CN101183219B - Alkali developable paste composition - Google Patents
Alkali developable paste composition Download PDFInfo
- Publication number
- CN101183219B CN101183219B CN2007101872572A CN200710187257A CN101183219B CN 101183219 B CN101183219 B CN 101183219B CN 2007101872572 A CN2007101872572 A CN 2007101872572A CN 200710187257 A CN200710187257 A CN 200710187257A CN 101183219 B CN101183219 B CN 101183219B
- Authority
- CN
- China
- Prior art keywords
- pattern
- paste composition
- overlay film
- alkali developable
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000000203 mixture Substances 0.000 title claims abstract description 100
- 239000003513 alkali Substances 0.000 title claims description 61
- -1 aluminum compound Chemical class 0.000 claims abstract description 61
- 239000011521 glass Substances 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 54
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 29
- 239000000428 dust Substances 0.000 claims description 19
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 18
- 239000004327 boric acid Substances 0.000 claims description 18
- 238000002835 absorbance Methods 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 239000000049 pigment Substances 0.000 claims description 14
- 239000005864 Sulphur Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 abstract description 7
- 238000003384 imaging method Methods 0.000 abstract description 6
- 150000003254 radicals Chemical class 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 230000005855 radiation Effects 0.000 abstract 1
- 230000001788 irregular Effects 0.000 description 43
- 238000011156 evaluation Methods 0.000 description 26
- 239000002253 acid Substances 0.000 description 24
- 239000000758 substrate Substances 0.000 description 24
- 230000006978 adaptation Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 238000009825 accumulation Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 13
- 229920002120 photoresistant polymer Polymers 0.000 description 13
- 229910052709 silver Inorganic materials 0.000 description 12
- 239000004332 silver Substances 0.000 description 12
- 239000002966 varnish Substances 0.000 description 12
- 206010034960 Photophobia Diseases 0.000 description 11
- 238000011161 development Methods 0.000 description 11
- 239000012530 fluid Substances 0.000 description 11
- 208000013469 light sensitivity Diseases 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 5
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- SKIIKRJAQOSWFT-UHFFFAOYSA-N 2-[3-[1-(2,2-difluoroethyl)piperidin-4-yl]oxy-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound FC(CN1CCC(CC1)OC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CC2=C(CC1)NN=N2)F SKIIKRJAQOSWFT-UHFFFAOYSA-N 0.000 description 3
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000005361 soda-lime glass Substances 0.000 description 3
- 230000004304 visual acuity Effects 0.000 description 3
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 2
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 2
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012675 alcoholic extract Substances 0.000 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 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 2
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- DGZIMLVEXGVYDW-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(O)COC(=O)C=C DGZIMLVEXGVYDW-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- ZKHQWZAMYRWXGA-KQYNXXCUSA-N Adenosine triphosphate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OP(O)(=O)OP(O)(O)=O)[C@@H](O)[C@H]1O ZKHQWZAMYRWXGA-KQYNXXCUSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- DNDQZTHFDBSFES-UHFFFAOYSA-N N(=O)OC(C)CCCCCC.P(O)(O)(O)=O Chemical compound N(=O)OC(C)CCCCCC.P(O)(O)(O)=O DNDQZTHFDBSFES-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- UDMBCSSLTHHNCD-KQYNXXCUSA-N adenosine 5'-monophosphate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(O)=O)[C@@H](O)[C@H]1O UDMBCSSLTHHNCD-KQYNXXCUSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- BQAQHFMZRLEURF-UHFFFAOYSA-N bromo(butyl)phosphane Chemical compound CCCCPBr BQAQHFMZRLEURF-UHFFFAOYSA-N 0.000 description 1
- DLVOLKJQRNEXQR-UHFFFAOYSA-N butoxy ethyl hydrogen phosphate Chemical compound CCCCOOP(O)(=O)OCC DLVOLKJQRNEXQR-UHFFFAOYSA-N 0.000 description 1
- OOSPDKSZPPFOBR-UHFFFAOYSA-N butyl dihydrogen phosphite Chemical compound CCCCOP(O)O OOSPDKSZPPFOBR-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- WZWSOGGTVQXXSN-UHFFFAOYSA-N cyclohexanone;toluene Chemical compound CC1=CC=CC=C1.O=C1CCCCC1 WZWSOGGTVQXXSN-UHFFFAOYSA-N 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
- MCJUWBUSIQXMPY-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical class [Ti].C1C=CC=C1 MCJUWBUSIQXMPY-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- WZPMZMCZAGFKOC-UHFFFAOYSA-N diisopropyl hydrogen phosphate Chemical compound CC(C)OP(O)(=O)OC(C)C WZPMZMCZAGFKOC-UHFFFAOYSA-N 0.000 description 1
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- QDHCHVWSKUMZDZ-UHFFFAOYSA-N ethyl dihydrogen phosphite Chemical compound CCOP(O)O QDHCHVWSKUMZDZ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000001153 fluoro group Chemical class F* 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- ZJTLZYDQJHKRMQ-UHFFFAOYSA-N menadiol Chemical compound C1=CC=CC2=C(O)C(C)=CC(O)=C21 ZJTLZYDQJHKRMQ-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 150000002921 oxetanes Chemical group 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical compound OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 description 1
- QASWQXKZQZCVST-UHFFFAOYSA-N propan-2-yl dihydrogen phosphite Chemical compound CC(C)OP(O)O QASWQXKZQZCVST-UHFFFAOYSA-N 0.000 description 1
- MHZDONKZSXBOGL-UHFFFAOYSA-N propyl dihydrogen phosphate Chemical compound CCCOP(O)(O)=O MHZDONKZSXBOGL-UHFFFAOYSA-N 0.000 description 1
- PRAHMDIEZMWIRW-UHFFFAOYSA-N propyl dihydrogen phosphite Chemical compound CCCOP(O)O PRAHMDIEZMWIRW-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011378 shotcrete Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
The invention provides an alkali-developed paste composition which is applicable to a laser direct imaging device using an active energy radiation with the maximum wave length of 350nm to 420nm, with the advantages of being beneficial for effectively forming a fine black matrix pattern and excellent disperse stability. The invention is characterized by comprising (A) carboxyl-included resin, (B) glass powders, (C) black paints, (D) a compound with at least one free radical polymerizability unsaturated radical, (E-1) NDM series photopolymerization evocating agent such as 2-(acetoxyl group imido group methyl) thioxanthene-9-keton, and (F) aluminum compound.
Description
Technical field
The paste composition that the present invention relates to alkali developable and the conductive pattern that uses it and formation method and this conductive pattern and the black matrix pattern of black matrix pattern, wherein the black paste composition of this alkali developable is suitable for the useful conductive pattern such as thin display and the formation of black matrix pattern.In addition, will indicate the information slip of conductive pattern and black matrix pattern to be shown as pattern below.Under the situation in addition, be expressed as conductive pattern, black matrix pattern.The present invention in more detail; The paste composition that relates to a kind of alkali developable; It has been suitable for using the laser direct imaging device of the active energy beam of maximum wavelength 350nm～420nm; It is useful that efficient is formed meticulous pattern well, and excellent storage stability, and the formation method and the pattern thereof that relate to the pattern that has used said composition.
Background technology
All the time, glass substrate of thin display etc. is formed with the conductive pattern as electrode.In addition, front panel uses black matrix pattern.And its forming method is following, for example, and on glass substrate; Be coated with the resist that dry pattern uses and form and film, this is filmed and uses the active energy beam exposure image through the photomask of describing circuit, electrode pattern, utilizes deliquescent different to developer solution of exposure portion and non-exposure portion then; Carry out development treatment with alkaline aqueous solution; Formation and circuit, resist layer that electrode pattern is corresponding burn till thus, thereby form the pattern with the glass substrate driving fit.
Make the composition of its sensitization, exposure through the laser scanning as this active energy beam, the composition that has proposed to contain specific dye sensitizing agent and two cyclopentadiene titanium compounds etc. is (for example, with reference to patent documentation 1 and patent documentation 2.), the laser photosensitive composition that contains specific two acylphosphine oxide is (for example, with reference to patent documentation 3.), but these compositions can not get the sufficient light sensitivity for active energy beam.
Patent documentation 1: TOHKEMY 2002-351071 communique (claims)
Patent documentation 2: TOHKEMY 2002-351072 communique (claims)
Patent documentation 3: TOHKEMY 2004-45596 communique (claims)
Summary of the invention
Invent problem to be solved
The present invention carries out in view of the above problems; Its fundamental purpose is to provide a kind of paste composition of alkali developable; It is high and to form meticulous pattern well for efficient useful to light sensitivity of active energy beam, and formation method and pattern thereof that the pattern that has used said composition is provided.
The method that is used to deal with problems
In order to solve above-mentioned problem, the present invention possesses following composition.
(1) a kind of paste composition of alkali developable; It is characterized in that; It comprises: (A) contain the compound, the oxime ester shown in (E-1) formula (I) that have free-radical polymerised unsaturated group more than at least 1 in carboxy resin, (B) glass dust, (C) inorganic powder, (D) a part and be Photoepolymerizationinitiater initiater and (F) sulphur compound shown in the formula (II)
In the formula, R
1The alkyl or the phenyl of expression hydrogen atom, carbon number 1～6, R
2The alkyl of expression hydrogen atom, carbon number 1～6,
In the formula, R
3Expression alkyl, aryl or substituted aryl, R
4Expression hydrogen atom or alkyl, in addition, R
3And R
4Expression mutually combines to form and can comprise heteroatomic 5 yuan of being selected from oxygen, sulphur and nitrogen-atoms and encircle 7 yuan of needed non-metallic atom crowds of ring.
According to the paste composition of (1) described alkali developable, it is characterized in that (2) said oxime ester is that Photoepolymerizationinitiater initiater (E-1) is a Photoepolymerizationinitiater initiater for (1) the described oxime ester shown in the formula (III),
In the formula, 1 or 2 R
5Shown in following general formula (I), 2 R wherein
5In the time of shown in general formula (I), comprise R
5Condition of different separately; All the other R
5Expression hydrogen atom, methyl, phenyl or halogen atom are comprising each R
5Condition of different separately,
In the formula, R
1The alkyl or the phenyl of expression hydrogen atom, carbon number 1～6, R
2The alkyl of expression hydrogen atom, carbon number 1～6.
According to the paste composition of (1) or (2) described alkali developable, it is characterized in that (3) the said carboxy resin (A) that contains further is the carboxy resin that contains that (A-1) has free-radical polymerised unsaturated group more than.
(4) according to the paste composition of (1) or (2) described alkali developable, it is characterized in that also comprising the phosphine oxide shown in (E-2) formula (IV) is Photoepolymerizationinitiater initiater,
In the formula, R
6, R
7The straight chain shape of independent respectively expression carbon number 1～10 or the alkyl of branched, cyclohexyl, cyclopentyl, aryl, or by the substituted aryl of halogen atom, alkyl or alkoxy, or arbitrary side be the carbonyl of carbon number 1～20.
According to the paste composition of (4) described alkali developable, it is characterized in that (5) the oxime ester shown in the said general formula (I) is that the use level of Photoepolymerizationinitiater initiater (E-1) is that the use level of Photoepolymerizationinitiater initiater (E-2) is lacked than the phosphine oxide shown in the said general formula (IV).
(6) according to the paste composition of (1) or (2) described alkali developable, it is characterized in that, also contain (G) boric acid.
(7) according to the paste composition of (1) or (2) described alkali developable, it is characterized in that, also contain the phosphorus compound shown in (H) formula (V) or the general formula (VI).
(8) according to the paste composition of (1)～(7) each described alkali developables, it is characterized in that dry each described composition of said (1)～(7) of coating and the absorbance of per 1 μ m thickness of filming of obtaining is 0.1～0.8.
(9) according to the paste composition of (1) or (2) described alkali developable, it is characterized in that said (C) inorganic powder is black pigment or silver powder.
(10) according to the paste composition of (1) or (2) described alkali developable, it is characterized in that the oxime ester shown in the said general formula (I) is that the use level of Photoepolymerizationinitiater initiater (E-1) is 0.1～1.0 quality % of total composition.
(11) a kind of formation method of pattern is characterized in that, has been to use the formation method of the pattern of each described compositions of (1)～(10), and wherein, this method comprises:
(1) through active energy beam carry out pattern exposure operation,
(2) optionally form through developing with the diluted alkaline property WS pattern operation,
The operation of (3) under 400～600 ℃, burning till.
(12) according to the formation method of (11) described pattern, it is characterized in that said active energy beam is laser generation light source or lamp source.
(13) a kind of pattern, its formation method through (11) or (12) described pattern obtains.
(14) according to (13) described pattern, it is characterized in that said pattern is a conductive pattern.
(15) according to (13) or (14) described pattern, it is characterized in that said pattern comprises black matrix pattern.
(16) a kind of Plasmia indicating panel, it comprises the paste composition of use (1)～(10) each described alkali developable and the pattern that forms.
(17) a kind of Plasmia indicating panel, it comprises each described pattern of (13)～(15).
The effect of invention
The paste composition of alkali developable of the present invention has sufficient light sensitivity to active energy beam, and can form pattern with high precision through cooperating the sulphur compound shown in the above-mentioned general formula (II).
In addition, therefore the aforesaid paste composition can make public in the short time because active energy beam is had sufficient light sensitivity, can improve the manufacturing efficient of pattern through the shortening needed time of exposure.
In addition,, therefore can use the laser direct imaging device, can form the high pattern of reliability as exposure device owing to the active energy beam that for maximum wavelength is 350nm～420nm shows excellent photo-curable.
Embodiment
The paste composition of alkali developable of the present invention has following characteristic: its comprise (A) contain have in carboxy resin, (B) glass dust, (C) inorganic powder, (D) a part the compound of at least more than one free radical repeatability unsaturated group and (E-1) the oxime ester shown in the aforementioned formula (I) be that light overlaps the sulphur compound shown in initiating agent, (F) aforementioned formula (II), this paste composition demonstrates excellent photo-curable for active energy beam.
In addition, in preferred form, can be provided in the above-mentioned composition and contain (G) boric acid, and the composition of excellent storage stability.In addition, can provide and contain (H) phosphorus compound, and the composition of excellent storage stability.
Below, each constituent of the paste composition of alkali developable of the present invention is elaborated.
(A) contain carboxy resin
As the paste composition of alkali developable of the present invention contained contain carboxy resin (A), can use the resin compound known commonly used that contains carboxyl in the molecule.
Particularly, can enumerate out the resin of enumerating as follows.
(1) contain through the compound copolymerization with unsaturated double-bond beyond it obtains with unsaturated carboxylic acid such as (methyl) acrylic acid with more than a kind carboxy resin,
(2) at unsaturated carboxylic acid such as (methyl) acrylic acid and more than a kind on the multipolymer of the compound beyond it with unsaturated double-bond; Through (methyl) glycidyl acrylate, (methyl) acrylic acid 3; 4-epoxycyclohexyl methyl esters etc. has addition ethylenically unsaturated groups such as the compound, (methyl) acrylic acid chloride of epoxy radicals and unsaturated double-bond as side chain, thus obtain contain the carboxyl photoresist,
(3) make (methyl) glycidyl acrylate, (methyl) acrylic acid 3; 4-epoxycyclohexyl methyl esters etc. has the compound and the compound copolymerization with unsaturated double-bond beyond it of epoxy radicals and unsaturated double-bond; Make unsaturated carboxylic acids reactions such as this multipolymer and (methyl) acrylic acid, the secondary hydroxyl that is generated react with multi-anhydride and obtain contain the carboxyl photoresist,
(4) make maleic anhydride etc. have the acid anhydrides and the compound copolymerization beyond it of unsaturated double-bond with unsaturated double-bond, the compound that makes this multipolymer and (methyl) acrylic acid 2-hydroxyl ethyl ester etc. have hydroxyl and unsaturated double-bond react and obtain contain the carboxyl photoresist,
(5) make the reaction of multi-group epoxy compound and unsaturated monocarboxylic, the hydroxyl that is generated and saturated or unsaturated multi-anhydride react and obtain contain the carboxyl photoresist,
(6) make the reaction of hydroxyl polymer-containing such as polyvinyl alcohol derivative and saturated or unsaturated multi-anhydride, the compound that has epoxy radicals and unsaturated double-bond in the carboxylic acid that makes generation then and a part react and the photoresist of the hydroxyl that obtains and carboxyl,
(7) make have in multi-group epoxy compound, unsaturated monocarboxylic, a part at least 1 alcoholic extract hydroxyl group and can with the compound reaction of 1 reactive group beyond the alcoholic extract hydroxyl group of epoxy reaction, this reaction product and saturated or unsaturated multi-anhydride are reacted and obtain contain the carboxyl photoresist,
(8) make the reaction of the polyfunctional group oxetane compound that has at least 2 oxetanes rings in a part and unsaturated monocarboxylic, make primary hydroxyl and saturated or unsaturated multi-anhydride in the modification oxetane resin of gained react gained contain the carboxyl photoresist and
(9) make the reaction of polyfunctional epoxy resin and unsaturated monocarboxylic; Make the reaction of itself and multi-anhydride then and obtain contain carboxy resin again with molecule in have the compound reaction of 1 oxirane ring and 1 above ethylenically unsaturated group and obtain contain carboxyl photoresist etc., but not limited by these.
As preferably containing the carboxyl photoresist in the middle of these illustrations, from photo-curable, burning till property aspect, what have ethylenical unsaturated double bonds in the molecule of preferably above-mentioned (2) and (3) contains the carboxyl photoresist.
In addition, in this instructions, (methyl) acrylic ester is the term of general name acrylic ester, methacrylate and their potpourri, and other similar expression too.
The above-mentioned carboxy resin (A) that contains has a plurality of free carboxyls on the side chain of trunk polymer, the diluted alkaline property WS therefore capable of using develops.
In addition, the above-mentioned acid number that contains carboxy resin (A) is the scope of 40～200mgKOH/g, more preferably the scope of 45～120mgKOH/g.When containing the acid number deficiency 40mgKOH/g of carboxy resin, be difficult to alkali and develop, on the other hand; When surpassing 200mgKOH/g, developer solution excessively carries out the dissolving of exposure portion, and line is thinner than needed; Perhaps according to circumstances; Exposure portion and unexposed are developed the liquid dissolving as broad as longly and peel off, and are difficult to describe normal resist pattern, so not preferred.
In addition, the above-mentioned weight-average molecular weight that contains carboxy resin (A) is different because of resin matrix, but be preferably 2000～150000 usually, further be 5000～100000 scope.During weight-average molecular weight less than 2000, tack-free performance is bad, and the moisture-proof of filming after the exposure is poor, occurs film during development and reduces, and resolving power deteriorates significantly.On the other hand, weight-average molecular weight surpasses at 150000 o'clock, and development property significantly worsens, and bin stability is poor.
Using (C-1) black pigment as under the situation of (C), such use level that contains carboxy resin (A) is preferably 10～80 quality % in whole compositions, 15～50 quality % more preferably.In addition, using (C-2) silver powder as under the situation of (C), the use level that contains carboxy resin (A) is preferably 2～50 quality % in whole compositions, 4～30 quality % more preferably.When use level was very few, coating strength reduced, so not preferred.On the other hand, when use level was too much, viscosity uprised, and so reductions such as coating are not preferred.
(B) glass dust
The employed glass dust of the paste composition of alkali developable of the present invention (B), can use softening point is 300～600 ℃ glass powder with low melting point, can suit to use with massicot, bismuth oxide or the zinc paste material as principal ingredient.In addition, from the resolving power aspect, preferably use mean grain size to be below the 20 μ m, be preferably the glass dust below the 5 μ m.As the preferred example that with massicot is the glass powder of principal ingredient, can enumerate out following amorphism frit:, have 48～82%PbO, 0.5～22%B in quality % based on oxide
2O
3, 3～32%SiO
2, 0～12%Al
2O
3, 0～10%BaO, 0～15%ZnO, 0～2.5%TiO
2, 0～25%Bi
2O
3Composition, and softening point is 420～590 ℃.
In addition, as the preferred example that with the bismuth oxide is the glass powder of principal ingredient, can enumerate out following amorphism frit: the quality % in based on oxide has 35～88%Bi
2O
3, 5～30%B
2O
3, 0～20%SiO2,0～5%Al
2O
3, 1～25%BaO, 1～20%ZnO composition, and softening point is 420～590 ℃.
In addition, as the preferred example that with zinc paste is the glass powder of principal ingredient, can enumerate out following amorphism frit:, have 25～60%ZnO, 2～15%K in quality % based on oxide
2O, 25～45%B
2O
3, 1～7%SiO
2, 0～10%Al
2O
3, 0～20%B aO, 0～10%MgO composition, and softening point is 420～590 ℃.
The use level of such glass dust is preferably 1～20 quality % in whole compositions, 2～10 quality % more preferably.When use level is very few, poor with the adaptation of base material, when use level is too much, possibly produce thickening, the gelation of composition.In addition, when forming conductive pattern, the rising of the ratio resistance value after possibly causing burning till, not preferred.
(C) inorganic powder
The paste composition of alkali developable of the present invention employed (C) inorganic powder comprises black pigment (C-1) or silver powder (C-2).
Black pigment (C-1)
The black pigment (C-1) of the employed composition of the paste composition of alkali developable of the present invention (C) can suit to use the single metal oxide of Cu, Fe, Cr, Mn, Co, Ru, La etc. and/or the composite oxides that formed by metallic element more than 2 kinds.From the resolving power aspect, use that its mean grain size is preferably below the 10 μ m, the black pigment below the 2.5 μ m more preferably.On the other hand, from the degree of blackness aspect, suitable use that mean grain size is preferably below the 1.0 μ m, the black pigment below the 0.6 μ m more preferably.
In this black pigment, especially preferably use specific surface area at 1.0～20m
2Cobaltosic oxide (the Co of the scope of/g
3O
4) particulate.Its reason be because, the not enough 1.0m of this specific surface area
2/ g, the precision that the pattern that utilizes exposure to carry out forms reduces, be difficult to obtain the rectilinearity at line edge or fully blackness burn till overlay film.On the other hand, surpass 20m
2/ g, the surface area of particle becomes excessive, is prone to produce undercutting (undercut) during development.
In addition, as the use level of black pigment (C-1), be that the scope of 10～100 mass parts is suitable with respect to the aforementioned carboxy resin (A) that contains of 100 mass parts.When very few, can not get sufficient blackness after burning till, not preferred.On the other hand, in the time of too much, light transmission reduces, and is prone to produce undercutting, so not preferred.
Silver powder (C-2)
The silver powder (C-2) of the employed composition of the paste composition of alkali developable of the present invention (C) is the material of paste being given electric conductivity; Can use known silver powder commonly used; But from burning till property aspect, the half breadth at Ag (111) face peak shows more than 0.15 °, is preferably the material of the value more than 0.19 ° in the preferred X-ray analysis pattern.The silver powder (C-2) that this half breadth less than is 0.15 °, the crystallization degree of silver powder is high, is difficult for producing intergranular sintering, and therefore resistance value does not reduce under the firing temperature below 620 ℃, so not preferred.In addition, preferably this half breadth is below 1.0 °.When half breadth surpassed 1.0 °, the crystallization degree of silver powder was low, and intergranular sintering excessively carries out, and line possibly produce irregular bending, twisted, so not preferred.
Such silver powder (C-2) is usually through method manufacturings such as atomizing (atomize) method, chemical reduction methods.Atomization is the method for utilizing the silver of gas, water or other fluid spraying fusion and obtaining silver powder, the spherical particle that is easy to get, and the property produced in batches is excellent.Chemical reduction method is to use reductive agent to make water soluble silver salt generation chemical reaction and obtains the method for silver powder.Particularly, be following method, that is, use silver nitrate as water soluble silver salt, use alkali such as caustic alkali as reductive agent, ammonium salt, hydrazine that argent is separated out, then with the silver-colored pulp-water of gained wash, drying, obtain silver powder.
The resulting silver powder of operation (C-2) can use the silver powder of different shape such as spherical, laminar, dendritic like this, especially considers light characteristic, when dispersed, preferably uses spherical silver powder.
In addition, when using electron microscope (SEM) to observe these silver powder (C-2) with 10000 times, this silver powder (C-2) is preferred to use at random that the mean grain size of 10 silver powder is 0.1～5 μ m, be preferably the silver powder of 0.4～2.0 μ m size.During this mean grain size less than 0.1 μ m, optical transmission property variation is difficult to describe high meticulous pattern, on the other hand, when mean grain size surpasses 5 μ m, is difficult to obtain the rectilinearity at line edge, so not preferred.In addition, the preferred mean grain size of measuring through Microtrac (laser particle size analyzer device) of using is the silver powder of 0.5～3.5 μ m size.
In addition, preferably to use specific surface area be 0.01～2.0m to this silver powder (C-2)
2/ g, be preferably 0.1～1.0m
2The silver powder of/g.The not enough 0.01m of this specific surface area
2During/g, be prone to cause sedimentation during preservation, on the other hand, specific surface area surpasses 2.0m
2During/g, the oil suction quantitative change is big, and so paste mobile impaired be not preferred.
With respect to the paste composition of 100 mass parts alkali developables, it is suitable that the use level of such silver powder (C-2) is preferably 50～90 mass parts.When the use level of silver powder is very few, can not get sufficient electric conductivity from the resulting conductive pattern of this paste, on the other hand, in the time of too much, with the adaptation variation of base material, so not preferred.
(D) has free-radical polymerised unsaturated group more than at least 1 in a part
Compound
As the compound (D) that has free-radical polymerised unsaturated group more than at least 1 in aforementioned a part used in the present invention, can enumerate out acrylic acid hydroxy alkyl ester classes such as acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol five acrylic ester; The mono acrylic ester or the diacrylate class of glycol such as monoethylene glycol, methoxyl TEG, polyglycol, propylene glycol; N, N-DMAA, N hydroxymethyl acrylamide, N, acrylic amides such as N-dimethylamino propyl acrylamide; Acrylic acid N, N-dimethylaminoethyl, acrylic acid N, acrylic-amino alkyl esters such as N-dimethylamino propyl ester; The multicomponent methacrylate class of polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or these ethylene oxide adduct or propylene oxide adduct etc.; The esters of acrylic acid of the ethylene oxide adduct of acrylic acid benzene oxygen ester, bisphenol a diacrylate and these phenols or propylene oxide adduct etc.; The esters of acrylic acid of glycidol ethers such as glycerine diglycidyl ether, glycerine triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group isocyanuric acid ester; The isocyanate-modified thing of aforesaid propylene acid hydroxy alkyl ester, that is, and polyfunctional group or simple function group urethane acrylate; And melamine acrylate and each (methyl) esters of acrylic acid corresponding with the aforesaid propylene acid esters, these can use separately or make up more than 2 kinds and use.In the middle of these, particularly have the compound of free-radical polymerised unsaturated group more than at least 2 in a part, for example pentaerythritol triacrylate, dipentaerythritol acrylate etc. are because photo-curable is excellent, so preferably.
In addition, below, abbreviate this compound as polymerizable monomer.
With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the use level that has (D) of free-radical polymerised unsaturated group more than at least 1 in such a part is preferably 5～100 mass parts, the ratio of 10～70 mass parts more preferably.When aforementioned use level was very few, photo-curable reduced, and developed through the alkali behind the irradiation active energy beam, was difficult to form pattern, so not preferred.On the other hand, in the time of too much, to the dissolubility reduction of alkaline aqueous solution, perhaps filming becomes fragile, so not preferred.
Oxime ester as shown in (E-1) aforementioned formula (I) is the object lesson of Photoepolymerizationinitiater initiater; Can enumerate out { 1-[4-(thiophenyl)-2-(O-benzoyl oxime)] } 1,2-(acetoxyl group iminomethyl) thioxanthene-9-one shown in 2-acetyl caproyl, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) ethyl ketone and the formula (VII).In the middle of these, compound, 2-(acetoxyl group iminomethyl) thioxanthene-9-one shown in the preferred especially following formula (VII).As commercially available article, the CGI-325 that has Xiba Special Chemical Product Co.,Ltd to produce.
Using (C-1) black pigment as under the situation of (C), with respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, such oxime ester is that the use level of Photoepolymerizationinitiater initiater (E-1) is preferably 0.01～20 mass parts, the ratio of 0.01～5 mass parts more preferably.In addition, using (C-2) silver powder as under the situation of (C), the oxime ester is the ratio that the use level of Photoepolymerizationinitiater initiater (E-1) is preferably 0.1～1.0 all quality % of composition.In addition at this moment; With the aforementioned carboxy resin (A) that contains of 100 mass parts is that the oxime ester of benchmark is that the suitable scope of the use level of Photoepolymerizationinitiater initiater (E-1) changes according to the compound that has free-radical polymerised unsaturated group more than 1 in glass dust, silver powder, a part and the use level of organic solvent at least, and the chances are, and aforementioned to contain carboxy resin (A) be 0.01～20 mass parts, be preferably 0.05～10 mass parts, the ratio of 0.5～5.0 mass parts more preferably with respect to 100 mass parts.The oxime ester is that the use level of Photoepolymerizationinitiater initiater (E-1) when very few, can not get sufficient photo-curable, so not preferred with respect to the aforementioned carboxy resin (A) that contains of 100 mass parts.On the other hand, in the time of too much, the thick film curable reduces, and the cost that involves product improves, so not preferred.
The paste composition of alkali developable of the present invention is in order further to improve light sensitivity, and the phosphine oxide that preferred cooperation comprises the structure shown in the above-mentioned general formula (IV) is Photoepolymerizationinitiater initiater (E-2).
As such phosphine oxide is Photoepolymerizationinitiater initiater (E-2), can enumerate out 2,4; 6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxide, two (2; 6-dimethoxy benzoyl)-2,4,4-trimethyl-amyl group phosphine oxide etc.
With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, such phosphine oxide is that the use level of Photoepolymerizationinitiater initiater (E-2) is, is preferably the ratio below 50 mass parts below 60 mass parts.Phosphine oxide is the use level of Photoepolymerizationinitiater initiater (E-2) when surpassing 60 mass parts, and the thick film curable reduces, and the cost that involves product improves, so not preferred.
In addition; For ISO and obtain the thick film curable; Oxime ester shown in the preferred aforementioned formula (I) is that the use level of Photoepolymerizationinitiater initiater (E-1) is that the use level of Photoepolymerizationinitiater initiater (E-2) is an equivalent with the phosphine oxide shown in the above-mentioned general formula (IV) at least, is that the use level of Photoepolymerizationinitiater initiater (E-2) is lacked than the phosphine oxide shown in the above-mentioned general formula (IV) perhaps.
The paste composition of alkali developable of the present invention can also make up as required and use known Photoepolymerizationinitiater initiater commonly used.Particularly, can enumerate out benzoin and benzoin alkylether classes such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether; Acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1, acetophenones such as 1-dichloroacetophenone; 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-aminoacetophenone classes such as 1-butanone; Anthraquinone classes such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone; 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, thioxanthene ketones such as 4-diisopropyl thioxanthones; Ketal classes such as acetophenone dimethyl ketal (acetophenone dimethyl ketal), benzil dimethyl ketal; Benzophenones such as benzophenone; Or xanthene ketone; (2,6-dimethoxy benzoyl)-2,4,4-amyl group phosphine oxide, two (2; 4, the 6-trimethylbenzoyl)-phenyl phosphine oxide, 2,4; 6-trimethylbenzoyl diphenyl phosphine oxide, ethyl-2,4, phosphinoxidess such as 6-trimethylbenzoyl phenyl-phosphonite ester etc.The curable aspect from the deep, special preferred compositions uses 2,4-dimethyl thioxanthones, 2; 4-diethyl thioxanthone, 2-clopenthixal ketone, 2; Thioxanthones such as 4-diisopropyl thioxanthones are Photoepolymerizationinitiater initiater or two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxide, 2; 4, phosphine oxides such as 6-trimethylbenzoyl diphenyl phosphine oxide are Photoepolymerizationinitiater initiater.
With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, such thioxanthones is that Photoepolymerizationinitiater initiater or phosphine oxide are that the use level of Photoepolymerizationinitiater initiater is preferably below 30 mass parts, row of the ratio below 20 mass parts more preferably.These thioxanthones are the use level of Photoepolymerizationinitiater initiater when too much, and the thick film curable reduces, and the cost that involves product improves, so not preferred.
(F) sulphur compound shown in the above-mentioned general formula (II)
Through cooperating this sulphur compound, can improve the light sensitivity about laser of composition, the inventor infers it the reasons are as follows.In the rayed position, along with Raolical polymerizable carries out, polymerizable monomer (D) is difficult to produce diffusion, and polymerization speed, conversion ratio reduce, and (D) is residual for unreacted polymerizable monomer.But, playing the sulphur compound (F) of the effect of chain-transferring agent through interpolation, polyreaction efficient is carried out well and conversion ratio improves, and the result thinks can reach ISOization.
(G) boric acid
In order to improve storage stability, the further preferred boric acid (G) that adds of paste composition of the present invention.
Such boric acid (G) can use and carry out micronized mean grain size (D50) through jet pulverizer, bowl mill, roller mill etc. and be below the 20 μ m, be preferably the boric acid below the 5 μ m.Micronized boric acid like this uses rapidly after therefore preferred the pulverizing owing to being prone to moisture absorption, reassociating.In addition, can also be in paste contained resin, solvent etc. are pulverized boric acid (G).
With respect to the aforementioned glass dust of 100 mass parts (B), it is suitable that the cooperation ratio of such boric acid (G) is preferably 0.01～10 mass parts, more preferably 0.1～2 mass parts.When the cooperation ratio of boric acid is very few with respect to the aforementioned glass dust of 100 mass parts (B), do not improve the effect of storage stability, so not preferred.
In addition, when cooperating boric acid (G) like this, must use solubleness to be the hydrophobic solvent below the 20g for the water of 25 ℃ of 100g.Use is during to the high organic solvent of the solubleness of water, and the water that dissolves in the organic solvent makes metallic ionization contained in the glass dust, becomes the reason of gelation, so not preferred.
(H) phosphorus compound
In addition, in order further to improve the storage stability of the paste composition of alkali developable of the present invention, preferably cooperate the phosphorus compound (H) shown in above-mentioned general formula (V) or the general formula (VI).
As such phosphorus compound (H), can enumerate out methyl orthophosphoric acid, etherophosphoric acid, phosphoric acid propyl ester, butylphosphoric acid ester, phenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutylphosphoric acid ester, di(2-ethylhexyl)phosphate propyl ester, diphenyl phosphate, p isopropylbenzoic acid ester, diisopropyl phosphate, phosphate n-butyl, methyl phosphite, phosphorous acid ethyl ester, phosphorous acid propyl ester, phosphorous acid butyl ester, phenyl-phosphite, dimethylphosphite, diethyl phosphite, dibutyl phosphite, phosphorous acid dipropyl, phosphorous acid diphenyl ester, phosphorous acid isopropyl ester, diisopropyl phosphite, normal-butyl-2-ethylhexyl phosphite ester hydroxy ethylene diphosphonic acid, atriphos, AMP, acid mono phosphoric acid ester (2-methacryloxyethyl) ester, acid mono phosphoric acid ester (2-acryloxy ethyl) ester, acid di(2-ethylhexyl)phosphate (2-methacryloxyethyl) ester, acid di(2-ethylhexyl)phosphate (2-acryloxy ethyl) ester, ethyl diehylphosphonoacetate, acid phosphate ester, acid butyl phosphate, pyrophosphoric acid butyl ester, acid phosphoric acid butoxy ethyl ester, acid phosphoric acid 2-Octyl Nitrite, acid phosphoric acid grease, acid di(2-ethylhexyl)phosphate myristyl ester, acid p diethylaminobenzoic acid diol ester, acid phosphoric acid methacrylic acid 2-hydroxyl ethyl ester etc.These phosphorus compounds can use separately or make up more than 2 kinds and use.
With respect to the aforementioned glass dust of 100 mass parts (B), the use level of these phosphorus compounds (H) is below 10 mass parts, be preferably 0.1～5 mass parts.When the use level of phosphorus compound (H) surpassed 10 mass parts with respect to the aforementioned glass dust of 100 mass parts (B), so the reduction of burning till property was not preferred.
Other complex
For synthetic aforementioned carboxy resin (A), the preparation composition of containing, perhaps adjust viscosity in order to be used to be applied to substrate, carrier film, the paste composition of alkali developable of the present invention can be with an organic solvent.Particularly, can enumerate out ketones such as MEK, cyclohexanone; Toluene, xylene, tetramethylbenzene etc. are aromatic hydrocarbon based; Glycol ethers such as cellosolve, methyl cellosolve, carbitol, methyl carbitol, BC, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, DPG list ether, Triethylene glycol ethyl ether; Acetate esters such as ethyl acetate, butyl acetate, cellosolve acetic acid esters, butyl cellosolve acetate, carbitol acetic acid esters, acetate of butyl carbitol, propylene glycol methyl ether acetate; Alcohols such as ethanol, propyl alcohol, monoethylene glycol, propylene glycol, terpinol; Aliphatic hydrocarbon such as octane, decane; Petroleum-type solvents such as sherwood oil, naphtha, hydrogenated naphtha, solvent naphtha etc., these can use separately or make up more than 2 kinds and use.
As required; The paste composition of alkali developable of the present invention can also cooperate following known additive kind commonly used: known thickening agents commonly used such as known hot polymerization inhibitor commonly used such as quinhydrones, hydroquinone monomethyl ether, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, phenothiazine, fine particle silica, organobentonite, polynite; Foam-breaking agent and/or levelling agents such as silicone, fluorine class, high score subclass, silane coupling agents such as imidazoles, thiazoles, triazole type etc.
The use of composition
The paste composition of the alkali developable of more than explaining of the present invention; For example adjust to the viscosity that is fit to coating process with aforementioned organic solvent; Be applied on the substrate through methods such as immersion coating method, cast cladding process, rolling method, line rod cladding process, silk screen print method, curtain formula cladding processes; At for example about 60～120 ℃ times dry about 5～40 minutes, thereby can form tack-free filming.Perhaps, above-mentioned composition is applied on the carrier film and dry and curl with film like, this is laminated on the substrate, thereby can forms tack-free filming.
In addition, from the pattern aspect that becomes second nature, the absorbance of dry per 1 μ m thickness of filming is preferably 0.1～0.8 like this.
, adopt contact (or noncontact mode), optionally make public with active energy beam, utilize the diluted alkaline property WS (for example 0.3～3% aqueous sodium carbonate) to develop and the formation pattern unexposed through forming figuratum photomask thereafter.
Shine employed exposure machine as above-mentioned active energy beam, can use direct drawing apparatus (for example according to the cad data of computer directly with the laser direct imaging device of laser rendering image).As the active energy beam source, can enumerate out and send maximum wavelength, preferred especially laser diode at the laser diode of the laser of the scope of 350nm～420nm, gas laser, solid state laser etc.
As above-mentioned direct drawing apparatus, can use for example Japanese Orbotech Ltd. company, PENTAX company, Hitachi Via Mechanics, the product that Ltd. company, BALLSemiconductor Inc. company etc. produce can use any device.
In addition, except above-mentioned direct drawing apparatus, can also use existing exposure machine.As its light source, can use Halogen lamp LED, high-pressure sodium lamp, laser, metal halide lamp, black lamp, electrodeless lamp etc.
In addition, aforementioned development can be used gunite, infusion process etc.As developer solution; Can suit to use the metal alkaline WS of NaOH, potassium hydroxide, sodium carbonate, sal tartari, sodium silicate etc.; Amine aqueous solutions such as monoethanolamine, diethanolamine, triethanolamine, TMAH; The diluted alkaline property WS of the concentration below particularly about 1.5 quality % as long as the carboxyl that contains carboxy resin (A) in the composition is removed by saponification, uncured (unexposed portion), does not receive the qualification of above-mentioned developer solution.In addition, in order to remove the unwanted developer solution in back that develops, preferably wash, the acid neutralization.
Form the substrate of pattern through above-mentioned development, in air or under nitrogen atmosphere, burnt till with about 400～600 ℃, can form desired pattern thus.
Embodiment
Below, embodiment is shown and comparative example specifies the present invention, certainly, the present invention is not limited to following embodiment.
Synthetic example 1: contain the synthetic of carboxy resin
In the flask that possesses thermometer, stirrer, tap funnel and reflux condenser; Add methyl methacrylate and methacrylic acid with 0.87: 0.13 mol ratio; Adding is as the dipropylene glycol monomethyl ether of solvent, as the azoisobutyronitrile of catalyzer; Under nitrogen atmosphere,, obtain containing carboxy resin solution in 80 ℃ of stirrings 6 hours.The weight-average molecular weight of this resin is about 10000, and acid number is 74mgKOH/g.In addition, the mensuration of the weight-average molecular weight of the copolymer resins of gained is the high performance liquid chromatograph mensuration through being connected to post Shodex (registered trademark) KF-804 that pump LC-6AD that (strain) Shimadzu Seisakusho Ltd. produces and clear and electrician's (strain) produce, KF-803, three posts of KF-802.Below, claim that this contains carboxy resin solution is A-1 varnish.
Synthetic example 2: contain the synthetic of carboxyl photoresist
In the flask that possesses thermometer, stirrer, tap funnel and reflux condenser; Is 0.76: 0.24 with the rate of charge of methyl methacrylate and methacrylic acid with molar ratio computing; Adding is as the dipropylene glycol monomethyl ether of solvent, as the azoisobutyronitrile of catalyzer; Under nitrogen atmosphere,, obtain containing carboxy resin solution in 80 ℃ of stirrings 6 hours.This is contained the cooling of carboxy resin solution; Use is as the methylnaphthohydroquinone of polymerization inhibitor, as the Si butyl phosphonium bromide of catalyzer; Under 95～105 ℃, 16 hours condition of reaction; Making GMA is the addition mol ratio generation addition reaction of 0.12 mole ratio with 1 mole of carboxyl with respect to above-mentioned resin, and take out the cooling back.The weight-average molecular weight that contains the carboxyl photoresist that generates through above-mentioned reaction is about 10000, and acid number is 59mgKOH/g, and two key equivalents are 950.Below, claim that this contains carboxyl photoresist solution is A-2 varnish.
Embodiment 1～18 and comparative example 1～2
With 3 roll-type roller mills the table 1 of the A-1 varnish that used aforementioned synthetic routine 1,2 gained and A-2 varnish and the gradation composition shown in the table 2 are carried out mixingly, obtain the paste composition of alkali developable.
Table 1
| Embodiment | Comparative example | |||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 1 | |
| A-1 varnish | 100 | 100 | 100 | - | 100 | 100 | 100 | 100 | 100 | 100 |
| A-2 varnish | - | - | - | 100 | - | - | - | - | - | - |
| Glass dust ※ 1 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Black pigment ※ 2 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| Polymerizable monomer ※ 3 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| Photoepolymerizationinitiater initiater (E-1) ※ 4 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | - | 2 | - |
| Photoepolymerizationinitiater initiater (E-1) ※ 5 | - | - | - | - | - | - | - | 2 | 0.5 | - |
| Photoepolymerizationinitiater initiater (E-2) ※ 6 | - | 30 | 30 | 30 | 50 | 30 | 30 | 30 | 30 | - |
| Sulphur compound ※ 7 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | - |
| Photoepolymerizationinitiater initiater ※ 8 relatively | - | - | - | - | - | - | - | - | - | 10 |
| Boric acid ※ 9 | - | - | 0.1 | 0.1 | 0.1 | 0.1 | - | 0.1 | 0.1 | - |
| Phosphorus compound ※ 10 | - | - | - | - | - | 1 | 1 | 1 | 1 | - |
| Remarks | ※ 1: will have 60%PbO, 20%B 2O 3、15％SiO 2、5％Al 2O 3Composition and thermalexpansioncoefficient 300=70 * 10 -7/ ℃, glass transition temperature is that to pulverize the mean grain size obtain be the glass dust ※ 2 of 1.6 μ m for the material of 445 ℃ character: the concentration with 70%; With maximum particle diameter is below the 5 μ m and mean grain size is that the cobaltosic oxide black particle of 0.2 μ m evenly spreads to the slurry ※ 3 that obtains in the tripropylene glycol monomethyl ether: pentaerythritol triacrylate ※ 4:2-(acetoxyl group iminomethyl) thioxanthene-9-one ※ 5:1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) ethyl ketone ※ 6:2; 4,6-trimethylbenzoyl diphenyl phosphine oxide ※ 7:2-mercaptobenzothiazoler ※ 8:2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone ※ 9: be ground into the boric acid ※ 10 below the mean grain size 5 μ m with jet pulverizer: acid phosphoric acid 2-methacryloxy ethyl ester | |||||||||
Table 2
| Embodiment | Comparative example | |||||||||
| 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 2 | |
| A-1 varnish | 100 | 100 | - | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| A-2 varnish | - | - | 100 | - | - | - | - | - | - | - |
| Glass dust ※ 1 | 25 | 25 | 25 | 25 | 25 | 25 | 25 | 25 | 25 | 25 |
| Silver powder ※ 2 | 450 | 450 | 450 | 450 | 450 | 450 | 650 | 450 | 450 | 450 |
| Polymerizable monomer ※ 3 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| Photoepolymerizationinitiater initiater (E-1) ※ 4 | 2 | 2 | 2 | 2 | 2 | 6 | 3 | - | 2 | - |
| Photoepolymerizationinitiater initiater (E-1) ※ 5 | - | - | - | - | - | - | - | 2 | 0.5 | - |
| Sulphur compound ※ 6 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | - |
| Other Photoepolymerizationinitiater initiater ※ 7 | - | - | - | - | - | - | - | - | 10 | - |
| Photoepolymerizationinitiater initiater ※ 8 relatively | - | - | - | - | - | - | - | - | - | 10 |
| Boric acid ※ 9 | - | 0.1 | 0.1 | 0.1 | - | 0.1 | 0.1 | 0.1 | 0.1 | - |
| Phosphorus compound ※ 10 | - | - | - | 1 | 1 | 1 | 1 | 1 | 1 | - |
| Remarks | ※ 1: will have 60%PbO, 20%B 2O 3、15％SiO 2、5％Al 2O 3Composition and thermalexpansioncoefficient 300=70 * 10 -7/ ℃, glass transition temperature is that to pulverize the mean grain size obtain be the glass dust ※ 2 of 1.6 μ m for the material of 445 ℃ character: mean grain size is the silver powder ※ 3 of 5 μ m, maximum particle diameter 15 μ m: pentaerythritol triacrylate ※ 4:2-(acetoxyl group iminomethyl) thioxanthene-9-one ※ 5:1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) ethyl ketone ※ 6:2-mercaptobenzothiazoler ※ 7:2; 4,6-trimethylbenzoyl diphenyl phosphine oxide ※ 8:2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone ※ 9: be ground into the boric acid ※ 10 below the mean grain size 5 μ m: acid phosphoric acid 2-methacryloxy ethyl ester with jet pulverizer | |||||||||
Use the black paste composition of the alkali developable of the foregoing description 1～9 and comparative example 1, be applied on the glass substrate with the whole face of 300 purpose polyester nets.Then, use the heated air circulation type drying oven, form the good overlay film of dry to touch property 90 ℃ of dryings 20 minutes.Then; Use the cad data of the striated of live width 100 μ m, interval width 150 μ m; Bluish violet color laser through having centre wavelength 405nm is 40mJ/cm as the laser direct imaging exposure device (PENTAX company produces, DI-μ 10) of light source with the accumulation light quantity on the composition
2Amount exposure.Use the 0.4wt%Na of 30 ℃ of fluid temperatures thereafter,
2CO
3The WS developed for 20 seconds, washing.At last, use electric furnace in air, to burn till.
In addition, carry out following operation in burning till: be warmed up to 590 ℃ with 5 ℃/minute programming rates from room temperature, kept 10 minutes, place cool to room temperature then at 590 ℃.
The result that the various characteristics of each substrate of such operation gained is estimated is shown in the table 3.
In addition, the evaluation method in the table 3 is following.
(1) mensuration of absorbance
Use ultraviolet-visible pectrophotometer to be determined at the absorbance of the evaluation substrate of filming that has formed dry film thickness 5 m and 10 μ m on the soda-lime glass.Go out the absorbance of per 1 μ m thickness under the 405nm from the data computation of gained.
(2) evaluation of laser-photosensitive
With 50mJ/cm
2The line of accumulation light quantity exposure L/S=100/150 μ m, use the 0.4wt%Na of 30 ℃ of fluid temperatures
2CO
3The WS developed for 20 seconds, whether can form line through the optical microscope evaluation.Metewand is following.
Zero: can't see shortcoming fully.
△: visible some shortcomings.
*: can not form line.
(3) calculating of lowest exposure amount
Change the accumulation light quantity and make public, determine the minimum exposure amount that can not form the line of L/S=100/150 μ m with being short of.In addition, comparative example is because long with the time shutter of laser, and impracticable, so do not implement the test of back.
The shape of the line after (4) pattern forms
When utilizing the exposure of aforesaid lowest exposure amount, with the pattern after the development of the black paste composition of microscopic alkali developable, the evaluation line has and do not have irregular skew, twisted etc.Metewand is following.
Zero: do not have irregular skew, do not have twisted etc.
△: some irregular skews, twisted etc. are arranged.
*: irregular skew, twisted etc. is arranged.
(5) shape of the line after burning till
The shape of the line after burning till be with microscopic up to burning till the pattern that is through with, estimate line have do not have irregular skew, twisted etc.Metewand is following.
Zero: do not have irregular skew, do not have twisted etc.
△: some irregular skews, twisted etc. are arranged.
*: irregular skew, twisted etc. is arranged.
(6) adaptation
Adaptation is to utilize the glass adhesive tape to peel off, and whether estimate has peeling off of pattern.Metewand is following.
Zero: do not have peeling off of pattern.
△: peeling off of plurality of patterns arranged.
*: usually figuratum peeling off.
Table 3
| Embodiment | Comparative example | |||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | ?7 | 8 | 9 | 1 | |
| Absorbance | 0.41 | 0.39 | 0.37 | 0.38 | 0.36 | 0.38 | ?0.38 | 0.36 | 0.38 | 0.4 |
| Laser-photosensitive | △ | ○ | ○ | ○ | ○ | ○ | ?○ | ○ | ○ | × |
| Essential exposure (mJ/cm 2) | 80 | 60 | 50 | 50 | 40 | 50 | ?50 | 40 | 30 | 300 |
| The shape of the line after pattern forms | ○ | ○ | ○ | ○ | ○ | ○ | ?○ | ○ | ○ | - |
| The shape of the line after burning till | ○ | ○ | ○ | ○ | ○ | ○ | ?○ | ○ | ○ | - |
| Adaptation | ○ | ○ | ○ | ○ | ○ | ○ | ?○ | ○ | ○ | - |
Can know that by the result shown in the table 3 black paste composition of alkali developable of the present invention has sufficient light sensitivity to active energy beam, can form high meticulous pattern.In addition, the shape of the line after burning till does not have irregular skew, and is excellent with the adaptation of base material yet.
In addition, also can satisfy the blackness after burning till, storage stability is also excellent.
Use the silver paste composition of the alkali developable of the foregoing description 10～18 and comparative example 2, be applied on the glass substrate with the whole face of 300 purpose polyester nets.Then, use the heated air circulation type drying oven to descend dry 20 minutes, form the good overlay film of dry to touch property at 90 ℃.Then; Use the cad data of the striated of live width 50 μ m, interval width 200 μ m; (PENTAX company produces bluish violet color laser through having centre wavelength 405nm as the laser direct imaging exposure device of light source; DI-μ 10), with the accumulation light quantity on the composition be the amount exposure of 40mJ/cm2.Use the 0.4wt%Na of 30 ℃ of fluid temperatures thereafter,
2CO
3The WS developed for 20 seconds, washing.At last, use electric furnace in air, to burn till.
In addition, carry out following operation in burning till: be warmed up to 590 ℃ with 5 ℃/minute programming rates from room temperature, kept 10 minutes, place cool to room temperature then at 590 ℃.
The result that the various characteristics of each substrate of such operation gained is estimated is shown in the table 4.
In addition, the evaluation method in the table 4 is following.
(1) mensuration of absorbance
Use ultraviolet-visible pectrophotometer to be determined at the absorbance of the evaluation substrate of filming that is formed with dry film thickness 5 μ m and 10 μ m on the soda-lime glass.Go out the absorbance of per 1 μ m thickness under the 405nm from the data computation of gained.
(2) evaluation of laser-photosensitive
With 50mJ/cm
2The line of accumulation light quantity exposure L/S=50/200 μ m, use the 0.4wt%Na of 30 ℃ of fluid temperatures
2CO
3The WS developed for 20 seconds, whether can form line through the optical microscope evaluation.Metewand is following.
Zero: can't see shortcoming fully.
△: visible some shortcomings.
*: can not form line.
(3) calculating of lowest exposure amount
Change the accumulation light quantity and make public, determine the minimum exposure amount that can not form the line of L/S=50/200 μ m with being short of.In addition, comparative example is because long with the time shutter of laser, and impracticable, so do not implement the test of back.
The shape of the line after (4) pattern forms
When utilizing the exposure of aforesaid lowest exposure amount, with the pattern after the development of the silver paste composition of microscopic alkali developable, the evaluation line has and do not have irregular skew, twisted etc.Metewand is following.
Zero: do not have irregular skew, do not have twisted etc.
△: some irregular skews, twisted etc. are arranged.
*: irregular skew, twisted etc. is arranged.
(5) shape of the line after burning till
The shape of the line after burning till be with microscopic up to burning till the pattern that is through with, estimate line have do not have irregular skew, twisted etc.Metewand is following.
Zero: do not have irregular skew, do not have twisted etc.
△: some irregular skews, twisted etc. are arranged.
*: irregular skew, twisted etc. is arranged.
(6) adaptation
Adaptation is to utilize the glass adhesive tape to peel off, and whether estimate has peeling off of pattern.Metewand is following.
Zero: do not have peeling off of pattern.
△: peeling off of plurality of patterns arranged.
*: usually figuratum peeling off.
(7) than the mensuration of resistance value
Except using the cad data exposure of pattern dimension, operate preparation test substrate equally with the evaluation of above-mentioned " wire shaped after burning till " as 0.4cm * 10cm.To the test substrate that obtains like this, use Milliohm HiTester to measure the resistance value of burning till overlay film, then, use SURFCORDER to measure the thickness that burns till overlay film, calculate the ratio resistance value of burning till overlay film.
Table 4
| Embodiment | Comparative example | |||||||||
| 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 2 | |
| Absorbance | 0.16 | 0.16 | 0.15 | 0.15 | 0.14 | 0.19 | 0.35 | 0.14 | 0.20 | 0.14 |
| Laser-photosensitive | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × |
| Essential exposure (mJ/cm 2) | 30 | 30 | 20 | 30 | 30 | 70 | 70 | 30 | 30 | 300 |
| The shape of the line after pattern forms | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | - |
| The shape of the line after burning till | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | - |
| Adaptation | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | - |
| Than resistance value (* 10 -6Ω·cm) | 3.2 | 3.3 | 3.4 | 3.5 | 3.5 | 3.4 | 3.2 | 3.5 | 3.3 | - |
Can know that by the result shown in the table 4 silver paste composition of alkali developable of the present invention has sufficient light sensitivity to laser, can form high meticulous pattern.In addition, the shape of the line after burning till does not have irregular skew, and is more abundant as electrode material than resistance value yet, good with the adaptation of base material, excellent storage stability.
Then, implement to form through the pattern of lamp formula exposure.Use the black paste composition of the alkali developable of the foregoing description 1～9 and comparative example 1, be applied on the glass substrate with the whole face of 300 purpose polyester nets.Then, use the heated air circulation type drying oven, form the good overlay film of dry to touch property 90 ℃ of dryings 20 minutes.Then; The glass dry plate of the negative pattern of the striated that has formed live width 100 μ m, interval width 150 μ m is used as photomask; (Bai Dong company produces, and MAT-5301), is 50mJ/cm with the accumulation light quantity on the paste as the exposure device of light source through possessing ultrahigh pressure mercury lamp
2Amount exposure.Use 0.4 quality %Na of 30 ℃ of fluid temperatures thereafter,
2CO
3The WS developed for 20 seconds, washing.At last, use electric furnace in air, to burn till.
In addition, carry out following operation in burning till: be warmed up to 590 ℃ with 5 ℃/minute programming rates from room temperature, kept 10 minutes, place cool to room temperature then at 590 ℃.
The result that the various characteristics of each substrate of such operation gained is estimated is shown in the table 5.In addition, the evaluation method in the table 5 is following.
(1) photosensitive evaluation
With 50mJ/cm
2The line of accumulation light quantity exposure L/S=100/150 μ m, use the 0.4wt%Na of 30 ℃ of fluid temperatures
2CO
3The WS developed for 20 seconds, whether can form line through the optical microscope evaluation.Metewand is following.
Zero: can't see shortcoming fully.
△: visible some shortcomings.
*: can not form line.
(2) calculating of lowest exposure amount
Change the accumulation light quantity and make public, determine the minimum exposure amount that can not form the line of L/S=100/150 μ m with being short of.
The shape of the line after (3) pattern forms
When utilizing the exposure of aforesaid lowest exposure amount, with the pattern after the development of the black paste composition of microscopic alkali developable, the evaluation line has and do not have irregular skew, twisted etc.Metewand is following.
Zero: do not have irregular skew, do not have twisted etc.
△: some irregular skews, twisted etc. are arranged.
*: irregular skew, twisted etc. is arranged.
(4) shape of the line after burning till
The shape of the line after burning till be with microscopic up to burning till the pattern that is through with, estimate line have do not have irregular skew, twisted etc.Metewand is following.
Zero: do not have irregular skew, do not have twisted etc.
△: some irregular skews, twisted etc. are arranged.
*: irregular skew, twisted etc. is arranged.
(5) adaptation
Adaptation is to utilize the glass adhesive tape to peel off, and whether estimate has peeling off of pattern.Metewand is following.
Zero: do not have peeling off of pattern.
△: peeling off of plurality of patterns arranged.
*: usually figuratum peeling off.
Table 5
| Embodiment | Comparative example | |||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 1 | |
| Photonasty | △ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × |
| Essential exposure (mJ/cm 2) | 80 | 60 | 50 | 50 | 40 | 50 | 50 | 40 | 30 | 300 |
| The shape of the line after pattern forms | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The shape of the line after burning till | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Adaptation | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
Can know that by the result shown in the table 5 black paste composition of alkali developable of the present invention also has sufficient light sensitivity when using ultrahigh pressure mercury lamp as light source, can form high meticulous pattern.
Then, implement to form through the pattern of lamp formula exposure.Use the silver paste composition of the alkali developable of the foregoing description 10～18 and comparative example 2, be applied on the glass substrate with the whole face of 300 purpose polyester nets.Then, use the heated air circulation type drying oven to descend dry 20 minutes, form the good overlay film of dry to touch property at 90 ℃.Then; The glass dry plate of the negative pattern of the striated that has formed live width 50 μ m, interval width 200 μ m is used as photomask; (Bai Dong company produces, and MAT-5301), is 40mJ/cm with the accumulation light quantity on the paste as the exposure device of light source through possessing ultrahigh pressure mercury lamp
2Amount exposure.Use 0.4 quality %Na of 30 ℃ of fluid temperatures thereafter,
2CO
3The WS developed for 20 seconds, washing.At last, use electric furnace in air, to burn till.
In addition, carry out following operation in burning till: be warmed up to 590 ℃ with 5 ℃/minute programming rates from room temperature, kept 10 minutes, place cool to room temperature then at 590 ℃.
The result that the various characteristics of each substrate of such operation gained is estimated is shown in the table 6.In addition, the evaluation method in the table 6 is following.
(1) photosensitive evaluation
With 50mJ/cm
2The line of accumulation light quantity exposure L/S=50/200 μ m, use the 0.4wt%Na of 30 ℃ of fluid temperatures
2CO
3The WS developed for 20 seconds, whether can form line through the optical microscope evaluation.Metewand is following.
Zero: can't see shortcoming fully.
△: visible some shortcomings.
*: can not form line.
(2) calculating of lowest exposure amount
Change the accumulation light quantity and make public, determine the minimum exposure amount that can not form the line of L/S=50/200 μ m with being short of.
The shape of the line after (3) pattern forms
When utilizing the exposure of aforesaid lowest exposure amount, with the pattern after the development of the silver paste composition of microscopic alkali developable, the evaluation line has and do not have irregular skew, twisted etc.Metewand is following.
Zero: do not have irregular skew, do not have twisted etc.
△: some irregular skews, twisted etc. are arranged.
*: irregular skew, twisted etc. is arranged.
(4) shape of the line after burning till
The shape of the line after burning till be with microscopic up to burning till the pattern that is through with, estimate line have do not have irregular skew, twisted etc.Metewand is following.
Zero: do not have irregular skew, do not have twisted etc.
△: some irregular skews, twisted etc. are arranged.
*: irregular skew, twisted etc. is arranged.
(5) adaptation
Adaptation is to utilize the glass adhesive tape to peel off, and whether estimate has peeling off of pattern.Metewand is following.
Zero: do not have peeling off of pattern.
△: peeling off of plurality of patterns arranged.
*: usually figuratum peeling off.
Table 6
| Embodiment | Comparative example | |||||||||
| 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 2 | |
| Photonasty | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × |
| Essential exposure (mJ/cm 2) | 30 | 30 | 20 | 30 | 30 | 70 | 70 | 30 | 30 | 300 |
| The shape of the line after pattern forms | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | - |
| The shape of the line after burning till | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | - |
| Adaptation | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | - |
Result by shown in the table 6 finds out that obviously the silver paste composition of alkali developable of the present invention also has sufficient light sensitivity when using ultrahigh pressure mercury lamp as light source, can form high meticulous pattern.
Embodiment 19～26 and comparative example 3
With 3 roll-type roller mills the gradation composition shown in the table 7 of the A-1 varnish that used aforementioned synthetic routine gained and A-2 varnish is carried out mixingly, obtain the black silver paste composition of alkali developable.
Table 7
| Embodiment | Comparative example | ||||||||
| 19 | 20 | 21 | 22 | 23 | 24 | 25 | 26 | 3 | |
| A-1 varnish | 100 | 100 | - | 100 | 100 | 100 | 100 | 100 | 100 |
| A-2 varnish | - | - | 100 | - | - | - | - | - | - |
| Glass dust ※ 1 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| Silver powder ※ 2 | 600 | 600 | 600 | 600 | 600 | 600 | 600 | 600 | 600 |
| Black pigment ※ 3 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
| Polymerizable monomer ※ 4 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| Photoepolymerizationinitiater initiater (E-1) ※ 5 | 2 | 2 | 2 | 2 | 2 | 2 | - | 2 | - |
| Photoepolymerizationinitiater initiater (E-1) ※ 6 | - | - | - | - | - | - | 2 | - | - |
| Sulphur compound ※ 7 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 1.5 | 0.5 | 0.5 | - |
| Other Photoepolymerizationinitiater initiater ※ 8 | - | - | - | - | - | - | - | 10 | - |
| Photoepolymerizationinitiater initiater ※ 9 relatively | - | - | - | - | - | - | - | - | 10 |
| Boric acid ※ 10 | - | 0.1 | 0.1 | 0.1 | - | - | 0.1 | - | - |
| Phosphorus compound ※ 11 | - | - | - | 1 | 1 | 1 | 1 | 1 | - |
| Remarks | ※ 1: will have 60%PbO, 20%B 2O 3、15％SiO 2、5％Al 2O 3Composition and thermalexpansioncoefficient 300=70 * 10 -7/ ℃, glass transition temperature is that to pulverize the mean grain size obtain be the glass dust ※ 2 of 1.6 μ m for the material of 445 ℃ character: the silver powder ※ 3 of mean grain size 5 μ m, maximum particle diameter 15 μ m: the concentration with 70%; With maximum particle diameter is below the 5 μ m and mean grain size is that the cobaltosic oxide black particle of 0.2 μ m evenly spreads to the slurry ※ 4 that obtains in the tripropylene glycol monomethyl ether: pentaerythritol triacrylate ※ 5:2-(acetoxyl group iminomethyl) thioxanthene-9-one ※ 6:1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) ethyl ketone ※ 7:2-mercaptobenzothiazoler ※ 8:2; 4,6-trimethylbenzoyl diphenyl phosphine oxide ※ 9:2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone ※ 10: be ground into the boric acid ※ 11 below the mean grain size 5 μ m: acid phosphoric acid 2-methacryloxy ethyl ester with jet pulverizer | ||||||||
Also carried out containing the evaluation of black pigment and silver powder as the black silver paste composition of the alkali developable of inorganic constituents.Use the black silver paste composition of the foregoing description 19～26 and comparative example 3, be applied on the glass substrate with the whole face of 300 purpose polyester nets.Then, use the heated air circulation type drying oven, form the good overlay film of dry to touch property 90 ℃ of dryings 20 minutes.Then; The glass dry plate of the negative pattern of the striated that has formed live width 50 μ m, interval width 200 μ m is used as photomask; (Bai Dong company produces, and MAT-5301), is 40mJ/cm with the accumulation light quantity on the paste as the exposure device of light source through possessing ultrahigh pressure mercury lamp
2Amount exposure.Use 0.4 quality %Na of 30 ℃ of fluid temperatures thereafter,
2CO
3The WS developed for 20 seconds, washing.At last, use electric furnace in air, to burn till.
In addition, carry out following operation in burning till: be warmed up to 590 ℃ with 5 ℃/minute programming rates from room temperature, kept 10 minutes, place cool to room temperature then at 590 ℃.
The result that the various characteristics of each substrate of such operation gained is estimated is shown in the table 8.In addition, the evaluation method in the table 8 is following.
(1) mensuration of absorbance
Use ultraviolet-visible pectrophotometer to measure for the absorbance of the evaluation substrate of filming that on soda-lime glass, has formed dry film thickness 5 μ m and 10 μ m.Go out the absorbance of per 1 μ m thickness under the 405nm from the data computation of gained.
(2) photosensitive evaluation
With 50mJ/cm
2The line exposing of accumulation light quantity exposure L/S=50/200 μ m, use the 0.4wt%Na of 30 ℃ of fluid temperatures
2CO
3The WS developed for 20 seconds, whether can form line through the optical microscope evaluation.Metewand is following.
Zero: can't see shortcoming fully.
△: visible some shortcomings.
*: can not form line.
(3) calculating of lowest exposure amount
Change the accumulation light quantity and make public, determine the minimum exposure amount that can not form the line of L/S=50/200 μ m with being short of.
The shape of the line after (4) pattern forms
When utilizing the exposure of aforesaid lowest exposure amount, with the pattern after the development of the black silver paste composition of microscopic alkali developable, the evaluation line has and do not have irregular skew, twisted etc.Metewand is following.
Zero: do not have irregular skew, do not have twisted etc.
△: some irregular skews, twisted etc. are arranged.
*: irregular skew, twisted etc. is arranged.
(5) shape of the line after burning till
The shape of the line after burning till be with microscopic up to burning till the pattern that is through with, estimate line have do not have irregular skew, twisted etc.Metewand is following.
Zero: do not have irregular skew, do not have twisted etc.
△: some irregular skews, twisted etc. are arranged.
*: irregular skew, twisted etc. is arranged.
(6) adaptation
Adaptation is to utilize the glass adhesive tape to peel off, and whether estimate has peeling off of pattern.Metewand is following.
Zero: do not have peeling off of pattern.
△: peeling off of plurality of patterns arranged.
*: usually figuratum peeling off.
(7) than the mensuration of resistance value
Be formed with pattern dimension makes public as the photomask of the pattern of 0.4cm * 10cm except using, operate preparation test substrate equally with the evaluation of above-mentioned " wire shaped after burning till ".To the test substrate that obtains like this, use Milliohm HiTester to measure the resistance value of burning till overlay film, then, use SURFCORDER to measure the thickness that burns till overlay film, calculate the ratio resistance value of burning till overlay film.
Table 8
| Embodiment | Comparative example | ||||||||
| 19 | 20 | 21 | 22 | 23 | 24 | 25 | 26 | 3 | |
| Absorbance | 0.50 | 0.52 | 0.51 | 0.50 | 0.55 | 0.56 | 0.53 | 0.59 | 0.50 |
| Photonasty | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × |
| Essential exposure (mJ/cm 2) | 50 | 50 | 50 | 50 | 50 | 70 | 50 | 40 | 300 |
| Line after pattern forms | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The shape of the line after burning till | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Adaptation | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Than resistance value [* 10 -6Ω·cm] | 4.0 | 4.2 | 4.2 | 4.2 | 4.0 | 4.0 | 4.2 | 4.1 | 3.9 |
Can know that by the result shown in the table 8 the black silver paste composition of alkali developable of the present invention has sufficient light sensitivity, can form high meticulous pattern.
Claims (13)
1. the paste composition of an alkali developable is characterized in that, it comprises:
(A) contain carboxy resin,
(B) glass dust,
(C) inorganic powder, it is selected from least a in black pigment (C-1) or the silver powder (C-2),
(D) have the compound of free-radical polymerised unsaturated group more than at least 1 in a part,
(E-1) the oxime ester is a Photoepolymerizationinitiater initiater; It is selected from { 1-[4-(thiophenyl)-2-(O-benzoyl oxime)] } 1; Oxime ester shown in 2-acetyl caproyl, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) ethyl ketone and the formula (III) is at least a in the Photoepolymerizationinitiater initiater
In the formula, 1 or 2 R
5Shown in following general formula (I), 2 R wherein
5In the time of shown in general formula (I), comprise R
5Condition of different separately; All the other R
5Expression hydrogen atom, methyl, phenyl or halogen atom are comprising each R
5Condition of different separately,
In the formula, R
1The alkyl or the phenyl of expression hydrogen atom, carbon number 1～6, R
2The alkyl of expression hydrogen atom or carbon number 1～6,
And
(F) sulphur compound shown in the formula (II),
In the formula, R
3And R
4Expression mutually combines and forms 5 yuan of needed non-metallic atom crowds of ring that comprise any heteroatom that is selected from oxygen, sulphur and nitrogen-atoms.
2. the paste composition of alkali developable according to claim 1 is characterized in that, the said carboxy resin (A) that contains further is the carboxy resin that contains that (A-1) has free-radical polymerised unsaturated group more than.
3. the paste composition of alkali developable according to claim 1 is characterized in that, also contains (G) boric acid.
4. the paste composition of alkali developable according to claim 1 is characterized in that, also contains the phosphorus compound shown in (H) formula (V) or the general formula (VI)
5. the paste composition of alkali developable according to claim 1 is characterized in that, said oxime ester is that the use level of Photoepolymerizationinitiater initiater (E-1) is 0.1～1.0 quality % of total composition.
6. according to the paste composition of each described alkali developable of claim 1～5, it is characterized in that, be coated with each described composition of dry said claim 1～5 and the absorbance of per 1 μ m thickness of filming of obtaining is 0.1～0.8.
7. the formation method that pattern burns till overlay film is characterized in that, the formation method that has been to use the pattern of the paste composition of each described alkali developable of claim 1～6 to burn till overlay film, and wherein, this method comprises:
(1) through active energy beam carry out pattern exposure operation,
(2) optionally form through developing with the diluted alkaline property WS pattern operation,
The operation of (3) under 400～600 ℃, burning till.
8. pattern according to claim 7 burns till the formation method of overlay film, it is characterized in that, said active energy beam is laser generation light source or lamp source.
9. a pattern burns till overlay film, and it obtains through the formation method that claim 7 or 8 described patterns burn till overlay film.
10. pattern according to claim 9 burns till overlay film, it is characterized in that, it is that conductive pattern burns till overlay film that said pattern burns till overlay film.
11. burn till overlay film, it is characterized in that said pattern burns till overlay film and comprises black matrix pattern and burn till overlay film according to claim 9 or 10 described patterns.
12. a Plasmia indicating panel, it comprises the paste composition that uses each described alkali developable of claim 1～6 and the pattern that forms burns till overlay film.
13. a Plasmia indicating panel, it comprises each described pattern of claim 9～11 and burns till overlay film.
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| JP2006309104 | 2006-11-15 | ||
| JP2006-309104 | 2006-11-15 | ||
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| JP2006309103 | 2006-11-15 | ||
| JP2006309104 | 2006-11-15 | ||
| JP2006-309103 | 2006-11-15 |
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| KR (1) | KR20080044184A (en) |
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| JP5236557B2 (en) * | 2009-03-31 | 2013-07-17 | 太陽ホールディングス株式会社 | Pattern formation method using laser |
| JP5561989B2 (en) * | 2009-10-02 | 2014-07-30 | 太陽ホールディングス株式会社 | Pattern formation method using laser |
| KR101277020B1 (en) * | 2010-09-30 | 2013-06-24 | 다이요 홀딩스 가부시키가이샤 | Photosensitive conductive paste |
| JP5825963B2 (en) * | 2011-09-30 | 2015-12-02 | 太陽ホールディングス株式会社 | Photosensitive conductive resin composition, photosensitive conductive paste, and conductor pattern |
| JP6058890B2 (en) * | 2012-01-11 | 2017-01-11 | 株式会社Adeka | Curable resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1726434A (en) * | 2002-12-16 | 2006-01-25 | 昭和电工株式会社 | Color filter black matrix resist composition |
| CN1779568A (en) * | 2003-11-27 | 2006-05-31 | 太阳油墨制造株式会社 | Hardenable resin composition, hardened body thereof, and printed wiring board |
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| JP2000338322A (en) * | 1999-05-26 | 2000-12-08 | Mitsubishi Chemicals Corp | Photopolymerizable composition for color filter and color filter |
| JP4489566B2 (en) * | 2003-11-27 | 2010-06-23 | 太陽インキ製造株式会社 | Curable resin composition, cured product thereof, and printed wiring board |
| JP4830310B2 (en) * | 2004-02-23 | 2011-12-07 | 三菱化学株式会社 | Oxime ester-based compound, photopolymerizable composition, and color filter using the same |
| JP4556479B2 (en) * | 2004-04-27 | 2010-10-06 | Ｊｓｒ株式会社 | Radiation-sensitive composition for forming colored layer, color filter, and liquid crystal display panel |
| JP2006268027A (en) * | 2005-02-23 | 2006-10-05 | Jsr Corp | Method for manufacturing plasma display panel and transfer film |
| JP4253306B2 (en) * | 2005-03-01 | 2009-04-08 | 太陽インキ製造株式会社 | Photosensitive paste and fired product pattern formed using the same |
| JP2006309157A (en) * | 2005-04-01 | 2006-11-09 | Jsr Corp | Radiation-sensitive resin composition, protrusion and spacer formed of the same, and liquid crystal display element equipped with them |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1726434A (en) * | 2002-12-16 | 2006-01-25 | 昭和电工株式会社 | Color filter black matrix resist composition |
| CN1779568A (en) * | 2003-11-27 | 2006-05-31 | 太阳油墨制造株式会社 | Hardenable resin composition, hardened body thereof, and printed wiring board |
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| JP5183161B2 (en) | 2013-04-17 |
| JP2008146042A (en) | 2008-06-26 |
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| TW200844660A (en) | 2008-11-16 |
| KR20080044184A (en) | 2008-05-20 |
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