CN114450633A - Photosensitive transfer member, method for manufacturing resin pattern, method for manufacturing circuit wiring, and method for manufacturing touch panel - Google Patents
Photosensitive transfer member, method for manufacturing resin pattern, method for manufacturing circuit wiring, and method for manufacturing touch panel Download PDFInfo
- Publication number
- CN114450633A CN114450633A CN202080066629.XA CN202080066629A CN114450633A CN 114450633 A CN114450633 A CN 114450633A CN 202080066629 A CN202080066629 A CN 202080066629A CN 114450633 A CN114450633 A CN 114450633A
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- China
- Prior art keywords
- resin layer
- transfer member
- photosensitive
- thermoplastic resin
- temporary support
- 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.)
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- 229920005989 resin Polymers 0.000 title claims abstract description 186
- 239000011347 resin Substances 0.000 title claims abstract description 186
- 238000012546 transfer Methods 0.000 title claims abstract description 125
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims description 125
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 168
- 239000013039 cover film Substances 0.000 claims abstract description 69
- 239000000758 substrate Substances 0.000 claims description 46
- 238000011161 development Methods 0.000 claims description 23
- 238000005530 etching Methods 0.000 claims description 19
- 238000005096 rolling process Methods 0.000 claims description 12
- 238000003475 lamination Methods 0.000 abstract description 24
- 230000000903 blocking effect Effects 0.000 abstract description 13
- 239000010410 layer Substances 0.000 description 329
- 239000010408 film Substances 0.000 description 46
- 150000001875 compounds Chemical class 0.000 description 42
- -1 polyethylene terephthalate Polymers 0.000 description 39
- 239000000126 substance Substances 0.000 description 28
- 239000000975 dye Substances 0.000 description 23
- 239000002253 acid Substances 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 18
- 239000004094 surface-active agent Substances 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 16
- 239000003999 initiator Substances 0.000 description 15
- 239000011342 resin composition Substances 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
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- 239000010949 copper Substances 0.000 description 11
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- 239000011248 coating agent Substances 0.000 description 8
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
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- 239000005038 ethylene vinyl acetate Substances 0.000 description 6
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- 229920000573 polyethylene Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000004793 Polystyrene Substances 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
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- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
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- 239000002904 solvent Substances 0.000 description 3
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- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- QTUVQQKHBMGYEH-UHFFFAOYSA-N 2-(trichloromethyl)-1,3,5-triazine Chemical class ClC(Cl)(Cl)C1=NC=NC=N1 QTUVQQKHBMGYEH-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- PLXMOAALOJOTIY-FPTXNFDTSA-N Aesculin Natural products OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)[C@H]1Oc2cc3C=CC(=O)Oc3cc2O PLXMOAALOJOTIY-FPTXNFDTSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical class C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
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- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 description 2
- 229930192627 Naphthoquinone Natural products 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- SEEVRZDUPHZSOX-WPWMEQJKSA-N [(e)-1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(\C)=N\OC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-WPWMEQJKSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 125000005529 alkyleneoxy group Chemical group 0.000 description 2
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 2
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- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 2
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- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 2
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 2
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- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
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- 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 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
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- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- IICHURGZQPGTRD-UHFFFAOYSA-N 4-phenyldiazenylnaphthalen-1-amine Chemical compound C12=CC=CC=C2C(N)=CC=C1N=NC1=CC=CC=C1 IICHURGZQPGTRD-UHFFFAOYSA-N 0.000 description 1
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- XPKVSFHMZHXKIX-UHFFFAOYSA-N 9h-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1.C1=CC=C2CC3=CC=CC=C3OC2=C1 XPKVSFHMZHXKIX-UHFFFAOYSA-N 0.000 description 1
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- JUQPZRLQQYSMEQ-UHFFFAOYSA-N CI Basic red 9 Chemical compound [Cl-].C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)=C1C=CC(=[NH2+])C=C1 JUQPZRLQQYSMEQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/161—Coating processes; Apparatus therefor using a previously coated surface, e.g. by stamping or by transfer lamination
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- 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
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- 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
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- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
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- G—PHYSICS
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- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/115—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having supports or layers with means for obtaining a screen effect or for obtaining better contact in vacuum printing
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- G—PHYSICS
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- 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
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- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
- H05K3/064—Photoresists
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Human Computer Interaction (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention provides a photosensitive transfer member which has excellent lamination performance and can inhibit blocking when a temporary support body and a thermoplastic resin layer are separated, a manufacturing method of a resin pattern, a manufacturing method of a circuit wiring and a manufacturing method of a touch panel. The photosensitive transfer member comprises a temporary support, a thermoplastic resin layer, a photosensitive resin layer and a cover film in this order, wherein the vicat softening point of the thermoplastic resin layer is 50-120 ℃, the tensile elastic modulus is 10-200 MPa, and the peel strength between the temporary support and the thermoplastic resin layer is greater than the peel strength between the thermoplastic resin layer and the photosensitive resin layer.
Description
Technical Field
The invention relates to a photosensitive transfer printing component, a manufacturing method of a resin pattern, a manufacturing method of a circuit wiring and a manufacturing method of a touch panel.
Background
In a display device (such as an organic Electroluminescence (EL) display device and a liquid crystal display device) including a touch panel such as a capacitive input device, a conductive layer pattern such as a sensor electrode pattern corresponding to a visual recognition portion, a peripheral wiring portion, and a wiring for taking out the wiring portion is provided inside the touch panel.
In general, in the formation of a patterned layer, the number of steps for obtaining a desired pattern shape is small, and therefore, a method of performing development after exposure through a mask having a desired pattern is widely used for a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer member.
For example, patent document 1 describes a pattern forming material having a cushion layer containing a thermoplastic resin and a photosensitive layer in this order on a support ([ claim 1] [ claim 5]), and as a pattern forming method using the pattern forming material, a method of exposing the photosensitive layer after peeling off the support ([ claim 15 ]).
Prior art documents
Patent document
Patent document 1: japanese patent laid-open publication No. 2007-178459
Disclosure of Invention
Technical problem to be solved by the invention
The present inventors have studied a pattern forming method using the pattern forming material (photosensitive transfer member) described in patent document 1, and have found that although the lamination property is good, there is a problem that blocking occurs and transportation becomes impossible when a laminate of a temporary support and a thermoplastic resin layer is wound in a roll-to-roll manner and recovered by a method of peeling off a cushion layer (thermoplastic resin layer) together with the support (temporary support) before performing a development treatment from the viewpoint of productivity (for example, developability and the like).
Accordingly, the present invention has an object to provide a photosensitive transfer member having excellent lamination properties and capable of suppressing blocking when peeling a temporary support and a thermoplastic resin layer, a method for producing a resin pattern, a method for producing a circuit wiring, and a method for producing a touch panel.
Means for solving the technical problems
The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that: in a photosensitive transfer member comprising a temporary support, a thermoplastic resin layer, a photosensitive resin layer, and a cover film in this order, the vicat softening point and the tensile elastic modulus of the thermoplastic resin layer are adjusted to specific ranges, and the peel strength between the temporary support and the thermoplastic resin layer is set to be greater than the peel strength between the thermoplastic resin layer and the photosensitive resin layer, so that the lamination property is excellent and blocking can be suppressed when the temporary support and the thermoplastic resin layer are peeled, and the present invention has been completed.
That is, the present inventors have found that the above-described problems can be achieved by the following configuration.
[1] A photosensitive transfer member comprising a temporary support, a thermoplastic resin layer, a photosensitive resin layer and a cover film in this order,
the thermoplastic resin layer has a Vicat softening point of 50 to 120 ℃ and a tensile elastic modulus of 10 to 200MPa,
the peel strength between the temporary support and the thermoplastic resin layer is greater than the peel strength between the thermoplastic resin layer and the photosensitive resin layer.
[2] The photosensitive transfer member according to [1], wherein the thickness of the thermoplastic resin layer is more than 2 μm and less than 20 μm.
[3] The photosensitive transfer member according to [1] or [2], wherein the thickness of the temporary support is 6 to 50 μm.
[4] The photosensitive transfer member according to any one of [1] to [3], wherein the temporary support has a haze of 0.5% or less.
[5] The photosensitive transfer member according to any one of [1] to [4], wherein a haze of a laminate between the temporary support and the thermoplastic resin layer is 0.9% or less.
[6] The photosensitive transfer member according to any one of [1] to [5], wherein the thermoplastic resin layer has a tensile elastic modulus of 50 to 200 MPa.
[7] The photosensitive transfer member according to any one of [1] to [6], wherein among the peel strengths between the respective layers of the temporary support, the thermoplastic resin layer, the photosensitive resin layer, and the cover film, the peel strength between the temporary support and the thermoplastic resin layer is strongest, and the peel strength between the photosensitive resin layer and the cover film is weakest.
[8] A method for producing a resin pattern by a roll-to-roll method using the photosensitive transfer member according to any one of [1] to [7], the method comprising:
a peeling step of peeling the cover film from the photosensitive transfer member;
a bonding step of bonding the photosensitive resin layer in the photosensitive transfer member from which the cover film has been peeled, in contact with a substrate having a conductive layer;
an exposure step of pattern-exposing the photosensitive resin layer; and
a developing step of developing the exposed photosensitive resin layer to form a resin pattern,
the method includes a step of simultaneously peeling the temporary support and the thermoplastic resin layer from the photosensitive transfer member between the bonding step and the exposure step or between the exposure step and the development step.
[9] A method for manufacturing a circuit wiring by a roll-to-roll method using the photosensitive transfer member according to any one of [1] to [7], the method comprising:
a peeling step of peeling the cover film from the photosensitive transfer member;
a bonding step of bonding the photosensitive resin layer in the photosensitive transfer member from which the cover film has been peeled, in contact with a substrate having a conductive layer;
an exposure step of pattern-exposing the photosensitive resin layer; and
a developing step of developing the exposed photosensitive resin layer to form a resin pattern; and
a step of etching the conductive layer located in the region where the resin pattern is not disposed,
the method includes a step of simultaneously peeling the temporary support and the thermoplastic resin layer from the photosensitive transfer member between the bonding step and the exposure step or between the exposure step and the development step.
[10] A method for manufacturing a touch panel by a roll-to-roll method using the photosensitive transfer member according to any one of [1] to [7], the method comprising:
a peeling step of peeling the cover film from the photosensitive transfer member;
a bonding step of bonding the photosensitive resin layer in the photosensitive transfer member from which the cover film has been peeled, in contact with a substrate having a conductive layer;
an exposure step of pattern-exposing the photosensitive resin layer; and
a developing step of developing the exposed photosensitive resin layer to form a resin pattern; and
a step of etching the conductive layer located in the region where the resin pattern is not disposed,
the method includes a step of simultaneously peeling the temporary support and the thermoplastic resin layer from the photosensitive transfer member between the bonding step and the exposure step or between the exposure step and the development step.
Effects of the invention
According to the present invention, it is possible to provide a photosensitive transfer member having excellent lamination properties and capable of suppressing blocking when peeling the temporary support and the thermoplastic resin layer, a method for producing a resin pattern, a method for producing a circuit wiring, and a method for producing a touch panel.
Drawings
FIG. 1 is a cross-sectional view schematically showing an example of an embodiment of a photosensitive transfer member of the present invention
Fig. 2 is a schematic diagram showing the pattern a.
Fig. 3 is a schematic diagram showing the pattern B.
Detailed Description
The present invention will be described in detail below.
The following description of the constituent elements may be made in accordance with a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.
In the present specification, the numerical range expressed by the term "to" means a range in which the numerical values before and after the term "to" are included as the lower limit value and the upper limit value.
In the present specification, one kind of substance corresponding to each component may be used alone for each component, or two or more kinds may be used in combination. Here, when two or more substances are used in combination for each component, the content of the component refers to the total content of the substances used in combination unless otherwise specified.
In the present specification, "(meth) acrylic acid" represents either or both of acrylic acid and methacrylic acid, and "(meth) acrylate" represents either or both of acrylate and methacrylate.
The term "exposure" in the present specification includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam unless otherwise specified. Examples of the light used for exposure include active rays (active energy rays) such as far ultraviolet rays typified by a bright line spectrum of a mercury lamp and an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
[ photosensitive transfer Member ]
The photosensitive transfer member of the present invention comprises a temporary support, a thermoplastic resin layer, a photosensitive resin layer, and a cover film in this order.
In the photosensitive transfer member of the present invention, the thermoplastic resin layer has a Vicat softening point of 50 to 120 ℃ and a tensile elastic modulus of 10 to 200 MPa.
In the photosensitive transfer member of the present invention, the peeling strength between the temporary support and the thermoplastic resin layer is greater than the peeling strength between the thermoplastic resin layer and the photosensitive resin layer.
Here, the phrase "the peel strength between the temporary support and the thermoplastic resin layer is greater than the peel strength between the thermoplastic resin layer and the photosensitive resin layer" means a rule that the thermoplastic resin layer is intended to be peeled together with the temporary support when the temporary support is peeled before the developing step in a method for producing a resin pattern using the photosensitive transfer material of the present invention or the like.
The magnitude relationship of the peel strength can be confirmed by: an adhesive tape was stuck to both sides of a test piece (5cm wide × 10cm long) cut out from a photosensitive transfer material, the non-temporary support side (cover film side) was fixed to a horizontal base, the temporary support side was peeled off in the horizontal direction, and then the peeling interface was observed with an optical microscope or the like.
The photosensitive transfer member of the present invention having such a structure is excellent in the laminating property, and can suppress blocking when the temporary support and the thermoplastic resin layer are peeled off.
Although the specific reason is not clear, the present inventors speculate as follows.
Namely, the present inventors considered that: when the vicat softening point of the thermoplastic resin layer is 50 to 120 ℃, the photosensitive resin layer adjacent to the thermoplastic resin layer can follow the unevenness of the substrate when the photosensitive transfer member is laminated on the substrate, and thus the lamination property is improved.
The inventor also believes that: when the peeling strength between the temporary support and the thermoplastic resin layer is greater than the peeling strength between the thermoplastic resin layer and the photosensitive resin layer, and the tensile elastic modulus of the thermoplastic resin layer is 10 to 200MPa, the independence of the thermoplastic resin layer is improved when the temporary support and the thermoplastic resin layer are simultaneously peeled, and the occurrence of blocking with the temporary support can be suppressed.
[ temporary support body ]
The temporary support of the photosensitive transfer member of the present invention supports the photosensitive resin layer or the laminate including the photosensitive resin layer, and is a releasable support.
In the pattern exposure of the photosensitive resin layer, the temporary support preferably has light-transmitting properties from the viewpoint that the exposure of the photosensitive resin layer through the temporary support becomes possible.
Here, "having light transmittance" means that the transmittance of light of a wavelength used for pattern exposure is 50% or more.
From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the transmittance of light of a wavelength (preferably, a wavelength of 365nm) used for pattern exposure of the temporary support is preferably 60% or more, and more preferably 70% or more.
Further, as a method for measuring the transmittance, a method of measuring using MCPD Series manufactured by Otsuka Electronics co.
Examples of the temporary support include a resin film and paper, and the resin film is preferable from the viewpoint of strength and flexibility.
Specific examples of the resin film include a polyethylene terephthalate (PET) film, a cellulose triacetate (tac) film, a polystyrene film, a polycarbonate film, a polyethylene film, a polypropylene film, and a polyimide film. Among them, a 2-axis stretched polyethylene terephthalate film is preferable.
The resin film may be a single layer or a laminate of 2 or more layers.
The thickness of the temporary support is not particularly limited, and may be selected according to the material from the viewpoints of the strength of the support, the flexibility required for bonding the circuit wiring forming substrate, and the light transmittance required in the initial exposure step.
The thickness of the temporary support is preferably 5 to 300 μm, and more preferably 6 to 50 μm for the reason of excellent handleability.
Here, regarding the thickness of the temporary support, in a cross-sectional observation image in the thickness direction of the temporary support, measurement is performed at randomly selected 10 points and the arithmetic average of the thicknesses of the temporary support is found, and the obtained value is taken as the thickness of the temporary support. A cross-sectional observation image along the thickness direction of the temporary support can be obtained using a Scanning Electron Microscope (SEM). The thickness of the thermoplastic resin layer and the photosensitive resin layer described below can also be measured by the same method as described above.
The haze of the temporary support is preferably 0.5% or less, and more preferably 0.4% or less, from the viewpoint of the satisfactory resolution of the photosensitive transfer member.
The haze of the temporary support is preferably 0.05% or more, and more preferably 0.1% or more, from the viewpoint of transportability in the production of the temporary support.
Wherein the haze is measured in accordance with JIS K7136: 2000, can be measured using a haze meter (apparatus name: HZ-2, manufactured by Suga Test Instruments Co., Ltd.) as the total haze.
In the present invention, from the viewpoint of improving the adhesion to the thermoplastic resin layer described later, the surface of the temporary support may be subjected to the following treatments, for example: surface treatments such as glow discharge treatment, corona treatment, and ultraviolet irradiation treatment; and bottom coating treatment of polyvinylidene chloride resin, styrene butadiene rubber, gelatin, etc.
In the present invention, when a temporary support subjected to a surface treatment or an undercoating treatment is used, the temporary support after the treatment is defined in terms of peel strength, thickness, haze, and the like.
Further, the film used as the temporary support is preferably free from deformation such as wrinkles, scratches, and the like.
Pattern exposure from a temporary supportIn view of the pattern formability and the transparency of the temporary support, the number of fine particles, foreign substances, and defects contained in the temporary support is preferably small. The number of particles, foreign matters and defects having a diameter of 1 μm or more is preferably 50/10 mm2Hereinafter, more preferably 10 pieces/10 mm2Hereinafter, more preferably 3/10 mm2The average particle size is preferably 0/10 mm2。
Preferable examples of the temporary support include paragraphs 0017 to 0018 in Japanese patent laid-open publication No. 2014-085643), paragraphs 0019 to 0026 in Japanese patent laid-open publication No. 2016-027363, paragraphs 0041 to 0057 in International patent publication No. 2012/081680, and paragraphs 0029 to 0040 in International patent publication No. 2018/179370, the contents of which are incorporated herein by reference.
[ thermoplastic resin layer ]
The thermoplastic resin layer of the photosensitive transfer member of the present invention has a Vicat softening point of 50 to 120 ℃ and a tensile elastic modulus of 10 to 200 MPa.
Here, the vicat softening point is a value measured in the following order.
(1) Test piece
A test piece having a thermoplastic resin layer with a thickness of 3 to 4mm formed on a PET film with a thickness of 10 to 100 μm is used. The thermoplastic resin layer on the test piece may be formed by any of coating, melt extrusion, and thermal lamination of a thin film several times to form a thick film.
(2) Measuring
The measurement was carried out by a method based on the Viker Vicat method (polymer softening point measurement based on American materials testing method ASTM D1525).
The tensile modulus is a value measured in the following order.
(1) Test piece
A test piece having a thermoplastic resin layer with a thickness of 3 to 4mm formed on a PET film with a thickness of 10 to 100 μm is used. The thermoplastic resin layer on the test piece may be formed by any of coating, melt extrusion, and thermal lamination of a thin film several times to form a thick film.
(2) Measuring
The measurement was performed by a method based on a tensile test according to astm d 882.
In the present invention, the vicat softening point of the thermoplastic resin layer is preferably 70 to 100 ℃.
In the present invention, the thermoplastic resin layer preferably has a tensile elastic modulus of 50 to 200MPa, from the viewpoint of further suppressing blocking when the temporary support and the thermoplastic resin layer are peeled off.
< thermoplastic resin >
The thermoplastic resin layer preferably has a thermoplastic resin.
Specific examples of such thermoplastic resins include:
polyolefins such as polyethylene and polypropylene;
olefin copolymers such as copolymers of ethylene and vinyl acetate and saponified products thereof;
vinyl chloride-based copolymers such as copolymers of ethylene and acrylic acid esters and saponified products thereof, polyvinyl chloride, and copolymers of vinyl chloride and vinyl acetate and saponified products thereof;
styrene copolymers such as polyvinylidene chloride, vinylidene chloride copolymers, polystyrene, and copolymers of styrene and (meth) acrylic acid esters and saponified products thereof;
vinyltoluene copolymers such as polyvinyltoluene and copolymers of vinyltoluene and (meth) acrylic acid esters and saponified products thereof;
(meth) acrylate copolymers such as poly (meth) acrylate and a copolymer of butyl (meth) acrylate and vinyl acetate;
polyamide resins such as vinyl acetate copolymer nylon, copolymerized nylon, N-alkoxymethylated nylon, and N-dimethylaminated nylon;
and the like.
Among them, polyolefin, olefin copolymer or vinyl chloride copolymer is preferable.
In the present invention, the dissolution property of the thermoplastic resin may be sufficiently matched with the dissolution property of the photosensitive resin layer described later, or the photosensitive resin layer described later may have a dissolution property of dissolving in a solvent which is not dissolved at all.
The thermoplastic resin layer may contain 1 kind of thermoplastic resin alone, or may contain 2 or more kinds.
From the viewpoint of better lamination properties, the content of the thermoplastic resin is preferably 10 mass% or more and 99 mass% or less, more preferably 20 mass% or more and 90 mass% or less, and further preferably 30 mass% or more and 80 mass% or less, with respect to the total mass of the thermoplastic resin layers.
< plasticizer >
From the viewpoint of adjusting the vicat softening point, the thermoplastic resin layer may contain a plasticizer having compatibility with the thermoplastic resin. For example, even when a thermoplastic resin having a vicat softening point of 120 ℃ or higher is used, the vicat softening point of the thermoplastic resin layer can be adjusted to 50 to 120 ℃ by adding a plasticizer having compatibility with the thermoplastic resin.
The plasticizer is not particularly limited as long as it is a compound that is compatible with the thermoplastic resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and more preferably is a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer is more preferably a polyethyleneoxy structure or a polypropyleneoxy structure.
The thermoplastic resin layer may contain 1 kind of plasticizer alone, or may contain 2 or more kinds.
When the thermoplastic resin layer contains a plasticizer, the content of the plasticizer is preferably 1 to 70% by mass, more preferably 5 to 50% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint that the lamination property of the photosensitive transfer member at high speed is more excellent.
< other ingredients >
From the viewpoint of adjusting the adhesion force to the temporary support, various polymers or supercooled substances, adhesion improving agents, and release agents can be added to the thermoplastic resin layer within a range in which the actual softening point does not exceed 80 ℃.
In addition, an organic filler or an inorganic filler may be added from the viewpoint of further preventing blocking with the temporary support.
Further, the dye may contain other components such as an acid-reactive dye or a base-reactive dye (hereinafter, simply referred to as "dye B"), a photoacid generator or a photobase generator, a surfactant, and a sensitizer.
(pigment B)
The thermoplastic resin layer preferably contains an acid-reactive dye or a base-reactive dye (dye B). The pigment B represents a pigment whose maximum absorption wavelength is changed by an acid or an alkali. The dye B preferably has a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm during color development.
Here, the term "the dye changes the maximum absorption wavelength by an acid or an alkali" means any of a method in which a dye in a colored state is decolored by an acid or an alkali, a method in which a dye in a decolored state is colored by an acid or an alkali, and a method in which a dye in a colored state is changed to a colored state of another color by an acid or an alkali.
From the viewpoint of visibility and resolution of the exposed portion and the non-exposed portion, the mode in which the dye B is a dye whose maximum absorption wavelength is changed by an acid is preferable, and the mode in which the dye B is a dye whose maximum absorption wavelength is changed by an acid and a photoacid generator described later is used in combination is particularly preferable.
Examples of the coloring mechanism of the dye B in the present invention include a method in which a photoacid generator or a photobase generator is added to a thermoplastic resin layer, and an acid or a base generated from the photoacid generator or the like after exposure causes an acid-reactive dye or a base-reactive dye (e.g., leuco dye) to develop color.
The measurement method of the maximum absorption wavelength is set as follows: the transmission spectrum was measured in the range of 400nm to 780nm under an atmospheric atmosphere and at 25 ℃ using a spectrophotometer (device name: UV3100, manufactured by SHIMADZU CORPORATION), and the wavelength at which the light intensity was the smallest (maximum absorption wavelength) was measured.
Examples of the dye B include leuco compounds, diarylmethane dyes, piperazine dyes, xanthene (xanthene) dyes, iminonaphthoquinone dyes, azomethine dyes, anthraquinone dyes, and the like, and leuco compounds are preferable from the viewpoint of visibility of exposed portions and unexposed portions.
Preferable examples of the dye B include those similar to the specific latent dyes described in paragraphs 0023 to 0039 of International publication No. 2019/022089.
Specific examples of the pigment B include brilliant green, ethyl violet, methyl green, crystal violet, basic magenta, methyl violet 2B, quinaldine red, bengal red, m-aniline yellow, rui-vanillin blue, phloroglucinol blue, methyl orange, p-methyl red, congo red, bengal violet 4B, α -naphthyl red, nile blue 2B, nile blue a, methyl violet, malachite green, parafuchsin, victoria pure blue-naphthalene sulfonate, victoria pure blue BOH (manufactured by Hodogaya Chemical co., ltd.), oil blue #603 (manufactured by duent Chemical INDUSTRIES co., ltd.), oil powder #312 (manufactured by orint Chemical INDUSTRIES co., ltd 5B (ordant CHEMICALs standards co., ltd., ltd.d., ltd.g.), deep red #308 (orque., oil CHEMICALs co., ltd.g., ltd., ltd.g., ltd., l., ltd., l., ltd., d., ltd., e., ltd., d., e., ltd., t., ltd., t., ltd., t, LTD.; manufactured), Spiron Red BEHS facial color (manufactured by Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol Red, rose bengal B, rose bengal 6G, sulfanilamide B, auramine, 4-p-diethylaminophenylimino naphthoquinone, 2-carboxyanilino-4-p-diethylaminophenylimino naphthoquinone, 2-carboxystearylamino-4-p-N, N-bis (hydroxyethyl) amino-phenylimino naphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and dyes such as 1- β -naphthalene-4-p-diethylaminophenylimino-5-pyrazolone, or p, p' -hexamethyltriaminotriphenylmethane (colorless crystal violet) Leuco compounds such as Pergascript Blue SRB (Ciba Geigy).
The pigment B may be used alone in 1 kind, or in 2 or more kinds.
When the thermoplastic resin layer contains the pigment B, the content of the pigment B is preferably 0.01% by mass or more, and more preferably 0.02% by mass to 6% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility of the exposed portions and the unexposed portions.
(photoacid generators or photobase generators)
From the viewpoint of enhancing the visibility of the exposed portion and the non-exposed portion, the thermoplastic resin layer is preferably used in combination with the pigment B and contains a photoacid generator or a photobase generator. More preferred is a mode including an acid-reactive dye and a photoacid generator.
The photoacid generator or the photobase generator used in the present invention is a compound that can generate an acid or a base by irradiation with active light such as ultraviolet light, far ultraviolet light, X-rays, and electron beams.
The photoacid generator or the photobase generator used in the present invention is preferably a compound that generates an acid or a base by being induced by active light having a wavelength of 300nm or more, preferably 300nm to 450nm, and the chemical structure thereof is not limited. Further, as for the photoacid generator or the photobase generator which is not directly sensitive to the active light having a wavelength of 300nm or more, a compound which is sensitive to the active light having a wavelength of 300nm or more and generates an acid or a base by being used in combination with a sensitizer can be preferably used in combination with a sensitizer.
Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.
Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, quaternary ammonium salts, and the like. Among them, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.
As the ionic photoacid generator, the ionic photoacid generators described in paragraphs 0114 to 0133 of Japanese patent application laid-open No. 2014-085643 can also be preferably used.
Examples of the nonionic photoacid generator include trichloromethyl s-triazine compounds, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds, and the like. Specific examples of trichloromethyl s-triazine compounds, diazomethane compounds and imide sulfonate compounds include the compounds described in paragraphs 0083 to 0088 of Japanese patent laid-open publication No. 2011-221494.
Among them, the photoacid generator is preferably an oxime sulfonate compound from the viewpoint of sensitivity, resolution, and adhesion.
As the oxime sulfonate compound, the compounds described in paragraphs 0084 to 0088 of International publication No. 2018/179640 can be preferably used.
The thermoplastic resin layer may use 1 kind of photoacid generator or photobase generator alone, or may use 2 or more kinds.
(surfactant)
The thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.
Examples of the surfactant include anionic, cationic, nonionic (nonionic), and amphoteric surfactants. Preferred surfactants are nonionic surfactants.
Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants, and a fluorine surfactant can be preferably used.
Examples of the surfactant include surfactants described in paragraphs 0120 to 0125 of international publication No. 2018/179640, paragraphs 0017 of japanese patent No. 4502784, and paragraphs 0060 to 0071 of japanese patent application laid-open No. 2009-237362.
As a commercially available surfactant, for example, Megaface F-552 or F-554 (manufactured by DIC CORPORATION, supra) can be used.
From the viewpoint of environmental compatibility, it is also preferable to use, as one mode of the surfactant, a surfactant using an alternative material to PFOA (perfluorooctanoic acid) or PFOS (perfluorooctane sulfonic acid) instead of the compound having a linear perfluoroalkyl group having 7 or more carbon atoms.
When the thermoplastic resin layer contains a surfactant, the content of the surfactant is preferably 0.001 to 10% by mass, and more preferably 0.01 to 3% by mass, based on the total mass of the thermoplastic resin layer.
The thermoplastic resin layer may use 1 kind of surfactant alone, or may use 2 or more kinds.
The thermoplastic resin layer may contain other additives than the above. The other additives are not particularly limited, and known additives can be used.
Further, regarding a preferable embodiment of the thermoplastic resin layer, reference can also be made to paragraphs 0189 to 0193 of japanese patent laid-open No. 2014-085643.
From the viewpoint of better lamination properties, the thickness of the thermoplastic resin layer is preferably 1 μm or more. The upper limit is not particularly limited in terms of performance, but is preferably 100 μm or less, and more preferably 50 μm or less, from the viewpoint of manufacturing suitability.
In the present invention, the thickness of the thermoplastic resin layer is preferably more than 2 μm and less than 20 μm from the viewpoint of the reason that the lamination property becomes better and/or the reason that the pattern resolution becomes better.
In the present invention, the thermoplastic resin layer is preferably optically transparent.
Further, the haze measured in the state of the laminate between the temporary support and the thermoplastic resin layer is preferably 0.9% or less, more preferably 0.8% or less, from the viewpoint of forming a high-resolution image even when exposure is performed through the temporary support and the thermoplastic resin layer.
Wherein the haze is measured in accordance with JIS K7136: 2000, can be measured using a haze meter (apparatus name: HZ-2, manufactured by Suga Test Instruments Co., Ltd.) as the total haze.
[ photosensitive resin layer ]
The photosensitive transfer member of the present invention has a photosensitive resin layer.
In the present invention, the photosensitive resin layer is preferably provided so as to be in direct contact with the thermoplastic resin layer. That is, the photosensitive transfer member of the present invention preferably does not have another layer (for example, a water-soluble resin layer) between the thermoplastic resin layer and the photosensitive resin layer of the present invention.
The photosensitive resin layer is not particularly limited, and a known photosensitive resin layer can be used, but a negative photosensitive resin layer is preferable from the viewpoint of more excellent laminatability at high speed.
The negative photosensitive resin layer is a photosensitive resin layer whose solubility in a developer is reduced by exposure to light.
From the viewpoint of pattern formability, the photosensitive resin layer preferably contains a polymerizable compound, a polymer having an acid group, and a photopolymerization initiator.
The photosensitive resin layer may be, for example, the photosensitive resin layer described in Japanese patent application laid-open No. 2016-224162.
< polymerizable Compound >
The photosensitive resin layer preferably contains a polymerizable compound.
The polymerizable compound is a component contributing to the photosensitivity (i.e., photocurability) of the negative photosensitive resin layer and the strength of the cured film.
The polymerizable compound is preferably an ethylenically unsaturated compound, and more preferably an ethylenically unsaturated compound having 2 or more functions.
Here, the ethylenically unsaturated compound means a compound having 1 or more ethylenically unsaturated groups, and the ethylenically unsaturated compound having 2 or more functions means a compound having 2 or more ethylenically unsaturated groups in 1 molecule.
As the ethylenically unsaturated group, (meth) acryloyl group is preferable.
As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.
The 2-functional ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds. Specific examples thereof include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin Nakamura Chemical Industry Co., LTD.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin Nakamura Chemical Industry Co., LTD.), 1, 9-nonanediol diacrylate (A-NOD-N, manufactured by Shin Nakamura Chemical Industry Co., LTD.), 1, 6-hexanediol diacrylate (A-HD-N, manufactured by Shin Nakamura Chemical Industry Co., LTD.), and the like.
Further, as the 2-functional ethylenically unsaturated compound, a 2-functional ethylenically unsaturated compound having a bisphenol structure can also be suitably used.
Examples of the 2-functional ethylenically unsaturated compound having a bisphenol structure include compounds described in paragraphs 0072 to 0080 of Japanese patent laid-open publication No. 2016-224162.
Specific examples thereof include alkylene oxide-modified bisphenol A di (meth) acrylate, and preferable examples thereof include 2, 2-bis (4- (methacryloyloxydiethoxy) phenyl) propane, 2-bis (4- (methacryloyloxyethoxypropoxy) phenyl) propane, and dimethacrylate of polyethylene glycol (BPE-500, manufactured by Shin Nakamura Chemical Industry Co., LTD.) obtained by adding an average of 5 moles of ethylene oxide to each terminal of bisphenol A.
The ethylenically unsaturated compound having 3 or more functions is not particularly limited, and can be appropriately selected from known compounds. For example, dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and (meth) acrylate compounds of glycerol tri (meth) acrylate skeleton can be mentioned.
In the above description, "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.
Examples of the ethylenically unsaturated compound include caprolactone-modified (meth) acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by LTD., Ltd.), alkylene oxide-modified (meth) acrylate compounds (Nippon Kayaku Co., KAYARAD RP-1040 manufactured by Ltd., Shin Nakamura Chemical Industry Co., ATM-35E, A-9300 manufactured by LTD., EBECRYL (registered trademark) 135 manufactured by ICEL-ALLNEX LTD., Ltd.), ethoxylated glycerol triacrylate (Shin Nakamura Chemical Industry Co., Ltd., A-GLY-9E manufactured by LTD., Ltd.), ARONEI (registered trademark) TO-2349 (AGOSCO., LTD. manufactured by ARIXM-520, ARITO-AGO., AGO.510, ARONEI., AGO.270, ARONEI.S., AGO., ltd. manufacture), and the like.
As the ethylenically unsaturated compound, a urethane (meth) acrylate compound (preferably a 3-or more-functional urethane (meth) acrylate compound) can be used, and examples thereof include 8UX-015A (TAISEI FINE CHEMICAL CO, manufactured by LTD.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., LTD.) and the like.
Further, as the ethylenically unsaturated compound, a polymerizable compound having an acid group as described in paragraphs 0025 to 0030 of Japanese patent laid-open No. 2004-239942 can be used.
The polymerizable compound used in the present invention preferably has a weight average molecular weight (Mw) of 200 to 3,000, more preferably 280 to 2,200, and still more preferably 300 to 2, 200.
The polymerizable compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
When the photosensitive resin layer contains a polymerizable compound, the content of the polymerizable compound is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and still more preferably 20 to 50% by mass, based on the total mass of the photosensitive resin layer.
< polymers having acid groups >
The photosensitive resin layer preferably contains a polymer having an acid group.
Preferred examples of the polymer having an acid group contained in the photosensitive resin layer include the same polymers having an acid group exemplified as the thermoplastic resin contained in the thermoplastic resin layer.
The photosensitive resin layer may contain 1 kind of polymer having an acid group alone, or may contain 2 or more kinds.
When the photosensitive resin layer contains a polymer having an acid group, the content of the polymer having an acid group is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and further preferably 30% by mass or more and 70% by mass or less with respect to the total mass of the photosensitive resin layer, from the viewpoint of photosensitivity.
< photopolymerization initiator >
The photosensitive resin layer preferably contains a photopolymerization initiator.
The photopolymerization initiator receives active light such as ultraviolet light or visible light to initiate polymerization of the polymerizable compound.
The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator, and a photo radical polymerization initiator is preferable.
In addition, the photopolymerization initiator in the photosensitive resin layer preferably contains at least 1 selected from 2, 4, 5-triarylimidazole dimer and derivatives thereof from the viewpoint of photosensitivity and resolution.
Further, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of Japanese patent application laid-open No. 2011-095716 and paragraphs 0064 to 0081 of Japanese patent application laid-open No. 2015-014783 can be used.
Examples of commercially available photopolymerization initiators include 1- [4- (phenylthio) ] -1, 2-octanedione-2- (o-benzoyloxime) [ product name: IRGACURE (registered trademark) OXE-01, manufactured by BASF corporation ], 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (o-acetyloxime) (product name: IRGACURE (registered trademark) OXE-02, manufactured by BASF corporation ], IRGACURE (registered trademark) OXE-03 (manufactured by BASF corporation), 2- (dimethylamino-) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone [ product name: IRGACURE (registered trademark) 379EG, manufactured by BASF corporation ], 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [ product name: IRGACURE (registered trademark) 907, manufactured by BASF corporation), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one [ product name: IR6ACURE (registered trademark) 127, manufactured by BASF corporation), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 [ product name: IRGACURE (registered trademark) 369 manufactured by BASF corporation, 2-hydroxy-2-methyl-1-phenylpropan-1-one [ product name: IRGACURE (registered trademark) 1173, manufactured by BASF corporation, 1-hydroxycyclohexyl phenyl ketone [ product name: IRGACURE (registered trademark) 184, manufactured by BASF corporation), 2-dimethoxy-1, 2-diphenylethan-1-one [ product name: IRGACURE 651, manufactured by BASF corporation), oxime ester system [ product name: lunar (registered trademark) 6, DKSH Japan K.K., manufactured by King et al.
Further, 2, 4-bis (trichloromethyl) -6- (N, N-dioxocarbonylmethylamino) -3-bromophenyl ] s-triazine and the like can be used as a photopolymerization initiator.
The photosensitive resin layer may contain 1 kind of photopolymerization initiator alone, or may contain 2 or more kinds.
When the photosensitive resin layer contains a photopolymerization initiator, the content of the photopolymerization initiator is not particularly limited, and is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more, based on the total mass of the photosensitive resin layer.
The content of the photopolymerization initiator is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the photosensitive resin layer.
< other additives >
The photosensitive resin layer may contain known additives in addition to the above components as needed.
As the other additives, known additives can be used, and examples thereof include a polymerization inhibitor, a plasticizer, a sensitizer, a hydrogen donor, a heterocyclic compound, a coloring agent, a decoloring agent, and a solvent.
As the polymerization inhibitor, for example, a thermal polymerization inhibitor described in paragraph 0018 of japanese patent No. 4502784 can be used. Among them, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.
When the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 3% by mass, more preferably 0.01 to 1% by mass, and still more preferably 0.01 to 0.8% by mass, based on the total mass of the photosensitive resin layer.
Examples of the sensitizer include known sensitizers, dyes, and pigments.
Examples of the plasticizer and the heterocyclic compound include those described in paragraphs 0097 to 0103 and paragraphs 0111 to 0118 of International publication No. 2018/179640.
As the color former, for example, the color former described in 0417 of japanese patent application laid-open No. 2007-178459 can be used, and leuco crystal violet, crystal violet lactone, victoria pure blue-naphthalene sulfonate, or the like can be preferably used.
When the photosensitive resin layer contains a color former, the content of the color former is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass, with respect to the total mass of the photosensitive resin layer, from the viewpoint of visibility and resolution of exposed portions and non-exposed portions.
The photosensitive resin layer may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid proliferators, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors.
Preferable embodiments of the other components are described in paragraphs 0165 to 0184 of Japanese patent application laid-open No. 2014-085643, the contents of which are incorporated in the present specification.
From the viewpoint of pattern resolution, the thickness of the photosensitive resin layer is preferably 0.5 to 20 μm, more preferably 0.8 to 15 μm, and still more preferably 1.0 to 10 μm.
[ covering film ]
The photosensitive transfer member of the present invention has a cover film.
The cover film may be a resin film, paper, or the like, and is preferably a resin film from the viewpoint of strength, flexibility, or the like. Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, polyethylene film, polypropylene film and polyethylene terephthalate film are preferable.
The thickness of the cover film is not particularly limited, and for example, a thickness of 1 μm to 2mm is preferable.
[ other layers ]
The photosensitive transfer member of the present invention may have a layer other than the above (hereinafter, simply referred to as "other layer"). Examples of the other layers include a contrast enhancement layer, an easy-peeling layer, and a BARC layer.
A preferred embodiment of the contrast enhancement layer is described in paragraph 0134 of international publication No. 2018/179640, the contents of which are incorporated in the present specification.
Here, referring to fig. 1, an example of the layer structure of the photosensitive transfer member of the present invention is schematically shown.
The photosensitive transfer member 100 shown in fig. 1 is formed by laminating a temporary support 10, a thermoplastic resin layer 12, a photosensitive resin layer 14, and a cover film 16 in this order.
In the method for producing a resin pattern using the photosensitive transfer material of the present invention, when the temporary support is peeled off before the developing step, it is preferable that the peeling strength between the temporary support and the thermoplastic resin layer is the strongest and the peeling strength between the photosensitive resin layer and the cover film is the weakest among the peeling strengths between the temporary support, the thermoplastic resin layer, the photosensitive resin layer, and the cover film, from the viewpoint of easier peeling of the thermoplastic resin layer together with the temporary support.
[ method for producing photosensitive transfer Member ]
The method for producing the photosensitive transfer member of the present invention is not particularly limited, and a known production method can be used.
Specifically, a photosensitive transfer member having a temporary support, a thermoplastic resin layer, a photosensitive resin layer, and a cover film in this order can be obtained by preparing a composition such as a thermoplastic resin composition by mixing the constituent components of each layer with a solvent, and applying the composition to the temporary support or the cover film.
Specifically, as a method for producing the photosensitive transfer member, a method comprising the steps of: a step of forming a thermoplastic resin layer by applying and drying the thermoplastic resin composition on the temporary support; a step of forming a photosensitive resin layer by coating and drying a photosensitive resin composition on a thermoplastic resin layer; and a step of providing a cover film on the photosensitive resin layer.
As another method for producing the photosensitive transfer member, there is a method including the steps of: a step of forming a thermoplastic resin layer by applying and drying the thermoplastic resin composition on the temporary support; a step of forming a photosensitive resin layer by coating and drying a photosensitive resin composition on a cover film; and a step of bonding the temporary support with the thermoplastic resin layer and the cover film with the photosensitive resin layer, which are the laminate produced in the two steps, so that the thermoplastic resin layer and the photosensitive resin layer are in contact with each other.
In the present invention, from the viewpoint of reducing the load on the environment, when forming the thermoplastic resin layer, it is preferable to provide the temporary support by a melt extrusion method, rather than a method of coating and drying using an organic solvent in the past.
[ method for producing resin Pattern ]
The method for producing a resin pattern of the present invention is a method for producing a resin pattern by a roll-to-roll method using the photosensitive transfer member of the present invention, the method comprising: a peeling step of peeling the cover film from the photosensitive transfer member (hereinafter, also referred to as "cover film peeling step"); a bonding step of bonding the photosensitive resin layer in the photosensitive transfer member from which the cover film has been peeled, in contact with a substrate having a conductive layer; an exposure step of pattern-exposing the photosensitive resin layer; and a developing step of developing the exposed photosensitive resin layer to form a resin pattern, and the step of simultaneously peeling the temporary support and the thermoplastic resin layer from the photosensitive transfer member between the bonding step and the exposure step or between the exposure step and the developing step (hereinafter, also referred to as a "simultaneous peeling step").
[ method for manufacturing Circuit Wiring ]
The method for manufacturing a circuit wiring of the present invention is a method for manufacturing a circuit wiring by a roll-to-roll method using the photosensitive transfer member of the present invention, the method comprising the steps of: a peeling step (cover film peeling step) of peeling the cover film from the photosensitive transfer member; a bonding step of bonding the photosensitive resin layer in the photosensitive transfer member from which the cover film has been peeled, in contact with a substrate having a conductive layer; an exposure step of pattern-exposing the photosensitive resin layer; a developing step of developing the exposed photosensitive resin layer to form a resin pattern; and a step of etching the conductive layer located in the region where the resin pattern is not arranged, wherein a step of simultaneously peeling the temporary support and the thermoplastic resin layer from the photosensitive transfer member (simultaneous peeling step) is provided between the bonding step and the exposure step or between the exposure step and the development step.
Hereinafter, each step including the method of manufacturing the resin pattern and the method of manufacturing the circuit wiring will be described, and first, the roll-to-roll method will be described.
The roll-to-roll system is a system in which a substrate capable of being wound and unwound is used as the substrate, a step of unwinding the substrate or a structure including the substrate (also referred to as an "unwinding step") is included before any one of the steps included in the method for manufacturing a resin pattern or the method for manufacturing a circuit wiring, and a step of winding the base or the structure including the substrate (also referred to as a "winding step") after any one of the steps, and at least any one of the steps (preferably all the steps) is performed while conveying the substrate or the structure including the substrate.
The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and any known method may be used in the manufacturing method to which the roll-to-roll method is applied.
[ procedure for peeling off coating film ]
The peeling step included in the method for manufacturing a resin pattern and the method for manufacturing a circuit wiring according to the present invention is a step of peeling a cover film from a photosensitive transfer member.
The method of peeling is not particularly limited, and peeling may be performed by a known method. For example, the cover film peeling mechanism described in paragraphs [0161] to [0162] of japanese patent application laid-open No. 2010-072589 can be used.
[ attaching Process ]
The bonding step included in the method for manufacturing a resin pattern and the method for manufacturing a circuit wiring according to the present invention is a step of bonding a photosensitive resin layer in a photosensitive transfer member from which a cover film is peeled, in contact with a substrate having a conductive layer.
In the bonding step, the conductive layer is preferably pressure-bonded so as to be in contact with a surface of the photosensitive resin layer of the photosensitive transfer member opposite to the thermoplastic resin layer. In the above aspect, the exposed and developed photosensitive resin layer with a pattern can be preferably used as an etching resist in etching the conductive layer.
The method for pressure-bonding the substrate and the photosensitive transfer member is not particularly limited, and a known transfer method and lamination method can be used.
The photosensitive transfer member is preferably bonded to the substrate by laminating the substrate with a surface opposite to the intermediate layer of the photosensitive resin layer of the photosensitive transfer member, and applying pressure and heat with a roller or the like. In the bonding, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator capable of further improving productivity can be used.
The substrate having a conductive layer has a conductive layer on a base material such as glass, silicon, or a thin film, and an arbitrary layer may be formed as necessary.
A preferred embodiment of the substrate is described in, for example, paragraph 0140 of international publication No. 2018/155193, which is incorporated herein.
From the viewpoint of roll-to-roll manufacturing, the base material of the substrate is preferably a film base material. When the circuit wiring for a touch panel is manufactured by a roll-to-roll method, the substrate is preferably a sheet-like resin composition.
From the viewpoint of conductivity and fine line formability, the conductive layer included in the substrate is preferably at least 1 layer selected from a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and particularly preferably a copper layer or a silver layer.
The substrate may have 1 conductive layer or 2 or more conductive layers. When the conductive layer is 2 or more layers, the conductive layers preferably have different materials.
A preferred embodiment of the conductive layer is described in, for example, paragraph 0141 of international publication No. 2018/155193, which is incorporated herein.
[ Exposure procedure ]
The exposure step included in the method for manufacturing a resin pattern and the method for manufacturing a circuit wiring according to the present invention is a step of pattern-exposing the photosensitive resin layer.
The detailed configuration and specific dimensions of the pattern at the time of pattern exposure are not particularly limited. In order to improve the display quality of a display device (for example, a touch panel) including an input device having circuit wirings manufactured by a method for manufacturing circuit wirings and to reduce the area occupied by extraction wirings, at least a part of the pattern (preferably, an electrode pattern of the touch panel and/or a part of the extraction wirings) preferably includes a thin wire having a width of 20 μm or less, and more preferably includes a thin wire having a width of 10 μm or less.
Preferable examples of the light source, the exposure amount, and the exposure method used for the exposure are described in, for example, paragraphs 0146 to 0147 of International publication No. 2018/155193, which are incorporated herein by reference.
[ development procedure ]
The developing step of the method for manufacturing a resin pattern and the method for manufacturing a circuit wiring according to the present invention is a step of forming a resin pattern by developing the exposed photosensitive resin layer.
The photosensitive resin layer exposed in the developing step may be developed using a developer.
The developing solution and the developing method are not particularly limited as long as the non-image portion of the photosensitive resin layer can be removed, and known developing solutions and developing methods can be used. As the developer that can be preferably used in the present invention, for example, the developer described in paragraph 0194 of international publication No. 2015/093271 can be cited, and as the development method that can be preferably used, for example, the development method described in paragraph 0195 of international publication No. 2015/093271 can be cited.
[ Simultaneous peeling Process ]
The simultaneous peeling step included in the method for manufacturing a resin pattern and the method for manufacturing a circuit wiring according to the present invention is a step of simultaneously peeling the temporary support and the thermoplastic resin layer from the photosensitive transfer member between the bonding step and the exposure step, or between the exposure step and the development step.
As the peeling method, a method of winding the temporary support and the thermoplastic resin layer in a laminate around a winding shaft and collecting them is preferable, and for example, the same mechanism as the cover film peeling mechanism described in paragraphs [0161] to [0162] of jp 2010-072589 a can be used.
[ post exposure and post baking ]
The method for manufacturing a resin pattern and the method for manufacturing a circuit wiring according to the present invention may include a step of subjecting the resin pattern obtained through the above-described developing step to exposure (hereinafter, also referred to as "post-exposure") and/or heat treatment (hereinafter, also referred to as "post-baking").
When both the post-exposure step and the post-baking step are included, it is preferable to perform post-baking after the post-exposure.
[ etching Process ]
The etching step in the method for manufacturing a circuit wiring according to the present invention is a step of etching the conductive layer located in the region where the resin pattern is not arranged.
In the etching step, the pattern formed of the photosensitive resin layer by the developing step is used as an etching resist, and the conductive layer is etched.
As a method of the etching treatment, known methods such as a method described in paragraphs 0209 to 0210 of japanese patent application laid-open No. 2017-120435, a method described in paragraphs 0048 to 0054 of japanese patent application laid-open No. 2010-152155, and a method based on dry etching such as known plasma etching can be applied.
[ removal Process ]
The method for manufacturing a circuit wiring according to the present invention preferably performs a step of removing the resin pattern (hereinafter, simply referred to as "removal step").
The removal step is not particularly limited and may be performed as needed, but is preferably performed after the etching step.
The method for removing the residual photosensitive resin layer is not particularly limited, and a method for removing by a chemical treatment may be mentioned, and particularly, a removing liquid may be preferably used.
As a method for removing the photosensitive resin layer, a method of immersing a substrate having a photosensitive resin layer or the like in a removing solution during stirring at preferably 30 to 80 ℃, more preferably 50 to 80 ℃ for 1 to 30 minutes can be mentioned.
Examples of the removal solution include a solution obtained by dissolving an inorganic base component such as sodium hydroxide or potassium hydroxide or an organic base component such as a primary amine compound, a secondary amine compound, a tertiary amine compound, or a quaternary ammonium salt compound in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
Further, the removal liquid may be used to perform removal by a spray method, a shower method, a liquid coating method, or the like.
[ other procedures ]
The method of manufacturing a circuit wiring of the present invention may include any process (other process) other than the above. For example, the step of reducing the visible light reflectance described in paragraph 0172 of international publication No. 2019/022089, the step of forming a new conductive layer on an insulating film described in paragraph 0172 of international publication No. 2019/022089, and the like can be mentioned, but these steps are not limited.
Further, as examples of the exposure step, the development step, and other steps in the present invention, the methods described in paragraphs 0035 to 0051 of jp 2006-alpine 023696 can also be preferably used in the present invention.
The circuit wiring manufactured by the method for manufacturing a circuit wiring of the present invention can be applied to various devices. Examples of the device including the circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention include an input device, and the like, and preferably include a touch panel, and more preferably a capacitive touch panel. The input device can be applied to display devices such as organic EL display devices and liquid crystal display devices.
[ method for manufacturing touch Panel ]
A method for manufacturing a touch panel of the present invention is a method for manufacturing a touch panel by a roll-to-roll method using the photosensitive transfer member of the present invention, the method comprising the steps of: a peeling step (cover film peeling step) of peeling the cover film from the photosensitive transfer member; a bonding step of bonding the photosensitive resin layer in the photosensitive transfer member from which the cover film has been peeled, in contact with a substrate having a conductive layer; an exposure step of pattern-exposing the photosensitive resin layer; a developing step of developing the exposed photosensitive resin layer to form a resin pattern; and a step of etching the conductive layer located in the region where the resin pattern is not arranged, wherein a step of simultaneously peeling the temporary support and the thermoplastic resin layer from the photosensitive transfer member (simultaneous peeling step) is provided between the bonding step and the exposure step or between the exposure step and the development step.
The preferred embodiments of the method for manufacturing a touch panel according to the present invention, including the specific embodiments of the respective steps and the order of performing the respective steps, are the same as described in the above "method for manufacturing a circuit wiring".
In addition to the above, a known method for manufacturing a touch panel can be used for the method for manufacturing a touch panel of the present invention.
The method of manufacturing a touch panel of the present invention may include any process (other process) other than the above.
Fig. 2 and 3 show an example of a pattern of a mask used in the method for manufacturing a touch panel according to the present invention.
In the pattern a shown in fig. 2 and the pattern B shown in fig. 3, SL and G are image portions (opening portions), and DL is a frame which virtually shows alignment. In the method for manufacturing a touch panel of the present invention, for example, a touch panel in which circuit wirings having patterns a corresponding to SL and G are formed can be manufactured by exposing a photosensitive resin layer through a mask having the pattern a shown in fig. 2.
The touch panel of the present invention is a touch panel having at least a circuit wiring manufactured by the method for manufacturing a circuit wiring of the present invention.
Further, the touch panel of the present invention preferably has at least a transparent substrate, an electrode, an insulating layer, or a protective layer.
The detection method in the touch panel of the present invention may be any of known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the electrostatic capacitance system is preferable.
Examples of the Touch panel type include a so-called inline type (described in, for example, fig. 5, 6, 7, and 8 of japanese laid-open patent publication No. 2012-517051), a so-called inline type (described in, for example, fig. 19 of japanese laid-open patent publication No. 2013-168125, fig. 1 and 5 of japanese laid-open patent publication No. 2012-089102), an ogs (one Glass solution) type, a TOL (Touch-on-Lens) type (described in, for example, fig. 2 of japanese laid-open patent publication No. 2013-054727), other structures (described in, for example, fig. 6 of japanese laid-open patent publication No. 2013-164871), and various types of external-embedded type (so-called GG, G1/G2, GFF, GF2, GF1, G1F).
Examples of the touch panel of the present invention include the touch panel described in paragraph 0229 of japanese patent application laid-open No. 2017-120345.
Examples
The present invention will be described in further detail below with reference to examples. The materials, the amounts used, the ratios, the contents of the treatments, and the procedures of the treatments shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. The scope of the invention should therefore not be construed in a limiting sense by the examples shown below.
In the following, unless otherwise specified, "%" and "part(s)" are based on mass.
[ Synthesis of Polymer A-1 ]
PGMEA (116.5 parts) was added to a three-necked flask and warmed to 90 ℃ under nitrogen atmosphere. A solution to which St (52.0 parts), MMA (19.0 parts), MAA (29.0 parts), V-601(4.0 parts) and PGMEA (116.5 parts) were added was added dropwise over 2 hours to a three-necked flask solution maintained at 90 ℃. + -. 2 ℃. After completion of the dropwise addition, polymer A-1 (solid content concentration 30.0%) was obtained by stirring at 90 ℃. + -. 2 ℃ for 2 hours.
In addition, abbreviations in the above synthesis examples represent the following compounds, respectively.
St: styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation)
MAA: methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)
MMA: methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)
PGMEA: propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K.)
MEK: methyl ethyl ketone (SANKYO CHEMICAL Co., Ltd.; manufactured by Ltd.)
V-601: dimethyl-2, 2' -azobis (2-methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Corporation)
[ preparation of photosensitive resin composition 1]
The following components were mixed and the photosensitive resin composition 1 was prepared. The unit of the amount of each component is part by mass.
Polymer A-1 (solid content concentration 30.0%): 21.87 parts
D-2(ARONIXM270(TOAGOSEI CO., LTD. manufactured)): 0.51 part
D-1(NK EsterBPE-500(Shin Nakamura Chemical Industry Co., manufactured by LTD)): 4.85 parts of
C-2(B-CIM, manufactured by Hampford Research Inc.): 0.89 part
C-3 (photo radical polymerization initiator (sensitizer), 4, 4' -bis (diethylamino) benzophenone, manufactured by Tokyo Chemical Industry Co., Ltd.): 0.05 part
Phenothiazine (manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.025 parts
1-phenyl-3-pyrazolidinone (manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.001 portion
B-2(LCV, colorless crystal violet, YAMADA CHEMICAL co., ltd., manufactured): 0.053 portion
E-1(Megaface F552 (manufactured by DIC CORPORATION)): 0.02 portion
Methyl ethyl ketone (MEK, SANKYO CHEMICAL co., ltd.): 30.87 parts of
Propylene glycol monomethyl ether acetate (PGMEA, manufactured by SHOWA DENKO k.k.): 33.92 parts
Tetrahydrofuran (THF, manufactured by Mitsubishi Chemical Corporation): 6.93 parts
[ example 1]
A PET film (16KS40, manufactured by TORAY INDUSTRIES, inc.) having a thickness of 16 μm was used as a temporary support, and a coating liquid composed of the following formulation H1 was applied to the temporary support and dried to form a thermoplastic resin layer having a dry film thickness of 5 μm.
Subsequently, a photosensitive resin composition 1 was applied to the thermoplastic resin layer using a slit nozzle, and the resultant was passed through a drying zone at 80 ℃ for 40 seconds to form a photosensitive resin layer having a thickness of 3 μm.
Next, a PET film (16KS40, manufactured by TORAY INDUSTRIES, inc.) having a thickness of 16 μm was laminated as a cover film on the photosensitive resin layer to prepare a photosensitive transfer member, and the photosensitive transfer member was wound up to be in a roll form.
< formulation H1>
Ethylene vinyl acetate copolymer (Evaflex P1007, DOW-MITSUI polycephalals co., ltd.): 70g
Toluene: 1000g
[ example 2]
A16 μm thick PET film (16KS40, TORAY INDUSTRIES, manufactured by INC.) was subjected to corona discharge treatment for 3 seconds using a high-frequency oscillator with a wire electrode having a diameter of 1.2mm at an output voltage of 250W and an output voltage of 100% with an electrode length of 240mm and a working electrode pitch of 1.5mm, and surface-modified to be used as a temporary support.
On the temporary support, a thermoplastic resin layer having a thickness of 5 μm composed of an ethylene vinyl acetate copolymer (Evaflex P1007, manufactured by DOW-MITSUI polymers co., ltd.) was formed by melt extrusion.
Next, the photosensitive resin layer and the cover film were formed in the same manner as in example 1, and a photosensitive transfer member was produced and wound up to be in a roll form.
[ example 3]
A PET film (16KS40, manufactured by TORAY additives, inc.) having a thickness of 16 μm was used as a temporary support, on which a thermoplastic resin layer having a thickness of 5 μm composed of a vinyl methacrylate copolymer (Nukurel 4214C, manufactured by DOW-MITSUI polymers co., ltd.) was provided by melt extrusion.
Next, the photosensitive resin layer and the cover film were formed in the same manner as in example 1, and a photosensitive transfer member was produced and wound up to be in a roll form.
[ example 4]
On the temporary support subjected to the same surface treatment as in example 2, a thermoplastic resin layer having a thickness of 5 μm composed of a polyethylene-based compound (Kernel KF380, manufactured by Japan polyethylene Corporation) was provided by a melt extrusion method.
Next, the photosensitive resin layer and the cover film were formed in the same manner as in example 1, and a photosensitive transfer member was produced and wound up to be in a roll form.
[ example 5]
A photosensitive transfer member was produced in the same manner as in example 1, except that the thickness of the thermoplastic resin layer was set to 2 μm, and the photosensitive transfer member was wound up to be in a roll form.
[ example 6]
A photosensitive transfer member was produced in the same manner as in example 2, except that the thickness of the thermoplastic resin layer was set to 10pm, and the photosensitive transfer member was wound up to be in a roll form.
[ example 7]
A photosensitive transfer member was produced in the same manner as in example 2, except that the thickness of the thermoplastic resin layer was 20 μm, and the photosensitive transfer member was wound up to be in a roll form.
[ example 8]
On the temporary support subjected to the same surface treatment as in example 2, a thermoplastic resin layer having a thickness of 5 μm composed of an ethylene vinyl acetate copolymer (manufactured by Evaflex EV550, DOW-MITSUI polychrome co., ltd.) was provided by melt extrusion.
Next, the photosensitive resin layer and the cover film were formed in the same manner as in example 1, and a photosensitive transfer member was produced and wound up to be in a roll form.
[ example 9]
A thermoplastic resin layer having a thickness of 5 μm made of an ethylene vinyl acetate copolymer (Evaflex EV450, DOW-MITSUI polychemials co., ltd.) was provided on the temporary support subjected to the same surface treatment as in example 2 by melt extrusion.
Next, the photosensitive resin layer and the cover film were formed in the same manner as in example 1, and a photosensitive transfer member was produced and wound up to be in a roll form.
[ example 10]
A PET film (16KS40, manufactured by TORAY INDUSTRIES, inc.) having a thickness of 16 μm was used as a cover film, and on the cover film, the photosensitive resin composition 1 was applied using a slit nozzle, and passed through a drying region at 80 ℃ for 40 seconds to form a photosensitive resin layer having a thickness of 3 μm, and a cover film with a photosensitive resin layer was produced.
Next, a thermoplastic resin layer having a thickness of 5 μm made of an ethylene vinyl acetate copolymer (Evaflex P1007, manufactured by DOW-MITSUI polycephalals co., ltd.) was formed on the temporary support subjected to the surface treatment by a melt extrusion method in the same manner as in example 2, and a temporary support to which the thermoplastic resin layer was attached was produced.
Next, a photosensitive resin layer-attached cover film and a thermoplastic resin layer-attached temporary support are laminated so that the photosensitive resin layer and the thermoplastic resin layer are in contact with each other, whereby a photosensitive transfer member is produced, and wound up into a roll form.
[ example 11]
A16 μm thick PET film (haze: 0.20%, manufactured by FUJIFILM Corporation) was subjected to corona discharge treatment for 3 seconds using a high-frequency oscillator with a wire electrode having a diameter of 1.2mm under an output voltage of 100% and an output of 250W under conditions of an electrode length of 240mm and a working electrode pitch of 1.5mm, and surface-modified to be used as a temporary support.
A photosensitive transfer member was produced in the same manner as in example 2, except that the temporary support was used, and was wound up to be in a roll form.
[ example 12]
A photosensitive transfer member was produced in the same manner as in example 1 except that the thickness of the thermoplastic resin layer was 0.8 μm, and was wound up to be in a roll form.
[ example 13]
A16 μm thick PET film (haze: 0.80%, manufactured by FUJIFILM Corporation) was subjected to corona discharge treatment for 3 seconds using a high-frequency oscillator with a wire electrode having a diameter of 1.2mm under an output voltage of 100% and an output of 250W under conditions of an electrode length of 240mm and a working electrode pitch of 1.5mm, and subjected to surface modification, which was used as a temporary support.
A photosensitive transfer member was produced in the same manner as in example 2, except that the temporary support was used, and was wound up to be in a roll form.
Comparative example 1
On the temporary support subjected to the same surface treatment as in example 2, a thermoplastic resin layer having a thickness of 5 μm composed of a Polypropylene-based polymer (Wintech WFX4M, manufactured by Japan Polypropylene Corporation) was provided by a melt extrusion method.
Next, the photosensitive resin layer and the cover film were formed in the same manner as in example 1, and a photosensitive transfer member was produced and wound up to be in a roll form.
Comparative example 2
On the temporary support subjected to the same surface treatment as in example 2, a thermoplastic resin layer having a thickness of 5 μm composed of an ethylene vinyl acetate copolymer (manufactured by Evaflex EV150, DOW-MITSUI polychrome co., ltd.) was provided by melt extrusion.
Next, the photosensitive resin layer and the cover film were formed in the same manner as in example 1, and a photosensitive transfer member was produced and wound up to be in a roll form.
Comparative example 3
A photosensitive transfer member was produced in the same manner as in example 1, except that the thermoplastic resin layer was not provided, and was wound up to be in a roll form.
[ Peel Strength ]
As a result of measuring the peel strength between the respective layers of the temporary support, the thermoplastic resin layer, the photosensitive resin layer, and the cover film for the photosensitive transfer members produced in examples 1 to 13 and comparative examples 1 to 2, it was confirmed that the peel strength between the temporary support and the thermoplastic resin layer was the strongest and the peel strength between the photosensitive resin layer and the cover film was the weakest in all of examples 1 to 13 and comparative examples 1 to 2.
In the photosensitive transfer member produced in comparative example 3 in which no thermoplastic resin layer was provided, the peel strength between the respective layers of the temporary support, the photosensitive resin layer, and the cover film was measured, and as a result, it was confirmed that the peel strength between the temporary support and the photosensitive resin layer was the strongest and the peel strength between the photosensitive resin layer and the cover film was the weakest.
[ Vicat softening point and tensile elastic modulus ]
The vicat softening point and the tensile elastic modulus of the thermoplastic resin layer of the produced photosensitive transfer member were measured by the methods described above. These results are shown in table 1 below.
[ haze ]
The haze of the photosensitive transfer member thus produced, and the temporary support and the laminate having the thermoplastic resin layer provided on the temporary support were measured by the above-described method. The results are shown in table 1 below.
[ laminatability ]
After the photosensitive transfer member thus produced was unwound and the cover film was peeled off, thermal compression bonding was performed between hot rolls having a temperature of 100 ℃ at a speed of 2m/min and a pressure of 0.8MPa on a glass substrate having a thickness of 0.7mm so that the photosensitive resin layers were in contact with each other.
Next, whether or not air bubbles remained between the glass substrate and the photosensitive resin layer was observed with an optical microscope, and evaluated based on the following criteria. The results are shown in table 1 below.
A：100mm2The number of bubbles in the area is 0
B：100mm2The number of bubbles in the area is 1 to 5
C：100mm2The number of bubbles in the area is more than 6 and 10Below one
D：100mm2The number of bubbles in the area is 11 to 50
E：100mm2The number of bubbles in the area is more than 51
[ adhesion ]
After unwinding the produced photosensitive transfer member and peeling off the cover film, a PET substrate having a thickness of 100 μm and a width of 500mm was continuously thermocompression bonded to a support in a roll-to-roll manner at a speed of 2m/min and a pressure of 0.8MPa between hot rolls having a temperature of 100 ℃, and the photosensitive resin layer, the thermoplastic resin layer and the temporary support were wound in a roll form on the support.
Then, the temporary support and the thermoplastic resin layer were simultaneously peeled off and conveyed at a speed of 2 m/min. At this time, the peeled temporary support and the laminate composed of the thermoplastic resin layer were wound in a roll shape with a winding tension of 25N. Whether or not the roll was stuck was observed in the state of the roll at the time when the roll was wound for 100m, and evaluated by the following criteria. The results are shown in table 1 below. In addition, when blocking occurs, appearance abnormalities such as wrinkles and corner curl occur.
A: the appearance is free from any problem
B: although acceptable levels of wrinkling, corner crimping, were observed, transport was not affected.
C: wrinkles and corner beads occur and stable conveyance is not possible
[ Pattern resolution ]
A copper layer having a thickness of 500nm was formed on a glass plate having a thickness of 0.7mm by an evaporation method, and a glass substrate having the copper layer was prepared.
After the produced photosensitive transfer member was unwound and the cover film was peeled off, the resultant was laminated on the copper-clad glass substrate so that the copper layer was in contact with the photosensitive resin layer under lamination conditions of a roll temperature of 100 ℃, a line pressure of 0.8MPa, and a line speed of 2.0 m/min.
Then, a photomask having various line width patterns (2 to 20 μm) of line/space 1/1 was used, and 80mJ/cm was performed on the PET surface2Exposure ofThen, the temporary support and the thermoplastic resin layer are simultaneously peeled off and removed.
Next, a predetermined pattern was formed on the copper by performing shower development using a 1% sodium carbonate aqueous solution having a liquid temperature of 25 ℃ and water washing.
Then, the minimum line width of the space opening was evaluated by an optical microscope (using a mask size value). The results are shown in table 1 below. In comparative examples 1 and 3, since the lamination property was poor and a large number of bubbles were present, the pattern resolution could not be evaluated, and the mark is "-" in table 1 below.
[ Table 1]
The laminate is as follows: laminate comprising temporary support and thermoplastic resin layer
From the results shown in table 1, it is understood that when the tensile elastic modulus of the thermoplastic resin layer is more than 200MPa, the lamination property is poor (comparative example 1).
Further, it is found that when the tensile elastic modulus of the thermoplastic resin layer is less than 10MPa, blocking occurs when the temporary support and the thermoplastic resin layer are peeled off (comparative example 2).
Further, it is found that the lamination property is poor when the thermoplastic resin layer is not provided (comparative example 3).
On the other hand, it is found that when the vicat softening point of the thermoplastic resin layer is 50 to 120 ℃ and the tensile elastic modulus is 10 to 200MPa, the lamination property is excellent and blocking can be suppressed when the temporary support and the thermoplastic resin layer are peeled off (examples 1 to 13).
In particular, from the comparison of examples 1 to 4, it is understood that when the tensile elastic modulus of the thermoplastic resin layer is 50 to 200MPa, blocking can be further suppressed from occurring when the temporary support and the thermoplastic resin layer are peeled.
Further, as is clear from the comparison of examples 1, 2, 5 to 7 and 12, when the thickness of the thermoplastic resin layer is more than 2 μm and less than 20 μm, both of the excellent lamination property and the excellent pattern resolution can be satisfied.
(example 101)
A circuit-forming substrate was prepared by sputtering ITO on a 100 μm thick PET substrate to form a 150nm thick film as a 2 nd conductive layer, forming copper thereon to form a 200nm thick film as a 1 st conductive layer by vacuum deposition, and winding the substrate into a roll form.
Next, after the photosensitive transfer member produced in example 3 was unwound and the cover film was peeled off, the photosensitive resin layer was laminated on the copper layer of the unwound circuit-forming substrate so as to be in contact therewith, and the substrate was wound into a roll shape. Further, lamination was carried out under conditions of a line pressure of 0.6MPa, a line speed of 3.6m/min and a roll temperature of 100 ℃.
Next, without peeling off the temporary support, a contact pattern exposure (1 st exposure step) was performed using a mask provided with a pattern a shown in fig. 2 having a structure in which a conductive layer pad was connected in one direction, and the mask was wound into a roll shape. In the pattern a shown in fig. 2, as described above, SL and G are openings, and DL is a frame which virtually shows alignment. The solid line portion is a thin line of 70 μm or less.
Then, while simultaneously peeling the temporary support and the thermoplastic resin layer, development using a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution was performed (1 st development step), and then, a resist image having a shape of the 1 st pattern (pattern of the shape of the opening region of pattern a) was formed by water washing. Finally, the film with the resist image and the peeled temporary support with the thermoplastic resin are wound into a roll.
Next, after etching the copper layer (1 st conductive layer) using a copper etching solution (Cu-02, KANTO CHEMICAL co., inc., manufactured), the ITO layer (2 nd conductive layer) was etched using an ITO etching solution (ITO-02, KANTO CHEMICAL co., inc., manufactured), and a substrate in which the copper layer (1 st conductive layer) and the ITO layer (2 nd conductive layer) were drawn together with the 1 st pattern (pattern of the shape of the opening region of pattern a) was obtained (1 st etching step). The remaining resist image was further peeled off using a peeling liquid (KP-301 manufactured by Kanto Chemical co., inc.). Finally, the film is wound into a roll shape.
Next, the photosensitive transfer member produced in example 3 was unwound, and the cover film was peeled off, followed by lamination. Further, lamination was carried out under conditions of a line pressure of 0.6MPa, a line speed of 3.6m/min and a roll temperature of 100 ℃.
Next, without peeling off the temporary support, a contact pattern exposure is performed in an aligned state using a mask provided with a pattern B shown in fig. 3 (2 nd exposure step), and the substrate is wound into a roll shape. In the pattern B shown in fig. 3, G is an opening and DL is a frame showing alignment in a virtual manner, as described above.
Next, the temporary support and the thermoplastic resin were simultaneously peeled off, and subjected to development using a TMAH aqueous solution at 2.38% (2 nd development step), and then subjected to water washing to obtain a resist image having a shape of the 2 nd pattern (a pattern in which the openings of pattern a and the openings of pattern B overlap).
Then, the copper layer was etched using Cu-02, and the remaining resist image was peeled off using a peeling liquid (KP-301, KANTO CHEMICAL co., inc.
The circuit of the obtained circuit wiring board was observed with a microscope, and as a result, a clear pattern with high image quality was obtained without peeling, chipping, or the like.
(formation of protective film Pattern 1)
A protective film was formed on the circuit wiring substrate obtained in the above manner in the following manner.
First, a photosensitive transfer member was produced in the same manner as in example 3, except that a photosensitive resin composition having the following formulation was used for the photosensitive resin layer and the film thickness was set to 8 μm.
Next, the produced photosensitive transfer member was unwound, and the cover film was peeled off, followed by lamination such that the photosensitive resin layer was in contact with the circuit pattern. Further, lamination was carried out under conditions of a line pressure of 0.6MPa, a line speed of 3.6m/min and a roll temperature of 100 ℃.
Next, without peeling off the temporary support, contact pattern exposure was performed using a mask provided with a partially unexposed portion (contact hole).
Then, the temporary support and the thermoplastic resin layer were peeled off at the same time, and development was performed using a 1.0% aqueous solution of sodium carbonate having a liquid temperature of 30 ℃, followed by water washing to obtain a protective film pattern image.
Then, heat treatment was performed at 140 ℃ for 60 minutes, and the resultant was thermally cured to form a protective film on the circuit board.
< photosensitive resin composition >
A 41 mass% ethyl cellosolve solution of methacrylic acid/cyclohexyl acrylate/methyl methacrylate copolymer (monomer mass ratio of 20/25/55, mass average molecular weight 8 ten thousand): 51.0 parts by mass
Dipentaerythritol hexaacrylate: 10.0 parts by mass
Fluorine-based surfactant F176PF (manufactured by DIC Corporation): 0.25 parts by mass
Victoria pure blue BOH (HODOGAYA CHEMICAL co., ltd., manufactured): 0.225 parts by mass
2, 4-bis (trichloromethyl) -6- (N, N-dioxocarbonylamino) -3-bromophenyl ] s-triazine: 0.45 part by mass
Methyl ethyl ketone: 13.0 parts by mass
(formation of protective film Pattern 2)
A protective film was formed on the circuit wiring substrate obtained in the above manner in the following manner.
First, a photosensitive transfer member was produced in the same manner as in example 3, except that a non-photosensitive resin composition having the following formulation was used for the photosensitive resin layer and the film thickness was set to 8 μm.
Portions where the non-photosensitive resin layer is not desired to be provided are further cut off.
Then, alignment was performed so that the non-photosensitive resin layer was in contact with the circuit pattern, and lamination was performed. Further, lamination was carried out under conditions of a line pressure of 0.6MPa, a line speed of 3.6m/min and a roll temperature of 100 ℃.
Subsequently, the temporary support and the thermoplastic resin are simultaneously peeled off, and a protective film pattern image is obtained.
Further, heat treatment was performed at 140 ℃ for 60 minutes, and the resultant was thermally cured to form a protective film on the circuit board.
< non-photosensitive resin composition >
A 41 mass% ethyl cellosolve solution of methacrylic acid/cyclohexyl acrylate/methyl methacrylate copolymer (monomer mass ratio of 20/25/55, mass average molecular weight 8 ten thousand): 51.0 parts by mass
Dipentaerythritol hexaacrylate: 10.0 parts by mass
Fluorine-based surfactant F176PF (manufactured by DIC Corporation): 0.25 parts by mass
Victoria pure blue BOH (HODOGAYA CHEMICAL co., ltd., manufactured): 0.225 parts by mass
Methyl ethyl ketone: 13.0 parts by mass
(production of image display device (touch Panel))
An image display device including a capacitance-type input device as a constituent element is manufactured by a known method by bonding the circuit wiring board with the protective film to the liquid crystal display element manufactured by the method described in japanese patent application laid-open No. 2009-047936.
Description of the symbols
10-temporary support, 12-thermoplastic resin layer, 14-photosensitive resin layer, 16-cover film, 100-photosensitive transfer member, SL-non-image portion (exposed portion), G-non-image portion (exposed portion), DL-alignment frame.
Claims (10)
1. A photosensitive transfer member comprising a temporary support, a thermoplastic resin layer, a photosensitive resin layer and a cover film in this order,
the Vicat softening point of the thermoplastic resin layer is 50-120 ℃, and the tensile elastic modulus is 10-200 MPa,
the peel strength between the temporary support and the thermoplastic resin layer is greater than the peel strength between the thermoplastic resin layer and the photosensitive resin layer.
2. The photosensitive transfer member according to claim 1,
the thickness of the thermoplastic resin layer is greater than 2 μm and less than 20 μm.
3. The photosensitive transfer member according to claim 1 or 2,
the thickness of the temporary support is 6 to 50 μm.
4. The photosensitive transfer member according to any one of claims 1 to 3,
the temporary support has a haze of 0.5% or less.
5. The photosensitive transfer member according to any one of claims 1 to 4,
the haze of the laminate between the temporary support and the thermoplastic resin layer is 0.9% or less.
6. The photosensitive transfer member according to any one of claims 1 to 5,
the thermoplastic resin layer has a tensile elastic modulus of 50MPa to 200 MPa.
7. The photosensitive transfer member according to any one of claims 1 to 6,
among the peel strengths of the respective layers of the temporary support, the thermoplastic resin layer, the photosensitive resin layer, and the cover film, the peel strength between the temporary support and the thermoplastic resin layer is the strongest, and the peel strength between the photosensitive resin layer and the cover film is the weakest.
8. A method for producing a resin pattern by a roll-to-roll method using the photosensitive transfer member according to any one of claims 1 to 7, the method comprising:
a peeling step of peeling the cover film from the photosensitive transfer member;
a bonding step of bonding the photosensitive resin layer in the photosensitive transfer member from which the cover film has been peeled, in contact with a substrate having a conductive layer;
an exposure step of pattern-exposing the photosensitive resin layer; and
a developing step of developing the exposed photosensitive resin layer to form a resin pattern,
the method includes a step of simultaneously peeling the temporary support and the thermoplastic resin layer from the photosensitive transfer member between the bonding step and the exposure step or between the exposure step and the development step.
9. A method for manufacturing a circuit wiring by a roll-to-roll method using the photosensitive transfer member according to any one of claims 1 to 7, the method comprising:
a peeling step of peeling the cover film from the photosensitive transfer member;
a bonding step of bonding the photosensitive resin layer in the photosensitive transfer member from which the cover film has been peeled, in contact with a substrate having a conductive layer;
an exposure step of pattern-exposing the photosensitive resin layer;
a developing step of developing the exposed photosensitive resin layer to form a resin pattern; and
a step of etching the conductive layer located in a region where the resin pattern is not arranged,
the method includes a step of simultaneously peeling the temporary support and the thermoplastic resin layer from the photosensitive transfer member between the bonding step and the exposure step or between the exposure step and the development step.
10. A method for manufacturing a touch panel by a roll-to-roll method using the photosensitive transfer member according to any one of claims 1 to 7, the method comprising:
a peeling step of peeling the cover film from the photosensitive transfer member;
a bonding step of bonding the photosensitive resin layer in the photosensitive transfer member from which the cover film has been peeled, in contact with a substrate having a conductive layer;
an exposure step of pattern-exposing the photosensitive resin layer;
a developing step of developing the exposed photosensitive resin layer to form a resin pattern; and
a step of etching the conductive layer located in a region where the resin pattern is not arranged,
the method further comprises a step of simultaneously peeling the temporary support and the thermoplastic resin layer from the photosensitive transfer member between the bonding step and the exposure step or between the exposure step and the development step.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-177169 | 2019-09-27 | ||
| JP2019177169 | 2019-09-27 | ||
| PCT/JP2020/035288 WO2021060148A1 (en) | 2019-09-27 | 2020-09-17 | Photosensitive transfer member, method for producing resin pattern, method for producing circuit wiring, and method for producing touch panel |
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| Publication Number | Publication Date |
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| CN114450633A true CN114450633A (en) | 2022-05-06 |
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| Country | Link |
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| JP (1) | JP7340616B2 (en) |
| KR (1) | KR20220053615A (en) |
| CN (1) | CN114450633A (en) |
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| CN118475879A (en) * | 2021-12-27 | 2024-08-09 | 富士胶片株式会社 | Method for producing resist pattern, method for producing laminate, and photosensitive transfer material for direct image-forming exposure |
| KR102718423B1 (en) | 2024-05-17 | 2024-10-17 | 이수애 | Safety lamp device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05273759A (en) * | 1992-03-25 | 1993-10-22 | Fuji Photo Film Co Ltd | Photosensitive material |
| JPH09179306A (en) * | 1995-12-26 | 1997-07-11 | Konica Corp | Image forming material, image receiving sheet material, and method for producing releasable cushion layer |
| US5858609A (en) * | 1992-01-27 | 1999-01-12 | Konica Corporation | Image-forming material and method for forming transferred image |
| CN1950753A (en) * | 2004-03-02 | 2007-04-18 | 富士胶片株式会社 | Pattern forming method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005286308A (en) * | 2004-03-02 | 2005-10-13 | Fuji Photo Film Co Ltd | Pattern forming method |
| JP2007178459A (en) | 2005-12-26 | 2007-07-12 | Fujifilm Corp | Pattern forming material, pattern forming apparatus and pattern forming method |
-
2020
- 2020-09-17 CN CN202080066629.XA patent/CN114450633A/en active Pending
- 2020-09-17 KR KR1020227009592A patent/KR20220053615A/en active Pending
- 2020-09-17 WO PCT/JP2020/035288 patent/WO2021060148A1/en active Application Filing
- 2020-09-17 JP JP2021548861A patent/JP7340616B2/en active Active
- 2020-09-24 TW TW109132995A patent/TW202113484A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5858609A (en) * | 1992-01-27 | 1999-01-12 | Konica Corporation | Image-forming material and method for forming transferred image |
| JPH05273759A (en) * | 1992-03-25 | 1993-10-22 | Fuji Photo Film Co Ltd | Photosensitive material |
| JPH09179306A (en) * | 1995-12-26 | 1997-07-11 | Konica Corp | Image forming material, image receiving sheet material, and method for producing releasable cushion layer |
| CN1950753A (en) * | 2004-03-02 | 2007-04-18 | 富士胶片株式会社 | Pattern forming method |
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| TW202113484A (en) | 2021-04-01 |
| WO2021060148A1 (en) | 2021-04-01 |
| JP7340616B2 (en) | 2023-09-07 |
| JPWO2021060148A1 (en) | 2021-04-01 |
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