copper pyrophosphate plating bath of 55°C.
Eksempel 3 Example 3
Et kobberbelagt stykke av en epoksyfiberglassplate ble renset slik som beskrevet i eks. 1. Den rensede, tørkede plate ble gjort følsom.ved helling av den følgende oppløsning over platens overflate: A copper-coated piece of an epoxy fiberglass plate was cleaned as described in ex. 1. The cleaned, dried plate was sensitized by pouring the following solution over the surface of the plate:
Den overskytende oppløsning ble helt av platen ved rom-temperatur i 2 min. Belegget ble ytterligere tørket ved opp-varming i en luftstrømsovn ved 60°C i 5 min. Etter avkjøling ble den belagte plate eksponert slik som beskrevet i eks. 1. Resisten ble fremkalt ved agitering av platen i en oppløsning The excess solution was poured off the plate at room temperature for 2 min. The coating was further dried by heating in an air flow oven at 60°C for 5 min. After cooling, the coated plate was exposed as described in ex. 1. The resist was developed by agitating the plate in a solution
av 2% trinatriumfosfat i vann i 1 min, fulgt av en vannskylling. Platen ble nå etset i jern(III)klorid slik som beskrevet i eks. 1. Etter etsing ble den eksponerte resist fjernet fra det beskyttede of 2% trisodium phosphate in water for 1 min, followed by a water rinse. The plate was now etched in iron (III) chloride as described in ex. 1. After etching, the exposed resist was removed from the protected one
kobber ved å dyppe platen i en 3%-ig oppløsning av natriumhydroksyd i vann av 50°C i 2 min. Resultatet er en trykket kretsplate med høy kvalitet. copper by immersing the plate in a 3% solution of sodium hydroxide in water at 50°C for 2 min. The result is a high-quality printed circuit board.
Eksempel 4 Example 4
Den følgende oppløsning ble belagt på en 0,025 mm tykk polyesterfilm og tørket i luft. The following solution was coated on a 0.025 mm thick polyester film and dried in air.
Tørrtykkelsen av det følsommgjorte sjikt var omkring 0,025 mm. Det ble preparert en kobberbelagt plate, resistbeleg-get laminert på denne og det resulterende element eksponert nøyaktig slik som i eks. 1. Bærerfilmen ble trukket av og det eksponerte resistsjikt fremkalt ved agitering av platen i et kar inneholdende 2% trinatriumfosfat i 2 min, fulgt av en vannskylling. The dry thickness of the sensitized layer was about 0.025 mm. A copper-coated plate was prepared, the resist coating laminated on this and the resulting element exposed exactly as in ex. 1. The support film was peeled off and the exposed resist layer developed by agitating the plate in a vessel containing 2% trisodium phosphate for 2 min, followed by a water rinse.
Platen ble nå etset slik som i eks. 1,slik at det ga The plate was now etched as in ex. 1, so that it gave
en tr 0ykket kretsplate av høy kvalitet. a high quality printed circuit board.
Eksempel 5 Example 5
Den fotosensitive oppløsning som er beskrevet i eks. 1, ble belagt på sink-, magnesium- og kobbertrykkplater. Etter tørking i varm luft til en tørrtykkelse på omkring 0,025 mm, ble det fotosensitive sjikt belagt med en fortynnet vandig opp-løsning av polyvinylalkohol og tørket igjen med varmluft. Den vannoppløselige polymer dannet et tynt beskyttende sjikt overfor oksygen. Disse forfølsomgjorte metallplater kan lagres i utstrakte perioder. The photosensitive solution described in ex. 1, was coated on zinc, magnesium and copper printing plates. After drying in hot air to a dry thickness of about 0.025 mm, the photosensitive layer was coated with a dilute aqueous solution of polyvinyl alcohol and dried again with hot air. The water-soluble polymer formed a thin protective layer against oxygen. These presensitized metal sheets can be stored for extended periods.
Ved eksponering til aktinisk lys gjennom et egnet fotografisk negativ, kan det ikke-eksponerte fotosensitive sjikt og det vannoppløselige toppsjikt fremkalles samtidig, og metall-platen er ferdig for etsing. Det fotopolymeriserte billedareal tjener deretter som et utmerket dekkmiddel for dypetsingspros-esser slik som vanlig i fremstilling av metalltrykkplater. Resultatene er mostandsdyktige overfor vanlige etsemidler, f.eks. jern(III)klorid og salpetersyre, filmdannende midler og midler som vanligvis tilsettes til etsingsblandingen for å regulere etsingens geometri. By exposure to actinic light through a suitable photographic negative, the unexposed photosensitive layer and the water-soluble top layer can be developed simultaneously, and the metal plate is ready for etching. The photopolymerized image area then serves as an excellent masking agent for deep etching processes as usual in the production of metal printing plates. The results are resistant to common etchants, e.g. ferric chloride and nitric acid, film-forming agents and agents usually added to the etching mixture to control the geometry of the etch.
Eksempel 6 Example 6
Fremgangsmåten i eks. 5 ble fulgt, bortsett fra at det benyttes en 0,025 mm tykk film av polyester som beskyttende sjikt i stedet for en vannoppløselig polymer. Etter eksponeringen til aktinisk lys, trekkes det beskyttende sjikt av før fremkalling i en vandig alkalisk oppløsning. Som i eks. 5, tjener det fotopolymeriserte billedareal som en utmerket resist for dypetsing av trykkplater. The procedure in ex. 5 was followed, except that a 0.025 mm thick film of polyester is used as the protective layer instead of a water-soluble polymer. After the exposure to actinic light, the protective layer is removed before developing in an aqueous alkaline solution. As in ex. 5, the photopolymerized image area serves as an excellent resist for deep etching printing plates.
E ksempel 7 Example 7
Den fotosensitive oppløsning som er beskrevet i eks. 1, belegges på en 0,025 mm tykk polyesterfilm, tørkes i luft og dekkes med en 0,025 mm tykk polyetylenfilm. Denne tresjikts-film kan lagres i ark eller ruller lyssikkert i ubegrenset tidsrom. Før bruk trekkes polyetylenfilmen av og det fotosensitive sjikt anbringes i kontakt med en metallisk plate av den type som er beskrevet i eks. 5 og festes ved laminering. Ved eksponering til aktinisk lys trekkes det beskyttende polyestersjikt av, og fremkallingen skjer i vandig alkalisk oppløsning. Slik som i eks. 5, er det fotopolymeriserte billedareal et utmerket dekksjikt for dypetsing av trykkplater. The photosensitive solution described in ex. 1, is coated on a 0.025 mm thick polyester film, dried in air and covered with a 0.025 mm thick polyethylene film. This three-layer film can be stored in sheets or rolls light-proof for an unlimited period of time. Before use, the polyethylene film is pulled off and the photosensitive layer is placed in contact with a metallic plate of the type described in ex. 5 and attached by lamination. When exposed to actinic light, the protective polyester layer is removed, and the development takes place in an aqueous alkaline solution. As in ex. 5, the photopolymerized image area is an excellent cover layer for deep etching printing plates.
Eksempel 8 Example 8
Den fotosensitive oppløsning slik den er beskrevet i eks. 1, belegges på tynne aluminiumplater slik de vanligvis brukes ved offsetlitografi, ved fremgangsmåter beskrevet i eks. 5, 6 og 7. Etter eksponering til aktinisk lys og fremkalling i vandig alkalisk oppløsning, tjener det fotopolymeriserte billedareal som en utmerket trykksvertemottaker. Det har også overlegen slitasjonemotstandsdyktighet. De resulterende plater kan med utmerkede resultater benyttes til offsetlitografisk trykking. The photosensitive solution as described in ex. 1, are coated on thin aluminum plates as they are usually used in offset lithography, by methods described in ex. 5, 6 and 7. After exposure to actinic light and development in aqueous alkaline solution, the photopolymerized image area serves as an excellent printing ink receiver. It also has superior abrasion resistance. The resulting plates can be used with excellent results for offset lithographic printing.
Eksempel 9 Example 9
Den fotosensitive oppløsning slik den er beskrevet i eks. 1, belegges på et vevet nettlignende substrat ved fremgangsmåter som er beskrevet i eks. 5, 6 og 7. Etter eksponering til aktinisk lys og fremkalling i vandig alkalisk oppløsning, The photosensitive solution as described in ex. 1, is coated on a woven net-like substrate by methods described in ex. 5, 6 and 7. After exposure to actinic light and development in aqueous alkaline solution,
tjener det fotopolymeriserte billedareal som en utmerket maske. the photopolymerized image area serves as an excellent mask.
Denne anvendelse har vist brukbarhet ved trykking av silketrykk- This application has shown its usefulness when printing screen-printed
typen. the type.
Claims (9)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11279771A | 1971-02-04 | 1971-02-04 |
Publications (2)
Publication Number | Publication Date |
---|---|
NO141804B true NO141804B (en) | 1980-02-04 |
NO141804C NO141804C (en) | 1980-05-14 |
Family
ID=22345895
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO177/72A NO141804C (en) | 1971-02-04 | 1972-01-25 | PHOTOPOLYMERIZABLE PREPARATION |
Country Status (23)
Country | Link |
---|---|
JP (2) | JPS5538961B1 (en) |
AU (1) | AU461461B2 (en) |
BE (1) | BE778729A (en) |
BG (1) | BG26673A3 (en) |
CA (1) | CA965291A (en) |
CH (1) | CH592322A5 (en) |
DD (1) | DD101035A5 (en) |
DE (1) | DE2205146C2 (en) |
DK (2) | DK142623B (en) |
ES (1) | ES399317A1 (en) |
FI (1) | FI57429C (en) |
FR (1) | FR2124974A5 (en) |
GB (1) | GB1361298A (en) |
HK (1) | HK28382A (en) |
IL (1) | IL38677A (en) |
IT (1) | IT949005B (en) |
LU (1) | LU64712A1 (en) |
NL (1) | NL176021C (en) |
NO (1) | NO141804C (en) |
PL (1) | PL83391B1 (en) |
RO (1) | RO64896A (en) |
SE (1) | SE390218B (en) |
ZA (1) | ZA72345B (en) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1056189A (en) * | 1974-04-23 | 1979-06-12 | Ernst Leberzammer | Polymeric binders for aqueous processable photopolymer compositions |
ZA757984B (en) * | 1974-10-04 | 1976-12-29 | Dynachem Corp | Polymers for aqueous processed photoresists |
JPS5917414B2 (en) * | 1975-10-07 | 1984-04-21 | 村上スクリ−ン (株) | Photosensitive composition and photosensitive film for screen plates |
JPS5944615B2 (en) * | 1976-02-16 | 1984-10-31 | 富士写真フイルム株式会社 | Photosensitive resin composition and metal image forming material using the same |
SU941918A1 (en) * | 1976-08-10 | 1982-07-07 | Предприятие П/Я Г-4444 | Dry film protoresist material |
US4239849A (en) | 1978-06-19 | 1980-12-16 | Dynachem Corporation | Polymers for aqueous processed photoresists |
JPS55501072A (en) * | 1978-12-25 | 1980-12-04 | ||
DE3034343A1 (en) * | 1979-02-21 | 1981-04-09 | Panelgraphic Corp | RADIATION CURABLE CELLULOSIC POLYACRYLIC ABRASION RESISTANT COATING |
JPS5619752A (en) * | 1979-07-27 | 1981-02-24 | Hitachi Chemical Co Ltd | Photosensitive resin composition laminate |
DE3560654D1 (en) * | 1984-02-18 | 1987-10-22 | Basf Ag | Photosensitive recording material |
DD250593A1 (en) * | 1984-04-03 | 1987-10-14 | Wolfen Filmfab Veb | PHOTOPOLYMERIZABLE MATERIAL |
DE3504254A1 (en) | 1985-02-08 | 1986-08-14 | Basf Ag, 6700 Ludwigshafen | LIGHT SENSITIVE RECORDING ELEMENT |
DE3619129A1 (en) * | 1986-06-06 | 1987-12-10 | Basf Ag | LIGHT SENSITIVE RECORDING ELEMENT |
DE3841025A1 (en) * | 1988-12-06 | 1990-06-07 | Hoechst Ag | POLYMERIZABLE MIXTURE BY RADIATION AND RECORDING MATERIAL MADE THEREOF |
JP2613462B2 (en) * | 1988-12-28 | 1997-05-28 | コニカ株式会社 | Image forming material and image forming method |
JP2515885Y2 (en) * | 1990-09-28 | 1996-10-30 | アンリツ株式会社 | Display of measuring device |
DE19638032A1 (en) * | 1996-09-18 | 1998-03-19 | Du Pont Deutschland | Photopolymerizable mixture with lower oxygen sensitivity for the production of color proofs |
US7052824B2 (en) | 2000-06-30 | 2006-05-30 | E. I. Du Pont De Nemours And Company | Process for thick film circuit patterning |
US20100209843A1 (en) | 2009-02-16 | 2010-08-19 | E. I. Du Pont De Nemours And Company | Process for thick film circuit patterning |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA614181A (en) * | 1961-02-07 | J. Mcgraw William | Photopolymerizable compositions, elements and processes | |
US2893868A (en) * | 1955-08-22 | 1959-07-07 | Du Pont | Polymerizable compositions |
NL218803A (en) * | 1956-07-09 | |||
GB835849A (en) * | 1957-04-26 | 1960-05-25 | Du Pont | Photopolymerisable compositions and uses thereof |
US3458311A (en) * | 1966-06-27 | 1969-07-29 | Du Pont | Photopolymerizable elements with solvent removable protective layers |
US3469982A (en) * | 1968-09-11 | 1969-09-30 | Jack Richard Celeste | Process for making photoresists |
-
1972
- 1972-01-18 ZA ZA720345A patent/ZA72345B/en unknown
- 1972-01-25 NO NO177/72A patent/NO141804C/en unknown
- 1972-01-27 AU AU38392/72A patent/AU461461B2/en not_active Expired
- 1972-01-29 ES ES399317A patent/ES399317A1/en not_active Expired
- 1972-01-31 BE BE778729A patent/BE778729A/en not_active IP Right Cessation
- 1972-01-31 FR FR7203150A patent/FR2124974A5/fr not_active Expired
- 1972-01-31 IL IL38677A patent/IL38677A/en unknown
- 1972-02-01 RO RO7269624A patent/RO64896A/en unknown
- 1972-02-01 SE SE7201145A patent/SE390218B/en unknown
- 1972-02-01 CH CH142672A patent/CH592322A5/xx not_active IP Right Cessation
- 1972-02-02 FI FI271/72A patent/FI57429C/en active
- 1972-02-02 GB GB481472A patent/GB1361298A/en not_active Expired
- 1972-02-02 LU LU64712A patent/LU64712A1/xx unknown
- 1972-02-02 JP JP1214572A patent/JPS5538961B1/ja active Pending
- 1972-02-02 CA CA133,755A patent/CA965291A/en not_active Expired
- 1972-02-03 IT IT67324/72A patent/IT949005B/en active
- 1972-02-03 DE DE2205146A patent/DE2205146C2/en not_active Expired - Lifetime
- 1972-02-03 PL PL1972153265A patent/PL83391B1/pl unknown
- 1972-02-03 DK DK48172AA patent/DK142623B/en not_active IP Right Cessation
- 1972-02-04 NL NLAANVRAGE7201460,A patent/NL176021C/en not_active IP Right Cessation
- 1972-02-04 BG BG019648A patent/BG26673A3/en unknown
- 1972-12-08 DD DD167452A patent/DD101035A5/xx unknown
-
1973
- 1973-01-03 DK DK1773A patent/DK144184C/en active
-
1982
- 1982-06-24 HK HK283/82A patent/HK28382A/en unknown
- 1982-11-26 JP JP57207462A patent/JPS58144824A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
AU461461B2 (en) | 1975-05-12 |
JPS58144824A (en) | 1983-08-29 |
RO64896A (en) | 1980-01-15 |
DE2205146A1 (en) | 1972-11-23 |
SE390218B (en) | 1976-12-06 |
LU64712A1 (en) | 1973-09-04 |
NL176021B (en) | 1984-09-03 |
IL38677A0 (en) | 1972-03-28 |
NL176021C (en) | 1987-07-16 |
PL83391B1 (en) | 1975-12-31 |
AU3839272A (en) | 1973-08-02 |
NO141804C (en) | 1980-05-14 |
FR2124974A5 (en) | 1972-09-22 |
DD101035A5 (en) | 1973-10-12 |
BG26673A3 (en) | 1979-05-15 |
BE778729A (en) | 1972-07-31 |
DE2205146C2 (en) | 1990-03-08 |
IT949005B (en) | 1973-06-11 |
HK28382A (en) | 1982-07-02 |
ES399317A1 (en) | 1974-12-16 |
ZA72345B (en) | 1973-03-28 |
CH592322A5 (en) | 1977-10-31 |
DK142623C (en) | 1981-08-03 |
DK142623B (en) | 1980-12-01 |
DK144184C (en) | 1982-06-14 |
JPH0136924B2 (en) | 1989-08-03 |
CA965291A (en) | 1975-04-01 |
NL7201460A (en) | 1972-08-08 |
IL38677A (en) | 1974-12-31 |
FI57429B (en) | 1980-04-30 |
JPS5538961B1 (en) | 1980-10-07 |
FI57429C (en) | 1980-08-11 |
GB1361298A (en) | 1974-07-24 |
DK144184B (en) | 1982-01-04 |
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