CN110357989B - Tertiary amine photosensitizer, preparation method thereof, photosensitive resin composition containing tertiary amine photosensitizer and application of photosensitive resin composition - Google Patents
Tertiary amine photosensitizer, preparation method thereof, photosensitive resin composition containing tertiary amine photosensitizer and application of photosensitive resin composition Download PDFInfo
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- CN110357989B CN110357989B CN201810322343.8A CN201810322343A CN110357989B CN 110357989 B CN110357989 B CN 110357989B CN 201810322343 A CN201810322343 A CN 201810322343A CN 110357989 B CN110357989 B CN 110357989B
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- Prior art keywords
- photosensitive resin
- acridine
- meth
- resin composition
- acrylate
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- 239000011342 resin composition Substances 0.000 title claims abstract description 81
- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 44
- 150000003512 tertiary amines Chemical class 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 22
- MKZHJJQCUIZEDE-UHFFFAOYSA-N 1-[(2-hydroxy-3-naphthalen-1-yloxypropyl)-propan-2-ylamino]-3-naphthalen-1-yloxypropan-2-ol Chemical compound C1=CC=C2C(OCC(O)CN(CC(O)COC=3C4=CC=CC=C4C=CC=3)C(C)C)=CC=CC2=C1 MKZHJJQCUIZEDE-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 80
- -1 2-hydroxypropyl Chemical group 0.000 claims description 50
- 239000000178 monomer Substances 0.000 claims description 38
- 229920000642 polymer Polymers 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical compound C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 claims description 24
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 18
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 229920000058 polyacrylate Polymers 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000005864 Sulphur Chemical group 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 150000001251 acridines Chemical class 0.000 claims description 9
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 claims description 7
- 238000005530 etching Methods 0.000 claims description 7
- YDTZWEXADJYOBJ-UHFFFAOYSA-N 9-(7-acridin-9-ylheptyl)acridine Chemical compound C1=CC=C2C(CCCCCCCC=3C4=CC=CC=C4N=C4C=CC=CC4=3)=C(C=CC=C3)C3=NC2=C1 YDTZWEXADJYOBJ-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-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
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000012965 benzophenone Substances 0.000 claims description 5
- 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 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- CYPATAPWKWHTFV-UHFFFAOYSA-N 9-(3-butylphenyl)acridine Chemical compound CCCCC1=CC=CC(C=2C3=CC=CC=C3N=C3C=CC=CC3=2)=C1 CYPATAPWKWHTFV-UHFFFAOYSA-N 0.000 claims description 4
- KGWGFYSRASGBKP-UHFFFAOYSA-N 9-(4-bromophenyl)acridine Chemical compound C1=CC(Br)=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 KGWGFYSRASGBKP-UHFFFAOYSA-N 0.000 claims description 4
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- LRMDXTVKVHKWEK-UHFFFAOYSA-N 1,2-diaminoanthracene-9,10-dione Chemical group C1=CC=C2C(=O)C3=C(N)C(N)=CC=C3C(=O)C2=C1 LRMDXTVKVHKWEK-UHFFFAOYSA-N 0.000 claims description 3
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 3
- YWUGWLNBQIOMHO-UHFFFAOYSA-N 1-(3-acridin-9-ylphenyl)ethanone Chemical compound CC(=O)C1=CC=CC(C=2C3=CC=CC=C3N=C3C=CC=CC3=2)=C1 YWUGWLNBQIOMHO-UHFFFAOYSA-N 0.000 claims description 3
- LEHKKZRCBHDAEI-UHFFFAOYSA-N 1-(4-acridin-9-ylphenyl)ethanone Chemical compound C1=CC(C(=O)C)=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 LEHKKZRCBHDAEI-UHFFFAOYSA-N 0.000 claims description 3
- GZGOUGNVUQIJJG-UHFFFAOYSA-N 1-phenylbenzo[a]acridine Chemical compound C1(=CC=CC=C1)C1=CC=CC=2C=CC=3N=C4C=CC=CC4=CC=3C=21 GZGOUGNVUQIJJG-UHFFFAOYSA-N 0.000 claims description 3
- 125000001617 2,3-dimethoxy phenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C(OC([H])([H])[H])=C1[H] 0.000 claims description 3
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 claims description 3
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 3
- 125000005809 3,4,5-trimethoxyphenyl group Chemical group [H]C1=C(OC([H])([H])[H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 claims description 3
- GKOIZIJVSXORSJ-UHFFFAOYSA-N 3-acridin-9-yl-n,n-diethylaniline Chemical compound CCN(CC)C1=CC=CC(C=2C3=CC=CC=C3N=C3C=CC=CC3=2)=C1 GKOIZIJVSXORSJ-UHFFFAOYSA-N 0.000 claims description 3
- YSWZNKFDSSGXIS-UHFFFAOYSA-N 3-acridin-9-yl-n,n-dimethylaniline Chemical compound CN(C)C1=CC=CC(C=2C3=CC=CC=C3N=C3C=CC=CC3=2)=C1 YSWZNKFDSSGXIS-UHFFFAOYSA-N 0.000 claims description 3
- CJCNCXPDKKIMNX-UHFFFAOYSA-N 3-acridin-9-ylbenzonitrile Chemical compound N#CC1=CC=CC(C=2C3=CC=CC=C3N=C3C=CC=CC3=2)=C1 CJCNCXPDKKIMNX-UHFFFAOYSA-N 0.000 claims description 3
- WNLBSXDSYUMNDJ-UHFFFAOYSA-N 4-acridin-9-yl-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 WNLBSXDSYUMNDJ-UHFFFAOYSA-N 0.000 claims description 3
- BJUZAWLLCOKWGO-UHFFFAOYSA-N 4-acridin-9-ylbenzonitrile Chemical compound C1=CC(C#N)=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 BJUZAWLLCOKWGO-UHFFFAOYSA-N 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 3
- VJCPYDVHUJPWDY-UHFFFAOYSA-N 9-(2-chloroethoxy)acridine Chemical compound C1=CC=C2C(OCCCl)=C(C=CC=C3)C3=NC2=C1 VJCPYDVHUJPWDY-UHFFFAOYSA-N 0.000 claims description 3
- WXKYFUDFQSTRHX-UHFFFAOYSA-N 9-(3-bromophenyl)acridine Chemical compound BrC1=CC=CC(C=2C3=CC=CC=C3N=C3C=CC=CC3=2)=C1 WXKYFUDFQSTRHX-UHFFFAOYSA-N 0.000 claims description 3
- KTPOHTDATNALFV-UHFFFAOYSA-N 9-(3-chlorophenyl)acridine Chemical compound ClC1=CC=CC(C=2C3=CC=CC=C3N=C3C=CC=CC3=2)=C1 KTPOHTDATNALFV-UHFFFAOYSA-N 0.000 claims description 3
- VJGXNHAKTHFWKE-UHFFFAOYSA-N 9-(3-ethoxyphenyl)acridine Chemical compound CCOC1=CC=CC(C=2C3=CC=CC=C3N=C3C=CC=CC3=2)=C1 VJGXNHAKTHFWKE-UHFFFAOYSA-N 0.000 claims description 3
- ZRODAHDDPILBSK-UHFFFAOYSA-N 9-(3-methoxyphenyl)acridine Chemical compound COC1=CC=CC(C=2C3=CC=CC=C3N=C3C=CC=CC3=2)=C1 ZRODAHDDPILBSK-UHFFFAOYSA-N 0.000 claims description 3
- DOGGTYYFTFGYQM-UHFFFAOYSA-N 9-(3-methylphenyl)acridine Chemical compound CC1=CC=CC(C=2C3=CC=CC=C3N=C3C=CC=CC3=2)=C1 DOGGTYYFTFGYQM-UHFFFAOYSA-N 0.000 claims description 3
- YVQFMSIAMGCKOK-UHFFFAOYSA-N 9-(3-propan-2-ylphenyl)acridine Chemical compound CC(C)C1=CC=CC(C=2C3=CC=CC=C3N=C3C=CC=CC3=2)=C1 YVQFMSIAMGCKOK-UHFFFAOYSA-N 0.000 claims description 3
- SSRIAPNARMCGDT-UHFFFAOYSA-N 9-(3-propylphenyl)acridine Chemical compound CCCC1=CC=CC(C=2C3=CC=CC=C3N=C3C=CC=CC3=2)=C1 SSRIAPNARMCGDT-UHFFFAOYSA-N 0.000 claims description 3
- BEMKEPNSCSVFMZ-UHFFFAOYSA-N 9-(3-tert-butylphenyl)acridine Chemical compound CC(C)(C)C1=CC=CC(C=2C3=CC=CC=C3N=C3C=CC=CC3=2)=C1 BEMKEPNSCSVFMZ-UHFFFAOYSA-N 0.000 claims description 3
- IEFIKULVPIMIPQ-UHFFFAOYSA-N 9-(4-butylphenyl)acridine Chemical compound C1=CC(CCCC)=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 IEFIKULVPIMIPQ-UHFFFAOYSA-N 0.000 claims description 3
- VZRCSQXNWRZMAR-UHFFFAOYSA-N 9-(4-chlorophenyl)acridine Chemical compound C1=CC(Cl)=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 VZRCSQXNWRZMAR-UHFFFAOYSA-N 0.000 claims description 3
- HANIQCCYEOXWSU-UHFFFAOYSA-N 9-(4-ethoxyphenyl)acridine Chemical compound C1=CC(OCC)=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 HANIQCCYEOXWSU-UHFFFAOYSA-N 0.000 claims description 3
- RZALXPATCFPFDA-UHFFFAOYSA-N 9-(4-ethylphenyl)acridine Chemical compound C1=CC(CC)=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 RZALXPATCFPFDA-UHFFFAOYSA-N 0.000 claims description 3
- MQMCZRZPDPSXTD-UHFFFAOYSA-N 9-(4-methoxyphenyl)acridine Chemical compound C1=CC(OC)=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MQMCZRZPDPSXTD-UHFFFAOYSA-N 0.000 claims description 3
- OALXUIAACCQZQP-UHFFFAOYSA-N 9-(4-propan-2-ylphenyl)acridine Chemical compound C1=CC(C(C)C)=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 OALXUIAACCQZQP-UHFFFAOYSA-N 0.000 claims description 3
- UMXFXGSHCWIHKN-UHFFFAOYSA-N 9-(4-propylphenyl)acridine Chemical compound C1=CC(CCC)=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 UMXFXGSHCWIHKN-UHFFFAOYSA-N 0.000 claims description 3
- IANFMESFDABWRB-UHFFFAOYSA-N 9-(4-tert-butylphenyl)acridine Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 IANFMESFDABWRB-UHFFFAOYSA-N 0.000 claims description 3
- CVPHOGZTLPMGBU-UHFFFAOYSA-N 9-ethylacridine Chemical compound C1=CC=C2C(CC)=C(C=CC=C3)C3=NC2=C1 CVPHOGZTLPMGBU-UHFFFAOYSA-N 0.000 claims description 3
- FLDRLXJNISEWNZ-UHFFFAOYSA-N 9-methylacridine Chemical compound C1=CC=C2C(C)=C(C=CC=C3)C3=NC2=C1 FLDRLXJNISEWNZ-UHFFFAOYSA-N 0.000 claims description 3
- REIHTKGNTQFKOQ-UHFFFAOYSA-N 9-propan-2-yloxyacridine Chemical compound C1=CC=C2C(OC(C)C)=C(C=CC=C3)C3=NC2=C1 REIHTKGNTQFKOQ-UHFFFAOYSA-N 0.000 claims description 3
- ZSGMOQYDNJRFDX-UHFFFAOYSA-N 9-propylacridine Chemical compound C1=CC=C2C(CCC)=C(C=CC=C3)C3=NC2=C1 ZSGMOQYDNJRFDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- ZYDPIQPABGIROU-UHFFFAOYSA-N [3-(dimethylamino)phenyl]-(4-methoxyphenyl)methanone Chemical compound CN(C=1C=C(C=CC=1)C(=O)C1=CC=C(C=C1)OC)C ZYDPIQPABGIROU-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
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000008365 aromatic ketones Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000847 nonoxynol Polymers 0.000 claims description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000003918 triazines Chemical class 0.000 claims description 3
- DMEUUKUNSVFYAA-UHFFFAOYSA-N trinaphthalen-1-ylphosphane Chemical compound C1=CC=C2C(P(C=3C4=CC=CC=C4C=CC=3)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 DMEUUKUNSVFYAA-UHFFFAOYSA-N 0.000 claims description 3
- GIIXTFIYICRGMZ-UHFFFAOYSA-N tris(2,3-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(P(C=2C(=C(C)C=CC=2)C)C=2C(=C(C)C=CC=2)C)=C1C GIIXTFIYICRGMZ-UHFFFAOYSA-N 0.000 claims description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 2
- SANDMWGTFWJWOL-UHFFFAOYSA-N 2-(methoxyamino)-2-phenylacetic acid Chemical compound CONC(C(O)=O)C1=CC=CC=C1 SANDMWGTFWJWOL-UHFFFAOYSA-N 0.000 claims description 2
- CFNMUZCFSDMZPQ-GHXNOFRVSA-N 7-[(z)-3-methyl-4-(4-methyl-5-oxo-2h-furan-2-yl)but-2-enoxy]chromen-2-one Chemical compound C=1C=C2C=CC(=O)OC2=CC=1OC/C=C(/C)CC1OC(=O)C(C)=C1 CFNMUZCFSDMZPQ-GHXNOFRVSA-N 0.000 claims description 2
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims description 2
- HDLFSWMFFDMLRQ-UHFFFAOYSA-N 9-propan-2-ylacridine Chemical compound C1=CC=C2C(C(C)C)=C(C=CC=C3)C3=NC2=C1 HDLFSWMFFDMLRQ-UHFFFAOYSA-N 0.000 claims description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004056 anthraquinones Chemical class 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- GZWRQDVFLUPFCI-UHFFFAOYSA-N butyl 2-anilinoacetate Chemical compound CCCCOC(=O)CNC1=CC=CC=C1 GZWRQDVFLUPFCI-UHFFFAOYSA-N 0.000 claims description 2
- RFCHXXFHULMCDW-UHFFFAOYSA-N ethyl 2-(4-methylanilino)acetate Chemical compound CCOC(=O)CNC1=CC=C(C)C=C1 RFCHXXFHULMCDW-UHFFFAOYSA-N 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 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 claims 2
- 238000000034 method Methods 0.000 abstract description 22
- 230000035945 sensitivity Effects 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002244 precipitate Substances 0.000 abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 12
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 12
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 238000004128 high performance liquid chromatography Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 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
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- JJVKJJNCIILLRP-UHFFFAOYSA-N 2-ethyl-6-methylaniline Chemical compound CCC1=CC=CC(C)=C1N JJVKJJNCIILLRP-UHFFFAOYSA-N 0.000 description 2
- AKHRGCACVSPHGC-UHFFFAOYSA-N 4-acridin-9-ylphenol Chemical compound Oc1ccc(cc1)-c1c2ccccc2nc2ccccc12 AKHRGCACVSPHGC-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-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
- 239000004698 Polyethylene Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229940027998 antiseptic and disinfectant acridine derivative Drugs 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 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
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- GJCXHYNLSNVSQZ-UHFFFAOYSA-L [Cu](Cl)Cl.Cl Chemical compound [Cu](Cl)Cl.Cl GJCXHYNLSNVSQZ-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 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
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- IQUGDGIIAQZHGL-UHFFFAOYSA-L iron(2+);dichloride;hydrochloride Chemical compound Cl.[Cl-].[Cl-].[Fe+2] IQUGDGIIAQZHGL-UHFFFAOYSA-L 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000002386 leaching Methods 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
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 238000012719 thermal polymerization Methods 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
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
Abstract
The invention discloses a tertiary amine photosensitizer, a preparation method thereof, a photosensitive resin composition containing the tertiary amine photosensitizer and application of the photosensitive resin composition. The tertiary amine photosensitizer at least contains a tertiary amine derivative shown in a general formula (I);
Description
Technical Field
The invention relates to the technical field of photosensitive materials, in particular to a tertiary amine photosensitizer, a preparation method thereof, a photosensitive resin composition containing the tertiary amine photosensitizer and application of the photosensitive resin composition.
Background
In recent years, printed wiring boards have been produced by photolithography, which is a method of forming a conductor pattern on a substrate by applying a photosensitive resin composition to the substrate, pattern-exposing the photosensitive resin composition to polymerize and cure the exposed portion of the photosensitive resin composition, removing the unexposed portion with a developer to form a resist pattern on the substrate, etching or plating the resist pattern, and finally peeling and removing the resist pattern from the substrate.
As a method for forming a resist pattern, a method of performing exposure through a photomask using a mercury lamp as a light source has been conventionally used, but in recent years, a direct drawing method of drawing digital data of a pattern on a photosensitive resin composition layer using a digital optical process or a laser direct imaging method has been started. This direct writing exposure method is more accurate in position than exposure method using a photomask, and can obtain a high-definition pattern, and therefore is particularly suitable for use in the production of high-precision package substrates. In the above exposure method, monochromatic light such as laser light is used as a light source, and a longer exposure time tends to be required than in the conventional exposure method using a photomask. Further, since the conventional photosensitive resin composition or photoresist film is designed for exposure to light of all wavelengths of a mercury lamp light source centering on 365nm light, it is difficult to obtain a sufficient resolution and a good resist pattern by exposure to active light obtained by cutting 99.5% or more of light of 365nm or less of the mercury lamp light source or light of 405nm of a semiconductor laser, for example, with a filter or the like. Adding a photosensitizer while adjusting components in a photocuring system is an effective means for shortening the exposure time and improving the photosensitive resin composition, and for example, documents JP2005208561, JP2006154740 and JP2010093694 in the prior art are reported. Among them, a photosensitive resin composition containing a benzidine derivative sensitizer (also referred to as a photosensitizer) used in JP2010093694 has sufficient sensitivity and resolution and stable production amount with respect to any light source of 355nm, 365nm and 405nm, and is superior to other photosensitive compositions containing a pyrazoline sensitizer.
However, in the application, it was found that the solubility of the biphenyl structure amine derivative sensitizer in a solvent is low, and the sensitizer precipitates after the photosensitive resin composition is coated on a support film and dried, and therefore there is room for improvement in the solubility of the compound.
Disclosure of Invention
The invention aims to provide a tertiary amine photosensitizer, a preparation method thereof, a photosensitive resin composition containing the tertiary amine photosensitizer and application of the photosensitive resin composition, and aims to solve the technical problem that the photosensitizer is precipitated after the photosensitive resin composition is dried in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a tertiary amine photosensitizer. The tertiary amine photosensitizer at least contains a tertiary amine derivative shown in a general formula (I);
wherein A is selected from any one of the following groups:
wherein denotes a chaining bit;
R1is selected from C1-C10Or a linear or branched alkyl group of (1), optionally, wherein-CH2-substituted by oxygen, sulphur or phenylene;
R2and R3Each independently represents hydrogen or C1-C10Or a linear or branched alkyl group of (1), optionally, wherein-CH2-substituted by oxygen, sulphur or phenylene;
R4is selected from-H, C1-C10Straight or branched alkyl of, or C3-C10Cycloalkyl groups of (a);
R5is selected from C1-C10Straight or branched alkyl of (2), C3-C10Cycloalkyl of, C4-C10Cycloalkylalkyl or C4-C10Alkylcycloalkyl of (A), or
R6Is selected from-H, C1-C10Linear or branched alkyl of (2), C3-C10Cycloalkyl of, C4-C10Or alkylcycloalkyl or cycloalkylalkyl, or C2-C10optionally-CH in these radicals2Can be covered by-O-substitution.
According to another aspect of the present invention, there is provided a photosensitive resin composition. The photosensitive resin composition contains any of the above-described tertiary amine photosensitizers.
Further, the photosensitive resin composition further includes a binder polymer, a photopolymerizable monomer, and a photoinitiator.
Further, the binder polymer is one or more selected from the group consisting of a (meth) acrylic polymer, a (meth) acrylate polymer, a styrenic polymer, an epoxy polymer, an aliphatic urethane (meth) acrylate polymer, and an aromatic urethane (meth) acrylate polymer.
Further, the binder polymer is a carboxyl group-containing polymer; preferably, the binder polymer is a (meth) acrylate-based polymer obtained by copolymerizing a (meth) acrylate, an ethylenically unsaturated carboxylic acid, and another copolymerizable monomer.
Further, the weight average molecular weight of the binder polymer is 7000 to 150000, and the acid value is 30 to 500 mgKOH/g.
Further, the photopolymerizable monomer is selected from one or more of a monomer having one polymerizable unsaturated functional group, a monomer having two polymerizable unsaturated functional groups, and a monomer having three or more polymerizable unsaturated functional groups;
preferably, the monomer having one polymerizable unsaturated functional group is one or more selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, pentyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isooctyl (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol mono (meth) acrylate;
preferably, the monomer having two polymerizable unsaturated functional groups is one or more selected from the group consisting of tripropylene glycol di (meth) acrylate, propylene glycol polypropylene ether di (meth) acrylate, ethoxylated bisphenol a di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, ethoxylated polytetrahydrofuran glycol di (meth) acrylate and ethoxylated polypropylene glycol di (meth) acrylate;
preferably, the monomer having three or more polymerizable unsaturated functional groups is one or more selected from the group consisting of trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexaacrylate; .
Further, the photoinitiator is one or more selected from the group consisting of a hexaarylbisimidazole derivative, an N-arylglycine, an alkylaminobenzophenone, an acridine derivative, an anthraquinone derivative such as diaminoanthraquinone, an aromatic ketone, an oxime ester derivative, a benzophenone, a benzildimethylketal, a thioxanthone derivative, an alkylaminobenzoate, a triazine derivative, a coumarin derivative, triphenylphosphine, tricresylphosphine, trixylylphosphine, terphenylphosphine, trinaphthylphosphine, and triphenanthylphosphine;
preferred hexaarylbisimidazole derivatives are selected from the group consisting of 2,2 ' -bis (2, 3-dichlorophenyl) -4,4 ', 5,5 ' -tetrakis (3-methoxyphenyl) bisimidazole, 2 ' -bis (2, 3-dichlorophenyl) -4,4 ', 5,5 ' -tetrakis (4-methoxyphenyl) bisimidazole, 2 ' -bis (2, 4-dichlorophenyl) -4,4 ', 5,5 ' -tetrakis (3-methoxyphenyl) phenylbisimidazole, 2 ' -bis (2, 5-dichlorophenyl) -4,4 ', 5,5 ' -tetrakis (3-methoxyphenyl) bisimidazole, 2 ', 4,4 ' -tetrakis (2-chlorophenyl) -5,5 ' -bis (3-methoxyphenyl) bisimidazole, 2,2 ', 4,4 ' -tetrakis (2-chlorophenyl) -5,5 ' -bis (2, 3-dimethoxyphenyl) bisimidazole, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetrakis (3,4, 5-trimethoxyphenyl) bisimidazole, 2 ' -bis (2-chlorophenyl) -4, 5-bis (3-methoxyphenyl) -4 ', 5 ' -diphenylbisimidazole, preferably 2,2 ' -bis (2, 3-dichlorophenyl) -4,4 ', 5,5 ' -tetrakis (3-methoxyphenyl) bisimidazole, 2 ' -bis (2, 5-dichlorophenyl) -4,4 ', 5,5 ' -tetrakis (3-methoxyphenyl) bisimidazole, And 2,2 ' -bis (2-chlorophenyl) -4, 5-bis (3-methoxyphenyl) -4 ', 5 ' -diphenylbisimidazole;
preferably, the N-aryl glycine is one or more selected from the group consisting of N-phenyl glycine, N-phenyl glycine butyl ester, N-p-methylphenyl glycine ethyl ester and N-methoxyphenyl glycine, and more preferably, the N-aryl glycine is N-phenyl glycine;
preferably, the alkylamino benzophenone is one or more selected from the group consisting of 4,4 '-bis (diethylamino) benzophenone, 3' -dimethylamino-4-methoxybenzophenone, 4 '-bis (dimethylamino) benzophenone, and the like, and more preferably, the alkylamino benzophenone is 4, 4' -bis (diethylamino) benzophenone;
preferably, the acridine derivative is selected from the group consisting of 9-phenylacridine, 9- (p-hydroxyphenyl) acridine, 9- (p-ethylphenyl) acridine, 9- (p-n-propylphenyl) acridine, 9- (p-isopropylphenyl) acridine, 9- (p-n-butylphenyl) acridine, 9- (p-tert-butylphenyl) acridine, 9- (p-methoxyphenyl) acridine, 9- (p-ethoxyphenyl) acridine, 9- (p-acetylphenyl) acridine, 9- (p-dimethylaminophenyl) acridine, 9- (p-cyanophenyl) acridine, 9- (p-chlorophenyl) acridine, 9- (p-bromophenyl) acridine, 9- (m-methylphenyl) acridine, 9- (m-n-propylphenyl) acridine, 9- (m-isopropylphenyl) acridine, 9- (m-n-butylphenyl) acridine, 9- (m-butylphenyl) acridine, one or more members selected from the group consisting of 9- (m-t-butylphenyl) acridine, 9- (m-methoxyphenyl) acridine, 9- (m-ethoxyphenyl) acridine, 9- (m-acetylphenyl) acridine, 9- (m-dimethylaminophenyl) acridine, 9- (m-diethylaminophenyl) acridine, 9- (m-cyanophenyl) acridine, 9- (m-chlorophenyl) acridine, 9- (m-bromophenyl) acridine, 9-methylacridine, 9-ethylacridine, 9-n-propylacridine, 9-n-propoxycaridine, 9-isopropoxyacridine, 1, 7-bis (9-acridinyl) heptane, phenylbenzacridine, and 9-chloroethoxyacridine, more preferably, the acridine derivative is 9-phenylacridine or 1, 7-bis (9-acridinyl) heptane.
Further, the photoinitiator consists of a hexaarylbisimidazole derivative and an N-arylglycine.
According to still another aspect of the present invention, there is provided a method for producing the above-mentioned tertiary amine photosensitizer. The preparation method comprises the following steps: 1) reacting the raw material a with the raw material b to obtain an intermediate a; 2) reacting the intermediate a with the raw material c in an organic solvent containing a catalyst to obtain an intermediate b; 3) carrying out catalytic reaction on the raw material d and the raw material e by using a catalyst under the protection of nitrogen to obtain an intermediate c; 4) carrying out catalytic reaction on the intermediate b and the intermediate c by a catalyst under the protection of nitrogen to obtain a product; the reaction equation is as follows:
according to still another aspect of the present invention, a photoresist film is provided. The photoresist film comprises a support and a photosensitive resin layer formed on the support, wherein the photosensitive resin layer is composed of any one of the photosensitive resin compositions.
According to still another aspect of the present invention, there is provided a use of the photosensitive resin composition of any one of the above as a photocurable coating, a photocurable ink or a photoresist.
Further, the application is the application of the photosensitive resin composition as a photoresist in a printed wiring board, and the method comprises the following steps: 1) coating a coating liquid of a photosensitive resin composition on one surface of a support and drying the coating liquid to obtain a photoresist film; 2) irradiating a predetermined portion of the photoresist film with light having a wavelength of 350 to 410nm, and then removing a portion other than the predetermined portion by development with a developing solution to form a resist pattern: 3) the circuit-forming substrate is etched or plated with an etching solution using the resist pattern as a mask, and then the resist pattern is removed by peeling to obtain a printed wiring board.
The tertiary amine photosensitizer has high sensitivity to a light source with a wavelength of 350-410 nm, can obtain sufficient resolution and stable production when a photosensitive resin composition prepared by the tertiary amine photosensitizer is used for drawing by using any single-wavelength light source, has good compatibility with the tertiary amine photosensitizer, does not generate precipitates after the photosensitive resin composition added with the tertiary amine photosensitizer is dried, and can be used for preparing a photoresist film, a resist pattern and a printed circuit board by a direct drawing exposure method.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
Aiming at the technical problem that the photosensitizer is precipitated after the photosensitive resin composition is dried in the prior art, the invention provides the following technical scheme.
According to an exemplary embodiment of the present invention, a tertiary amine photosensitizer is provided. The tertiary amine photosensitizer at least contains a tertiary amine derivative shown in a general formula (I);
wherein A is selected from any one of the following groups:
wherein denotes a chaining bit;
R1is selected from C1-C10Or a linear or branched alkyl group of (1), optionally, wherein-CH2-substituted by oxygen, sulphur or phenylene;
R2and R3Each independently represents hydrogen or C1-C10Or a linear or branched alkyl group of (1), optionally, wherein-CH2-substituted by oxygen, sulphur or phenylene;
R4is selected from-H, C1-C10Straight or branched alkyl of, or C3-C10Cycloalkyl groups of (a);
R5is selected from C1-C10Straight or branched alkyl of (2), C3-C10Cycloalkyl of, C4-C10Cycloalkylalkyl or C4-C10Alkylcycloalkyl of (A), or
R6Is selected from-H, C1-C10OfChain or branched alkyl, C3-C10Cycloalkyl of, C4-C10Or alkylcycloalkyl or cycloalkylalkyl, or C2-C10optionally-CH in these radicals2-may be substituted by-O-.
The tertiary amine photosensitizer has high sensitivity to a light source with a wavelength of 350-410 nm, can obtain sufficient resolution and stable production when a photosensitive resin composition prepared by the tertiary amine photosensitizer is used for drawing by using any single-wavelength light source, has good compatibility with the tertiary amine photosensitizer, does not generate precipitates after the photosensitive resin composition added with the tertiary amine photosensitizer is dried, and can be used for preparing a photoresist film, a resist pattern and a printed circuit board by a direct drawing exposure method.
According to a typical embodiment of the present invention, a photosensitive resin composition is provided. The photosensitive resin composition contains any of the above-described tertiary amine photosensitizers.
The photosensitive resin composition uses the tertiary amine derivative shown in the general formula (I) as the photosensitizer, so that the photosensitive resin composition has very high sensitivity to light with the wavelength of 365-405nm, high resolution, good hole covering performance and excellent printing-out performance after exposure. The tertiary amine derivative represented by the general formula (I) has more excellent solubility in a solvent, and does not cause defects such as disconnection and short circuit of a wiring pattern due to the generation of precipitates on a resist pattern caused by low solubility of a photosensitizer and the failure of curing of a lower resin caused by the inhibition of the transmission of an optical fiber. The photoresist film prepared by the photosensitive resin composition has high resolution, excellent adhesiveness and stable photosensitivity, the photoresist pattern formed by the photoresist film has high precision and rapid and efficient pattern formation, and the prepared printed circuit board has stable yield and high qualification rate.
According to a typical embodiment of the present invention, the photosensitive resin composition of the present invention comprises (a) a binder polymer, (B) a photopolymerizable monomer, (C) a photoinitiator, and (D) a tertiary amine derivative represented by general formula (I).
The components are specifically described below.
(A) Binder polymers
Examples of the binder polymer (a) used in the present invention include: one or a mixture of two or more of a (meth) acrylic polymer, a (meth) acrylate polymer, a styrene polymer, an epoxy polymer, an aliphatic urethane (meth) acrylate polymer, and an aromatic urethane (meth) acrylate polymer.
Among the above polymers, carboxyl group-containing polymers, particularly (meth) acrylate polymers obtained by copolymerizing (meth) acrylate, ethylenically unsaturated carboxylic acid and other copolymerizable monomers, are preferably used. The (meth) acrylic acid ester may be methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, furfuryl (meth) acrylate, or glycidyl (meth) acrylate, and these (meth) acrylic acid esters may be used alone or in combination of two or more kinds. The ethylenically unsaturated carboxylic acid is preferably acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and particularly preferably acrylic acid or methacrylic acid. These ethylenically unsaturated carboxylic acids may be used alone or in combination of two or more. The other copolymerizable monomer is preferably (meth) acrylamide, n-butyl (meth) acrylate, styrene, vinylnaphthalene, (meth) acrylonitrile, vinyl acetate, or vinylcyclohexane, and these monomers may be used alone or in combination of two or more.
The weight average molecular weight of the binder polymer is preferably 7000 to 150000, and more preferably 30000 to 120000. The acid value is preferably 30 to 500mgKOH/g, and more preferably 100 to 400 mgKOH/g.
(B) Photopolymerizable monomers
The photopolymerizable monomer (B) used in the present invention is not particularly limited in kind, and may be, for example, a monomer having one polymerizable unsaturated functional group, a monomer having two polymerizable unsaturated functional groups, and/or a monomer having three or more polymerizable unsaturated functional groups. These monomers may be used alone or in combination of two or more.
The monomer having one polymerizable unsaturated functional group may be 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, pentyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isooctyl (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and these monomers may be used alone or in combination of two or more.
The monomer having two polymerizable unsaturated functional groups may be tripropylene glycol di (meth) acrylate, propylene glycol polypropylene ether di (meth) acrylate, ethoxylated bisphenol a di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, ethoxylated polytetrahydrofuran glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, and these monomers may be used alone or in combination of two or more kinds.
The monomer having three or more polymerizable unsaturated functional groups may be trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexaacrylate, and these monomers may be used alone or in combination of two or more.
In the photosensitive resin composition of the present invention, the content of the photopolymerizable monomer (B) is 10 to 300 parts, preferably 40 to 200 parts, and most preferably 65 to 100 parts, based on 100 parts by weight of the binder polymer (a).
(C) Photoinitiator
Examples of the photoinitiator (C) used in the present invention include: examples of the photopolymerization initiator include anthraquinone derivatives such as hexaarylbisimidazole derivatives, N-arylglycines, alkylaminobenzophenones, acridine derivatives, diaminoanthraquinones, aromatic ketones, oxime ester derivatives, benzophenones, benzildimethylketals, thioxanthone derivatives, alkylaminobenzoate alkyl esters, triazine derivatives, coumarin derivatives, triphenylphosphine, tritolylphosphine, trixylylphosphine, terphenylphosphine, trinaphthylphosphine, triphenanthrylphosphine, and the like, and these photopolymerization initiators may be used alone or in combination of two or more kinds.
The hexaarylbisimidazole derivative as the photoinitiator may be 2,2 ' -bis (2, 3-dichlorophenyl) -4,4 ', 5,5 ' -tetrakis (3-methoxyphenyl) bisimidazole, 2 ' -bis (2, 3-dichlorophenyl) -4,4 ', 5,5 ' -tetrakis (4-methoxyphenyl) bisimidazole, 2 ' -bis (2, 4-dichlorophenyl) -4,4 ', 5,5 ' -tetrakis (3-methoxyphenyl) phenylbisimidazole, 2 ' -bis (2, 5-dichlorophenyl) -4,4 ', 5,5 ' -tetrakis (3-methoxyphenyl) bisimidazole, 2 ', 4,4 ' -tetrakis (2-chlorophenyl) -5,5 ' -bis (3-methoxyphenyl) bisimidazole, 2,2 ', 4,4 ' -tetrakis (2-chlorophenyl) -5,5 ' -bis (2, 3-dimethoxyphenyl) bisimidazole, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetrakis (3,4, 5-trimethoxyphenyl) bisimidazole, 2 ' -bis (2-chlorophenyl) -4, 5-bis (3-methoxyphenyl) -4 ', 5 ' -diphenylbisimidazole, preferably 2,2 ' -bis (2, 3-dichlorophenyl) -4,4 ', 5,5 ' -tetrakis (3-methoxyphenyl) bisimidazole, 2 ' -bis (2, 5-dichlorophenyl) -4,4 ', 5,5 ' -tetrakis (3-methoxyphenyl) bisimidazole, 2,2 ' -bis (2-chlorophenyl) -4, 5-bis (3-methoxyphenyl) -4 ', 5 ' -diphenylbisimidazole. These hexaarylbisimidazole derivatives may be used alone or in combination of two or more.
Examples of the N-arylglycine include N-phenylglycine, N-phenylglycine butyl ester, N-p-methylphenylglycine ethyl ester, N-methoxyphenylglycine and the like, among which N-phenylglycine is preferable, and these N-arylglycines may be used alone or in combination of two or more kinds.
Examples of the alkylaminobenzophenones include: 4,4 '-bis (diethylamino) benzophenone, 3' -dimethylamino-4-methoxybenzophenone, 4 '-bis (dimethylamino) benzophenone and the like, and among them, 4' -bis (diethylamino) benzophenone is particularly preferable, and these alkylaminobenzophenones may be used alone or in combination of two or more kinds.
As the acridine derivative, for example, there can be mentioned: 9-phenylacridine, 9- (p-hydroxyphenyl) acridine, 9- (p-ethylphenyl) acridine, 9- (p-n-propylphenyl) acridine, 9- (p-isopropylphenyl) acridine, 9- (p-n-butylphenyl) acridine, 9- (p-tert-butylphenyl) acridine, 9- (p-methoxyphenyl) acridine, 9- (p-ethoxyphenyl) acridine, 9- (p-acetylphenyl) acridine, 9- (p-dimethylaminophenyl) acridine, 9- (p-cyanophenyl) acridine, 9- (p-chlorophenyl) acridine, 9- (p-bromophenyl) acridine, 9- (m-methylphenyl) acridine, 9- (m-n-propylphenyl) acridine, 9- (m-isopropylphenyl) acridine, 9- (m-n-butylphenyl) acridine, 9- (m-tert-butylphenyl) acridine, 9- (m-methoxyphenyl) acridine, 9- (m-ethoxyphenyl) acridine, 9- (m-acetylphenyl) acridine, 9- (m-dimethylaminophenyl) acridine, 9- (m-diethylaminophenyl) acridine, 9- (m-cyanophenyl) acridine, 9- (m-chlorophenyl) acridine, 9- (m-bromophenyl) acridine, 9-methylacridine, 9-ethylacridine, 9-n-propylacridine, 9-isopropylacridine, 9-n-propoxycaridine, 9-isopropoxyacridine, 1, 7-bis (9-acridinyl) heptane, phenylbenzacridine, 9-chloroethoxyacridine, and the like, among them, 9-phenylacridine and 1, 7-bis (9-acridinyl) heptane are preferable, and these acridine derivatives can be used alone or in combination of two or more kinds.
In the photosensitive composition of the present invention, it is preferable to use a hexaarylbisimidazole derivative and an N-arylglycine compound in combination from the viewpoint of high sensitivity.
In the photosensitive resin composition of the present invention, the content of the (C) photoinitiator is preferably 0.5 to 10 parts by mass, particularly preferably 1 to 8 parts by mass, and further preferably 1.5 to 6 parts by mass, based on 100 parts by mass of the total amount of the (a) binder polymer and the (B) photopolymerizable monomer.
In the case of using the hexaarylbisimidazole derivative and the other photopolymerization initiator in combination, for example, in the case of using the hexaarylbisimidazole derivative and N-arylglycine as the composition, the hexaarylbisimidazole derivative is preferably 0.5 to 10 parts by mass, particularly preferably 1 to 8 parts by mass, and further preferably 2 to 5.5 parts by mass, and the N-arylglycine is preferably 0.005 to 2 parts by mass, particularly preferably 0.01 to 1 part by mass, and further preferably 0.03 to 0.5 part by mass, based on 100 parts by mass of the total amount of the binder polymer (a) and the photopolymerizable monomer (B).
(D) Tertiary amine photosensitizers
The tertiary amine photosensitizer used in the present invention has a tertiary amine derivative represented by the general formula (I):
wherein A is selected from any one of the following groups:
wherein denotes a chaining bit;
R1is selected from C1-C10Is a straight or branched alkyl group of (a), optionally (optionally), wherein-CH2-may be substituted by oxygen, sulphur or phenylene;
R2and R3Each independently represents hydrogen or C1-C10Or a linear or branched alkyl group of (1), optionally, wherein-CH2-may be substituted by oxygen, sulphur or phenylene;
R4is selected from-H, C1-C10Straight or branched alkyl of, or C3-C10Cycloalkyl groups of (a);
R5is selected from C1-C10Straight or branched alkyl of (2), C3-C10Cycloalkyl of, C4-C10Cycloalkylalkyl or C4-C10Alkylcycloalkyl of (A), or
R6Is selected from-H, C1-C10Linear or branched alkyl of (2), C3-C10Cycloalkyl of, C4-C10Or alkylcycloalkyl or cycloalkylalkyl, or C2-C10optionally-CH in these radicals2-may be substituted by-O-;
the structure shown in the general formula (I) forms a special rigid plane biphenyl structure by taking carbazole or fluorene as a matrix, has high thermal stability and photochemical stability, forms a larger conjugated group in a molecule, has the maximum absorption wavelength of 365-405nm, and has molar absorption coefficients of more than 42000 at the positions of 365nm and 405 nm.
The content of the tertiary amine photosensitizer (D) is preferably 0.005 to 2 parts by mass, and particularly preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total amount of the binder polymer (a) and the photopolymerizable monomer (B).
The photosensitive resin composition of the present invention may contain, in addition to the compounds a to D, additives such as a colorant, an adhesion-imparting agent, a plasticizer, an antioxidant, a thermal polymerization inhibitor, a solvent, a surface tension-modifying material, a stabilizer, a chain transfer agent, an antifoaming agent, and a flame retardant in an appropriate amount as required.
Further, if the ink further contains an acid or tribromomethylphenyl sulfone, the printability after exposure can be optimized, and therefore, the ink is preferable. For example, phthalic acid and oxalic acid are preferable, and the amount of the acid is usually preferably 0.005 to 1 part by mass.
The photosensitive resin composition of the present invention can be dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof as required to prepare a solution having a solid content of 30 to 60%.
According to an exemplary embodiment of the present invention, there is provided a method of preparing the above-described tertiary amine photosensitizer. The preparation method comprises the following steps: 1) reacting the raw material a with the raw material b to obtain an intermediate a; 2) reacting the intermediate a with the raw material c in an organic solvent containing a catalyst to obtain an intermediate b; 3) carrying out catalytic reaction on the raw material d and the raw material e by using a catalyst under the protection of nitrogen to obtain an intermediate c; (4) carrying out catalytic reaction on the intermediate b and the intermediate c by a catalyst under the protection of nitrogen to obtain a product; the reaction equation is as follows:
knowing the above reaction scheme, the specific reaction conditions in steps 1) to 4) are readily determinable by the skilled person.
The reaction of step 1) can be carried out in the absence of a catalyst and in the absence of a solvent. The reaction temperature is slightly different according to different raw material types, and is usually 80-100 ℃.
In step 2), the catalyst may be sodium methoxide, sodium hydroxide, sodium ethoxide, potassium methoxide, potassium hydroxide, potassium ethoxide, or the like. The type of the organic solvent is not particularly limited as long as the reaction raw material can be dissolved and the reaction is not adversely affected, and examples thereof include acetone, acetonitrile, dichloromethane, and N, N-dimethylformamide. The reaction temperature is slightly different according to different raw material types, and is usually 10-20 ℃.
The reaction of step 3) is preferably carried out in an organic solvent system, and the type of solvent is not particularly limited as long as it can dissolve the reaction raw materials and does not adversely affect the reaction, and examples thereof include acetone, acetonitrile, dichloromethane, and toluene. The catalyst can be one or the combination of more than two of sodium hydroxide, sodium tert-butoxide, triphenylphosphine, tri-tert-butylphosphine and tetrakis (triphenylphosphine) palladium. The reaction temperature is usually 70 to 100 ℃.
The reaction of step 4) is preferably carried out in an organic solvent system, and the type of solvent is not particularly limited as long as it can dissolve the reaction raw materials and does not adversely affect the reaction, and examples thereof include acetone, acetonitrile, dichloromethane, and toluene. The catalyst is selected from one or the combination of more than two of sodium hydroxide, sodium tert-butoxide, triphenylphosphine, tri-tert-butylphosphine and tetrakis (triphenylphosphine) palladium. The reaction temperature is usually 75 to 120 ℃.
According to an exemplary embodiment of the present invention, a photoresist film is provided. The photoresist film comprises a support and a photosensitive resin layer formed on the support, wherein the photosensitive resin layer is composed of the photosensitive resin composition.
According to an exemplary embodiment of the present invention, a method of forming a printed wiring board is provided. The forming method of the printed circuit board comprises the following steps:
(1) method for forming photoresist film: the coating liquid of the photosensitive resin composition of the present invention is applied to one surface of a support, dried, and the coated surface is covered with a protective film as necessary. More specifically, the coating method can be a method comprising uniformly coating the photosensitive resin composition of the present invention by a roll coating method, a bar coating method or the like, drying the coating in an oven at 50 to 120 ℃ or at a temperature which is raised in order to form a photosensitive resin composition layer having a thickness of 10 to 70 μm, and then laminating a protective film on the upper surface of the layer by pressing;
(2) method for forming resist pattern: a predetermined portion of the photosensitive resin layer is irradiated with light having a wavelength of 350 to 410nm, and the portion other than the predetermined portion is removed by development with a developer, which may be usually 0.1 to 5% alkali solution such as sodium carbonate, potassium carbonate, tetramethylammonium bromide, sodium hydroxide, or the like.
(3) The manufacturing method of the printed circuit board comprises the following steps: the resist pattern formed after development is used as a mask, and then the circuit-forming substrate is etched or plated with an etching solution. As the etching solution, an acidic etching solution such as a copper chloride-hydrochloric acid aqueous solution or an iron chloride-hydrochloric acid aqueous solution is generally used. After the etching or plating is finished, the resist pattern is stripped and removed by using a solution containing sodium hydroxide, potassium hydroxide and the like with the mass concentration of 0.1-10% or an organic amine solution with the concentration of 3-15%.
In addition to the above applications, the photosensitive resin composition of the present invention can be used in other photo-curing application fields including, but not limited to, photo-curing coatings, inks, photoresists, and the like.
The present invention will be described in further detail with reference to specific examples, which should not be construed as limiting the scope of the present invention.
Example 1
Preparation of component D, a tertiary amine derivative of formula (I)
(1) Preparation of intermediate a1
63g of benzyl chloride and 100g of triethyl phosphite are added into a 500ml four-mouth bottle, stirred and heated to 80-90 ℃, and reacted for 3 hours. And controlling the content of benzyl chloride to be less than 1% in GC (gas chromatography), and finishing the reaction. Distilling at 90 ℃ under normal pressure to distill out chloroethane serving as a reaction by-product, continuously distilling under reduced pressure to distill out unreacted triethyl phosphite, and cooling to 30 ℃ after no fraction is distilled out to obtain 105g of intermediate a1 with the yield of 92.1%.
The structure of the intermediate a1 is shown by1H-NMR and LCMS were confirmed.
1H-NMR(CDCl3，500MHz)：δ1.11(6H，m)，δ3.57(4H，s)，δ5.33(2H，s)，δ7.06-7.14(5H，m)。
MS(m/z):229(M+1)。
(2) Preparation of intermediate b1
Adding 114g of intermediate a1, 92.5g of p-bromobenzaldehyde and 200g of dichloromethane into a 1000mL four-neck flask, stirring and dissolving, controlling the temperature to be 10-20 ℃, adding 35g of potassium methoxide in batches, continuing to react for 3 hours after the addition is finished, and performing HPLC tracking until the raw material intermediate a1 disappears (HPLC: < 1%) after the reaction is finished. Slowly dropwise adding 200g of pure water, separating out a water layer, evaporating most of solvent under reduced pressure, recrystallizing with methanol, leaching, and drying to obtain 103.6g of solid, namely the intermediate b1, with the yield of 80%.
The structure of intermediate b1 was determined by LCMS and1H-NMR was confirmed.
1H-NMR(CDCl3，500MHz)：δ6.99(6H，d)，δ7.11-7.43(9H，m)。
MS(m/z):260(M+1)。
(3) Preparation of intermediate c1
64.8g of raw material d1, 108.2g of 2-ethyl-6-methylaniline and 200g of toluene are added into a 1000mL four-neck flask, 19.6g of sodium tert-butoxide, 18g of tri-tert-butylphosphine and 0.8g of tetrakis (triphenylphosphine) palladium are added under the protection of nitrogen, the temperature is increased to 80-85 ℃, the reaction is kept for 10 hours, and the HPLC is controlled until the raw material d1 and intermediate state monosubstitutes thereof are completely reacted (HPLC: < 0.1%). Filtering while hot, evaporating the solvent from the mother liquor under reduced pressure, adding 200g of n-hexane, cooling to 10 ℃, stirring for crystallization, and performing suction filtration to obtain 82.1g of an intermediate c1 with the yield of 95.0%.
The structure of intermediate c1 was determined by LCMS and1H-NMR was confirmed.
1H-NMR(CDCl3，500MHz)：δ1.24(6H，m)，δ2.35-2.59(10H，m)，δ3.87(2H，s)，δ4.0(2H，s)，δ6.45-7.30(12H，m)。
MS(m/z):433(M+1)。
(4) Preparation of product 1
65g of intermediate b1, 43.2g of intermediate c1 and 150g of toluene are added into a 1000mL four-neck flask, 33g of sodium tert-butoxide, 52g of tri-tert-butylphosphine and 0.52g of tetrakis (triphenylphosphine) palladium are added under the protection of nitrogen, the temperature is raised to 80-85 ℃, the reaction is kept for 10 hours, and the HPLC is controlled until the raw material intermediate c1 and the intermediate state monosubstituted product are completely reacted (HPLC: < 0.1%). Filtering while hot, evaporating the solvent from the mother liquor under reduced pressure, adding 200g of normal hexane, cooling to 10 ℃, stirring, crystallizing, and performing suction filtration to obtain 71.6g of the product 1 with the yield of 90.8%.
Structure of product 1 by LCMS and1H-NMR was confirmed.
1H-NMR(CDCl3，500MHz)：δ1.24-2.59(16H，m)，δ3.87(2H，s)，δ6.45-7.30(34H，m)。
MS(m/z):790(M+1)。
Example 2
(1) Preparation of intermediate c2
Adding 162.5g d2 raw materials, 216g of 2-ethyl-6-methylaniline and 400g of toluene into a 1000mL four-neck flask, adding 40g of sodium tert-butoxide, 36g of tri-tert-butylphosphine and 1.6g of tetrakis (triphenylphosphine) palladium under the protection of nitrogen, heating to 80-85 ℃, carrying out heat preservation reaction for 10h, and controlling the HPLC until the raw material d2 and intermediate state monosubstitutes thereof are completely reacted (HPLC: < 0.1%). Filtering while hot, evaporating the solvent from the mother liquor under reduced pressure, adding 200g of n-hexane, cooling to 10 ℃, stirring for crystallization, and performing suction filtration to obtain 197.1g of intermediate c2 with the purity of 91%.
Structure of product 1 by LCMS and1H-NMR was confirmed.
1H-NMR(CDCl3，500MHz)：δ1.24-2.59(16H，m)，δ4.01(2H，s)，δ6.28-7.15(12H，m)，δ10.1(1H，s)。
MS(m/z):434(M+1)。
(2) Preparation of product 2
A1000 mL four-neck flask is added with 208g of intermediate b1, 108g of intermediate c2 and 300g of toluene, 82.5g of sodium tert-butoxide, 130g of tri-tert-butylphosphine and 1.3g of tetrakis (triphenylphosphine) palladium are added under the protection of nitrogen, the temperature is raised to 80-85 ℃, the reaction is kept for 10h, and the HPLC is controlled until the raw material intermediate c2 and intermediate state monosubstitutes thereof are completely reacted (HPLC: < 0.1%). Filtering while hot, evaporating the solvent from the mother liquor under reduced pressure, adding 400g of normal hexane, cooling to 10 ℃, stirring for crystallization, and performing suction filtration to obtain 213g of product 2 with the yield of 88%.
Structure of product 2 by LCMS and1H-NMR was confirmed.
1H-NMR(CDCl3，500MHz)：δ1.24-2.59(16H，m)，δ6.28-7.42(45H，m)。
MS(m/z):969(M+1)。
Examples 3 to 12:
referring to the methods of examples 1 and 2, products 3 to 12 having the following structures were synthesized.
Performance testing
1. Preparation of test samples
The application properties of the photosensitive resin composition of the present invention were evaluated by formulating an exemplary photosensitive resin composition. Unless otherwise indicated, the following "parts" are by weight.
< preparation of photosensitive resin laminate >
A photosensitive resin composition having a composition shown in Table 1 and propylene glycol monoethyl ether acetate were sufficiently stirred and mixed, the composition was applied onto the surface of a polyethylene terephthalate film having a thickness of 19 μm as a support using a wire bar, and then dried in a dryer at 95 ℃ for 4min to form a photosensitive resin layer having a thickness of 40 μm. Subsequently, a polyethylene film having a thickness of 23 μm was laminated as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated, to obtain a photosensitive resin laminate.
< leveling of substrate surface >
As a substrate for sensitivity and resolution evaluation, a ketone-coated laminate treated with a jet-cleaning grinder under a spray pressure of 0.20MPa was prepared.
< lamination >
While peeling off the polyethylene film of the photosensitive resin laminate, the surface was flattened, and the laminate was laminated on a ketone-coated laminate preheated to 60 ℃ by a hot roll laminator at a roll temperature of 105 ℃ under a gas pressure of 0.35MPa and a lamination speed of 1.5 m/min.
< Exposure >
Exposure was performed by an h-ray type direct writing exposure apparatus (Digital Light Processing) with an exposure amount of 8 in a stepwise exposure table evaluated in terms of sensitivity as described below.
TABLE 1
Note: the names/compositions of the components denoted by the symbols in table 1 are shown in table 2.
TABLE 2
2. Performance evaluation method
(1) Compatibility test
A photosensitive resin composition having a composition shown in Table 1 was sufficiently stirred and mixed, and uniformly applied to the surface of a polyethylene terephthalate film having a thickness of 19 μm as a support by using a wire bar coater. Drying at 95 deg.C for 4min to form a photosensitive resin layer of 20 μm thickness, visually observing the coated surface, and classifying in the following manner:
v: the coating surface is uniform;
x: undissolved matter was precipitated on the coated surface.
(2) Presence or absence of precipitates
The photosensitive resin composition and dichloroethane were prepared in a mass ratio of 1:15, stirred to be clear, left at room temperature (25 ℃) for 24 hours, and then the presence or absence of precipitates was visually observed.
(3) Absorbance at 365nm and 405nm (Abs)
The light at 300-700nm was measured continuously using a UV spectrophotometer, and the values of absorbance at 365nm and 405nm were read, and the results are summarized in Table 3.
(4) Sensitivity evaluation at 365nm and 405nm wavelengths
A21-stage exposure table manufactured by Stouffer, which uses a 21-stage brightness change from clear to black, was overlaid on top of the photosensitive resin composition, and it was placed under 365nm and 405nm exposure machines for uniform exposure to evaluate the sensitivity. After the same exposure time, the resist was developed with a 0.5% aqueous solution of sodium carbonate for 1min, and the resist was classified into 21 stages in total, and the higher the number of stages, the higher the sensitivity.
(5) Resolution evaluation at 365nm and 405nm wavelengths
The pattern data of the exposure dose direct line width/line distance of 400/12.5-400/50 (mum) with the number of stages of the stepwise exposure table being 7 stages is evaluated from the minimum value of the line distance width which can completely remove the unexposed part by the same developing treatment as described above, and the smaller the value, the higher the resolution.
O: resolution value is below 30 μm;
very good: resolution values of 30 μm to 50 μm (not inclusive);
●: the resolution value is 50 μm or more.
(6) Adhesion at 365nm and 405nm
The pattern data of the exposure dose direct line-sight exposure line width/line distance of 12.5/400 to 50/400 (mum) with the number of stages of the stepwise exposure table being 7 stages was evaluated from the minimum value of the line distance width between line widths that can be generated by the same development process without generating snaking or chipping in the lines, and the smaller the value, the better the adhesion.
3. Results of Performance evaluation
The results of the property evaluations are shown in Table 3.
TABLE 3
As can be seen from the evaluation results in Table 3, the photosensitive resin compositions (embodiments 1 to 13) of the present invention have good compatibility, high sensitivity, good resolution and adhesion, and high solubility in solvents, thereby avoiding the defects of disconnection, short circuit, etc. of wiring patterns and improving the yield of the process. In addition, the photosensitive resin compositions of embodiments 1 to 13 have a small difference in absorbance at 365 to 405nm, so that the difference in exposure amount (sensitivity) required for curing is small, and a stable production amount can be obtained. In comparative examples 1 and 2, since the sensitivity was different between 365nm and 405nm and the difference in absorbance between 365 and 405nm was large, the difference in exposure amount required for curing was large, and it was difficult to obtain a stable throughput; and the solubility is unstable, and there are significant differences in sensitivity, resolution, adhesion, and adhesion.
In conclusion, the photosensitive resin composition disclosed by the invention has very excellent application performance in the field of photocuring and has a very good application prospect.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (24)
1. A photosensitive resin composition comprising a tertiary amine photosensitizer, a binder polymer, a photopolymerizable monomer and a photoinitiator, wherein the tertiary amine photosensitizer contains at least one tertiary amine derivative represented by the general formula (I);
wherein A is selected from any one of the following groups:
wherein denotes a chaining bit;
R1is selected from C1-C10Or a linear or branched alkyl group of (1), optionally, wherein-CH2-substituted by oxygen, sulphur or phenylene;
R2and R3Each independently represents hydrogen or C1-C10Or a linear or branched alkyl group of (1), optionally, wherein-CH2-substituted by oxygen, sulphur or phenylene;
R4is selected from-H, C1-C10Straight or branched alkyl of, or C3-C10Cycloalkyl groups of (a);
R5is selected from C1-C10Straight or branched alkyl of (2), C3-C10Cycloalkyl of, C4-C10Cycloalkylalkyl or C4-C10Alkylcycloalkyl of (A), or
2. The photosensitive resin composition according to claim 1, wherein the binder polymer is one or more selected from the group consisting of a (meth) acrylic polymer, a (meth) acrylate polymer, a styrenic polymer, an epoxy polymer, an aliphatic urethane (meth) acrylate polymer, and an aromatic urethane (meth) acrylate polymer.
3. The photosensitive resin composition according to claim 2, wherein the binder polymer is a carboxyl group-containing polymer.
4. The photosensitive resin composition according to claim 3, wherein the binder polymer is a (meth) acrylate-based polymer obtained by copolymerizing a (meth) acrylate, an ethylenically unsaturated carboxylic acid, and another copolymerizable monomer.
5. The photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the binder polymer is 7000 to 150000, and the acid value is 30 to 500 mgKOH/g.
6. The photosensitive resin composition according to claim 1, wherein the photopolymerizable monomer is one or more selected from the group consisting of a monomer having one polymerizable unsaturated functional group, a monomer having two polymerizable unsaturated functional groups, and a monomer having three or more polymerizable unsaturated functional groups.
7. The photosensitive resin composition according to claim 6, wherein the monomer having one polymerizable unsaturated functional group is one or more selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, pentyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isooctyl (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, polypropylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate.
8. The photosensitive resin composition according to claim 6, wherein the monomer having two polymerizable unsaturated functional groups is one or more selected from the group consisting of tripropylene glycol di (meth) acrylate, propylene glycol polypropylene ether di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, ethoxylated polytetrahydrofurandiol di (meth) acrylate and ethoxylated polypropylene glycol di (meth) acrylate.
9. The photosensitive resin composition according to claim 6, wherein the monomer having three or more polymerizable unsaturated functional groups is one or more selected from the group consisting of trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexaacrylate.
10. The photosensitive resin composition according to claim 1, wherein the photoinitiator is one or more selected from the group consisting of a hexaarylbisimidazole derivative, an N-arylglycine, an alkylaminobenzophenone, an acridine derivative, an anthraquinone derivative, an aromatic ketone, an oxime ester derivative, a benzophenone, a benzildimethylketal, a thioxanthone derivative, an alkylaminobenzoate, a triazine derivative, a coumarin derivative, triphenylphosphine, tricresylphosphine, trixylylphosphine, terphenylphosphine, trinaphthylphosphine, trianthrylphosphine, and triphenanthrylphosphine.
11. The photosensitive resin composition according to claim 10, wherein the anthraquinone derivative is diaminoanthraquinone.
12. The photosensitive resin composition according to claim 10, wherein the hexaarylbisimidazole derivative is selected from the group consisting of 2,2 '-bis (2, 3-dichlorophenyl) -4, 4', 5,5 '-tetrakis (3-methoxyphenyl) bisimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4 ', 5, 5' -tetrakis (4-methoxyphenyl) bisimidazole, 2 '-bis (2, 4-dichlorophenyl) -4, 4', 5,5 '-tetrakis (3-methoxyphenyl) phenylbisimidazole, 2' -bis (2, 5-dichlorophenyl) -4,4 ', 5, 5' -tetrakis (3-methoxyphenyl) bisimidazole, 2 ', 4, 4' -tetrakis (2-chlorophenyl) -5,5 '-bis (3-methoxyphenyl) bisimidazole, 2', 4,4 '-tetrakis (2-chlorophenyl) -5, 5' -bis (2, 3-dimethoxyphenyl) bisimidazole, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetrakis (3,4, 5-trimethoxyphenyl) bisimidazole, 2' -bis (2-chlorophenyl) -4, 5-bis (3-methoxyphenyl) -4 ', 5' -diphenylbisimidazole.
13. The photosensitive resin composition according to claim 12, wherein the hexaarylbisimidazole derivative is one or more selected from the group consisting of 2,2 ' -bis (2, 3-dichlorophenyl) -4,4 ', 5,5 ' -tetrakis (3-methoxyphenyl) bisimidazole, 2 ' -bis (2, 5-dichlorophenyl) -4,4 ', 5,5 ' -tetrakis (3-methoxyphenyl) bisimidazole, and 2,2 ' -bis (2-chlorophenyl) -4, 5-bis (3-methoxyphenyl) -4 ', 5 ' -diphenylbisimidazole.
14. The photosensitive resin composition according to claim 10, wherein the N-arylglycine is one or more selected from the group consisting of N-phenylglycine, N-phenylglycine butyl ester, N-p-methylphenylglycine ethyl ester and N-methoxyphenylglycine.
15. The photosensitive resin composition according to claim 14, wherein the N-arylglycine is N-phenylglycine.
16. The photosensitive resin composition according to claim 10, wherein the alkylaminobenzophenone is one or more selected from the group consisting of 4,4 ' -bis (diethylamino) benzophenone, 3 ' -dimethylamino-4-methoxybenzophenone, and 4,4 ' -bis (dimethylamino) benzophenone.
17. The photosensitive resin composition according to claim 16, wherein the alkylaminobenzophenone is 4, 4' -bis (diethylamino) benzophenone.
18. The photosensitive resin composition according to claim 10, wherein the acridine derivative is selected from the group consisting of 9-phenylacridine, 9- (p-phenylphenyl) acridine, 9- (p-ethylphenyl) acridine, 9- (p-n-propylphenyl) acridine, 9- (p-isopropylphenyl) acridine, 9- (p-n-butylphenyl) acridine, 9- (p-t-butylphenyl) acridine, 9- (p-methoxyphenyl) acridine, 9- (p-ethoxyphenyl) acridine, 9- (p-acetylphenyl) acridine, 9- (p-dimethylaminophenyl) acridine, 9- (p-cyanophenyl) acridine, 9- (p-chlorophenyl) acridine, 9- (p-bromophenyl) acridine, 9- (m-methylphenyl) acridine, 9- (m-n-propylphenyl) acridine, 9- (p-bromophenyl) acridine, and, 9- (m-isopropylphenyl) acridine, 9- (m-n-butylphenyl) acridine, 9- (m-tert-butylphenyl) acridine, 9- (m-methoxyphenyl) acridine, 9- (m-ethoxyphenyl) acridine, 9- (m-acetylphenyl) acridine, 9- (m-dimethylaminophenyl) acridine, 9- (m-diethylaminophenyl) acridine, 9- (m-cyanophenyl) acridine, 9- (m-chlorophenyl) acridine, 9- (m-bromophenyl) acridine, 9-methylacridine, 9-ethylacridine, 9-n-propylacridine, 9-isopropylacridine, 9-n-propoxycaridine, 9-isopropoxyacridine, 1, 7-bis (9-acridinyl) heptane, phenylbenzacridine, and 9-chloroethoxyacridine.
19. The photosensitive resin composition according to claim 18, wherein the acridine derivative is 9-phenylacridine or 1, 7-bis (9-acridinyl) heptane.
20. The photosensitive resin composition according to any one of claims 10 to 18, wherein the photoinitiator consists of a hexaarylbisimidazole derivative and an N-arylglycine.
21. A preparation method of a tertiary amine photosensitizer is characterized by comprising the following steps:
1) reacting the raw material a with the raw material b to obtain an intermediate a;
2) reacting the intermediate a with the raw material c in an organic solvent containing a catalyst to obtain an intermediate b;
3) carrying out catalytic reaction on the raw material d and the raw material e by using a catalyst under the protection of nitrogen to obtain an intermediate c;
4) carrying out catalytic reaction on the intermediate b and the intermediate c under the protection of nitrogen by using a catalyst to obtain a product;
the reaction equation is as follows:
the tertiary amine photosensitizer at least contains a tertiary amine derivative shown in a general formula (I);
wherein A is selected from any one of the following groups:
wherein denotes a chaining bit;
R1is selected from C1-C10Or a linear or branched alkyl group of (1), optionally, wherein-CH2-substituted by oxygen, sulphur or phenylene;
R2and R3Each independently represents hydrogen or C1-C10Or a linear or branched alkyl group of (1), optionally, wherein-CH2-substituted by oxygen, sulphur or phenylene;
R4is selected from-H, C1-C10Straight or branched alkyl of, or C3-C10Cycloalkyl groups of (a);
R5is selected from C1-C10Straight or branched alkyl of (2), C3-C10Cycloalkyl of, C4-C10Cycloalkylalkyl or C4-C10Alkylcycloalkyl of (A), or
R6Is selected from-H, C1-C10Linear or branched alkyl of (2), C3-C10Cycloalkyl of, C4-C10Or alkylcycloalkyl or cycloalkylalkyl, or C2-C10optionally-CH in these radicals2-may be substituted by-O-.
22. A photoresist film comprising a support and a photosensitive resin layer formed on the support, wherein the photosensitive resin layer is composed of the photosensitive resin composition according to any one of claims 1 to 20.
23. Use of the photosensitive resin composition according to any one of claims 1 to 20 as a photocurable coating, a photocurable ink or a photoresist.
24. The use of claim 23, wherein the use is of the photosensitive resin composition as a photoresist in a printed wiring board, comprising the steps of:
1) coating the coating liquid of the photosensitive resin composition on one surface of a support and drying to obtain a photoresist film;
2) irradiating a predetermined portion of the photoresist film with light having a wavelength of 350 to 410nm, and then removing a portion other than the predetermined portion by developing with a developing solution to form a resist pattern:
3) the circuit-forming substrate is etched or plated with an etching solution using the resist pattern as a mask, and then the resist pattern is removed by peeling to obtain a printed wiring board.
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| JP2004030942A (en) * | 2002-06-21 | 2004-01-29 | Fuji Xerox Co Ltd | Organic electroluminescent element |
| CN101196686A (en) * | 2006-12-04 | 2008-06-11 | 旭化成电子材料元件株式会社 | Photosensitive resin composition and use of the same |
| CN102844709A (en) * | 2010-04-15 | 2012-12-26 | 日合墨东株式会社 | Photosensitive resin composition, photoresist film using same, method for forming resist pattern, and method for manufacturing printed wiring board |
| CN105130860A (en) * | 2015-08-09 | 2015-12-09 | 同济大学 | Fluorene structure-containing double-branched photosensitive compound, preparation method and applications thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004030942A (en) * | 2002-06-21 | 2004-01-29 | Fuji Xerox Co Ltd | Organic electroluminescent element |
| CN101196686A (en) * | 2006-12-04 | 2008-06-11 | 旭化成电子材料元件株式会社 | Photosensitive resin composition and use of the same |
| CN102844709A (en) * | 2010-04-15 | 2012-12-26 | 日合墨东株式会社 | Photosensitive resin composition, photoresist film using same, method for forming resist pattern, and method for manufacturing printed wiring board |
| CN105130860A (en) * | 2015-08-09 | 2015-12-09 | 同济大学 | Fluorene structure-containing double-branched photosensitive compound, preparation method and applications thereof |
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