JP4108243B2 - Photosensitive resin laminate - Google Patents
Photosensitive resin laminate Download PDFInfo
- Publication number
- JP4108243B2 JP4108243B2 JP2000019857A JP2000019857A JP4108243B2 JP 4108243 B2 JP4108243 B2 JP 4108243B2 JP 2000019857 A JP2000019857 A JP 2000019857A JP 2000019857 A JP2000019857 A JP 2000019857A JP 4108243 B2 JP4108243 B2 JP 4108243B2
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive resin
- acrylate
- resin layer
- meth
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920005989 resin Polymers 0.000 title claims description 83
- 239000011347 resin Substances 0.000 title claims description 83
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- HGVHMIAKUYLQLL-UHFFFAOYSA-N ethene;propane-1,2,3-triol Chemical group C=C.OCC(O)CO HGVHMIAKUYLQLL-UHFFFAOYSA-N 0.000 claims description 5
- JOLPFRQHFARWCF-UHFFFAOYSA-N propane-1,2,3-triol;prop-1-ene Chemical group CC=C.OCC(O)CO JOLPFRQHFARWCF-UHFFFAOYSA-N 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 42
- 238000007747 plating Methods 0.000 description 41
- 239000000243 solution Substances 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229910052802 copper Inorganic materials 0.000 description 18
- 239000010949 copper Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- -1 2-ethylhexyl Chemical group 0.000 description 17
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 239000004020 conductor Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZEDDAIJSZJHQKY-UHFFFAOYSA-N C(C=C)(=O)O.CC(COC(C)COC(C)CO)O.C(CCCCCCC)C1=CC=C(OC(COCCOCCOCCOCCO)O)C=C1 Chemical compound C(C=C)(=O)O.CC(COC(C)COC(C)CO)O.C(CCCCCCC)C1=CC=C(OC(COCCOCCOCCOCCO)O)C=C1 ZEDDAIJSZJHQKY-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- ADRHDZXSVIPHAF-UHFFFAOYSA-N 2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]-1-phenoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOCCOCCOCCOCCOCC(O)OC1=CC=CC=C1 ADRHDZXSVIPHAF-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- RSROEZYGRKHVMN-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;oxirane Chemical compound C1CO1.CCC(CO)(CO)CO RSROEZYGRKHVMN-UHFFFAOYSA-N 0.000 description 2
- NFOQRIXSEYVCJP-UHFFFAOYSA-N 2-propoxycarbonylbenzoic acid Chemical compound CCCOC(=O)C1=CC=CC=C1C(O)=O NFOQRIXSEYVCJP-UHFFFAOYSA-N 0.000 description 2
- LYCNQAIOLGIAFA-UHFFFAOYSA-N 4-[bis[4-(dimethylamino)-2-methylphenyl]methyl]-n,n,3-trimethylaniline Chemical compound CC1=CC(N(C)C)=CC=C1C(C=1C(=CC(=CC=1)N(C)C)C)C1=CC=C(N(C)C)C=C1C LYCNQAIOLGIAFA-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 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
- 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
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- RBKHNGHPZZZJCI-UHFFFAOYSA-N (4-aminophenyl)-phenylmethanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC=C1 RBKHNGHPZZZJCI-UHFFFAOYSA-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
- SDTXSEXYPROZSZ-UHFFFAOYSA-N 1,2-dibromo-2-methylpropane Chemical compound CC(C)(Br)CBr SDTXSEXYPROZSZ-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- BMNBJTUMFBHXKS-UHFFFAOYSA-N 1,4-di(propan-2-yl)cyclohexa-2,4-diene-1-carboxylic acid Chemical compound CC(C)C1=CCC(C(O)=O)(C(C)C)C=C1 BMNBJTUMFBHXKS-UHFFFAOYSA-N 0.000 description 1
- XNQWLNYPLRXFGM-UHFFFAOYSA-N 1,4-diethylcyclohexa-2,4-diene-1-carboxylic acid Chemical compound CCC1=CCC(CC)(C(O)=O)C=C1 XNQWLNYPLRXFGM-UHFFFAOYSA-N 0.000 description 1
- SLMUVSVDXGWVBG-UHFFFAOYSA-N 1,4-dimethylcyclohexa-2,4-diene-1-carboxylic acid Chemical compound CC1=CCC(C)(C(O)=O)C=C1 SLMUVSVDXGWVBG-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- HUDYANRNMZDQGA-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]ethanone Chemical compound CN(C)C1=CC=C(C(C)=O)C=C1 HUDYANRNMZDQGA-UHFFFAOYSA-N 0.000 description 1
- YXZFFTJAHVMMLF-UHFFFAOYSA-N 1-bromo-3-methylbutane Chemical compound CC(C)CCBr YXZFFTJAHVMMLF-UHFFFAOYSA-N 0.000 description 1
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 description 1
- VKQJCUYEEABXNK-UHFFFAOYSA-N 1-chloro-4-propoxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(OCCC)=CC=C2Cl VKQJCUYEEABXNK-UHFFFAOYSA-N 0.000 description 1
- FEWDXGMBVQULLN-UHFFFAOYSA-N 1-hydroxy-2-phenyl-1,5,6,7-tetrahydro-4H-benzimidazol-4-one Chemical compound ON1C=2CCCC(=O)C=2N=C1C1=CC=CC=C1 FEWDXGMBVQULLN-UHFFFAOYSA-N 0.000 description 1
- BTUGGGLMQBJCBN-UHFFFAOYSA-N 1-iodo-2-methylpropane Chemical compound CC(C)CI BTUGGGLMQBJCBN-UHFFFAOYSA-N 0.000 description 1
- BLXSFCHWMBESKV-UHFFFAOYSA-N 1-iodopentane Chemical compound CCCCCI BLXSFCHWMBESKV-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- UPQQXPKAYZYUKO-UHFFFAOYSA-N 2,2,2-trichloroacetamide Chemical compound OC(=N)C(Cl)(Cl)Cl UPQQXPKAYZYUKO-UHFFFAOYSA-N 0.000 description 1
- QJJOYFHFRQZRGA-UHFFFAOYSA-N 2,3-dioxo-3-phenylpropanoic acid Chemical compound OC(=O)C(=O)C(=O)C1=CC=CC=C1 QJJOYFHFRQZRGA-UHFFFAOYSA-N 0.000 description 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-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
- MZGMQAMKOBOIDR-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCO MZGMQAMKOBOIDR-UHFFFAOYSA-N 0.000 description 1
- ZZEANNAZZVVPKU-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-(2-hydroxypropoxy)propoxy]propoxy]propoxy]propoxy]propoxy]propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)COC(C)COC(C)COC(C)COC(C)COC(C)CO ZZEANNAZZVVPKU-UHFFFAOYSA-N 0.000 description 1
- JDPZLHCKBWMLDH-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOCCOCCOCCOCCOCCOC(=O)C=C JDPZLHCKBWMLDH-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- YTZRFUSYPGFDNC-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methyloxirane;oxirane Chemical compound C1CO1.CC1CO1.CCC(CO)(CO)CO YTZRFUSYPGFDNC-UHFFFAOYSA-N 0.000 description 1
- FUQUBWCLBBUXCM-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-1-ene Chemical group CC=C.CCC(CO)(CO)CO FUQUBWCLBBUXCM-UHFFFAOYSA-N 0.000 description 1
- VVZWCWXLBDGDPJ-UHFFFAOYSA-N 2-fluorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(F)=CC=C3SC2=C1 VVZWCWXLBDGDPJ-UHFFFAOYSA-N 0.000 description 1
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical class OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical compound CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 description 1
- BJUPZVQSAAGZJL-UHFFFAOYSA-N 2-methyloxirane;propane-1,2,3-triol Chemical compound CC1CO1.OCC(O)CO BJUPZVQSAAGZJL-UHFFFAOYSA-N 0.000 description 1
- AXYQEGMSGMXGGK-UHFFFAOYSA-N 2-phenoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)C(C=1C=CC=CC=1)OC1=CC=CC=C1 AXYQEGMSGMXGGK-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
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- JRJNSEMUYTUGLA-UHFFFAOYSA-N 3-phenoxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC1=CC=CC=C1 JRJNSEMUYTUGLA-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical compound Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 description 1
- SGSKTOKJZHJRCN-UHFFFAOYSA-N 4-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(Cl)=CC=C2 SGSKTOKJZHJRCN-UHFFFAOYSA-N 0.000 description 1
- SQVARBRTBLLAES-UHFFFAOYSA-N 4-fluorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(F)=CC=C2 SQVARBRTBLLAES-UHFFFAOYSA-N 0.000 description 1
- IKVYHNPVKUNCJM-UHFFFAOYSA-N 4-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(C(C)C)=CC=C2 IKVYHNPVKUNCJM-UHFFFAOYSA-N 0.000 description 1
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- YVGGHNCTFXOJCH-UHFFFAOYSA-N DDT Chemical compound C1=CC(Cl)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(Cl)C=C1 YVGGHNCTFXOJCH-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- ZGUNAGUHMKGQNY-ZETCQYMHSA-N L-alpha-phenylglycine zwitterion Chemical compound OC(=O)[C@@H](N)C1=CC=CC=C1 ZGUNAGUHMKGQNY-ZETCQYMHSA-N 0.000 description 1
- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 description 1
- WZKXBGJNNCGHIC-UHFFFAOYSA-N Leucomalachite green Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=CC=C1 WZKXBGJNNCGHIC-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- WMABJOOWQCYZKK-UHFFFAOYSA-N [2-(dibutylamino)phenyl]-phenylmethanone Chemical compound CCCCN(CCCC)C1=CC=CC=C1C(=O)C1=CC=CC=C1 WMABJOOWQCYZKK-UHFFFAOYSA-N 0.000 description 1
- BEUGBYXJXMVRFO-UHFFFAOYSA-N [4-(dimethylamino)phenyl]-phenylmethanone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=CC=C1 BEUGBYXJXMVRFO-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000001251 acridines Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- KSCQDDRPFHTIRL-UHFFFAOYSA-N auramine O Chemical compound [H+].[Cl-].C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 KSCQDDRPFHTIRL-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- FAJDWNKDRFAWLS-UHFFFAOYSA-N benzyl-[9-(diethylamino)benzo[a]phenoxazin-5-ylidene]azanium;chloride Chemical compound [Cl-].O1C2=CC(N(CC)CC)=CC=C2N=C(C2=CC=CC=C22)C1=CC2=[NH+]CC1=CC=CC=C1 FAJDWNKDRFAWLS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 1
- OQROAIRCEOBYJA-UHFFFAOYSA-N bromodiphenylmethane Chemical compound C=1C=CC=CC=1C(Br)C1=CC=CC=C1 OQROAIRCEOBYJA-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 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
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 238000002507 cathodic stripping potentiometry Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 235000012701 green S Nutrition 0.000 description 1
- 239000004120 green S Substances 0.000 description 1
- WDPIZEKLJKBSOZ-UHFFFAOYSA-M green s Chemical compound [Na+].C1=CC(N(C)C)=CC=C1C(C=1C2=CC=C(C=C2C=C(C=1O)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](C)C)C=C1 WDPIZEKLJKBSOZ-UHFFFAOYSA-M 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- DWCZIOOZPIDHAB-UHFFFAOYSA-L methyl green Chemical compound [Cl-].[Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)[N+](C)(C)C)=C1C=CC(=[N+](C)C)C=C1 DWCZIOOZPIDHAB-UHFFFAOYSA-L 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- XNGJNGFXWWYBJS-UHFFFAOYSA-N phosphoroso-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=C(C(=O)P=O)C(C)=C1 XNGJNGFXWWYBJS-UHFFFAOYSA-N 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical compound BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- JEVGKYBUANQAKG-UHFFFAOYSA-N victoria blue R Chemical compound [Cl-].C12=CC=CC=C2C(=[NH+]CC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JEVGKYBUANQAKG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Landscapes
- Materials For Photolithography (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は感光性樹脂積層体に関し、特にＣＳＰ(Chip Size Package)製造に好適な感光性樹脂積層体に関するものである。
【０００２】
【従来の技術】
ＣＳＰとは、ＬＳＩチップをパッケージ化された部品で、一般にＬＳＩチップサイズと同等あるいはわずかに大きいパッケージのことであり、最近の電子機器の小型化に伴い急速に普及している。ＣＳＰには、パッケージのタイプにより、ＢＧＡ（Ball Grid Array）タイプ、ＬＧＡ（Land Grid Array）タイプ、ＳＯＮ（Small Outline Non-leaded）タイプ等がある。
【０００３】
従来、ＬＳＩチップをＣＳＰにパッケージ化する方法は、ウエーハ上で作ったＬＳＩを個々のチップに裁断した後、外部端子を有する配線板にワイヤーボンディング、ソルダリング、超音波接合等の方法で接合してから、必要であれば有機樹脂で封止あるいはアンダーフィルする方法が用いられていた。
近年、シリコンウエーハ上に形成された複数個のＬＳＩに対して、裁断される前に一括して配線および外部端子を作り、必要であれば有機樹脂で封止することによりＣＳＰあるいはＢＧＡ等の部品にしてから、個々の部品として裁断する方法が採られ始めた。この方法により作られた部品は一般にウエーハ・レベルＣＳＰと呼ばれている。
【０００４】
ウエーハ・レベルＣＳＰを作る工程においては、ＬＳＩチップ端子と外部端子を接続するための配線が必要で、多くは導体をめっきによりつけることで形成されている。さらに詳しく述べると、金属層を施したウエーハ上に液状レジストを塗布・乾燥後、化学線を配線パターンマスクを介して露光し、レジストを現像除去することにより、導体配線を形成させたい部分のみ開口させ、これに電解金属めっきを行い、必要な配線を形成させる。
【０００５】
配線には、線状のものやビアホールを銅で充填した柱状のもの等がある。特に柱状の配線に関しては、めっき厚みが５０μｍ〜２００μｍと厚くすることが求められている。
上記配線を形成させる際に、レジストとして液状のものが使用されているが、液状レジストは１回の塗布で所望の厚みが得られない場合、複数回の塗布が必要になり工程数が増える問題があった。また、複数回の塗布・乾燥の繰り返しにより最終的なレジスト厚みの均一性が悪化したり、均一にするための塗布方法が操作上複雑となった。
【０００６】
また、めっき厚みが１００〜２００μｍと厚い場合に、電気導体めっきの時間が長くなるため、めっき液に浸漬している間にレジストが基材から一部はがれ、その結果としてめっきのもぐりが発生し不良となりやすかった。
【０００７】
【発明が解決しようとする課題】
本発明は、上記したＣＳＰの製造上の問題点を解決できる感光性樹脂積層体を提供することを目的とする。
【０００８】
【課題を解決するための手段】
本発明者は、上記の課題を解決すべく鋭意検討を重ねた結果、めっきによる配線形成のためのレジストとして、特定の重合性モノマーと光開始剤としてｐ−アミノフェニルケトンを含有する感光性樹脂組成物の層を有する感光性樹脂積層体を用いることにより、ウエーハ上へのレジストの密着性が向上し、さらに導体めっき工程での耐めっき性が著しく改善されることを見出した。また、特定の重合性モノマーの組合わせにより、前記性能向上に加えて、硬化レジストの剥離性も改善されることを見出した。
【０００９】
即ち、本発明は以下の通りのものである。
１．支持体と感光性樹脂層からなり、該感光性樹脂層が、（１）カルボキシル基含有量が酸当量で１００〜６００、かつ重量平均分子量が２万〜５０万の重合体：２０〜９０重量％、（２）下記式（１）で示される化合物、グリセリンプロピレンオキサイド付加トリ（メタ）アクリレート及びグリセリンエチレンオキサイド付加トリ（メタ）アクリレートからなる群から選ばれる１種または２種以上の重合性モノマー：１０〜６０重量％。
【００１０】
【化３】
２．支持体と感光性樹脂層からなり、該感光性樹脂層が、（１）カルボキシル基含有量が
酸等量で１００〜６００，重量平均分子量が２万〜５０万の重合体：２０〜９０重量％、（２）少なくともｉ）下記式（１）で示される化合物、グリセリンプロピレンオキサイド付加トリ（メタ）アクリレートおよびグリセリンエチレンオキサイド付加トリ（メタ）アクリレートからなる群から選ばれる少なくとも一つの化合物。
【００１１】
【化４】
３．ｐ−アミノフェニルケトンの含有量が０．０１〜０．０８重量％であることを特徴とする上記１または２に記載のＣＳＰ製造用感光性樹脂積層体。
本発明の感光性樹脂積層体は、支持層と感光性樹脂組成物からなるもので、一般に支持フィルム上に感光性樹脂組成物を積層し、多くの場合、さらに該組成物上に保護用のフィルムが積層される。
【００１２】
本発明において、感光性樹脂層の成分である（１）の重合体に含まれるカルボキシル基の量は、酸当量で１００〜６００である必要があり、３００〜４００が好ましい。ここで酸当量とは、その中に１等量のカルボキシル基を有するポリマーの重量をいう。酸当量の測定は、０．１Ｎ水酸化ナトリウムで電位差滴定法により行われる。酸当量が１００以下では、塗工溶媒またはモノマーとの相溶性が低下し、６００以上では現像性や剥離性が低下する。
【００１３】
重合体の重量平均分子量は、２万〜５０万である必要があり、より好ましくは４万〜２０万である。分子量の測定はゲル パーミエーション クロマトグラフィー（ＧＰＣ）により標準ポリスチレンの検量線を用いて行われる。５０万以上であると現像性が低下し、２万以下では感光性樹脂積層体に用いた場合に感光性樹脂層の厚みを均一に維持することが困難になる。
重合体は、下記の２種類の単量体の中より各々１種またはそれ以上の単量体を用い、共重合させることにより得られる。第１の単量体は分子中に炭素−炭素二重結合等の重合性不飽和基を１個有するカルボン酸である。例えば（メタ）アクリル酸、フマル酸、ケイ皮酸、クロトン酸、イタコン酸、マレイン酸半エステル等である。第２の単量体は分子中に炭素−炭素二重結合等の重合性不飽和基を有する非酸性単量体であり、感光性樹脂層の現像性、エッチング工程での耐性、硬化膜の可とう性等の種々の特性を保持するように選ばれる。例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸2-エチルヘキシル、（メタ）アクリル酸2-ヒドロキシエチル等の（メタ）アクリル酸アルキル類、（メタ）アクリル酸ベンジル、酢酸ビニル等のビニルアルコールのエステル類、スチレンまたは重合可能なスチレン誘導体および（メタ）アクリロニトリル等がある。
【００１４】
本発明の感光性樹脂層の成分である（２）の重合性モノマーについては、下記一般式（１）で示される化合物を少なくとも含む必要がある。
【００１５】
【化５】
（ここで、Ｘは水素原子、メチル基または水酸基を表す。ＡはＣＨ2ＣＨ（ＣＨ3）ＯおよびＣＨ2ＣＨ2Ｏの共重合体残基を表し、ｎは０〜５の整数を表す。Ｒは水素原子またはメチル基を表す。）
このような化合物の具体例としては、グリセリンプロピレンオキサイド付加トリ（メタ）アクリレート、グリセリンエチレンオキサイド付加トリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンプロピレンオキサイド付加トリ（メタ）アクリレート、トリメチロールプロパンエチレンオキサイド付加トリ（メタ）アクリレート、トリメチロールプロパンプロピレンオキサイドエチレンオキサイド付加トリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート等が挙げられる。
【００１７】
第二の発明によれば、感光性樹脂層の成分である（２）の重合性モノマーとしては、下記一般式（１）で示される化合物、
【００１８】
【化６】
（ここで、Ｘは水素原子、メチル基または水酸基を表す。ＡはＣＨ2ＣＨ（ＣＨ3）ＯおよびＣＨ2ＣＨ2Ｏの共重合体残基を表し、ｎは０〜５の整数を表す。Ｒは水素原子またはメチル基を表す。）
及び（メタ）アクリル酸エステル基を１個有する化合物とを少なくとも含む必要がある。
このような（メタ）アクリル酸エステル基を１個有する化合物の具体例としては、２−ヒドロキシ−３−フェノキシプロピルアクリレート（下記化合物）、
【００２０】
【化７】
フェノキシヘキサエチレングリコールアクリレート（下記化合物）、
【００２２】
【化８】
β−ヒドロキシプロピル−β’−（アクロイルオキシ）プロピルフタレート（下記化合物）、
【００２４】
【化９】
４−ノルマルオクチルフェノキシペンタエチレングリコールトリプロピレングリコールアクリレート（下記化合物）
【００２６】
【化１０】
等が挙げられる。
本発明に用いられる重合性モノマーとしては、上記以外の末端エチレン性不飽和基を１個以上有する不飽和化合物を含んでもよい。このような化合物の例として、１，４−テトラメチレングリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，４−シクロヘキサンジオールジ（メタ）アクリレート、オクタプロピレングリコールジ（メタ）アクリレート、２−ジ（ｐ−ヒドロキシフェニル）プロパンジ（メタ）アクリレート、グリセロールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ビスフェノールＡジグリシジルエーテルジ（メタ）アクリレート、イソシアヌル酸のエチレンオキサイド変性（メタ）アクリレート、ジアリルフタレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ビス（ポリエチレングリコール（メタ）アクリレート）ポリプロピレングリコール、等がある。また、ヘキサメチレンジイソシアナート、トリレンジイソシアナートなどの多価イソシアナート化合物と、２−ヒドロキシプロピル（メタ）アクリレートなどのヒドロキシアクリレート化合物とのウレタン化反応物などの例をあげることができる。
【００２８】
感光性樹脂層中に含有される重合性モノマーの量は、１０〜６０重量％の範囲であり、好ましくは２０〜５０重量％である。
本発明の感光性樹脂層には、少なくとも１種のｐ−アミノフェニルケトンを光開始剤として含むことが必要である。感光性樹脂層中に含有されるｐ−アミノフェニルケトンの量は、０．００１〜０．１重量％の範囲であり、好ましくは０，０１〜０．０８重量％である。具体的な例として、ｐ−アミノフェニルケトンについては、好ましいものとして例えばｐ−アミノベンゾフェノン、ｐ−ブチルアミノフェノン、ｐ−ジメチルアミノアセトフェノン、ｐ−ジメチルアミノベンゾフェノン、ｐ，ｐ’−ビス（エチルアミノ）ベンゾフェノン、ｐ，ｐ’−ビス（ジメチルアミノ）ベンゾフェノン［ミヒラーズケトン］、ｐ，ｐ’−ビス（ジエチルアミノ）ベンゾフェノン、ｐ，ｐ’−ビス（ジブチルアミノ）ベンゾフェノン等が用いられる。
【００２９】
ｐ−アミノフェニルケトンの構造としてさらに好ましくは、ｐ，ｐ’−ビス（ジメチルアミノ）ベンゾフェノンあるいはｐ，ｐ’−ビス（ジエチルアミノ）ベンゾフェノンが良い。
本発明の感光性樹脂層に含まれる他の開始剤としては、特に制限は無く、公知のあらゆる化合物を用いることができる。具体例としては、ベンジルジメチルケタール、ベンジルジエチルケタール、ベンジルジプロピルケタール、ベンジルジフェニルケタール、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインピロピルエーテル、ベンゾインフェニルエーテル、２、４、５−トリアリールイミダゾリル二量体、ベンゾフェノン、９−フェニルアクリジン等のアクリジン類、α、α−ジメトキシ−α−モルホリノ−メチルチオフェニルアセトフェノン、２，４，６−トリメチルベンゾイルホスフォンオキシド、フェニルグリシン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ーブタノン−１、チオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２−イソプロピルチオキサントン、４−イソプロピルチオキサントン、２，４ージイソプロピルチオキサントン、２−フルオロチオキサントン、４−フルオロチオキサントン、２−クロロチオキサントン、４−クロロチオキサントン、１−クロロ−４−プロポキシチオキサントン、ｐ−ジメチル安息香酸、ｐ−ジエチル安息香酸及びｐ−ジイソプロピル安息香酸及びこれらと下記のアルコールのエステル化物が使用することができる。アルコールとしては、メチルアルコール、エチルアルコール、プロピルアルコール、イソプロピルアルコール、ブチルアルコール、イソブチルアルコール、ｓｅｃ−ブチルアルコール、ｔｅｒｔ−ブチルアルコール、ｎ−アミルアルコール、イソアミルアルコール、ヘキシルアルコール、オクチルアルコール等がある。さらに１−フェニル−１、２−プロパンジオン−２−Ｏ−ベンゾイルオキシム、２，３−ジオキソ−３−フェニルプロピオン酸エチル−２−（Ｏ−ベンゾイルカルボニル）−オキシム等のオキシムエステル類がある。
【００３０】
本発明に用いられる感光性樹脂の熱安定性、保存安定性を向上させるために、感光性樹脂層にラジカル重合禁止剤を含有させることは好ましいことである。例えば、p−メトキシフェノール、ハイドロキノン、ピロガロール、ナフチルアミン、tert−ブチルカテコール、塩化第一銅、２，６−ジ−tert−ブチル−p−クレゾール、２，２’−メチレンビス（４−エチル−６−tert−ブチルフェノール）、２，２’−メチレンビス（４−メチル−６−tert−ブチルフェノール）等がある。
【００３１】
本発明の感光性樹脂層には染料、顔料等の着色物質を含有してもよい。例えばフクシン、フタロシアニングリーン、オーラミン塩基、カルコキシドグリーンS、パラマジエンタ、クリスタルバイオレット、メチルオレンジ、ナイルブルー２B、ビクトリアブルー、マラカイトグリーン、ベイシックブルー２０、ダイヤモンドグリーン等がある。
また、光照射により発色する発色系染料を含有しても良い。発色系染料としては、ロイコ染料とハロゲン化合物の組み合わせが良く知られている。ロイコ染料としては、例えばトリス（４−ジメチルアミノ−２−メチルフェニル）メタン［ロイコクリスタルバイオレット］、トリス（４−ジメチルアミノ−２−メチルフェニル）メタン［ロイコマラカイトグリーン］等が挙げられる。一方ハロゲン化合物としては臭化アミル、臭化イソアミル、臭化イソブチレン、臭化エチレン、臭化ジフェニルメチル、臭化ベンザル、臭化メチレン、トリブロモメチルフェニルスルホン、四臭化炭素、トリス（２，３−ジブロモプロピル）ホスフェート、トリクロロアセトアミド、ヨウ化アミル、ヨウ化イソブチル、１，１，１−トリクロロ−２，２−ビス（p−クロロフェニル）エタン、ヘキサクロロエタン等がある。
【００３２】
さらに本発明の感光性樹脂層には、必要に応じて可塑剤等の添加剤を含有しても良い。例えばジエチルフタレート等のフタル酸エステル類、ｏ−トルエンスルホン酸アミド、ｐ−トルエンスルホン酸アミド、クエン酸トリブチル、クエン酸トリエチル、アセチルクエン酸トリエチル、アセチルクエン酸トリ−ｎ−プロピル、アセチルクエン酸トリ−ｎ−ブチル、ポリプロピレングリコール等が例示できる。
【００３３】
本発明の感光性樹脂層の厚みは、必要な配線の厚みに対応して調整する。５０〜２５０μｍであり、好ましくは８０〜２００μｍであり、さらに好ましくは１００〜１５０μｍである。
本発明に用いられる支持体としては、紫外線に対して透明性の高いポリマーフィルムを用いる。例えばポリエチレンテレフテレートフィルム、ポリエチレンナフタレートフィルム、ポリビニルアルコールフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリ塩化ビニリデンフィルム、塩化ビニリデン共重合体フィルム、ポリメタクリル酸メチル共重合体フィルム、ポリスチレンフィルム、ポリアクリロニトリルフィルム、スチレン共重合体フィルム、ポリアミドフィルム、セルロース誘導体フィルム等が挙げられる。これらのフィルムは必要に応じ延伸されたものも使用可能である。
【００３４】
保護フィルムを設ける場合、該保護フィルムと感光性樹脂層の密着力が支持体と感光性樹脂層の密着力より小さい特性を有するフィルムが選ばれる。例えばポリエリレンフィルム、ポリプロピレンフィルム等が挙げられる。
本発明の感光性樹脂積層体は、ＣＳＰ製造において、以下のように用いられる。
まず、保護フィルムがある場合には、感光性樹脂積層体から保護フィルムを剥離した後、加熱された１対のロールにより基材と感光性樹脂積層体とを熱圧着（ラミネート）することで基材表面にレジスト膜を形成させる。ここで用いられる熱圧着装置（以下、ラミネーターという）としては、加熱ロールが２対以上ある多段式ラミネーターやロール部雰囲気を減圧にしたいわゆる真空ラミネーターが挙げられる。この際の加熱ロールの温度は４０〜１６０℃、好ましくは６０℃〜１２０℃である。
【００３５】
基材としては、個々のＬＳＩチップに対しても適応できるが、シリコンウエーハがより好ましい。シリコンウエーハ表面は一般にチップ端子以外を有機樹脂により保護されており、さらにめっきをかけるためにスパッタリング等の方法で全面に下地金属層が設けられている場合が多い。
ラミネート後の感光性樹脂積層体は、支持体のついたままかあるいは支持体を剥離した後に、所望の配線が得られるように作られたマスクを介して化学線により露光する。化学線としては、Ｘ線、電子線、紫外線、可視光線等が使用できるが、２００〜５００ｎｍの波長のものが好ましい。また、化学線によって露光された部分（感光性樹脂）は硬化する。
【００３６】
露光装置としては、超高圧水銀灯を光源とした散乱露光機、平行露光機等が使用される。また、ＬＳＩの製造で一般的なマスクアライナ、ステッパーも使用できる。フィルターにより単色化された紫外線による露光も可能である。
また、露光した後速やかにウエーハを加熱する工程（ＰＥＢ；Post Exposure Bake）を行っても良い。ＰＥＢ工程により硬化レジストのウエーハとの密着性が向上する。加熱温度は５０〜１００℃、加熱時間は３０秒〜１０分が好ましい。
【００３７】
露光後のレジストは無機または有機アルカリ液により現像する。その結果未露光部分が溶解除去され、露光部分のみに硬化レジストが残される。ここで用いられる現像液としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア水等の無機アルカリ類、エチルアミン、ｎ−プロピルアミン等の第１アミン類、ジエチルアミン、ジ−ｎ−プロピルアミン等の第２アミン類、トリエチルアミン、メチルジエチルアミン等の第３アミン類、ジメチルエタノールアミン、トリエタノールアミン等のアルコールアミン類、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド等の第４級アンモニウム塩等のアルカリ類の水溶液等が使用できる。ウエーハに残る微量の無機アルカリイオン（ナトリウムイオン、カリウムイオン）がＣＳＰの性能に影響を及ぼす場合は、有機アルカリ液の使用が好ましい。現像方法としては、スプレー、パドル、浸漬、超音波等の方式が可能である。
【００３８】
これに電解金属めっきを行うことによって、硬化レジストが無い部分に所望の厚みの金属を形成させる。金属としては、銅、ニッケル、クロム、金、はんだ等が挙げられるが、特に、銅めっきが多用される。所望のめっき厚みに対して同等またはより厚い硬化レジストが必要となる。感光性樹脂層の厚みは露光、現像後の硬化レジストの厚みとほぼ等しいため、めっき厚みに対して同等またはより厚い感光性樹脂積層を有する感光性樹脂積層体を使用する。
【００３９】
上述のようにして導体配線を形成した後、硬化レジストを無機または有機アルカリ液により剥離除去する。一般に現像液に比べてアルカリ性が強く、液温度を高い条件で剥離する。ここで用いられる剥離液としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア水等の無機アルカリ類、エチルアミン、ｎ−プロピルアミン等の第１アミン類、ジエチルアミン、ジ−ｎ−プロピルアミン等の第２アミン類、トリエチルアミン、メチルジエチルアミン等の第３アミン類、２−アミノエタノール、ジメチルエタノールアミン、トリエタノールアミン等のアルコールアミン類、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド等の第４級アンモニウム塩等のアルカリ類の水溶液およびこれにメタノール、エタノール、ジメチルスルホキシド、Ｎ−メチルピロリドン、ジメチルホルムアミド等の有機溶剤を適量含んだ水溶液が使用できる。ウエーハに残る微量の無機アルカリイオン（ナトリウムイオン、カリウムイオン）がＣＳＰの性能に影響を及ぼす場合は、有機アルカリ液の使用が好ましい。剥離方法としては、スプレー、パドル、浸漬、超音波等の方式が可能である。
【００４０】
硬化レジストの剥離後、フラッシュエッチング、プラズマエッチング、リアクティブイオンエッチング等の方法でウエーハ上の下地金属層を除去し、必要な配線のみを残す。
さらに、必要に応じて有機樹脂で封止することによりＣＳＰを作製する。ウエーハ上でＣＳＰの集合体を作製した場合、ダイシングにより１個１個のＣＳＰに切り離す。
【００４１】
【発明の実施の形態】
以下、実施例により本発明をさらに詳しく説明する。
実施例中の特性評価は、次の方法で測定した。
１）解像度評価Ａ
８０μｍ幅のライン部と８０μｍ幅のスペース部が交互に５本ずつ並んだマスクを、感光性樹脂積層体がラミネートされたウエーハ上に置き、オーク社製平行光露光機ＨＭＷ−８０１で２００ｍＪ／ｃｍ2露光した。支持体を剥がした後、３０℃の１％炭酸ナトリウム水溶液を１２０秒間スプレーし、未露光部分の感光性樹脂層を現像除去し、５本並んでいるレジストパターンを形成させた。５本のレジストラインが独立して形成されている場合を○、５本のレジストラインの一部がつながっているかあるいはウエーハ表面から剥がれている場合を×とした。
２）解像度評価Ｂ
８０μｍ幅のライン部と８０μｍ幅のスペース部が交互に５本ずつ並んだマスクを、感光性樹脂積層体がラミネートされたウエーハ上に置き、キャノン社製マスクアライナＰＬＡ−５０１Ｆで１１秒間露光した。露光機の照度を測定したところ、６．３ｍＷ／ｃｍ2であり、計算すると７０ｍＪ／ｃｍ2の露光量となった。露光後すぐに８０℃のオーブンにウエーハを入れ、２分間露光後ベークを行った。支持体を剥がした後、室温で２．３８％テトラメチルアンモニウムヒドロキシド水溶液を用いてパドル現像した。パドル現像の現像時間の合計は２４０秒間だった。未露光部分の感光性樹脂層を現像除去し、５本並んでいるレジストパターンを形成させた。５本のレジストラインが独立して形成されている場合を○、５本のレジストラインの一部がつながっているかあるいはウエーハ表面から剥がれている場合を×とした。
【００４２】
３）めっきもぐり評価
剥離後のウエーハを光学顕微鏡およびＳＥＭ（走査型電子顕微鏡）で観察し、めっきもぐりの状態を調べた。次のようなランクで判定した。
○・・・めっきもぐりが全く無し
△・・・めっきもぐりが５μｍ未満
×・・・めっきもぐりが５μｍ以上
４）硬化レジストの剥離性評価
直径１５０μｍの（光を通さない）ドットが３００μｍピッチで縦１００列、横１００列（ドット総数：１００００個）並んだパターンのマスクを、感光性樹脂積層体がラミネートされたウエーハ上に置き、キャノン社製マスクアライナＰＬＡ−５０１Ｆで１１秒間露光した。支持体を剥がした後、室温で２．３８％テトラメチルアンモニウムヒドロキシド水溶液を用いてパドル現像し、約１５０μｍφの円孔を作った。パドル現像の現像時間の合計は２４０秒間だった。このウエーハを硫酸銅めっき液中で９０分間電解銅めっきし、円柱状の銅配線を作った。電流密度は５Ａ／ｄｍ２になるように調整した。銅めっきの高さは１００μｍだった。めっき後のウエーハを５０℃のアルカリ剥離液に浸漬１０分間してレジストを剥離した。アルカリ剥離液は、メルテックス社製フィルムストリップ５００の１０％水溶液を用いた。剥離後のウエーハを観察し、次のようなランクで判定した。
○・・・ウエーハ上に剥離残渣が全くなし。
△・・・円柱状の銅配線周辺に剥離残渣がある割合が、面積として１０％未満。
×・・・円柱状の銅配線周辺に剥離残渣がある割合が、面積として１０％以上。
【００４３】
【実施例１】
メチルメタクリレート／メタクリル酸／エチルアクリレート＝５５／２５／２０ｗｔ％で重量平均分子量が２０万の重合体を６０重量部、重合性モノマーとしてトリメチロールプロパントリアクリレートを３０重量部、光開始剤として２、４、５−トリアリールイミダゾリル二量体を５重量部とｐ，ｐ’−ビス（ジメチルアミノ）ベンゾフェノン０．０５重量部および溶剤としてメチルエチルケトンを１００重量部を混合溶解した液を、支持体（１６μｍ厚みのポリエチレンテレフタレートフィルム）にバーコーターを用いて塗布、乾燥し、保護フィルム（２３μｍ厚みのポリエチレンフィルム）をかぶせることにより感光性樹脂積層体（感光性樹脂層の厚み：１００μｍ）を調製した。
＜評価１＞
５インチのシリコンウエーハ上にアネルバ製スパッタリング装置により２０００オングストローム厚みのクロム層を形成し、さらに２０００オングストロームの銅層を形成させた。
【００４４】
これに上記で調製した感光性樹脂積層体を旭化成製ラミネーターＡＬ−７０により、保護フィルムを剥がしながら、感光性樹脂層の面がシリコンウエーハに密着するようにラミネートした。ラミネートはロール温度を１００℃、圧力はエアー圧で３ｋｇ／ｃｍ2、速度は１．５ｍ／分で行った。
感光性樹脂積層体がラミネートされたウエーハにマスクを置き、オーク社製平行光露光機ＨＭＷ−８０１で２００ｍＪ／ｃｍ2露光した。
【００４５】
支持体を剥がした後、３０℃の１％炭酸ナトリウム水溶液を１２０秒間スプレーし、未露光部分の感光性樹脂層を現像除去し、レジストパターンを形成させた。
解像度評価Ａの結果は○であった。
レジストが形成されたウエーハを、３０℃の酸性クリーナー（アトテックジャパン製ＦＲＸ）に３分間浸漬することで脱脂を行った後、硫酸銅めっき液（メルテックス社製カパーグリーム１２５）中で６時間電解銅めっきした。電流密度は２Ａ／ｄｍ2になるように調整した。銅めっきの高さは、９０μｍだった。
めっき後のウエーハを５０℃の３％水酸化ナトリウム水溶液に１０分間浸漬してレジストを剥離した。
めっきもぐりの評価は○であった。
【００４６】
【実施例２〜６、比較例１〜５】
表１、表2に示した感光性樹脂積層を有する感光性樹脂積層体を調製し、実施例１と同様の方法により、ウエーハ上の電気銅めっきの配線を形成させた。解像度評価およびめっきもぐり評価の結果も表1、表2に示す。
表1、表2中の感光性樹脂原料の略号の意味は下記の通りである。
Ａ−１：メチルメタクリレート／メタクリル酸／エチルアクリレート＝５５／２５／２０ｗｔ％で重量平均分子量が２０万の重合体
Ａ−２：メチルメタクリレート／メタクリル酸／スチレン／ブチルメタクリレート＝４５／２５／２０／１０ｗｔ％で重量平均分子量が１０万の重合体
Ａ−３：メチルメタクリレート／メタクリル酸／スチレン／ブチルメタクリレート／アクリロニトリル＝３７／２２／９／１９／１３ｗｔ％で重量平均分子量が１２万の重合体
Ｂ−１：トリメチロールプロパントリアクリレート
Ｂ−２：トリメチロールプロパンエチレンオキサイド６モル付加トリアクリレート
ＣＨ3−ＣＨ2−Ｃ［ＣＨ2−Ｏ−（ＣＨ2ＣＨ2Ｏ）2−ＣＯ−ＣＨ＝ＣＨ2］3
Ｂ−３：トリメチロールプロパントリメタクリレート
Ｂ−４：ビス（トリエチレングリコールメタクリレート）ポリプロピレングリコール
ＣＨ2＝Ｃ（ＣＨ3）−ＣＯ−Ｏ−（ＣＨ2ＣＨ2Ｏ）3−
−（ＣＨ（ＣＨ3）ＣＨ2Ｏ）12−（ＣＨ2ＣＨ2Ｏ）3−
−ＣＯ−Ｃ（ＣＨ3）＝ＣＨ2
Ｂ−５：ノナエチレングリコールジアクリレート
ＣＨ2＝ＣＨ−ＣＯ−Ｏ−（ＣＨ2ＣＨ2Ｏ）9−ＣＯ−ＣＨ＝ＣＨ2
Ｂ−６：ビスフェノールＡのエチレンオキサイド付加ジメタクリレート
ＣＨ2＝Ｃ（ＣＨ3）−ＣＯ−Ｏ−（ＣＨ2ＣＨ2Ｏ）5−
−φ−Ｃ（ＣＨ3）2−φ−Ｏ−（ＣＨ2ＣＨ2Ｏ）5−
−ＣＯ−Ｃ（ＣＨ3）＝ＣＨ2
（ここで、φはベンゼン環）
Ｃ−１：ｐ，ｐ’−ビス（ジメチルアミノ）ベンゾフェノン
Ｃ−２：ｐ，ｐ’−ビス（ジエチルアミノ）ベンゾフェノン
Ｃ−３：２−（ｏ−クロロフェニル）−４・５−ジフェニルイミダゾリル二量体
Ｃ−４：ベンゾフェノン
Ｃ−５：２ーベンジル−２−ジメチルアミノ−１−（４ーモルフォリノフェニル）ーブタノンー１（チバガイギー社製、商標名：イルガキュアー３６９）
【００４７】
＜評価２＞
５インチのシリコンウエーハ上にアネルバ製スパッタリング装置により２０００オングストローム厚みのクロム層を形成し、さらに２０００オングストロームの銅層を形成させた。
これに実施例１と同じ方法で実施例１の感光性樹脂積層体をラミネートした。
感光性樹脂積層体がラミネートされたウエーハにマスクを置き、オーク社製平行光露光機ＨＭＷ−８０１で２００ｍＪ／ｃｍ2露光した。
支持体を剥がした後、３０℃の１％炭酸ナトリウム水溶液を１２０秒間スプレーし、未露光部分の感光性樹脂層を現像除去し、レジストパターンを形成させた。
【００４８】
解像度評価Ａの結果は○であった。
レジストが形成されたウエーハを、３０℃の酸性クリーナー（アトテックジャパン製ＦＲＸ）に３分間浸漬することで脱脂を行った後、はんだめっき液（メルテックス社製プルティンＬＡホウフッ化はんだ浴）中で４時間電解はんだめっきした。電流密度は１．５Ａ／ｄｍ2になるように調整した。はんだめっきの高さは、９０μｍだった。
めっき後のウエーハを５０℃の３％水酸化ナトリウム水溶液に１０分間浸漬してレジストを剥離した。
めっきもぐりの評価は○であった。
【００４９】
【実施例７】
メチルメタクリレート／メタクリル酸／エチルアクリレート＝５５／２５／２０ｗｔ％で重量平均分子量が２０万の重合体を６０重量部、重合性モノマーとしてトリメチロールプロパントリアクリレートを３０重量部、２−ヒドロキシ−３−フェノキシプロピルアクリレート１０重量部、光開始剤として２、４、５−トリアリールイミダゾリル二量体を５重量部とｐ，ｐ’−ビス（ジメチルアミノ）ベンゾフェノン０．０５重量部および溶剤としてメチルエチルケトンを１００重量部を混合溶解した液を、支持体（１９μｍ厚みのポリエチレンテレフタレートフィルム）にバーコーターを用いて塗布、乾燥し、保護フィルム（３０μｍ厚みのポリエチレンフィルム）をかぶせることにより感光性樹脂積層体（感光性樹脂層の厚み：１２０μｍ）を調製した。
【００５０】
５インチのシリコンウエーハ上に日本真空製スパッターにより２０００オングストローム厚みのクロム層を形成し、さらに２０００オングストロームの銅層を形成させた。
これに上記で調製した感光性樹脂積層体を旭化成製ラミネーターＡＬ−７０により、保護フィルムを剥がしながら、感光性樹脂層の面がシリコンウエーハに密着するようにラミネートした。ラミネートはロール温度を１００℃、圧力はエアー圧で３．５ｋｇ／ｃｍ2、速度は１．０ｍ／分で行った。
【００５１】
感光性樹脂積層体がラミネートされたウエーハにマスクを置き、キャノン社製マスクアライナＰＬＡ−５０１Ｆで１１秒露光した。露光機の照度を測定したところ、６．３ｍＷ／ｃｍ2であり、計算すると７０ｍＪ／ｃｍ2の露光量となった。露光後すぐに８０℃のオーブンにウエーハを入れ、２分間露光後ベークを行った。
支持体を剥がした後、室温で２．３８％テトラメチルアンモニウムヒドロキシド水溶液を用いてパドル現像した。パドル現像の現像時間の合計は２４０秒間だった。未露光部分の感光性樹脂層を現像除去し、レジストパターンを形成させた。
【００５２】
解像度評価Ｂの結果は○であった。
レジストが形成されたウエーハを、３０℃の酸性クリーナー（アトテックジャパン製ＦＲＸ）に３分間浸漬することで脱脂を行った後、硫酸銅めっき液（メルテックス社製カパーグリーム１２５）中で６時間電解銅めっきした。電流密度は２Ａ／ｄｍ2になるように調整した。銅めっきの高さは、９０μｍだった。
めっき後のウエーハを５０℃の３％水酸化ナトリウム水溶液に浸漬１０分間してレジストを剥離した。
【００５３】
めっきもぐりの評価は○であった。
直径１５０μｍのドットが並んだパターンのマスクを、感光性樹脂積層体がラミネートされたウエーハ上に置き、キャノン社製マスクアライナＰＬＡ−５０１Ｆで１１秒間露光した。支持体を剥がした後、室温で２．３８％テトラメチルアンモニウムヒドロキシド水溶液を用いてパドル現像た。このウエーハを硫酸銅めっき液中で電解銅めっきし、円柱状の銅配線を作った。めっき後のウエーハを５０℃のアルカリ剥離液に浸漬１０分間してレジストを剥離した。
硬化レジストの剥離性評価は○であった。
【００５４】
【実施例８〜１０、実施例１〜２、６】
表３に示した感光性樹脂積層を有する感光性樹脂積層体を調製し、実施例７と同様の方法により、ウエーハ上の電気銅めっきの配線を形成させた。解像度評価、めっきもぐり評価および硬化レジストの剥離性評価の結果も表３に示す。前述した原料以外の感光性樹脂原料の略号の意味は下記の通りである。
Ｂ−７：２−ヒドロキシ−３−フェノキシプロピルアクリレート
Ｂ−８：フェノキシヘキサエチレングリコールアクリレート
Ｂ−９：β−ヒドロキシプロピル−β’−（アクロイルオキシ）プロピルフタレート
Ｂ−１０：４−ノルマルオクチルフェノキシペンタエチレングリコールトリプロピレングリコールアクリレート
【００５５】
【表１】
【表２】
【表３】
【発明の効果】
以上説明したように、本願の第一の発明の感光性樹脂積層体を用いると、ＣＳＰの製造において、チップ端子と外部端子を接続する配線を形成させる際に、解像度が優れているため微細な配線を作ることができ、さらに導体めっき工程においてめっきもぐりの無い高品質な導体配線が得られ、ＣＳＰの製造に極めて好適である。
また、本願の第二の発明によれば、さらに、めっき後のレジスト剥離が容易かつ良好で剥離残渣の無い高信頼性の回路を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photosensitive resin laminate, and more particularly to a photosensitive resin laminate suitable for CSP (Chip Size Package) manufacture.
[0002]
[Prior art]
The CSP is a component in which an LSI chip is packaged, and is generally a package that is equal to or slightly larger than the LSI chip size, and is rapidly spreading with the recent miniaturization of electronic devices. CSP includes BGA (Ball Grid Array) type, LGA (Land Grid Array) type, SON (Small Outline Non-leaded) type, etc., depending on the package type.
[0003]
Conventionally, an LSI chip is packaged in a CSP by cutting an LSI made on a wafer into individual chips and then bonding them to a wiring board having external terminals by a method such as wire bonding, soldering, or ultrasonic bonding. Then, if necessary, a method of sealing or underfilling with an organic resin has been used.
In recent years, for a plurality of LSIs formed on a silicon wafer, parts such as CSP or BGA are formed by collectively forming wiring and external terminals before cutting and sealing with an organic resin if necessary. After that, the method of cutting as individual parts began to be adopted. A part made by this method is generally called a wafer level CSP.
[0004]
In the process of making the wafer level CSP, wiring for connecting the LSI chip terminal and the external terminal is necessary, and many are formed by attaching a conductor by plating. More specifically, after applying and drying a liquid resist on a wafer provided with a metal layer, actinic radiation is exposed through a wiring pattern mask, and the resist is developed and removed, so that only portions where conductor wiring is to be formed are opened. This is subjected to electrolytic metal plating to form necessary wiring.
[0005]
The wiring includes a linear one and a columnar one in which a via hole is filled with copper. In particular, regarding columnar wiring, it is required to increase the plating thickness to 50 μm to 200 μm.
When the wiring is formed, a liquid resist is used. However, if the liquid resist does not have a desired thickness by a single application, a plurality of processes are required and the number of processes increases. was there. In addition, the uniformity of the final resist thickness is deteriorated by repeating the coating and drying a plurality of times, and the coating method for making it uniform is complicated in operation.
[0006]
In addition, when the plating thickness is as thick as 100 to 200 μm, the electric conductor plating time becomes long, so that the resist is partially peeled off from the base material while being immersed in the plating solution, and as a result, plating is peeled off. It was easy to become defective.
[0007]
[Problems to be solved by the invention]
An object of this invention is to provide the photosensitive resin laminated body which can solve the problem on manufacture of above-mentioned CSP.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventor has developed a photosensitive resin containing a specific polymerizable monomer and p-aminophenyl ketone as a photoinitiator as a resist for wiring formation by plating. It has been found that by using a photosensitive resin laminate having a composition layer, the adhesion of the resist to the wafer is improved and the plating resistance in the conductor plating step is remarkably improved. Moreover, it discovered that the peeling property of the cured resist was improved in addition to the said performance improvement by the combination of a specific polymerizable monomer.
[0009]
That is,The present invention is as follows.
1. The photosensitive resin layer comprises a support and a photosensitive resin layer. (1) A polymer having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 20,000 to 500,000: 20 to 90 weights %, (2) one or more polymerizable monomers selected from the group consisting of a compound represented by the following formula (1), glycerin propylene oxide-added tri (meth) acrylate and glycerin ethylene oxide-added tri (meth) acrylate : 10 to 60% by weight.
[0010]
[Chemical Formula 3]
2. It consists of a support and a photosensitive resin layer, and the photosensitive resin layer has (1) carboxyl group content.
Polymer having an acid equivalent of 100 to 600 and a weight average molecular weight of 20,000 to 500,000: 20 to 90% by weight, (2) at least i) a compound represented by the following formula (1), glycerin propylene oxide addition tri (meta ) At least one compound selected from the group consisting of acrylate and glycerin ethylene oxide-added tri (meth) acrylate.
[0011]
[Formula 4]
3. 3. The photosensitive resin laminate for CSP production according to 1 or 2 above, wherein the content of p-aminophenyl ketone is 0.01 to 0.08% by weight.
The photosensitive resin laminate of the present invention is composed of a support layer and a photosensitive resin composition. In general, a photosensitive resin composition is laminated on a support film, and in many cases, a protective layer is further formed on the composition. Films are laminated.
[0012]
In this invention, the quantity of the carboxyl group contained in the polymer of (1) which is a component of the photosensitive resin layer needs to be 100-600 by an acid equivalent, and 300-400 are preferable. Here, the acid equivalent means the weight of a polymer having 1 equivalent of a carboxyl group therein. The acid equivalent is measured by potentiometric titration with 0.1N sodium hydroxide. When the acid equivalent is 100 or less, the compatibility with the coating solvent or the monomer is lowered, and when it is 600 or more, the developability and the peelability are lowered.
[0013]
The weight average molecular weight of the polymer needs to be 20,000 to 500,000, more preferably 40,000 to 200,000. The molecular weight is measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve. When it is 500,000 or more, developability is lowered, and when it is 20,000 or less, it is difficult to maintain a uniform thickness of the photosensitive resin layer when used in the photosensitive resin laminate.
The polymer can be obtained by copolymerization using one or more of the following two types of monomers. The first monomer is a carboxylic acid having one polymerizable unsaturated group such as a carbon-carbon double bond in the molecule. For example, (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic acid half ester and the like. The second monomer is a non-acidic monomer having a polymerizable unsaturated group such as a carbon-carbon double bond in the molecule, the developability of the photosensitive resin layer, the resistance in the etching process, and the cured film. It is selected so as to retain various characteristics such as flexibility. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, etc. There are alkyl (meth) acrylates, benzyl (meth) acrylate, esters of vinyl alcohol such as vinyl acetate, styrene or polymerizable styrene derivatives and (meth) acrylonitrile.
[0014]
About the polymerizable monomer of (2) which is a component of the photosensitive resin layer of this invention, it is necessary to contain at least the compound shown by following General formula (1).
[0015]
[Chemical formula 5]
(Here, X represents a hydrogen atom, a methyl group or a hydroxyl group. A represents CH.2CH (CHThree) O and CH2CH2O represents a copolymer residue, and n represents an integer of 0 to 5. R represents a hydrogen atom or a methyl group. )
Specific examples of such compounds include glycerin propylene oxide-added tri (meth) acrylate, glycerin ethylene oxide-added tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane propylene oxide-added tri (meth) acrylate. , Trimethylolpropane ethylene oxide addition tri (meth) acrylate, trimethylolpropane propylene oxide ethylene oxide addition tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like.
[0017]
According to 2nd invention, as a polymerizable monomer of (2) which is a component of the photosensitive resin layer, the compound shown by following General formula (1),
[0018]
[Chemical 6]
(Here, X represents a hydrogen atom, a methyl group or a hydroxyl group. A represents CH.2CH (CHThree) O and CH2CH2O represents a copolymer residue, and n represents an integer of 0 to 5. R represents a hydrogen atom or a methyl group. )
And a compound having one (meth) acrylic acid ester group.
Specific examples of the compound having one (meth) acrylic acid ester group include 2-hydroxy-3-phenoxypropyl acrylate (the following compound),
[0020]
[Chemical 7]
Phenoxyhexaethylene glycol acrylate (the following compound),
[0022]
[Chemical 8]
β-hydroxypropyl-β '-(acryloyloxy) propyl phthalate (the following compound),
[0024]
[Chemical 9]
4-normal octylphenoxypentaethylene glycol tripropylene glycol acrylate (the following compounds)
[0026]
Embedded image
Etc.
The polymerizable monomer used in the present invention may include an unsaturated compound having one or more terminal ethylenically unsaturated groups other than those described above. Examples of such compounds include 1,4-tetramethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, octapropylene glycol di ( (Meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A diglycidyl ether di (Meth) acrylate, ethylene oxide modified (meth) acrylate of isocyanuric acid, diallyl phthalate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate , Bis (polyethylene glycol (meth) acrylate) polypropylene glycol, and the like. In addition, examples include urethanation reaction products of polyvalent isocyanate compounds such as hexamethylene diisocyanate and tolylene diisocyanate and hydroxyacrylate compounds such as 2-hydroxypropyl (meth) acrylate.
[0028]
The amount of the polymerizable monomer contained in the photosensitive resin layer is in the range of 10 to 60% by weight, preferably 20 to 50% by weight.
The photosensitive resin layer of the present invention needs to contain at least one p-aminophenyl ketone as a photoinitiator. The amount of p-aminophenyl ketone contained in the photosensitive resin layer is in the range of 0.001 to 0.1% by weight, preferably 0.01 to 0.08% by weight. As specific examples, for p-aminophenyl ketone, preferred examples include p-aminobenzophenone, p-butylaminophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p, p′-bis (ethylamino). ) Benzophenone, p, p′-bis (dimethylamino) benzophenone [Michler's ketone], p, p′-bis (diethylamino) benzophenone, p, p′-bis (dibutylamino) benzophenone, and the like are used.
[0029]
The structure of p-aminophenyl ketone is more preferably p, p'-bis (dimethylamino) benzophenone or p, p'-bis (diethylamino) benzophenone.
There is no restriction | limiting in particular as another initiator contained in the photosensitive resin layer of this invention, All the well-known compounds can be used. Specific examples include benzyl dimethyl ketal, benzyl diethyl ketal, benzyl dipropyl ketal, benzyl diphenyl ketal, benzoin methyl ether, benzoin ethyl ether, benzoin pyropyr ether, benzoin phenyl ether, 2,4,5-triarylimidazolyl dimer. Acridines such as benzophenone and 9-phenylacridine, α, α-dimethoxy-α-morpholino-methylthiophenylacetophenone, 2,4,6-trimethylbenzoyl phosphine oxide, phenylglycine, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone-1, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4 Isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2-fluorothioxanthone, 4-fluorothioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, p-dimethylbenzoic acid, p-diethylbenzoic acid And p-diisopropylbenzoic acid and esterified products of these with the following alcohols can be used. Examples of the alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol, octyl alcohol and the like. Furthermore, there are oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 2,3-dioxo-3-phenylpropionic acid ethyl-2- (O-benzoylcarbonyl) -oxime.
[0030]
In order to improve the thermal stability and storage stability of the photosensitive resin used in the present invention, it is preferable that the photosensitive resin layer contains a radical polymerization inhibitor. For example, p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis (4-ethyl-6- tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol) and the like.
[0031]
The photosensitive resin layer of the present invention may contain coloring substances such as dyes and pigments. Examples include fuchsin, phthalocyanine green, auramin base, chalcoxide green S, paramadienta, crystal violet, methyl orange, nile blue 2B, Victoria blue, malachite green, basic blue 20, diamond green and the like.
Further, it may contain a coloring dye that develops color by light irradiation. A combination of a leuco dye and a halogen compound is well known as a coloring dye. Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and the like. On the other hand, halogen compounds such as amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2,3 -Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane and the like.
[0032]
Furthermore, you may contain additives, such as a plasticizer, in the photosensitive resin layer of this invention as needed. For example, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl tri-n-propyl citrate, acetyl tricitrate tri -N-butyl, polypropylene glycol, etc. can be illustrated.
[0033]
The thickness of the photosensitive resin layer of the present invention is adjusted according to the required wiring thickness. It is 50-250 micrometers, Preferably it is 80-200 micrometers, More preferably, it is 100-150 micrometers.
As the support used in the present invention, a polymer film having high transparency to ultraviolet rays is used. For example, polyethylene terephthalate film, polyethylene naphthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene Examples include films, polyacrylonitrile films, styrene copolymer films, polyamide films, and cellulose derivative films. These films can be stretched if necessary.
[0034]
When providing a protective film, the film which has the characteristic that the adhesive force of this protective film and the photosensitive resin layer is smaller than the adhesive force of a support body and the photosensitive resin layer is selected. For example, a polyerylene film, a polypropylene film, etc. are mentioned.
The photosensitive resin laminate of the present invention is used as follows in CSP production.
First, when there is a protective film, after peeling the protective film from the photosensitive resin laminate, the substrate and the photosensitive resin laminate are thermocompression bonded (laminated) with a pair of heated rolls. A resist film is formed on the material surface. Examples of the thermocompression bonding apparatus (hereinafter referred to as a laminator) used here include a multistage laminator having two or more pairs of heating rolls and a so-called vacuum laminator in which the roll portion atmosphere is reduced in pressure. The temperature of the heating roll at this time is 40 to 160 ° C, preferably 60 to 120 ° C.
[0035]
The substrate can be applied to individual LSI chips, but a silicon wafer is more preferable. In general, the surface of the silicon wafer is protected by an organic resin except for the chip terminals, and a base metal layer is often provided on the entire surface by a method such as sputtering for plating.
The photosensitive resin laminate after lamination is exposed to actinic radiation through a mask formed so as to obtain a desired wiring after the support is attached or after the support is peeled off. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable. Further, the portion exposed to actinic radiation (photosensitive resin) is cured.
[0036]
As the exposure apparatus, a scattering exposure machine, a parallel exposure machine or the like using an ultrahigh pressure mercury lamp as a light source is used. Further, a mask aligner and a stepper which are common in LSI manufacturing can also be used. Exposure with ultraviolet light monochromatized by a filter is also possible.
Moreover, you may perform the process (PEB; Post Exposure Bake) of heating a wafer immediately after exposure. The PEB process improves the adhesion of the cured resist to the wafer. The heating temperature is preferably 50 to 100 ° C., and the heating time is preferably 30 seconds to 10 minutes.
[0037]
The exposed resist is developed with an inorganic or organic alkaline solution. As a result, the unexposed part is dissolved and removed, and the cured resist is left only in the exposed part. Examples of the developer used here include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, and diethylamine. Secondary amines such as di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. An aqueous solution of an alkali such as a quaternary ammonium salt can be used. When a trace amount of inorganic alkali ions (sodium ion, potassium ion) remaining on the wafer affects the performance of CSP, it is preferable to use an organic alkali solution. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.
[0038]
By performing electrolytic metal plating on this, a metal having a desired thickness is formed in a portion where there is no cured resist. Examples of the metal include copper, nickel, chromium, gold, and solder, and copper plating is particularly frequently used. A cured resist equivalent or thicker to the desired plating thickness is required. Since the thickness of the photosensitive resin layer is substantially equal to the thickness of the cured resist after exposure and development, a photosensitive resin laminate having a photosensitive resin laminate equal to or thicker than the plating thickness is used.
[0039]
After the conductor wiring is formed as described above, the cured resist is peeled off with an inorganic or organic alkaline solution. In general, the alkalinity is stronger than that of the developer, and the film is peeled off at a high temperature. Examples of stripping solutions used here include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and the like. Secondary amines such as di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as 2-aminoethanol, dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethyl An aqueous solution of an alkali such as a quaternary ammonium salt such as ammonium hydroxide or an aqueous solution containing an appropriate amount of an organic solvent such as methanol, ethanol, dimethyl sulfoxide, N-methylpyrrolidone or dimethylformamide can be used. That. When a trace amount of inorganic alkali ions (sodium ion, potassium ion) remaining on the wafer affects the performance of CSP, it is preferable to use an organic alkali solution. As a peeling method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.
[0040]
After the cured resist is peeled off, the underlying metal layer on the wafer is removed by a method such as flash etching, plasma etching, reactive ion etching, or the like, leaving only necessary wiring.
Furthermore, CSP is produced by sealing with an organic resin as necessary. When an assembly of CSPs is produced on a wafer, it is cut into one CSP by dicing.
[0041]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail with reference to examples.
The characteristic evaluation in the examples was measured by the following method.
1) Resolution evaluation A
A mask in which five line portions each having 80 μm width and five space portions having 80 μm width are alternately arranged is placed on a wafer on which a photosensitive resin laminate is laminated, and 200 mJ / cm with a parallel light exposure machine HMW-801 manufactured by Oak Co., Ltd.2Exposed. After the support was peeled off, a 1% sodium carbonate aqueous solution at 30 ° C. was sprayed for 120 seconds to develop and remove the photosensitive resin layer in the unexposed portion, thereby forming a resist pattern in which five were aligned. The case where five resist lines were formed independently was marked with ○, and the case where a part of the five resist lines were connected or peeled off from the wafer surface was marked with x.
2) Resolution evaluation B
A mask in which five line portions each having 80 μm width and five space portions having 80 μm width were alternately arranged was placed on the wafer on which the photosensitive resin laminate was laminated, and exposed for 11 seconds with a mask aligner PLA-501F manufactured by Canon. When the illuminance of the exposure device was measured, it was 6.3 mW / cm.2And is calculated to be 70 mJ / cm2Exposure amount. Immediately after exposure, the wafer was placed in an oven at 80 ° C. and baked after exposure for 2 minutes. After peeling off the support, paddle development was performed using a 2.38% aqueous tetramethylammonium hydroxide solution at room temperature. The total development time for paddle development was 240 seconds. The unexposed portion of the photosensitive resin layer was developed and removed to form a resist pattern in which five were aligned. The case where five resist lines were formed independently was marked with ○, and the case where a part of the five resist lines were connected or peeled off from the wafer surface was marked with x.
[0042]
3) Plating drill evaluation
The peeled wafer was observed with an optical microscope and an SEM (scanning electron microscope), and the state of plating peeling was examined. Judgment was made according to the following rank.
○ ... No plating removal
△ ・ ・ ・ Plating is less than 5μm
× ・ ・ ・ Plating hole is 5μm or more
4) Evaluation of peelability of cured resist
A mask having a pattern in which dots having a diameter of 150 μm (impervious to light) are arranged in 100 rows and 100 rows in a row with a pitch of 300 μm (total number of dots: 10,000) is placed on a wafer laminated with a photosensitive resin laminate. It was exposed for 11 seconds with a mask aligner PLA-501F manufactured by the company. After peeling off the support, paddle development was performed using a 2.38% tetramethylammonium hydroxide aqueous solution at room temperature to form a circular hole of about 150 μmφ. The total development time for paddle development was 240 seconds. This wafer was subjected to electrolytic copper plating for 90 minutes in a copper sulfate plating solution to form a cylindrical copper wiring. The current density was adjusted to 5 A / dm2. The height of the copper plating was 100 μm. The plated wafer was immersed in an alkali stripping solution at 50 ° C. for 10 minutes to strip the resist. As the alkaline stripping solution, a 10% aqueous solution of Meltex Film Strip 500 was used. The wafer after peeling was observed and judged according to the following rank.
○: No peeling residue on the wafer.
Δ: Ratio of peeling residue around the cylindrical copper wiring is less than 10% in area.
X: The ratio of the peeling residue around the cylindrical copper wiring is 10% or more.
[0043]
[Example 1]
60 parts by weight of a polymer having a methyl methacrylate / methacrylic acid / ethyl acrylate = 55/25/20 wt% and a weight average molecular weight of 200,000, 30 parts by weight of trimethylolpropane triacrylate as a polymerizable monomer, 2, as a photoinitiator, A solution in which 5 parts by weight of 4,5-triarylimidazolyl dimer, 0.05 parts by weight of p, p′-bis (dimethylamino) benzophenone and 100 parts by weight of methyl ethyl ketone as a solvent were mixed and dissolved in a support (16 μm The photosensitive resin laminate (thickness of the photosensitive resin layer: 100 μm) was prepared by applying the film to a polyethylene terephthalate film (thickness) using a bar coater, drying, and covering with a protective film (23 μm thick polyethylene film).
<Evaluation 1>
A chromium layer having a thickness of 2000 angstroms was formed on a 5-inch silicon wafer by an Anelva sputtering apparatus, and a copper layer having a thickness of 2000 angstroms was further formed.
[0044]
The photosensitive resin laminate prepared above was laminated with the laminator AL-70 manufactured by Asahi Kasei while peeling the protective film so that the surface of the photosensitive resin layer was in close contact with the silicon wafer. Laminate roll temperature is 100 ° C, pressure is air pressure 3kg / cm2The speed was 1.5 m / min.
A mask is placed on the wafer laminated with the photosensitive resin laminate, and 200 mJ / cm with a parallel light exposure machine HMW-801 manufactured by Oak Co., Ltd.2Exposed.
[0045]
After peeling off the support, a 1% aqueous sodium carbonate solution at 30 ° C. was sprayed for 120 seconds to develop and remove the photosensitive resin layer in the unexposed portion, thereby forming a resist pattern.
The result of the resolution evaluation A was ◯.
The wafer on which the resist is formed is degreased by immersing it in an acidic cleaner (FRX manufactured by Atotech Japan) at 30 ° C. for 3 minutes, and then electrolyzed in a copper sulfate plating solution (Capper Grease 125 manufactured by Meltex Co., Ltd.) for 6 hours. Copper plated. Current density is 2 A / dm2It was adjusted to become. The height of the copper plating was 90 μm.
The plated wafer was immersed in a 3% aqueous sodium hydroxide solution at 50 ° C. for 10 minutes to remove the resist.
The evaluation of the plating hole was ○.
[0046]
Examples 2-6, Comparative Examples 1-5
A photosensitive resin laminate having the photosensitive resin laminate shown in Tables 1 and 2 was prepared, and an electrolytic copper-plated wiring on the wafer was formed in the same manner as in Example 1. Tables 1 and 2 also show the results of resolution evaluation and plating drilling evaluation.
The meanings of the abbreviations of the photosensitive resin raw materials in Tables 1 and 2 are as follows.
A-1: Polymer having methyl methacrylate / methacrylic acid / ethyl acrylate = 55/25/20 wt% and a weight average molecular weight of 200,000
A-2: Methyl methacrylate / methacrylic acid / styrene / butyl methacrylate = 45/25/20/10 wt% polymer having a weight average molecular weight of 100,000
A-3: Methyl methacrylate / methacrylic acid / styrene / butyl methacrylate / acrylonitrile = 37/22/9/19/13 wt% polymer having a weight average molecular weight of 120,000
B-1: Trimethylolpropane triacrylate
B-2: Trimethylolpropane ethylene oxide 6 mol addition triacrylate
CHThree-CH2-C [CH2-O- (CH2CH2O)2-CO-CH = CH2]Three
B-3: Trimethylolpropane trimethacrylate
B-4: Bis (triethylene glycol methacrylate) polypropylene glycol
CH2= C (CHThree) -CO-O- (CH2CH2O)Three−
-(CH (CHThree) CH2O)12-(CH2CH2O)Three−
-CO-C (CHThree) = CH2
B-5: Nonaethylene glycol diacrylate
CH2= CH-CO-O- (CH2CH2O)9-CO-CH = CH2
B-6: Ethylene oxide addition dimethacrylate of bisphenol A
CH2= C (CHThree) -CO-O- (CH2CH2O)Five−
-Φ-C (CHThree)2-Φ-O- (CH2CH2O)Five−
-CO-C (CHThree) = CH2
(Where φ is the benzene ring)
C-1: p, p'-bis (dimethylamino) benzophenone
C-2: p, p'-bis (diethylamino) benzophenone
C-3: 2- (o-chlorophenyl) -4 · 5-diphenylimidazolyl dimer
C-4: Benzophenone
C-5: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: Irgacure 369, manufactured by Ciba Geigy)
[0047]
<Evaluation 2>
A chromium layer having a thickness of 2000 angstroms was formed on a 5-inch silicon wafer by an Anelva sputtering apparatus, and a copper layer having a thickness of 2000 angstroms was further formed.
The photosensitive resin laminate of Example 1 was laminated thereon by the same method as Example 1.
A mask is placed on the wafer laminated with the photosensitive resin laminate, and 200 mJ / cm with a parallel light exposure machine HMW-801 manufactured by Oak Co., Ltd.2Exposed.
After peeling off the support, a 1% aqueous sodium carbonate solution at 30 ° C. was sprayed for 120 seconds to develop and remove the photosensitive resin layer in the unexposed portion, thereby forming a resist pattern.
[0048]
The result of the resolution evaluation A was ◯.
The wafer on which the resist was formed was degreased by immersing it in an acidic cleaner (FRX manufactured by Atotech Japan) at 30 ° C. for 3 minutes, and then in a solder plating solution (Plutin LA borofluoride solder bath manufactured by Meltex) 4 Time electrolytic solder plating. Current density is 1.5 A / dm2It was adjusted to become. The height of the solder plating was 90 μm.
The plated wafer was immersed in a 3% aqueous sodium hydroxide solution at 50 ° C. for 10 minutes to remove the resist.
The evaluation of the plating hole was ○.
[0049]
[Example 7]
60 parts by weight of a polymer having methyl methacrylate / methacrylic acid / ethyl acrylate = 55/25/20 wt% and a weight average molecular weight of 200,000, 30 parts by weight of trimethylolpropane triacrylate as a polymerizable monomer, 2-hydroxy-3- 10 parts by weight of phenoxypropyl acrylate, 5 parts by weight of 2,4,5-triarylimidazolyl dimer as a photoinitiator, 0.05 part by weight of p, p'-bis (dimethylamino) benzophenone and 100 parts of methyl ethyl ketone as a solvent A solution obtained by mixing and dissolving parts by weight is applied to a support (19 μm thick polyethylene terephthalate film) using a bar coater, dried, and covered with a protective film (30 μm thick polyethylene film) to form a photosensitive resin laminate (photosensitive). The thickness of the conductive resin layer: 120 μm) It was prepared.
[0050]
A chromium layer having a thickness of 2000 angstroms was formed on a 5-inch silicon wafer by sputtering made by Nippon Vacuum, and a copper layer having a thickness of 2000 angstroms was further formed.
The photosensitive resin laminate prepared above was laminated with the laminator AL-70 manufactured by Asahi Kasei while peeling the protective film so that the surface of the photosensitive resin layer was in close contact with the silicon wafer. Laminate roll temperature is 100 ° C, pressure is 3.5kg / cm at air pressure2The speed was 1.0 m / min.
[0051]
A mask was placed on the wafer laminated with the photosensitive resin laminate, and exposed for 11 seconds with Canon Mask Aligner PLA-501F. When the illuminance of the exposure device was measured, it was 6.3 mW / cm.2And is calculated to be 70 mJ / cm2Exposure amount. Immediately after exposure, the wafer was placed in an oven at 80 ° C. and baked after exposure for 2 minutes.
After peeling off the support, paddle development was performed using a 2.38% aqueous tetramethylammonium hydroxide solution at room temperature. The total development time for paddle development was 240 seconds. The unexposed portion of the photosensitive resin layer was developed and removed to form a resist pattern.
[0052]
The result of the resolution evaluation B was “good”.
The wafer on which the resist is formed is degreased by immersing it in an acidic cleaner (FRX manufactured by Atotech Japan) at 30 ° C. for 3 minutes, and then electrolyzed in a copper sulfate plating solution (Capper Grease 125 manufactured by Meltex Co., Ltd.) for 6 hours. Copper plated. Current density is 2 A / dm2It was adjusted to become. The height of the copper plating was 90 μm.
The plated wafer was immersed in a 3% aqueous sodium hydroxide solution at 50 ° C. for 10 minutes to remove the resist.
[0053]
The evaluation of the plating hole was ○.
A mask having a pattern in which dots having a diameter of 150 μm were arranged was placed on a wafer laminated with a photosensitive resin laminate, and exposed for 11 seconds with a mask aligner PLA-501F manufactured by Canon. After peeling off the support, paddle development was performed using a 2.38% aqueous tetramethylammonium hydroxide solution at room temperature. This wafer was subjected to electrolytic copper plating in a copper sulfate plating solution to form a cylindrical copper wiring. The plated wafer was immersed in an alkali stripping solution at 50 ° C. for 10 minutes to strip the resist.
The peelability evaluation of the cured resist was ○.
[0054]
Examples 8 to 10,Examples 1-2, 6]
A photosensitive resin laminate having the photosensitive resin laminate shown in Table 3 was prepared, and an electrolytic copper plating wiring on the wafer was formed in the same manner as in Example 7. Table 3 also shows the results of resolution evaluation, plating peeling evaluation and cured resist peelability evaluation. The meanings of the abbreviations of the photosensitive resin raw materials other than the raw materials described above are as follows.
B-7: 2-hydroxy-3-phenoxypropyl acrylate
B-8: Phenoxyhexaethylene glycol acrylate
B-9: β-hydroxypropyl-β '-(acryloyloxy) propyl phthalate
B-10: 4-Normal octylphenoxypentaethylene glycol tripropylene glycol acrylate
[0055]
[Table 1]
[Table 2]
[Table 3]
【The invention's effect】
As described above, when the photosensitive resin laminate of the first invention of the present application is used, the fine resolution because the resolution is excellent when forming the wiring connecting the chip terminal and the external terminal in the manufacture of the CSP. Wiring can be made, and furthermore, high-quality conductor wiring without plating is obtained in the conductor plating step, which is extremely suitable for manufacturing CSP.
In addition, according to the second invention of the present application, it is possible to obtain a highly reliable circuit that is easy and good in resist stripping after plating and has no stripping residue.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000019857A JP4108243B2 (en) | 1999-04-14 | 2000-01-28 | Photosensitive resin laminate |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11-107200 | 1999-04-14 | ||
| JP10720099 | 1999-04-14 | ||
| JP2000019857A JP4108243B2 (en) | 1999-04-14 | 2000-01-28 | Photosensitive resin laminate |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2000356852A JP2000356852A (en) | 2000-12-26 |
| JP2000356852A5 JP2000356852A5 (en) | 2007-02-08 |
| JP4108243B2 true JP4108243B2 (en) | 2008-06-25 |
Family
ID=26447250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000019857A Expired - Lifetime JP4108243B2 (en) | 1999-04-14 | 2000-01-28 | Photosensitive resin laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4108243B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003057821A (en) * | 2001-08-13 | 2003-02-28 | Showa Highpolymer Co Ltd | Photosensitive resin and photosensitive resin composition |
| CN1273867C (en) * | 2001-11-12 | 2006-09-06 | 旭化成电子材料元件株式会社 | Photosensitive resin composition and applications thereof |
| KR100521999B1 (en) * | 2002-09-03 | 2005-10-18 | 주식회사 코오롱 | Photopolymerizable Resin Composition For Sandblast Resist |
| JP2005031639A (en) * | 2003-06-16 | 2005-02-03 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element using the same, method for fabricating resist pattern, method for manufacturing printed wiring board, printed wiring board and electronic component using the same |
| JP4632117B2 (en) * | 2004-07-27 | 2011-02-16 | 日立化成工業株式会社 | Photosensitive resin composition, photosensitive element using the same, resist pattern manufacturing method, and printed wiring board manufacturing method |
| CN114585974A (en) | 2019-10-16 | 2022-06-03 | 昭和电工材料株式会社 | Photosensitive resin film, method for forming resist pattern, and method for forming wiring pattern |
| WO2022201432A1 (en) | 2021-03-25 | 2022-09-29 | 昭和電工マテリアルズ株式会社 | Photosensitive resin film, resist pattern forming method, and method for forming wiring pattern |
| WO2023238202A1 (en) | 2022-06-06 | 2023-12-14 | 株式会社レゾナック | Photosensitive element and formation method for resist pattern |
-
2000
- 2000-01-28 JP JP2000019857A patent/JP4108243B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000356852A (en) | 2000-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20100159691A1 (en) | Photosensitive resin composition and laminate | |
| JP5215473B2 (en) | Photosensitive resin composition for resist material and photosensitive resin laminate | |
| KR101207242B1 (en) | Layered photosensitive-resin product | |
| JPH11167203A (en) | Photosensitive resin composition and photosensitive element using same | |
| JP4749270B2 (en) | Photosensitive resin composition and laminate | |
| JP5221543B2 (en) | Photosensitive resin composition and laminate thereof | |
| JP5167347B2 (en) | Photosensitive resin composition and laminate thereof | |
| JP4108243B2 (en) | Photosensitive resin laminate | |
| JPWO2015174468A1 (en) | Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method | |
| JP2006234995A (en) | Photopolymerizable resin composition | |
| JP2006234995A5 (en) | ||
| KR101328840B1 (en) | Photosensitive resin composite and laminate thereof | |
| JP4885243B2 (en) | Photosensitive resin composition and laminate | |
| JP5646873B2 (en) | Photosensitive resin composition and laminate thereof | |
| JP4535851B2 (en) | Photopolymerizable resin composition | |
| JP4257106B2 (en) | Photosensitive resin composition and use thereof | |
| JPH07281437A (en) | Photosetting resin laminated body | |
| JP4338819B2 (en) | Photosensitive resin laminate | |
| JP3916605B2 (en) | Photosensitive resin composition and use thereof | |
| JP3782134B2 (en) | Method for manufacturing printed wiring board | |
| JP3267703B2 (en) | New photopolymerizable resin laminate | |
| JP3644731B2 (en) | Novel photocurable resin composition | |
| JP3883540B2 (en) | Photosensitive resin composition and use thereof | |
| JP2690494B2 (en) | Photoresist composition | |
| JP4488601B2 (en) | Photosensitive resin laminate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20061213 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061213 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20061213 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20071205 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080108 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080306 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080401 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080402 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110411 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4108243 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110411 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110411 Year of fee payment: 3 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110411 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110411 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120411 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120411 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130411 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130411 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140411 Year of fee payment: 6 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |