CN117687268A - Photosensitive resin composition, photosensitive dry film and copper-clad plate - Google Patents
Photosensitive resin composition, photosensitive dry film and copper-clad plate Download PDFInfo
- Publication number
- CN117687268A CN117687268A CN202410139831.0A CN202410139831A CN117687268A CN 117687268 A CN117687268 A CN 117687268A CN 202410139831 A CN202410139831 A CN 202410139831A CN 117687268 A CN117687268 A CN 117687268A
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- China
- Prior art keywords
- methyl
- acrylate
- ethylhexyl
- copper
- meth
- Prior art date
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- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052802 copper Inorganic materials 0.000 claims abstract description 60
- 239000010949 copper Substances 0.000 claims abstract description 60
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 230000007797 corrosion Effects 0.000 claims abstract description 35
- 238000005260 corrosion Methods 0.000 claims abstract description 35
- 239000003112 inhibitor Substances 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000013538 functional additive Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- -1 2-ethyl-N- (2-ethylhexyl) -N- ((3-phenyl-1H-pyrazol-1-yl) methyl) hexane-1-amine Chemical compound 0.000 claims description 62
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 39
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- PJAKWOZHTFWTNF-UHFFFAOYSA-N (2-nonylphenyl) prop-2-enoate Chemical compound CCCCCCCCCC1=CC=CC=C1OC(=O)C=C PJAKWOZHTFWTNF-UHFFFAOYSA-N 0.000 claims description 7
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 claims description 6
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 3
- XHXSXTIIDBZEKB-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octamethylanthracene-9,10-dione Chemical compound CC1=C(C)C(C)=C2C(=O)C3=C(C)C(C)=C(C)C(C)=C3C(=O)C2=C1C XHXSXTIIDBZEKB-UHFFFAOYSA-N 0.000 claims description 3
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 claims description 3
- KIJPZYXCIHZVGP-UHFFFAOYSA-N 2,3-dimethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=C(C)C(C)=C2 KIJPZYXCIHZVGP-UHFFFAOYSA-N 0.000 claims description 3
- LZWVPGJPVCYAOC-UHFFFAOYSA-N 2,3-diphenylanthracene-9,10-dione Chemical compound C=1C=CC=CC=1C=1C=C2C(=O)C3=CC=CC=C3C(=O)C2=CC=1C1=CC=CC=C1 LZWVPGJPVCYAOC-UHFFFAOYSA-N 0.000 claims description 3
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 3
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 3
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 3
- ARNIZPSLPHFDED-UHFFFAOYSA-N [4-(dimethylamino)phenyl]-(4-methoxyphenyl)methanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 ARNIZPSLPHFDED-UHFFFAOYSA-N 0.000 claims description 3
- 125000005605 benzo group Chemical group 0.000 claims description 3
- LHMRXAIRPKSGDE-UHFFFAOYSA-N benzo[a]anthracene-7,12-dione Chemical compound C1=CC2=CC=CC=C2C2=C1C(=O)C1=CC=CC=C1C2=O LHMRXAIRPKSGDE-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000539 dimer Substances 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- MOMDHKVDJYHNRF-UHFFFAOYSA-N hexan-1-one Chemical compound CCCCC[C]=O MOMDHKVDJYHNRF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000852 hydrogen donor Substances 0.000 claims description 3
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 229960005235 piperonyl butoxide Drugs 0.000 claims description 3
- 125000004591 piperonyl group Chemical group C(C1=CC=2OCOC2C=C1)* 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 150000003440 styrenes Chemical class 0.000 claims description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 12
- 230000008859 change Effects 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000010410 layer Substances 0.000 description 18
- 238000011161 development Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 230000003796 beauty Effects 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- HKEWOTUTAYJWQJ-UHFFFAOYSA-N 2-(1h-pyrazol-5-yl)pyridine Chemical compound N1N=CC=C1C1=CC=CC=N1 HKEWOTUTAYJWQJ-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
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2h-benzotriazole-5-carboxylic acid Chemical compound C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 description 1
- OEDUIFSDODUDRK-UHFFFAOYSA-N 5-phenyl-1h-pyrazole Chemical compound N1N=CC=C1C1=CC=CC=C1 OEDUIFSDODUDRK-UHFFFAOYSA-N 0.000 description 1
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 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
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 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
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical compound BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
The invention discloses a photosensitive resin composition, a photosensitive dry film and a copper-clad plate, wherein the photosensitive resin composition comprises the following raw material components in percentage by mass: 44-66% of alkali-soluble resin; 30-50% of a photopolymerization monomer; 0.2-5% of a photoinitiator; 3-4% of a functional additive; 0.05-0.5% of copper surface corrosion inhibitor. In the photosensitive resin composition provided by the invention, the five-membered heterocycle of the copper surface corrosion inhibitor plays a synergistic effect with the diisooctyl and the R groups, and the lone pair electrons on the nitrogen atoms in the five-membered heterocycle can coordinate with the copper atoms on the surface of the copper substrate, so that the copper surface is protected from oxidation, the adhesion force between the photosensitive dry film and the copper surface is improved, the color change problem of the copper substrate can be effectively relieved, and meanwhile, excellent water resistance and copper surface binding force of the photosensitive dry film are provided.
Description
Technical Field
The invention relates to the technical field of photosensitive materials, in particular to a photosensitive resin composition, a photosensitive dry film and a copper-clad plate.
Background
Dry film resists are widely used as materials for pattern transfer in printed circuit boards, lead frames, solar cells, conductor packages, BGA (ball grid array), CPS (chip size) packages. Taking a printed circuit board manufacturing process as an example, firstly, a dry film resist (film) is adhered on a copper substrate, and then the dry film resist is covered by a mask with a certain pattern to carry out pattern exposure (exposure); then, the unexposed portions are removed (developed) using a weakly alkaline aqueous solution as a developer, and a resist pattern is formed on the substrate. Etching the substrate with the resist pattern and stripping the resist layer to form a circuit pattern; or electroplating, stripping and removing the resist layer, and etching the metal surface covered by the resist layer to form a circuit pattern, thereby realizing pattern transfer.
In the above manufacturing process, the next process will not be performed immediately after film pasting, and if the dry film and the copper surface are left for too long, an oxide film will be formed on the dry film, which results in the color change of the substrate after development, which affects the subsequent etching process or electroplating process and causes poor processing. In addition, the dry film is in the higher environment of humidity, can appear being invaded by steam, and the steam can influence dry film curing process at follow-up exposure, leads to solidification inadequately, causes the quality problem.
In order to solve the problem of discoloration of the substrate, a compound containing a benzotriazole structure is usually selected to be added, but in the method, the additive is easy to precipitate and pollute the plating solution, and Chinese patent No. 104303106B discloses that the benzotriazole compound is matched with a diamine compound, so that both the prevention of the discoloration of the substrate and the reduction of the pollution of a plating bath are simultaneously realized. The scheme achieves an excellent effect on solving the problem of color change of the substrate, but has the defect of improving the water resistance of the dry film.
Disclosure of Invention
The invention provides a photosensitive resin composition, a photosensitive dry film and a copper-clad plate, which are used for solving the technical problem that the conventional photosensitive resin cannot improve the color change of a copper substrate and improve the water resistance of the photosensitive dry film.
According to one aspect of the present invention, there is provided a photosensitive resin composition comprising the following raw material components in mass percent: 44-66% of alkali-soluble resin; 30-50% of a photopolymerization monomer; 0.2-5% of a photoinitiator; 3-4% of a functional additive; 0.05-0.5% of copper surface corrosion inhibitor, wherein the structural general formula of the copper surface corrosion inhibitor is as follows:
wherein X is 1 Is a nitrogen atom or a carbon atom, when X 1 X is a carbon atom 1 Can be substituted by carboxyl, R is benzene ring, naphthalene ring, piperonyl, pyridine, benzene ring substituted by one selected from chlorine and carboxyl at para position, or benzene ring substituted by methoxy at meta position; when X is 1 When the R group is nitrogen atom, the R group is benzene ring, pyridine or benzene ring substituted by methyl or methoxy.
Further, the photosensitive resin composition comprises the following raw material components in percentage by mass: 56-66% of alkali-soluble resin; 30-48% of a photopolymerization monomer; 0.2-4.7% of photoinitiator; 3-3.5% of a functional additive; 0.05-0.45% of copper surface corrosion inhibitor.
Further, the copper surface corrosion inhibitor comprises 2-ethyl-N- (2-ethylhexyl) -N- ((3-phenyl-1H-pyrazol-1-yl) methyl) hexane-1-amine, N- ((3- (4-chlorophenyl) -1H-pyrazol-1-yl) methyl) -2-ethyl-N- (2-ethylhexyl) hexane-1-amine, 4- (1- ((bis (2-ethylhexyl) amino) methyl) -1H-pyrazol-3-yl) benzoic acid, 1- ((bis (2-ethylhexyl) amino) methyl) -3-phenyl-1H-pyrazole-5-carboxylic acid, 2-ethyl-N- (2-ethylhexyl) -N- ((3- (3-methoxyphenyl) -1H-pyrazol-1-yl) methyl) hexane-1-amine, 2-ethyl-N- (2-ethylhexyl) -N- ((3- (naphthalen-2-yl) -1H-pyrazol-1-yl) methyl) hexane-1-amine, N- ((3- (benzo [ d ] [1,3] dioxol-5-yl) -1H-pyrazol-1-yl) methyl) -2-ethyl-N- (2-ethylhexyl) hexan-1-amine, 2-ethyl-N- (2-ethylhexyl) -N- ((3- (pyridin-2-yl) -1H-pyrazol-1-yl) methyl) hexan-1-amine, 2-ethyl-N- (2-ethylhexyl) -N- ((5-phenyl-2H-tetrazol-2-yl) methyl) hexan-1-amine, 2-ethyl-N- (2-ethylhexyl) -N- ((5- (p-tolyl) -2H-tetrazol-2-yl) methyl) hexan-1-amine, one or more of 2-ethyl-N- (2-ethylhexyl) -N- ((5- (4-methoxyphenyl) -2H-tetrazol-2-yl) methyl) hexan-1-amine and 2-ethyl-N- (2-ethylhexyl) -N- ((5- (pyridin-2-yl) -2H-tetrazol-2-yl) methyl) hexan-1-amine.
Further, the functional additives include one or more of hydrogen donors, dyes, pigments, photo-developers, fillers, plasticizers, stabilizers, coating aids, and release promoters.
Further, the weight average molecular weight of the alkali-soluble resin is 30000-120000, the acid value of the resin is 120-250 mg KOH/g, and the dispersity is 1.0-3.0.
Further, the alkali-soluble resin is formed by copolymerizing two or more of methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, styrene, and a styrene derivative.
Further, the photopolymerizable monomers include one or more of nonylphenol acrylate, ethoxylated (propoxylated) nonylphenol acrylate, bisphenol a di (meth) acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri (meth) acrylate, ethoxylated (propoxylated) trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate, ethoxylated (propoxylated) pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated (propoxylated) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, isobornyl (meth) acrylate, tetrahydrofuranyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate.
Further, the photoinitiator includes 2,4, 5-triarylimidazole dimer and derivatives thereof, thioxanthone, benzoin phenyl ether, benzophenone, benzoin methyl ether, benzoin derivatives such as N, N '-tetramethyl-4, 4' -diaminobenzophenone, N '-tetraethyl-4, 4' -diaminobenzophenone, 4-methoxy-4 '-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1, 2-benzanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2, 3-dimethylanthraquinone, benzoin methyl ether, benzoin phenyl ether, benzoin dimethyl ketal, and the like benzoin derivatives such as 9-phenylacridine, 1, 7-bis (9, 9' -quinacridone compound, pyrazoline compound, and one or more of the coumarin compound.
According to another aspect of the present invention, there is also provided a photosensitive dry film including: and a photosensitive resist layer formed by coating and drying the surface of the PET layer with the photosensitive resin composition.
According to still another aspect of the present invention, there is also provided a copper-clad plate formed by covering the surface of a copper substrate with the photosensitive dry film.
The invention has the following beneficial effects:
according to the photosensitive resin composition provided by the invention, the five-membered heterocycle of the copper surface corrosion inhibitor has the synergistic effect with the diisooctyl and the R groups, and the copper surface corrosion inhibitor can be added to effectively relieve the problem of color change of a copper substrate, and meanwhile, excellent water resistance and copper surface binding force of the photosensitive dry film are provided. The lone pair electrons on the nitrogen atoms in the five-membered heterocycle can coordinate with the copper atoms on the surface of the copper substrate, thereby protecting the copper surface from oxidation and improving the adhesive force between the photosensitive dry film and the copper surface. The number of coordination sites on the structure can be flexibly adjusted by adjusting the number of nitrogen atoms on the five-membered heterocycle and the type of aromatic ring substituent groups or heterocycle on the R group, so that the binding force between the photosensitive dry film added with the five-membered heterocycle and the copper surface can be adjusted. The introduction of the diisooctyl imparts certain hydrophobicity to the photosensitive dry film, and the longer chain length ensures good dispersibility of the copper surface corrosion inhibitor in the photosensitive dry film, so that precipitation is not easy to occur in the subsequent development and electroplating processes.
In addition to the objects, features and advantages described above, the present invention has other objects, features and advantages. The present invention will be described in further detail with reference to the drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a reaction scheme of a copper face corrosion inhibitor D1 according to a preferred embodiment of the present invention;
FIG. 2 is a reaction scheme of a copper face corrosion inhibitor D2 according to a preferred embodiment of the present invention;
FIG. 3 is a reaction scheme of a copper face corrosion inhibitor D3 according to a preferred embodiment of the present invention;
FIG. 4 is a reaction scheme of a copper face corrosion inhibitor D4 of a preferred embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention clearer, the present invention will be further described in detail with reference to examples. It should be understood that the examples described in this specification are for the purpose of illustrating the invention only and are not intended to limit the invention.
For simplicity, only a few numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
In the description herein, unless otherwise indicated, "above" and "below" are intended to include the present number, "one or more" means two or more, and "one or more" means two or more.
An embodiment of the first aspect of the present application provides a photosensitive resin composition, including the following raw material components in percentage by mass: 44-66% of alkali-soluble resin; 30-50% of a photopolymerization monomer; 0.2-5% of a photoinitiator; 3-4% of a functional additive; 0.05-0.5% of copper surface corrosion inhibitor, wherein the structural general formula of the copper surface corrosion inhibitor is as follows:
wherein X is 1 Is a nitrogen atom or a carbon atom, when X 1 X is a carbon atom 1 Can be substituted by carboxyl, R is benzene ring, naphthalene ring, piperonyl, pyridine, benzene ring substituted by one selected from chlorine and carboxyl at para position, or benzene ring substituted by methoxy at meta position; when X is 1 When the R group is nitrogen atom, the R group is benzene ring, pyridine or benzene ring substituted by methyl or methoxy.
In embodiments of the present application, the alkali-soluble resin may be present in an amount of any of 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, or 66% by mass, or any combination thereof.
In embodiments of the present application, the mass percent of the photopolymerizable monomer may be any of 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 48%, 49%, or 50%, or any combination range of the foregoing.
In embodiments of the present application, the photoinitiator may be present in an amount of 0.2%, 0.3%, 0.5%, 0.8%, 1.0%, 1.5%, 1.6%, 1.8%, 2.0%, 2.2%, 2.5%, 2.8%, 3.0%, 3.2%, 3.5%, 3.8%, 4.0%, 4.2%, 4.5%, 4.8%, or 5% by mass, or any combination thereof.
In embodiments of the present application, the copper face corrosion inhibitor may be present in any amount of 0.05%, 0.10%, 0.15%, 0.20%, 0.25%, 0.30%, 0.35%, 0.40%, 0.45%, or 0.5% by mass, or any combination thereof.
In the examples of the present application, the functional additive means an additive which imparts a specific function to the photosensitive resin composition after addition, such as a function of imparting a color, a function of developing a light, a function of stabilizing a property, a function of improving a coating property, and the like.
According to the photosensitive resin composition provided by the embodiment of the invention, the five-membered heterocycle of the copper surface corrosion inhibitor has the synergistic effect with the diisooctyl and the R group, and the copper surface corrosion inhibitor can be added to effectively relieve the problem of color change of a copper substrate, and meanwhile, excellent water resistance and copper surface binding force of the photosensitive dry film are provided. The lone pair electrons on the nitrogen atoms in the five-membered heterocycle can coordinate with the copper atoms on the surface of the copper substrate, thereby protecting the copper surface from oxidation and improving the adhesive force between the photosensitive dry film and the copper surface. The number of coordination sites on the structure can be flexibly adjusted by adjusting the number of nitrogen atoms on the five-membered heterocycle and the type of aromatic ring substituent groups or heterocycle on the R group, so that the binding force between the photosensitive dry film added with the five-membered heterocycle and the copper surface can be adjusted. The introduction of the diisooctyl imparts certain hydrophobicity to the photosensitive dry film, and the longer chain length ensures good dispersibility of the copper surface corrosion inhibitor in the photosensitive dry film, so that precipitation is not easy to occur in the subsequent development and electroplating processes.
In some embodiments, to further optimize the effect of the photosensitive resin composition, the following raw material components are selected in mass percent: 56-66% of alkali-soluble resin; 30-48% of a photopolymerization monomer; 0.2-4.7% of photoinitiator; 3-3.5% of a functional additive; 0.05-0.45% of copper surface corrosion inhibitor.
In some embodiments, the copper-surface corrosion inhibitor comprises 2-ethyl-N- (2-ethylhexyl) -N- ((3-phenyl-1H-pyrazol-1-yl) methyl) hexane-1-amine, N- ((3- (4-chlorophenyl) -1H-pyrazol-1-yl) methyl) -2-ethyl-N- (2-ethylhexyl) hexane-1-amine, 4- (1- ((bis (2-ethylhexyl) amino) methyl) -1H-pyrazol-3-yl) benzoic acid, 1 bis (2-ethylhexyl) amino) methyl) -3-phenyl-1H-pyrazole-5-carboxylic acid, 2-ethyl-N- (2-ethylhexyl) -N- ((3- (3-methoxyphenyl) -1H-pyrazol-1-yl) methyl) hexane-1-amine, 2-ethyl-N- (2-ethylhexyl) -N- ((3- (naphthalen-2-yl) -1H-pyrazol-1-yl) methyl) hexane-1-amine, N- ((3- (benzo [ d ] [1,3] dioxol-5-yl) -1H-pyrazol-1-yl) methyl) -2-ethyl-N- (2-ethylhexyl) hexan-1-amine, 2-ethyl-N- (2-ethylhexyl) -N- ((3- (pyridin-2-yl) -1H-pyrazol-1-yl) methyl) hexan-1-amine, 2-ethyl-N- (2-ethylhexyl) -N- ((5-phenyl-2H-tetrazol-2-yl) methyl) hexan-1-amine, 2-ethyl-N- (2-ethylhexyl) -N- ((5- (p-tolyl) -2H-tetrazol-2-yl) methyl) hexan-1-amine, one or more of 2-ethyl-N- (2-ethylhexyl) -N- ((5- (4-methoxyphenyl) -2H-tetrazol-2-yl) methyl) hexan-1-amine and 2-ethyl-N- (2-ethylhexyl) -N- ((5- (pyridin-2-yl) -2H-tetrazol-2-yl) methyl) hexan-1-amine.
The specific structural formula of the copper surface corrosion inhibitor is as follows:
in some embodiments, the method of synthesizing the copper-surface corrosion inhibitor 2-ethyl-N- (2-ethylhexyl) -N- ((3-phenyl-1H-pyrazol-1-yl) methyl) hexane-1-amine (D1) comprises the following steps (reaction formula shown in fig. 1):
to a 250 mL three-necked flask equipped with a stirring paddle and a reflux condenser under nitrogen protection were successively added 3-phenylpyrazole (50 mmol, 1 eq, 7.2 g), methanol (120 mL), diisooctylamine (55 mmol, 1.1 eq, 13.3 g), 37wt.% aqueous formaldehyde solution (4.85 mL) was added dropwise after stirring for 10 min, after stirring for 1h at room temperature, diethyl ether (20 mL) was added, the temperature was raised to 70 ℃ for reflux reaction 12h, during which sampling TLC was detected, after the reaction was completed, the reaction solution was poured into ice water, extracted with EA, and after the organic phase was concentrated, the product D1 (16.9 g, 85% yield) was obtained by column chromatography purification (eluent PE).
The nmr structure is characterized as follows: 1H NMR (400 MHz, CDCl3, 300K): delta 7.82 (d, J=7.72 Hz, 2H), 7.41-7.35 (m, 3H), 7.28-7.23 (m, 1H), 6.56 (s, 1H), 4.95 (s, 2H), 2.35 (d, J=7.1 Hz, 4H), 1.62-1.55 (m, 2H), 1.45-1.38 (m, 2H), 1.35-1.26 (m, 14H), 0.91-0.85 (m, 12H).
In some embodiments, the method of synthesizing the copper surface corrosion inhibitor 2-ethyl-N- (2-ethylhexyl) -N- ((3- (pyridin-2-yl) -1H-pyrazol-1-yl) methyl) hexane-1-amine (D2) comprises the following steps (reaction formula shown in fig. 2):
to a 250 mL three-necked flask equipped with a stirring paddle and a reflux condenser under nitrogen protection were successively added 2- (1H-pyrazol-3-yl) pyridine (50 mmol, 1 eq, 7.3 g), methanol (120 mL), diisooctylamine (55 mmol, 1.1 eq, 13.3 g), 37wt.% aqueous formaldehyde solution (4.85 mL) was added dropwise after stirring for 10 min, after stirring at room temperature for 1H, diethyl ether (20 mL) was added, and the temperature was raised to 70 ℃ for reflux reaction 12H, during which time TLC detection was sampled, after completion of the reaction, the reaction solution was poured into ice water, extracted with EA, and after concentration of the organic phase, the column chromatography was purified (eluent PE) to obtain product D2 (15.9 g, yield 80%).
The nmr structure is characterized as follows: 1H NMR (400 MHz, CDCl3, 300K): delta 8.58 (d, J=4.6 Hz, 1H), 8.00 (d, J=8.0 Hz, 1H), 7.63 (t, J=7.8 Hz, 1H), 7.44 (d, J=8.4 Hz, 1H), 7.11 (t, J=6.3 Hz, 1H), 6.94 (s, 1H), 4.97 (s, 2H), 2.35 (d, J=7.2 Hz, 4H), 1.68-1.59 (m, 2H), 1.45-1.29 (m, 16H), 0.90-0.85 (m, 12H).
In some embodiments, the method of synthesizing the copper-surface corrosion inhibitor 2-ethyl-N- (2-ethylhexyl) -N- ((5-phenyl-2H-tetrazol-2-yl) methyl) hexane-1-amine (D3) includes the following steps (reaction scheme as shown in fig. 3):
to a 250 mL three-necked flask equipped with a stirring paddle and a reflux condenser under nitrogen protection were successively added 5-phenyltetrazole (50 mmol, 1 eq, 7.3 g), methanol (120 mL), diisooctylamine (55 mmol, 1.1 eq, 13.3 g), 37wt.% aqueous formaldehyde solution (4.85 mL) was added dropwise after stirring for 10 min, after stirring for 1h at room temperature, diethyl ether (20 mL) was added, the temperature was raised to 70 ℃ for reflux reaction 12h, during which sampling TLC detection was performed, after the reaction was completed, the reaction solution was poured into ice water, extracted with EA, and after the organic phase was concentrated, column chromatography was purified (eluent PE) to obtain product D3 (15.2 g, yield 76%).
The nmr structure is characterized as follows: 1H NMR (400 MHz, CDCl3, 300K): delta 8.16 (d, J=7.5 Hz, 2H), 7.46-7.38 (m, 3H), 5.47 (s, 2H), 2.39 (d, J=7.3 Hz, 4H), 1.43-1.24 (m, 18H), 0.90-0.86 (m, 12H).
In some embodiments, the method of synthesizing the copper-surface corrosion inhibitor N- ((1H-benzimidazol-1-yl) methyl) -2-ethyl-N- (2-ethylhexyl) hexane-1-amine (D4) includes the following steps (equation shown in fig. 4):
benzimidazole (50 mmol, 1 eq, 5.9 g), methanol (120 mL), diisooctylamine (55 mmol, 1.1 eq, 13.3 g) and 37wt.% aqueous formaldehyde solution (4.85 mL) were added sequentially to a 250 mL three-port flask equipped with a stirring paddle and a reflux condenser under nitrogen protection, stirred for 10 min, stirred for 1h at room temperature, diethyl ether (20 mL) was added, the temperature was raised to 70 ℃ for reflux reaction 12h, during which time TLC detection was sampled, after the reaction was completed, the reaction solution was poured into ice water, extracted with EA, and the organic phase was concentrated, and purified by column chromatography (eluent PE) to give product D4 (14.9 g, yield 80%).
The nmr structure is characterized as follows: 1H NMR (400 MHz, CDCl3, 300K): delta 7.90 (s, 1H), 7.79-7.77 (m, 1H), 7.44 (d, J=8.5 Hz, 1H), 7.28-7.19 (m, 2H), 4.82 (s, 2H), 2.29 (d, J=7.1 Hz, 4H), 1.51-1.45 (m, 2H), 1.34-1.19 (m, 16H), 0.87 (t, J=7.0 Hz, 6H), 0.80 (t, J=7.4 Hz, 6H).
In some embodiments, the functional additives include one or more of hydrogen donors, dyes, pigments, photo-developers, fillers, plasticizers, stabilizers, coating aids, and release promoters.
In some embodiments, the alkali-soluble resin has a weight average molecular weight of 30000-120000, a resin acid value of 120-250 mg KOH/g, and a dispersity of 1.0-3.0.
According to the embodiments of the present application, the alkali-soluble resin has a weight average molecular weight of 30000 to 120000, and when the weight average molecular weight is less than 30000, the resist pattern tends to be low in development resistance, and when the weight average molecular weight is more than 120000, the development time tends to be long. In terms of balancing the alkali developability and the adhesion of the resist pattern, the acid value of the resin of the alkali-soluble resin is 120 to 250mg KOH/g, and when the acid value is less than 120mgKOH/g, the development time tends to be long, and when the acid value is more than 250mgKOH/g, the development resistance of the photosensitive layer after the photo-curing after exposure tends to be lowered, and the adhesion of the resist pattern tends to be deteriorated. The dispersion degree of the alkali-soluble resin is 1.0 to 3.0, more preferably 1.0 to 2.0. If the dispersity exceeds 3.0, the adhesiveness and resolution tend to be lowered.
In the examples of the present application, the alkali-soluble resin is formed by copolymerizing two or more of methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, styrene, and a styrene derivative.
In embodiments of the present application, the photopolymerizable monomers include one or more of nonylphenol acrylate, ethoxylated (propoxylated) nonylphenol acrylate, bisphenol a di (meth) acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri (meth) acrylate, ethoxylated (propoxylated) trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate, ethoxylated (propoxylated) pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated (propoxylated) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, isobornyl (meth) acrylate, tetrahydrofuranyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate.
In embodiments of the present application, the photoinitiator includes 2,4, 5-triarylimidazole dimer and derivatives thereof, thioxanthone, benzoin phenyl ether, benzophenone, benzoin methyl ether, N '-tetramethyl-4, 4' -diaminobenzophenone, N '-tetraethyl-4, 4' -diaminobenzophenone, 4-methoxy-4 '-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1, 2-benzanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2, 3-dimethylanthraquinone, benzoin methyl ether, benzoin diethyl ether, benzoin dimethyl ketal, and the like benzoin derivatives, 9-phenylacridone, 1, 7-di (9, 9' -acridinyl) heptane, pyrazoline compounds, and oxazoline compounds.
An embodiment of the second aspect of the present application provides a photosensitive dry film comprising a PET support layer and a photosensitive resist layer, wherein the photosensitive resist layer is prepared by coating the above photosensitive resin composition on the surface of the PET support film by a coater and drying. In some embodiments, a PE protective layer may be provided on the surface of the photoresist layer for better protection of the photoresist layer.
An embodiment of a third aspect of the present application provides a copper-clad plate, which is formed by covering the photosensitive dry film on the surface of a copper substrate. According to the embodiment of the application, the photosensitive resist in the copper-clad plate has good water resistance and copper surface binding force, so that the color change problem of the copper substrate is effectively relieved.
Examples
The following examples more particularly describe the disclosure of the present application, which are intended as illustrative only, since numerous modifications and variations within the scope of the disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Preparing a photosensitive dry film:
the materials of examples 1 to 9 and comparative examples 1 to 4 listed in table 1 were mixed uniformly, respectively, to prepare photosensitive resin compositions. Subsequently, they were each coated on a 15 μm thick PET support film surface using a coater (model: AB4220, manufactured by the Netherlands TQC company). Baking at 80℃for 10 minutes gave a photosensitive layer having a thickness of 38. Mu.m. And finally, covering a PE film on the surface of the photosensitive layer for protection, and completing the preparation of the photosensitive dry film.
Table 1 Components of examples 1 to 9 and comparative examples 1 to 4
Note that: in Table 1, the weight is calculated as the solid content, and the solvent content is not calculated as the total content of the composition (the mass percentage of the solvent is calculated by taking the solvent as a molecule and the composition as a denominator).
The components of the code numbers of each component in table 1 are as follows:
alkali-soluble resin (a):
a1, an acrylic ester copolymer, a solution polymerization method, wherein methacrylic acid/methyl methacrylate/ethyl acrylate/butyl methacrylate= 24/41/25/10 are polymerized according to the mass ratio; the solvent was acetone, the solid content was 46%, the weight average molecular weight was 70000, and the acid value was 156mgKOH/g. (Hunan original New Material Co., ltd.).
Photopolymerization monomer (B):
b1, ethoxylated bisphenol A dimethacrylate, number of groups: 10 (beauty source specialty chemical);
b2. ethoxylated bisphenol a dimethacrylate, number of groups: 30 (beauty source specialty chemical);
b3: ethoxylated nonylphenol acrylate, number of groups: 8 (beauty source special chemical industry);
b4: polyethylene glycol (300) diacrylate (beauty source special chemical);
b5-ethoxylated trimethylolpropane triacrylate, number of groups: 6 (beauty source special chemical industry);
b6, pentaerythritol tetraacrylate (beauty source special chemical industry).
Photoinitiator (C):
c1:9-phenylacridine (An Naiji chemistry);
c2, N '-tetraethyl-4, 4' -diaminobenzophenone (An Naiji chemistry);
c3:2, 2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole (An Naiji chemical).
Copper surface corrosion inhibitor (D):
D1:2-ethyl-N- (2-ethylhexyl) -N- ((3-phenyl-1H-pyrazol-1-yl) methyl) hexan-1-amine;
d2. synthesizing copper surface corrosion inhibitor 2-ethyl-N- (2-ethylhexyl) -N- ((3- (pyridin-2-yl) -1H-pyrazol-1-yl) methyl) hexane-1-amine;
d3. synthesizing copper surface corrosion inhibitor 2-ethyl-N- (2-ethylhexyl) -N- ((5-phenyl-2H-tetrazol-2-yl) methyl) hexane-1-amine;
D4N- ((1H-benzimidazol-1-yl) methyl) -2-ethyl-N- (2-ethylhexyl) hexan-1-amine;
d5:1H-benzotriazole (An Naiji chemistry);
d6:5-carboxybenzotriazole (An Naiji chemical).
Additive (E):
e1-leuco crystal violet (An Naiji chemistry);
E2:N-phenylglycine (An Naiji chemistry);
e3 malachite green (An Naiji chemistry);
e4, tribromomethylphenyl sulfone (An Naiji chemistry);
e5: para-toluene sulfonamide (An Naiji chemistry).
Preparing a photosensitive dry film:
the materials of examples 1 to 5 and comparative examples 1 to 4 listed in Table 1 were mixed uniformly, respectively, to prepare photosensitive resin compositions. Subsequently, they were each coated on a 15 μm thick PET support film surface using a coater (model: AB4220, manufactured by the Netherlands TQC company). Baking at 80℃for 10 minutes gave a photosensitive layer having a thickness of 38. Mu.m. And finally, covering a PE film on the surface of the photosensitive layer for protection, and completing the preparation of the photosensitive dry film.
Film sticking process:
the copper substrate laminated with 35 μm thick rolled 1.2. 1.2 mm thick copper foil was subjected to surface treatment such as polishing, microetching, water washing, and wiping, and then preheated to 80 ℃. The film sticking machine is set at 110 ℃, the air pressure is 0.35 MPa, the laminating speed is 1.5m/min, the PE protective films on the surfaces of the photosensitive dry films obtained in the examples and the comparative examples are removed, and then the photosensitive resin composition is laminated on a copper substrate to obtain a film sticking test substrate.
Exposure procedure:
after film pasting, the sample is kept stand for 20min, an exposure machine (model: MAS-04L10-8, core size, main wavelength 405 nm) is used for exposure, a Stouffer 41-stage exposure ruler is used for carrying out a sensitivity test, and the number of exposure grids is controlled to be 18-22 grids.
Developing:
the sample was allowed to stand for 20 minutes or longer after exposure, the PET support film was peeled off, and developed using an alkali developer (manufactured by Julon printing Board Equipment Co., ltd., guangzhou Co., ltd.) and sprayed with 1wt% Na at 30℃for 2 times the minimum development time 2 CO 3 The aqueous solution was developed, washed with water, and dried to obtain a substrate having a cured film for evaluation. The minimum development time is taken as the minimum time required for the unexposed resist layer to be completely washed out in the development tank section.
Evaluation items:
1. sensitivity evaluation
And placing a Stouffer 41-stage exposure ruler on the test substrate after film pasting to perform sensitivity test. After the exposure process, the test substrate was left to stand for 20 minutes or more, then the PET film layer was peeled off, and a 1.0wt% aqueous sodium carbonate solution was sprayed at 30 ℃ to remove the unexposed resist layer, with a development time 2.0 times the minimum development time. After the above operation, a cured film obtained by curing the photosensitive resin composition is formed on the substrate surface. When the number of remaining stages of the step exposure rule obtained by curing the film is 20Exposure energy (mJ/cm) 2 ) The photosensitivity of the photosensitive resin composition was evaluated, and a smaller value indicates a better photosensitivity.
2. Evaluation of adhesion
On the test substrate after the film deposition, exposure was performed by using photomask data having a wiring pattern with a line width/space width of n:400 (unit: μm) so that the number of remaining stages after the development of the Stouffer41 stage exposure rule became 20. After the development process, the resist pattern was observed with an optical microscope, and the adhesion (μm) was evaluated using the value of the minimum line width at which the complete cured resist line was formed as the adhesion value. The smaller the number, the better the adhesion.
3. Resolution evaluation
On the test substrate after the film deposition, exposure was performed by using photomask data having a wiring pattern with a line width/space width of n: n (unit: μm) so that the number of remaining stages after the development of the Stouffer41 stage exposure rule became 20. After the development process, the resist pattern was observed with an optical microscope, and the adhesion (μm) was evaluated using the value of the minimum line width at which the complete cured resist line was formed as the adhesion value. The smaller the value, the better the resolution.
4. Evaluation of discoloration of substrate
Attaching the prepared photosensitive dry film to a copper substrate, covering half area of the copper substrate to prepare a test substrate, placing the test substrate in a constant temperature and humidity box under the condition of 30 ℃ and 90% RH, placing for 12h, 24h, 36h and 48h, taking out, developing, observing the color difference between the copper substrate attached with the photosensitive dry film and the unattached part, and grading according to the following modes:
● No color change
O is changed into pale reddish brown
■ Turn into reddish brown
And ∈10 turns brown
5. Evaluation of Water resistance of photosensitive Dry film
Dropping water drops on the test substrate after film sticking, standing for 12h, then exposing, developing, observing the film surface condition after development, observing the line condition of the positions of the water drops by using a microscope, classifying in the following way
The film surface has no watermark, and the circuit is normal
The delta film surface has slight watermark and the circuit is slightly abnormal
The film surface has obvious watermark and abnormal line
The above test results are summarized in table 2 below.
Table 2 experimental results of examples and comparative examples
From the results of comparative examples 1 to 9 and comparative examples 1 to 4, the following conclusions can be drawn: the copper surface corrosion inhibitor can effectively solve the problem of color change of a substrate and improve the water resistance of a photosensitive dry film. Further observing the results of examples 1-4, it was found that increasing the number of coordination points on the copper surface corrosion inhibitor structure can further improve the capability of solving the discoloration of the substrate (the number of coordination points is determined by the number of N atoms in the structural formula, and the number of coordination points is increased if the number of N atoms is increased), and the adhesion and resolution of the photosensitive dry film are increased to some extent. Comparative examples 2 to 4, although solving the discoloration of the substrate to some extent, had limited effects, but had no effect in improving the water resistance of the dry film.
While the present application has been described with reference to a preferred embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the present application, and in particular, the technical features mentioned in the various embodiments may be combined in any manner as long as there is no structural conflict. The present application is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.
Claims (10)
1. The photosensitive resin composition is characterized by comprising the following raw material components in percentage by mass: 44-66% of alkali-soluble resin; 30-50% of a photopolymerization monomer; 0.2-5% of a photoinitiator; 3-4% of a functional additive; 0.05-0.5% of copper surface corrosion inhibitor; wherein, the structural general formula of the copper surface corrosion inhibitor is as follows:
wherein X is 1 Is a nitrogen atom or a carbon atom, when X 1 X is a carbon atom 1 Can be substituted by carboxyl, R is benzene ring, naphthalene ring, piperonyl, pyridine, benzene ring substituted by one selected from chlorine and carboxyl at para position, or benzene ring substituted by methoxy at meta position; when X is 1 When the R group is nitrogen atom, the R group is benzene ring, pyridine or benzene ring substituted by methyl or methoxy.
2. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition comprises the following raw material components in percentage by mass: 56-66% of alkali-soluble resin; 30-48% of a photopolymerization monomer; 0.2-4.7% of photoinitiator; 3-3.5% of a functional additive; 0.05-0.45% of copper surface corrosion inhibitor.
3. The photosensitive resin composition of claim 1, wherein the copper-side corrosion inhibitor comprises 2-ethyl-N- (2-ethylhexyl) -N- ((3-phenyl-1H-pyrazol-1-yl) methyl) hexane-1-amine, N- ((3- (4-chlorophenyl) -1H-pyrazol-1-yl) methyl) -2-ethyl-N- (2-ethylhexyl) hexane-1-amine, 4- (1- ((bis (2-ethylhexyl) amino) methyl) -1H-pyrazol-3-yl) benzoic acid, 1- ((bis (2-ethylhexyl) amino) methyl) -3-phenyl-1H-pyrazole-5-carboxylic acid, 2-ethyl-N- (2-ethylhexyl) -N- ((3- (3-methoxyphenyl) -1H-pyrazol-1-yl) methyl) hexane-1-amine, 2-ethyl-N- (2-ethylhexyl) -N- ((3- (naphthalen-2-yl) -1H-pyrazol-1-yl) methyl) hexane-1-amine, N- ((3- (benzo [ d ] [1,3] dioxol-5-yl) -1H-pyrazol-1-yl) methyl) -2-ethyl-N- (2-ethylhexyl) hexan-1-amine, 2-ethyl-N- (2-ethylhexyl) -N- ((3- (pyridin-2-yl) -1H-pyrazol-1-yl) methyl) hexan-1-amine, 2-ethyl-N- (2-ethylhexyl) -N- ((5-phenyl-2H-tetrazol-2-yl) methyl) hexan-1-amine, 2-ethyl-N- (2-ethylhexyl) -N- ((5- (p-tolyl) -2H-tetrazol-2-yl) methyl) hexan-1-amine, one or more of 2-ethyl-N- (2-ethylhexyl) -N- ((5- (4-methoxyphenyl) -2H-tetrazol-2-yl) methyl) hexan-1-amine and 2-ethyl-N- (2-ethylhexyl) -N- ((5- (pyridin-2-yl) -2H-tetrazol-2-yl) methyl) hexan-1-amine.
4. The photosensitive resin composition according to claim 1 or 2, wherein the functional additive comprises one or more of a hydrogen donor, a dye, a pigment, a photo-developer, a filler, a plasticizer, a stabilizer, a coating aid, and a peeling accelerator.
5. The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin has a weight average molecular weight of 30000 to 120000, a resin acid value of 120 to 250mg KOH/g, and a dispersity of 1.0 to 3.0.
6. The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin is formed by copolymerizing two or more of methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, styrene, and a styrene derivative.
7. The photosensitive resin composition of claim 1 or 2, wherein the photopolymerizable monomer comprises one or more of nonylphenol acrylate, ethoxylated (propoxylated) nonylphenol acrylate, bisphenol a di (meth) acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri (meth) acrylate, ethoxylated (propoxylated) trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate, ethoxylated (propoxylated) pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated (propoxylated) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, isobornyl (meth) acrylate, tetrahydrofuran (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate.
8. The photosensitive resin composition according to claim 1 or 2, wherein the photoinitiator comprises 2,4, 5-triarylimidazole dimer and its derivative, thioxanthone, benzoin phenyl ether, benzophenone, benzoin methyl ether, N '-tetramethyl-4, 4' -diaminobenzophenone, N '-tetraethyl-4, 4' -diaminobenzophenone, 4-methoxy-4 '-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2, 3-dimethylanthraquinone, benzoin methyl ether, benzoin phenyl ether, benzil dimethyl, benzil and other benzil derivatives, 9-phenylacridine, 1, 7-diacetone, 9' -pyrazoline, and one or more of the like.
9. A photosensitive dry film, characterized in that the photosensitive dry film comprises: a PET layer, and a photosensitive resist layer formed by coating and drying the photosensitive resin composition according to any one of claims 1 to 8 on the surface of the PET layer.
10. A copper-clad plate characterized by being formed by covering the photosensitive dry film of claim 9 on the surface of a copper substrate.
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