JPH0269754A - Photosensitive laminated film for etching mask - Google Patents
Photosensitive laminated film for etching maskInfo
- Publication number
- JPH0269754A JPH0269754A JP22144988A JP22144988A JPH0269754A JP H0269754 A JPH0269754 A JP H0269754A JP 22144988 A JP22144988 A JP 22144988A JP 22144988 A JP22144988 A JP 22144988A JP H0269754 A JPH0269754 A JP H0269754A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- film
- photosensitive
- water
- compsn
- 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.)
- Granted
Links
- 238000005530 etching Methods 0.000 title description 13
- 239000000203 mixture Substances 0.000 claims description 29
- 230000001070 adhesive effect Effects 0.000 claims description 27
- 239000000853 adhesive Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 abstract description 20
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000010030 laminating Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 52
- 239000000463 material Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000005488 sandblasting Methods 0.000 description 18
- 239000011521 glass Substances 0.000 description 13
- 238000011161 development Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- -1 polypropylene Polymers 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 229920006267 polyester film Polymers 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000001856 Ethyl cellulose Substances 0.000 description 6
- 229920001249 ethyl cellulose Polymers 0.000 description 6
- 235000019325 ethyl cellulose Nutrition 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 239000003082 abrasive agent Substances 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- YVXDRFYHWWPSOA-BQYQJAHWSA-N 1-methyl-4-[(e)-2-phenylethenyl]pyridin-1-ium Chemical group C1=C[N+](C)=CC=C1\C=C\C1=CC=CC=C1 YVXDRFYHWWPSOA-BQYQJAHWSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 238000006359 acetalization reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 206010011732 Cyst Diseases 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000031513 cyst Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000001057 purple pigment Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
吏朶上■肌几公団
本発明は、ガラス、石材、陶磁器、金属、プラスチック
、木質材、皮革等の加工材料の表面に写真画、模様、文
字などをサンドブラストによる彫刻、または薬液による
食刻によって画像を現出させる工程において、彫食刻マ
スクとして用いられる感光性積層フィルムに関するもの
で、さらに詳しく述べれば、良好な写真感光性と水現像
により、微細で精巧な画像が容易に得られ、サンドブラ
ストまたは薬液に対する耐性に優れ、かつその表面は強
力な粘着性を有しているので、接着剤を用いることなく
、加工材料へ貼着、転写することができる彫食刻マスク
用感光性積層フィルムに関する。[Detailed Description of the Invention] 吏朏上■Hadako Corporation The present invention is for engraving photographic images, patterns, letters, etc. on the surface of processed materials such as glass, stone, ceramics, metal, plastic, wood, and leather by sandblasting. It also relates to a photosensitive laminated film used as an etching mask in the process of developing an image by etching with a chemical solution.More specifically, it relates to a photosensitive laminated film that is used as an etching mask in the process of developing an image by etching with a chemical solution. It is easily obtained, has excellent resistance to sandblasting or chemical solutions, and has a strong adhesive surface, so it can be affixed or transferred to processed materials without using adhesives. This invention relates to a photosensitive laminated film for masks.
促米■及■
ガラス、金属、プラスチック等の加工材料表面に画像を
彫刻出現させる表面加工法として従来からおこなわれて
いる方法は、加工材料表面に直接スクリーン印刷方式に
よって、レジストインキを印刷して目的の画像のレジス
ト膜を形成する方法やガラス繊維による不織布面に、ス
クリーン印刷によって同様に画像を印刷したものをマス
クと呼称して、これを加工材料表面に接着してレジスト
膜を形成する方法があり、いづれの場合にも、そのレジ
スト膜面にサンドブラスト加工を施し、しシスト膜のな
い部分を研麿、彫刻して画像を現出させるか、または加
工材料がガラスの場合はフ、7酸により、銅の場合は塩
化第二鉄の水溶液によって、レジスト膜のない部分を腐
食、彫刻して画像を現出させる方法である。The conventional surface processing method for engraving an image on the surface of processed materials such as glass, metal, and plastic is to print resist ink directly onto the surface of the processed material using a screen printing method. A method of forming a resist film with the desired image, and a method of printing a similar image on a non-woven fabric made of glass fiber by screen printing, which is called a mask, and bonding it to the surface of the processing material to form a resist film. In either case, the surface of the resist film is sandblasted, and the areas where there is no cyst film are sandblasted and engraved to reveal the image, or if the processed material is glass, it is This method involves corroding and engraving the areas where there is no resist film using an acid, or in the case of copper, an aqueous solution of ferric chloride to reveal an image.
しかしながら、以ト述べたような従来法においては、い
づれの場合にもスクリーン印刷によって図柄画像を印刷
するため、同一柄の加工数量が多い場合には、能率的で
有利であるが、例えば10個以下のように加工数量が少
ない場合には、印版の作製(製版)工程に多くの費用と
時間を要し、経済的にも能率的にも不利となる。However, in the conventional method described above, the pattern image is printed by screen printing in any case, so it is efficient and advantageous when a large number of the same pattern is processed. When the quantity to be processed is small as described below, the printing plate production (plate making) process requires a lot of cost and time, which is disadvantageous both economically and in terms of efficiency.
また、従来から液状感光性樹脂を用いて、サンドブラス
ト用マスクを作製する方法が種々提案されている。例え
ば、ガラス板などの加工材料上にゴム枠を作り、そこに
直接感光性樹脂を流し込んでセロファン紙で覆い、ネガ
フィルムを置き、露光し、次いでセロファン紙をはぎと
り、現像をおこなって画像マスクを形成する方法(特公
昭4635681号)、透明な二枚のフィルムの間に、
液状感光性樹脂組成物をはさみ込み、これに図柄フォト
マスクを密着させて露光し、フォトマスク側の透明フィ
ルムを?A’l r”4して、非硬化部を除去して図柄
を形成し、この面を加工材料面に貼り合わせ、反対側の
フィルムを剥■して図柄マスクを形成する方法(特開昭
53−99258号)等がある。次には、サンドブラス
ト可能な支持体層(例えば厚さ100μmのポリエステ
ルフィルム)にスペーサーによって構成された型枠に、
液状感光性樹脂(光硬化液の100%モジラスが500
kg/coりを注入して露光、現像し、図柄に対応した
貫通透孔を有する光硬化した感光性樹脂層とより成る画
像マスクを形成して、この支持体側にゴム糊を塗り、加
工材料に接着する方法(特開昭55−96270号)、
また、分子構造と成分性能の特定された液状感光性樹脂
組成物から成るマスクパターン層、これを保持するため
の支持体層、及びマスクパターン層と支持体層の間に位
置し、該マスクパターン層とはよく接着するが、該支持
体とは21)離可能であり、かつサンドブラストにより
、破壊される性質を有する保持層から成るサンドブラス
ト用マスク転写材(特開昭60−104939号)等が
提案されている。しかし、いづれの場合にも液状感光性
樹脂組成物を用いるため、型枠やスペーサーを用いて樹
脂組成物をこれに流入する操作を行うものであって、こ
れが複雑かつ熟練を要する操作である上に、露光装置も
専用機を必要とするためコスト高になる。さらにこれら
の液状感光性樹脂組成物の露光後の洗い出し現像には、
アセトン、ヘンゼンなどの有N?3剤、カセイソーダ、
ホウ酸ナトリウムなどのアルカリ水溶液、塩化カルシウ
ムアルコール溶液、中性洗剤などの界面活性剤水溶液を
使用しなければならず、経済的に不利であるばかりでな
く、取扱い者の安全衛生上の問題、回収や排水処理、装
置の腐蝕食に及ぼす影響等、種々の不利な問題を発生さ
せることになる。Furthermore, various methods have been proposed for producing sandblasting masks using liquid photosensitive resins. For example, a rubber frame is made on a processing material such as a glass plate, a photosensitive resin is directly poured into it, it is covered with cellophane paper, a negative film is placed, exposed, the cellophane paper is peeled off, and the image mask is developed. A method of forming (Japanese Patent Publication No. 4635681), between two transparent films,
Sandwich the liquid photosensitive resin composition, place a patterned photomask in close contact with it, expose it to light, and remove the transparent film on the photomask side. A method of forming a pattern by removing the non-hardened portion, bonding this surface to the surface of the processed material, and peeling off the film on the other side to form a pattern mask (Japanese Patent Application Laid-Open No. 53-99258) etc.Next, in a formwork constituted by a sandblasting support layer (for example, a 100 μm thick polyester film) and spacers,
Liquid photosensitive resin (100% modulus of photocuring liquid is 500
kg/co is injected, exposed and developed to form an image mask consisting of a photocured photosensitive resin layer having through-holes corresponding to the design. Rubber paste is applied to the support side, and the processing material is processed. (Japanese Unexamined Patent Publication No. 55-96270),
In addition, a mask pattern layer made of a liquid photosensitive resin composition having a specified molecular structure and component performance, a support layer for holding the same, and a mask pattern layer located between the mask pattern layer and the support layer, A sandblasting mask transfer material (Japanese Patent Application Laid-open No. 104939/1983), which has a retaining layer that adheres well to the layer but is separable from the support and has the property of being destroyed by sandblasting, etc. Proposed. However, since a liquid photosensitive resin composition is used in either case, the resin composition must be poured into the mold using a mold or a spacer, which is a complicated and skillful operation. Furthermore, the exposure equipment also requires a dedicated machine, which increases costs. Furthermore, for washing out and developing these liquid photosensitive resin compositions after exposure,
Do you use acetone, Hensen, etc.? 3 drugs, caustic soda,
Alkaline aqueous solutions such as sodium borate, calcium chloride alcoholic solutions, and surfactant aqueous solutions such as neutral detergents must be used, which is not only economically disadvantageous, but also poses safety and health problems for the handlers, and recalls. This results in various disadvantageous problems, such as the effects on water treatment, wastewater treatment, and corrosion of equipment.
また、加工材料への貼り付けも、特に接着剤を用いなけ
ればならないものは、手間がかかつて不便であり、感光
性樹脂組成物として、不飽和ポリエステルポリマーや不
飽和ポリウレタン系ポリマ成分の表面粘着性とサンドブ
ラスト耐性を発現させる組成物が開示されているが、い
づれの場合にも粘着力が不充分で、サンドブラスト中に
細かな図柄のマスクパターンが加工材料から、’?lI
jilI L、加工不良の発生を招く原因となる。In addition, it is time-consuming and inconvenient to attach the photosensitive resin composition to the processed material, especially when adhesives must be used. Compositions have been disclosed that exhibit adhesive properties and sandblasting resistance, but in all cases, the adhesion is insufficient, and during sandblasting, a fine mask pattern is removed from the processed material. lI
This may cause machining defects.
発■が解〆しようとする課
本発明は、畝上の状況に鑑みなされたものであって、ガ
ラス、金属、プラスチック等の加工材料の表面に彫食刻
を施す際に用いられるマスクの製作において、微細で精
巧な画像を写真法で容易に精度よく形成できること;フ
ィルム状で取扱うことができ、露光、現像の取扱いが簡
便であり、現像は水のみを用いいるので、安全で経済的
であり、現像後のマスク表面は強力な粘着性を示し、接
着剤なしで加工材料に貼着、転写ができること;また必
要に応じては保持層を設けて、微細な図柄の転写の際、
支持体の剥離を容易にし位置ズレをなくし、サンドブラ
スト加工時に微細ケ所の離脱を防止して正確な彫刻ので
きる彫食刻マスク用感光性積層フィルムを提供すること
を課題とする。The present invention was developed in view of the situation of ridges, and is useful in the production of masks used when engraving the surface of processed materials such as glass, metal, and plastic. , it is possible to easily and accurately form fine and delicate images using photographic methods; it can be handled in film form, exposure and development are easy to handle, and development uses only water, making it safe and economical. , The surface of the mask after development exhibits strong adhesiveness, allowing it to be attached to and transferred to processing materials without adhesive; and if necessary, a retaining layer may be provided to transfer minute designs.
It is an object of the present invention to provide a photosensitive laminated film for an engraving mask, which makes it easy to peel off a support, eliminates positional deviation, and prevents minute spots from coming off during sandblasting, allowing accurate engraving.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
課題を解決するための手段
本発明者らは、上述の既に知られているサンドブラスト
マスクの欠点をすべて解決するため、感光性積層フィル
ムについて、種々研究を重ねた結果、微細な原画像を忠
実に再現できる、写真感光性能を有し、水現像ができる
感光性組成物、および同様に水現像のできる光架橋性の
粘着組成物を、必要に応してマスク画像保持層を設けた
支持体に塗布して、サンドブラストまたは薬液にょる彫
食刻のレジスト層と転写のための粘着層を形成し、透明
な離型フィルムを被覆した感光性積層フィルムが彫食刻
のマスクとして、前述の目的を達成し得ることを見出し
、本発明を完成するに至った。Means for Solving the Problems In order to solve all the drawbacks of the already known sandblasting masks mentioned above, the present inventors have conducted various studies on photosensitive laminated films, and as a result, they have developed a method that faithfully reproduces minute original images. A photosensitive composition that has reproducible photographic sensitivity performance and can be developed with water, and a photocrosslinkable adhesive composition that can also be developed with water are applied to a support provided with a mask image-retaining layer if necessary. The photosensitive laminated film, which is coated with a transparent mold release film and coated with a resist layer for sandblasting or chemical engraving and an adhesive layer for transfer, can be used as a mask for engraving to achieve the above-mentioned purpose. The inventors have discovered what can be achieved and have completed the present invention.
すなわち、本発明の特徴は、(^)支持体、(B)水現
像のできる感光性組成物層、(C)水現像のできる感光
性粘着組成物層及び(D)透明性離型フィルムから順次
構成される感光性積層フィルムにある。That is, the characteristics of the present invention are as follows: (^) a support, (B) a water-developable photosensitive composition layer, (C) a water-developable photosensitive adhesive composition layer, and (D) a transparent release film. It consists of a photosensitive laminated film that is constructed in sequence.
さらに、本発明は必要に応じ、上記(A)支持体と(B
)の感光性組成物層の間に、該支持層から剥離可能なフ
ィルムとしての画像マスク保持層を介在させることにか
できる。Furthermore, the present invention can optionally provide the above (A) support and (B)
) An image mask holding layer as a film that can be peeled off from the support layer can be interposed between the photosensitive composition layers.
本発明の感光性積層フィルムにおける(八)支持体は、
積層体の製造上及び使用時の取扱い上必要なものであっ
て、ポリエステル、ポリプロピレン、ポリエチレン、ポ
リスチレン、ポリ塩化ビニル、ポリカーボネートなどの
合成樹脂フィルムや合成紙、合成樹脂をコートしたコー
ト紙などが挙げられ、取扱い保持性の上から、厚さは5
0μm〜500.171)の範囲のものが腰があって好
適である。(8) The support in the photosensitive laminated film of the present invention is
Materials that are necessary for the production and handling of laminates, such as synthetic resin films such as polyester, polypropylene, polyethylene, polystyrene, polyvinyl chloride, and polycarbonate, synthetic paper, and coated paper coated with synthetic resin. The thickness is 5 mm for ease of handling and retention.
A material having a diameter of 0 μm to 500.171) is suitable because it has a stiffness.
本発明の感光性積層フィルムにおいて、支持体と(B)
の感光性組成物層との間に介在させる画像マスク保持層
は、必須の構成材料ではないが、図柄画像が精密、微細
な場合に加工材料面に粘着貼付した後、支持体の剥離を
容易にして位置ズレをなくし、サンドブラスト加工時に
は、画像マスク全面を覆って微細ケ所の離脱を防止する
目的のものであり、図柄画像が比較的大きなものには、
特に必要でない。この画像マスク保持層はサンドブラス
トや素形に用いる薬液によって容易に破壊され、殆んど
彫刻、食刻の抵抗にならないものでなければならないた
め、フィルム層の厚さは30μm以下で特に1〜10μ
m厚みの範囲が好ましい。また、(八)支持体と軽度に
接着しているが、水現像時には支持体から剥離せず、加
工材料に貼り付は後、支持体を強制的に剥離する場合に
は容易に剥離できるものでなければならないため、支持
体材料との接着力よりも、(B)水現像のできる感光性
組成物層との接着力の方が大きい材料を用いればよい。In the photosensitive laminated film of the present invention, the support and (B)
The image mask holding layer interposed between the photosensitive composition layer and the photosensitive composition layer is not an essential constituent material, but if the design image is precise or minute, it can be used to easily peel off the support after being adhesively attached to the surface of the processed material. The purpose is to prevent positional deviation by covering the entire surface of the image mask during sandblasting to prevent minute spots from coming off.
Not particularly necessary. This image mask holding layer must be easily destroyed by sandblasting or the chemicals used in the molding, and must have little resistance to engraving or etching, so the thickness of the film layer should be 30 μm or less, especially 1 to 10 μm.
The thickness range is preferably m. (8) A substance that is slightly adhered to the support, but does not peel off from the support during water development, and can be easily peeled off when the support is forcibly peeled off after being attached to the processing material. Therefore, it is sufficient to use a material that has a stronger adhesive force with the water-developable photosensitive composition layer (B) than with the support material.
すなわち、ポリビニルアルコールとその誘導体、エチル
セルロース、酢酸セルロース、硝酸セルロースなどのセ
ルロース誘導体、支持体との異種材料の組合わせでポリ
塩化ビニル、ポリスチレン、ポリアミドなどの現像液と
しての水には不溶性で、自己保持性のフィルムを造膜で
きるポリマーが好適である。In other words, polyvinyl alcohol and its derivatives, cellulose derivatives such as ethyl cellulose, cellulose acetate, and cellulose nitrate, and polyvinyl chloride, polystyrene, polyamide, etc., which are insoluble in water and self-possessing as a developer, are used in combinations of different materials with supports. Polymers that can form a retentive film are preferred.
この画像マスク保護層の形成にあたっては、前述の造膜
性ポリマーを溶媒に溶かした塗料を調製し、支持体の一
面に塗布、乾燥して塗膜を形成すればよい。In forming this image mask protective layer, a coating material may be prepared by dissolving the above film-forming polymer in a solvent, applied to one surface of the support, and dried to form a coating film.
次に、(B)水現像のできる光架橋性組成物層の感光成
分としては、■不溶性高分子と光架橋剤、例えばポリビ
ニルアルコールとジアゾ樹脂(l−ジアゾジフェニルア
ミンのバラホルムアルデヒド縮合物の硫酸塩)、ポリビ
ニルピロリドンと447−ピスアジドスチルベンー2.
2′−ジスルホン酸ナトリウム、ポリビニルメチルエー
テルとモノ(ジ)アクリロキシエチルホスフェートなど
が挙げられる。Next, (B) the photosensitive components of the water-developable photocrosslinkable composition layer include (1) an insoluble polymer and a photocrosslinking agent, such as polyvinyl alcohol and a diazo resin (a sulfate of a formaldehyde condensate of l-diazodiphenylamine); ), polyvinylpyrrolidone and 447-pisazidostilbene-2.
Examples include sodium 2'-disulfonate, polyvinyl methyl ether and mono(di)acryloxyethyl phosphate.
■分子内に光架橋性基を有する水溶性高分子、例えば、
スチルバゾリウム基をアセタール化により導入したポリ
ビニルアルコール、N−メチロールアクリルアミドを付
加したポリビニルアルコールなどが挙げられる。■は■
または■の感光液に光重合性の不飽和化合物と光重合開
始剤を相溶もしくは分散させたもの、例えば、ポリビニ
ルアルコールとジアゾ樹脂の水溶液に、2−ヒドロキシ
エチルアクリレートとアンスラキノン−2−スルホン酸
ナトリウムを相溶させたもの、スチルバゾリウム基ヲj
4人したポリビニルアルコール水溶液にペンクエリスリ
トールトリアクリレートとベンゾフェノンを添加し、攪
拌によりエマルジョン化して分散させたものなどが挙げ
られる。さらに、これらの感光成分に対し、ポリ酢酸ビ
ニル、エチレン酢酸ビニル共重合体、ポリスチレン、ポ
リ塩化ビニルなどの高分子エマルジョンとその可塑剤、
シリカ、アルミナなどの微粉末、染料、顔料などの着色
剤や界面活性剤等各種の添加剤を混合することによって
得られる組成物の水性分散液を調製し、これを前述の支
持フィルムに塗布、乾燥して(C)水現像のできる感光
性組成物層を形成する。この層の厚さは、サンドブラス
ト加工の場合は、使用する研[9J才の粒度、噴射空気
圧、彫刻の深さ(同一ケ所への噴射時間)によって選択
され、また薬液による女形の場合には、薬液の浸食性、
濃度、浸漬時間に応して適正な厚みを選択すればよい。■Water-soluble polymers with photocrosslinkable groups in the molecule, e.g.
Examples include polyvinyl alcohol into which a stilbazolium group is introduced by acetalization, and polyvinyl alcohol to which N-methylolacrylamide is added. ■is■
Or, a photosensitive solution prepared by dissolving or dispersing a photopolymerizable unsaturated compound and a photopolymerization initiator in the photosensitive liquid of Compatible with sodium acid, stilbazolium group
An example is one in which penquerythritol triacrylate and benzophenone are added to an aqueous solution of polyvinyl alcohol prepared by four people, and then emulsified and dispersed by stirring. Furthermore, for these photosensitive components, polymer emulsions such as polyvinyl acetate, ethylene vinyl acetate copolymer, polystyrene, polyvinyl chloride and their plasticizers,
An aqueous dispersion of the composition obtained by mixing various additives such as fine powders such as silica and alumina, colorants such as dyes and pigments, and surfactants is prepared, and this is applied to the above-mentioned support film. It is dried to form (C) a water-developable photosensitive composition layer. In the case of sandblasting, the thickness of this layer is selected depending on the grain size of the grain used, the jet air pressure, and the depth of engraving (time of spraying on the same spot). erosive properties of chemical solutions;
An appropriate thickness may be selected depending on the concentration and immersion time.
通常その厚みは0.05〜21TII1)の範囲である
。Usually its thickness is in the range of 0.05 to 21TII1).
次に、(C)水現像のできる感光性粘着組成物層の粘着
剤成分としては特開昭48−56240号公報に記載さ
れている水溶性粘着剤が好適である。就中、2−ヒドロ
キシエチルアクリレート、2−ヒドロキシプロピルアク
リレートの70〜90重量%と2−ヒドロキシエチルメ
タクリレート、2−ヒドロキシプロピルメタクリレート
30〜10重量%のイソプロピルアルコール溶媒での溶
液重合体が、良好な水)容性と強力な粘着力を有し、か
つ優れた光架性性を有するので、本発明の粘着剤成分と
して好適である。Next, as the adhesive component of the water-developable photosensitive adhesive composition layer (C), a water-soluble adhesive described in JP-A-48-56240 is suitable. Among these, a solution polymer of 70 to 90% by weight of 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate and 30 to 10% by weight of 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate in an isopropyl alcohol solvent is a good solution. It is suitable as the adhesive component of the present invention because it has water compatibility, strong adhesive strength, and excellent photocrossability.
この粘着剤成分に、感光性を付与するには粘着成分のイ
ソプロパツール溶液に光架橋剤として多官能アクリレー
ト例えばトリメチロールプロパントリアクリレート、ペ
ンタエリスリトールトリアクリレート、4官能ウレタン
アクリレート、多官能エポキシアクリレートなどと光重
合開始剤、例えばベンゾフェノン、ベンジルベンジルジ
メチルケタール、ヘンジイン、チオキサンソンなどを添
加混合した組成物溶液を調製すればよい。To impart photosensitivity to this adhesive component, a polyfunctional acrylate such as trimethylolpropane triacrylate, pentaerythritol triacrylate, tetrafunctional urethane acrylate, polyfunctional epoxy acrylate, etc. is used as a photocrosslinking agent in the isopropanol solution of the adhesive component. A composition solution may be prepared by adding and mixing a photopolymerization initiator such as benzophenone, benzylbenzyl dimethyl ketal, hengeine, thioxanthone, and the like.
この(C)粘着組成物層の形成に当っては、これに隣接
する(D)透明離型フィルムの離型処理面に、前述の感
光性粘着組成物液を塗布、乾燥し、この粘着性を利用し
て、すでに作製した(A)支持体と(B)感光性組成物
層の2者積層体かもしくは両者の間に上記フィルムから
なる画像マスク保持層を介在させた3者積層体の(B)
感光性組成物層面に貼合せれば、本発明の感光性フィル
ム積層体が得られる。In forming this adhesive composition layer (C), the above-mentioned photosensitive adhesive composition liquid is applied to the release-treated surface of the transparent release film (D) adjacent thereto, dried, and this adhesive composition layer is formed. Either a two-part laminate of (A) the support and (B) the photosensitive composition layer already produced by using the method or a three-part laminate with an image mask holding layer made of the above film interposed between the two. (B)
If it is laminated onto the surface of the photosensitive composition layer, the photosensitive film laminate of the present invention can be obtained.
ここで用いる(C)感光性粘着組成物層の厚さは特に制
限はないが、20〜200μmの厚さが好ましい範囲で
あり、この層もサンドブラストなどの抵抗層としても働
くものである。次に、(D) 透明離型フィルムとして
は、ポリエステル、ポリプロピレン、ポリスチレン、ポ
リエチレンなどの透明フィルムにシリコン系のシU型剤
を塗布したフィルムであって、フィルムの厚さは、この
フィルム面に原画を密着して露光するため、厚みが余り
厚いとこの層内で光が散乱し、画像の再現性が低下する
ことになるので、できるだけ薄い方がよいが、加工取扱
いの面から20〜60μmが好ましい範囲である。The thickness of the photosensitive adhesive composition layer (C) used here is not particularly limited, but a thickness of 20 to 200 μm is preferably within the range, and this layer also functions as a resistance layer for sandblasting and the like. Next, (D) the transparent release film is a film made of a transparent film such as polyester, polypropylene, polystyrene, polyethylene, etc. coated with a silicone-based U-type agent, and the thickness of the film is the same as that of the film surface. Since the original image is exposed in close contact with the original image, if the layer is too thick, light will scatter within this layer and image reproducibility will deteriorate, so it is better to make it as thin as possible, but from the viewpoint of processing and handling, it should be 20 to 60 μm. is the preferred range.
さらに詳しく本発明の彫食刻マスク用感光性積層フィル
ムの使用方を説明する。まず原画ポジフィルムを感光性
積層フィルムの(D) 透明性離型フィルム面に密着し
、アーク灯、キセノン灯、メタルハライド灯、高圧水銀
灯など波長300〜500nmの活性光線を発生する光
源を有する通常のプリンター露光器により、感光性フィ
ルムの厚みに応した露光時間を設定して露光する。露光
後(D) 33明離型フイルムを剥離除去して常温の水
に数分間浸漬して非露光部を吸水膨潤させ、ブラシやス
ポンジ用いて軽くこすり、水をスプレーして、洗い出し
を完全におこなって乾燥する。現像後の彫食刻マスクを
保存する場合には、画像マスクの粘着面に一度?り離し
た透明離型フィルムを再び貼り付けておくとよい。In more detail, how to use the photosensitive laminated film for engraving masks of the present invention will be explained in more detail. First, the original positive film is placed in close contact with the (D) transparent release film surface of the photosensitive laminated film, and a normal light source that generates active light with a wavelength of 300 to 500 nm, such as an arc lamp, xenon lamp, metal halide lamp, or high-pressure mercury lamp, is used. Expose using a printer exposure device, setting an exposure time that corresponds to the thickness of the photosensitive film. After exposure (D) 33 Peel and remove the clear film, immerse it in water at room temperature for a few minutes to absorb water and swell the unexposed area, rub it lightly with a brush or sponge, and spray with water to completely wash it out. Wash and dry. If you want to save the etching mask after development, do you have to put it on the adhesive side of the image mask once? It is a good idea to reapply the transparent release film that you removed.
画像マスク表面の粘着層は光架橋された粘着剤層であり
、強力な粘着力を有するので、加工材料面に容易に画像
マスクを貼着固定することができる。しかる後に、表面
の支持体を剥離すれば、画像マスク面または必要に応し
て設けた画像マスク保持層の面が露出して、この面から
彫食刻の加工を行う。The adhesive layer on the surface of the image mask is a photo-crosslinked adhesive layer and has strong adhesive force, so that the image mask can be easily adhered and fixed to the surface of the processed material. Thereafter, when the surface support is peeled off, the image mask surface or the surface of the image mask holding layer provided as necessary is exposed, and the etching process is performed from this surface.
以上述べたように、本発明の彫食刻マスク用感光性積層
フィルムは、フィルム状で露光、現像をおこなうことが
できるため、取扱いがきわめて容易であり、かつ現像に
使用する洗い出し液は、常温の水であって、取扱い者に
とって安全であり、経済的にも有利である。さらに、得
られた画像マスクは表面に強力な粘着層を有するので、
接着剤を使用することなく、加工材料に貼着できるため
便利である。As mentioned above, the photosensitive laminated film for engraving masks of the present invention can be exposed and developed in film form, so it is extremely easy to handle, and the washing solution used for development can be kept at room temperature. water, which is safe for those who handle it and economically advantageous. Furthermore, the obtained image mask has a strong adhesive layer on the surface, so
It is convenient because it can be attached to processed materials without using adhesives.
また、感光性フィルム積層体の大きさについても、長さ
方向はエンドレスで、幅方向についても2m程度は特に
1UTfな制約はないので、大形の加工材料にも十分適
用することができ、その実用的な価値はきわめて大であ
る。In addition, regarding the size of the photosensitive film laminate, it is endless in the length direction, and there is no particular restriction of 1UTf of about 2 m in the width direction, so it can be fully applied to large processing materials. The practical value is extremely large.
このようにして、本発明の彫食刻マスクを形成した加工
材料を加工するに当っては、機械的な彫刻としてサンド
ブラスト加工、化学的な食刻として薬液によるエツチン
グ加工があり、いづれも通常おこなわれている方法が適
用される。すなわち、サンドブラスト加工は、種々の粒
度をもった金剛砂のような研磨材をノズルから噴射し、
マスクのない部分は研磨材との衝突摩擦によって研磨彫
刻され、レジスト膜の部分は研磨材の衝撃を吸収するた
め研磨されない。マスク膜厚は彫刻の深さによって異な
り、深彫りの場合は長時間の噴射に耐えられるよう膜厚
を厚くする。(例えば0.1〜2ffi1)1)また、
反対に浅彫りの場合は膜厚は薄くともよい。In processing the material from which the etched mask of the present invention is formed, mechanical engraving is performed by sandblasting, and chemical etching is performed by chemical etching, both of which are normally performed. The method described will be applied. In other words, sandblasting involves injecting abrasive materials such as diamond sand with various particle sizes from a nozzle.
The portions without the mask are polished and engraved due to the collision friction with the abrasive material, and the resist film portions are not polished because they absorb the impact of the abrasive material. The thickness of the mask film varies depending on the depth of the engraving, and in the case of deep engraving, the film thickness is increased to withstand long-term spraying. (e.g. 0.1-2ffi1) 1) Also,
On the other hand, in the case of shallow engraving, the film thickness may be thinner.
(例えば20〜80μm)
彫刻の深さの調整は噴射圧、噴射時間、加工材料と噴射
ノズルの距離、研磨材の粒度によっておこなわれる。(For example, 20 to 80 μm) The depth of engraving is adjusted by the injection pressure, injection time, distance between the processing material and the injection nozzle, and the particle size of the abrasive.
一方、薬液による食刻加工は、主としてガラス、石材の
場合はフッ酸水溶液を用い、銅及び銅合金の加工材料の
場合は塩化第二鉄水溶液、その他の金属類では塩酸、硝
酸、硫酸などの水溶液を用い塗布、浸漬して腐食彫刻を
おこなう。On the other hand, chemical engraving mainly uses hydrofluoric acid aqueous solution for glass and stone, ferric chloride aqueous solution for copper and copper alloy processing materials, and hydrochloric acid, nitric acid, sulfuric acid, etc. for other metals. Corrosion engraving is performed by applying and dipping using an aqueous solution.
以下、実施例を挙げて本発明の詳細な説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例1
平均重合度1700、ケン化度88モル%ポリビニルア
ルコール(信越化学工業性PA−18)15重量部を水
85重量部に溶解した溶液に固形分濃度50重量%のエ
チレン−酢酸ビニル共重合体エマルジョン(昭和高分子
型 EVA AD−50)120重量部、ジアゾ樹脂5
型看部、水分散性青色顔料0.2重量部、ポリオキシエ
チレンラウリルフェニルエーテル非イオン活性剤1重量
部を添加混合して、感光性組成物液を調製した。支持体
としては75μのポリエステルフィルムとし、画像マス
ク保持層の形成に当っては、支持体フィルムにエチルセ
ルロース(ダウケミカル社製、エトセル5TD−10)
をエチルアルコールとトルエン1:1の混合溶媒に10
重■%で熔かした溶液を塗布乾燥して、約5μmのエチ
ルセルロースの画像マスク保持層を形成し、この面に感
光性組成物液を塗布、乾燥して感光層の厚さが80μm
の積層フィルム(積層Aと称する)を作製した。Example 1 A solution of 15 parts by weight of polyvinyl alcohol (Shin-Etsu Chemical PA-18) dissolved in 85 parts by weight of water with an average degree of polymerization of 1700 and a degree of saponification of 88 mol% was mixed with ethylene-vinyl acetate with a solid content concentration of 50% by weight. 120 parts by weight of polymer emulsion (Showa Kobunshi type EVA AD-50), 5 parts by weight of diazo resin
A photosensitive composition liquid was prepared by adding and mixing a mold part, 0.2 parts by weight of a water-dispersible blue pigment, and 1 part by weight of a polyoxyethylene lauryl phenyl ether nonionic activator. A 75μ polyester film was used as the support, and when forming the image mask holding layer, ethyl cellulose (manufactured by Dow Chemical Company, Ethocel 5TD-10) was used as the support film.
in a mixed solvent of ethyl alcohol and toluene 1:1.
A solution melted at 5% by weight was applied and dried to form an image mask holding layer of ethyl cellulose having a thickness of approximately 5 μm.A photosensitive composition solution was applied to this surface and dried to form a photosensitive layer with a thickness of 80 μm.
A laminated film (referred to as Laminate A) was produced.
次に、2−ヒドロキシエチルアクリレート80重量部と
2−ヒドロキシエチルメタクリレート20重量部をイソ
プロピルアルコール200重量部を溶媒とし、重合触媒
としてベンゾイルパーオキサイド2重量部を加えて、窒
素気流中で温度60℃で2時間、溶液重合し、水溶性粘
着剤溶液を得た。この粘着剤に感光性を賦与するために
、光架橋剤としてペンタエリスリトールトリアクリレー
ト50重量部、光重合開始剤としてベンゾフェノン3重
量部を添加混合して怒光性粘着剤組成物溶液を調製し、
別に作製した厚さ18μmのポリプロピレン離型フィル
ムの離型面に、この溶液を乾燥後の厚さが50μmにな
るように塗布、積層して積層フィルム(積層Bと称する
)を形成し、乾燥して直ちに、すでに作製した積層Aの
積層フィルムの感光層面に圧着して貼合せて、感光性積
石フィルムを得た。Next, 80 parts by weight of 2-hydroxyethyl acrylate and 20 parts by weight of 2-hydroxyethyl methacrylate were added to 200 parts by weight of isopropyl alcohol as a solvent, 2 parts by weight of benzoyl peroxide was added as a polymerization catalyst, and the temperature was 60°C in a nitrogen stream. Solution polymerization was carried out for 2 hours to obtain a water-soluble adhesive solution. In order to impart photosensitivity to this adhesive, 50 parts by weight of pentaerythritol triacrylate as a photocrosslinking agent and 3 parts by weight of benzophenone as a photopolymerization initiator were added and mixed to prepare a photosensitive adhesive composition solution.
This solution was applied to the release surface of a separately prepared polypropylene release film with a thickness of 18 μm so that the thickness after drying would be 50 μm, and then laminated to form a laminated film (referred to as Laminate B), and then dried. Immediately, the photosensitive laminated stone film was bonded to the photosensitive layer surface of the laminated film of Laminated A, which had already been prepared, to obtain a photosensitive laminated stone film.
この感光性積層フィルムより、サンドブラスト彫刻マス
クを作製するに当り、該積層フィルムの透明離型フィル
ム面に微細な図柄の原画ポジフィルムを密着させ、3K
Wメタルハライドランプにより1mの距離から5分間露
光した。次いで透明離型フィルムを剥離し、常温の水に
約3分間浸漬して、非露光部を吸水膨潤させ、スポンジ
で軽くこすり洗い出し現像をして、50℃の熱風で乾燥
し、微細な図柄の画像マスクを作製した。現像工程中、
支持体と画像マスク保持層および光架橋組成物層間で全
く剥離は起らなかった。別に作製した試料により、マス
ク部表面の粘着力を測定するため、中15mm、長さl
oo+nI++の大きさの試料をガラス板に200g/
cJO力で圧着し、100n+m/minのスピードで
180’ 2.1)離抵抗を測定したところ、1400
gを示し、強力に接着していることが認められた。When producing a sandblasting engraving mask from this photosensitive laminated film, an original positive film with a fine pattern is brought into close contact with the transparent release film surface of the laminated film.
It was exposed for 5 minutes from a distance of 1 m using a W metal halide lamp. Next, peel off the transparent mold release film, immerse it in water at room temperature for about 3 minutes to absorb water and swell the non-exposed area, rub it lightly with a sponge, develop it, dry it with hot air at 50℃, and create a fine pattern. An image mask was created. During the development process,
No peeling occurred between the support, the image mask holding layer, and the photocrosslinking composition layer. In order to measure the adhesive strength of the surface of the mask part using a separately prepared sample, a medium size of 15 mm and a length of 1.
200 g of a sample of size oo+nI++ was placed on a glass plate.
Crimp with cJO force and 180' at a speed of 100n+m/min 2.1) When the separation resistance was measured, it was 1400.
g, indicating strong adhesion.
次に、このマスクを8mm厚さのガラス板に貼り、ポリ
エステルフィルム支持体を;/+1 Altしたところ
、画像マスク保持層とポリエステルフィルム支持体の間
で容易に剥離し、位置ズレなくマスクを転写することが
できた。Next, this mask was pasted on a glass plate with a thickness of 8 mm, and when the polyester film support was set to ;/+1 Alt, it was easily peeled off between the image mask holding layer and the polyester film support, and the mask was transferred without positional shift. We were able to.
このガラス板をサンドブラストa内に設置し、アランダ
ム#80の研溶剤を圧縮空気圧4kg/cJにて、口径
3.61のノズルから約10C++1の距離より噴射し
て研磨彫刻を行ったところ、マスク部は30秒間噴射し
ても、マスク膜が剥離または破を員することがなく、ガ
ラス板は全(研磨されることがなかった。This glass plate was placed in a sandblast a, and abrasive engraving was performed by spraying Alundum #80 abrasive solvent at a compressed air pressure of 4 kg/cJ from a distance of approximately 10C++1 from a nozzle with a diameter of 3.61. Even after spraying for 30 seconds, the mask film did not peel or break, and the entire glass plate was not polished.
反対にマスクがなくガラス面が画像マスク保持層のみで
覆われている部分は約10秒Eで約lIn1)1の深さ
で研磨彫刻が進行し、原画に忠実な画像が彫刻された。On the other hand, in the area where there was no mask and the glass surface was covered only with the image mask holding layer, polishing engraving progressed to a depth of about lIn1)1 in about 10 seconds E, and an image faithful to the original was engraved.
彫刻終了後には、加工材料を水で濡らして、マスク膜を
吸水させて、膜を剥離除去した。After the engraving was completed, the processed material was wetted with water, the mask film was absorbed, and the film was peeled off.
実施例2
平均重合度1700、けん化度88モル%ポリビニルア
ルコール(信越化学工業製PA−18)にアセタル化反
応により、N−メチル−γ−(p−ホルミルスチリル)
−ピリジニウムメトサルフェートを1.4モル%付加さ
せて得たスチルバゾリウム付加ポリビニルアルコール1
5重量部を水85重量部に溶かした溶液にアクリレート
オリゴマー(東亜合成化学製70ニツクスト8030)
15重計部、ペンタエクスリトルトリアクリレート1
5重量部、光重合開始剤として、2−クロロチオキサン
ソン(日本化薬製カヤキュアーCTX) 3重量部を攪
拌しながら添加して分散させた。さらに、この分散液に
50M1%濃度のポリ酢酸ビニル水性エマルジョン(ヘ
キスト合成製MA−6)55重量部と水分散性紫色顔料
0.2重量部を添加混合して感光性組成物液を調製した
。Example 2 N-methyl-γ-(p-formylstyryl) was added to polyvinyl alcohol (PA-18 manufactured by Shin-Etsu Chemical Co., Ltd.) with an average degree of polymerization of 1700 and a degree of saponification of 88 mol% by an acetalization reaction.
-Stilbazolium-added polyvinyl alcohol 1 obtained by adding 1.4 mol% of pyridinium methosulfate
Acrylate oligomer (70 Nixt 8030 manufactured by Toagosei Chemical Co., Ltd.) was added to a solution of 5 parts by weight dissolved in 85 parts by weight of water.
15-weight weighing section, pentaex-little triacrylate 1
5 parts by weight and 3 parts by weight of 2-chlorothioxanthone (Nippon Kayaku Kayacure CTX) as a photopolymerization initiator were added and dispersed with stirring. Further, 55 parts by weight of a 50M 1% aqueous polyvinyl acetate emulsion (MA-6 manufactured by Hoechst Synthesis) and 0.2 parts by weight of a water-dispersible purple pigment were added and mixed to this dispersion to prepare a photosensitive composition liquid. .
この感光液を実施例1で使用した75μ畑のポリエステ
ルフィルムのエチルセルロース塗膜面に塗布、乾燥して
、感光層の厚さが100μmの積層フィルム (以後積
層A′と称する)を作製した。This photosensitive solution was applied to the ethyl cellulose coated surface of the 75 μm polyester film used in Example 1 and dried to produce a laminated film (hereinafter referred to as Laminate A') having a photosensitive layer thickness of 100 μm.
この積層A′を実施例1と同一の積層Bと貼り合せて、
感光性積層フィルムを得た。This laminate A' is laminated with the same laminate B as in Example 1,
A photosensitive laminated film was obtained.
この感光性積層フィルムより、フッ酸食刻のためのマス
クを作製するに当り、実施例1と同様な操作により露光
、現像を行い微細な図柄の画像マスクを作製した。現像
工程中、支持体と画像マスク保持層および感光性組成物
層間で全く剥離は起らなかった。To prepare a mask for hydrofluoric acid etching from this photosensitive laminated film, exposure and development were carried out in the same manner as in Example 1 to produce an image mask with a fine pattern. During the development process, no peeling occurred between the support, the image mask holding layer, and the photosensitive composition layer.
次に、このマスクを8mm厚さのガラス板に貼り、ポリ
エステルフィルム支持体を剥離したところ、画像マスク
保持層とポリエステルフィルムの間で容易に剥離し、位
置ズレなくマスクを転写することができた。このガラス
板を食刻するに当り、50重量%のフッ酸水溶液をマス
ク面に像布して約2分経過後水洗し、腐食深度が50μ
mの画像を食刻することができた。この際マスク表面の
5μm厚さのエチルセルロース画像マスク保持層はフッ
酸液に対し、殆んど抵抗性を示さず、マスク全体は、全
くフッ酸に侵されないことが認められた。食刻終了後に
は、加工材料を水で濡らして、マスク膜を吸水させて、
膜を剥離除去した。Next, when this mask was attached to a glass plate with a thickness of 8 mm and the polyester film support was peeled off, it was easily peeled off between the image mask holding layer and the polyester film, and the mask could be transferred without positional shift. . When etching this glass plate, a 50% by weight aqueous hydrofluoric acid solution was applied to the mask surface and washed with water after about 2 minutes, so that the corrosion depth was 50 μm.
I was able to engrave the image of m. At this time, it was found that the 5 μm thick ethyl cellulose image mask holding layer on the mask surface showed almost no resistance to the hydrofluoric acid solution, and that the entire mask was not attacked by the hydrofluoric acid at all. After etching, the processed material is wetted with water to allow the mask film to absorb water.
The film was peeled off.
実施例3
実施例1の怒光性積層フィルムの構成において、エチル
セルロースの画像マスク保持層を省いた以外は実施例1
の怒光性積層フィルムと同一の構成で積層フィルムを作
製した。Example 3 Same as Example 1 except that the ethyl cellulose image mask holding layer was omitted in the structure of the photosensitive laminated film of Example 1.
A laminated film was produced with the same configuration as the photosensitive laminated film.
次に、比較的大なる図柄の原画ポジフィルムを用いて実
施例Iと同様な操作により露光、現像を行った画像マス
クを作製した。現像工程中、支持体から画像マスク部が
工II離することばなかった。Next, using an original positive film with a relatively large pattern, exposure and development were performed in the same manner as in Example I to prepare an image mask. During the development process, the image mask portion never separated from the support.
加工材料として厚さ2mmの銅板を用い、この表面に画
像マスクを圧着して貼り付け、ポリエステルフィルム支
持体を剥離したところ、画像マスクのみが銅板に転写さ
れた。これを食刻するに当り、比重1.3の塩化第二鉄
水溶液中に15分間浸漬したところ、マスク貼り付は面
には、腐食深度が20μmの画像を食刻することができ
た。腐食工程中、マスクが剥離したり、塩化第二鉄溶液
に浸されることは認められなかった。食刻終了後はマス
ク膜を剥離除去した。A copper plate with a thickness of 2 mm was used as a processing material, and when an image mask was pressed and pasted onto the surface of the plate and the polyester film support was peeled off, only the image mask was transferred to the copper plate. When etching this, it was immersed in an aqueous ferric chloride solution with a specific gravity of 1.3 for 15 minutes, and an image with a corrosion depth of 20 μm could be etched on the masked surface. During the corrosion process, no peeling of the mask or immersion in the ferric chloride solution was observed. After etching was completed, the mask film was peeled off and removed.
Claims (2)
物層、(C)水現像の可能な感光性粘着組成物層及び(
D)透明離型フィルムが順次的に積層された積層体から
成ることを特徴とする彫食刻マスク用感光性積層フィル
ム。(1) (A) support, (B) water-developable photosensitive composition layer, (C) water-developable photosensitive adhesive composition layer, and (
D) A photosensitive laminated film for an engraving mask, comprising a laminate in which transparent release films are sequentially laminated.
物層の間に該支持体から剥離可能なフィルムとしての画
像マスク保持層を介在させた請求項(1)に記載の彫食
刻マスク用感光性積層フィルム。(2) According to claim (1), an image mask holding layer as a film that can be peeled from the support is interposed between the (A) support and (B) the water-developable photosensitive composition layer. Photosensitive laminated film for engraving masks.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63221449A JP2562954B2 (en) | 1988-09-06 | 1988-09-06 | Photosensitive laminated film for engraving mask |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63221449A JP2562954B2 (en) | 1988-09-06 | 1988-09-06 | Photosensitive laminated film for engraving mask |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0269754A true JPH0269754A (en) | 1990-03-08 |
JP2562954B2 JP2562954B2 (en) | 1996-12-11 |
Family
ID=16766909
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63221449A Expired - Lifetime JP2562954B2 (en) | 1988-09-06 | 1988-09-06 | Photosensitive laminated film for engraving mask |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2562954B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0770923A1 (en) | 1995-10-27 | 1997-05-02 | Tokyo Ohka Kogyo Co., Ltd. | Photosensitive resin composition and photosensitive resin laminated film containing the same |
US6322947B1 (en) | 1998-08-17 | 2001-11-27 | Tokyo Ohka Kogyo Co., Ltd. | Photosensitive composition for sandblasting and photosensitive film laminate comprising the same |
US6897011B2 (en) | 2000-11-07 | 2005-05-24 | Tokyo Ohka Kogyo Co., Ltd. | Photosensitive composition for sandblasting and photosensitive film using the same |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5596270A (en) * | 1979-01-05 | 1980-07-22 | Asahi Chem Ind Co Ltd | Engraving method using sand blast |
JPS58196971A (en) * | 1982-05-13 | 1983-11-16 | Asahi Chem Ind Co Ltd | Manufacture of mask for sandblast |
JPS60104938A (en) * | 1982-05-13 | 1985-06-10 | Asahi Chem Ind Co Ltd | Mask transferring material for working surface of solid |
-
1988
- 1988-09-06 JP JP63221449A patent/JP2562954B2/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5596270A (en) * | 1979-01-05 | 1980-07-22 | Asahi Chem Ind Co Ltd | Engraving method using sand blast |
JPS58196971A (en) * | 1982-05-13 | 1983-11-16 | Asahi Chem Ind Co Ltd | Manufacture of mask for sandblast |
JPS60104938A (en) * | 1982-05-13 | 1985-06-10 | Asahi Chem Ind Co Ltd | Mask transferring material for working surface of solid |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0770923A1 (en) | 1995-10-27 | 1997-05-02 | Tokyo Ohka Kogyo Co., Ltd. | Photosensitive resin composition and photosensitive resin laminated film containing the same |
US6322947B1 (en) | 1998-08-17 | 2001-11-27 | Tokyo Ohka Kogyo Co., Ltd. | Photosensitive composition for sandblasting and photosensitive film laminate comprising the same |
US6897011B2 (en) | 2000-11-07 | 2005-05-24 | Tokyo Ohka Kogyo Co., Ltd. | Photosensitive composition for sandblasting and photosensitive film using the same |
Also Published As
Publication number | Publication date |
---|---|
JP2562954B2 (en) | 1996-12-11 |
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