JPH0379270A - Photosensitive lamination film for engraving and corrosion curving mask - Google Patents
Photosensitive lamination film for engraving and corrosion curving maskInfo
- Publication number
- JPH0379270A JPH0379270A JP21195789A JP21195789A JPH0379270A JP H0379270 A JPH0379270 A JP H0379270A JP 21195789 A JP21195789 A JP 21195789A JP 21195789 A JP21195789 A JP 21195789A JP H0379270 A JPH0379270 A JP H0379270A
- Authority
- JP
- Japan
- Prior art keywords
- film
- water
- mask
- exposure
- engraving
- 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
- 238000003475 lamination Methods 0.000 title abstract 2
- 230000007797 corrosion Effects 0.000 title description 6
- 238000005260 corrosion Methods 0.000 title description 6
- 239000011342 resin composition Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- 238000011161 development Methods 0.000 abstract description 14
- 229910001507 metal halide Inorganic materials 0.000 abstract description 3
- 150000005309 metal halides Chemical class 0.000 abstract description 3
- 239000007921 spray Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052753 mercury Inorganic materials 0.000 abstract description 2
- 229910052724 xenon Inorganic materials 0.000 abstract description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008961 swelling Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 36
- 239000000463 material Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 18
- 238000005488 sandblasting Methods 0.000 description 17
- 239000011521 glass Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000012545 processing Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000005530 etching Methods 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229920006267 polyester film Polymers 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000001856 Ethyl cellulose Substances 0.000 description 5
- 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 5
- 229920001249 ethyl cellulose Polymers 0.000 description 5
- 235000019325 ethyl cellulose Nutrition 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene 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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- 239000006185 dispersion Substances 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
- 150000002739 metals Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229920003169 water-soluble polymer Polymers 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 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
- 238000006359 acetalization reaction Methods 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
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 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
- 238000007127 saponification reaction Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004575 stone Substances 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
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 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
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 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
- 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 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 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
- 235000011148 calcium chloride Nutrition 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
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 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
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing 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
- 239000003960 organic solvent Substances 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
- 229920002037 poly(vinyl butyral) polymer Polymers 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
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene 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
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000001057 purple pigment Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-M sodium 2-anthraquinonesulfonate Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)[O-])=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-M 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
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 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
- 239000002023 wood Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
【発明の詳細な説明】
産業上皇剋■分立
本発明は、ガラス、石材、陶磁器、金属、プラスチック
、木質剤、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] Industrial Empowerment ■ Separation The present invention is a method for engraving photographs, patterns, letters, etc. on the surface of processed materials such as glass, stone, ceramics, metals, plastics, wood agents, and leather by sandblasting, or This relates to a photosensitive laminated film used as an etching mask in the process of developing images by etching with a chemical solution.More specifically, it has good photographic sensitivity and water development, making it easy to create fine and precise images. For use in engraving masks, it has excellent resistance to sandblasting or chemical solutions, and its surface has strong adhesive properties, so it can be attached or transferred to processed materials without using adhesives. It relates to a photosensitive laminated film.
従来立技丘
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、いずれの場合にも、そのレジ
スト膜面にサンドブラスト加工を施し、レジスト膜のな
い部分を研磨、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ッ酸により、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. There is a method of forming a resist film with the image of In either case, the resist film surface is sandblasted, and the areas where there is no resist film are polished and engraved to reveal the image, or if the processing material is glass, copper is removed using hydrofluoric acid. In this case, an aqueous solution of ferric chloride is used to corrode and engrave the areas where there is no resist film to reveal the image.
しかしながら、以上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、印刷版の作製（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 to be processed. When the quantity to be processed is small, as in the above case, 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、つ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４６−３５６８１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
ィルムを剥離して、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
剥離して図柄マスクを形成する方法（特開昭５３−９９
２５８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１００χモジラスが５００ ｋｇ ／
ｃ４ ）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
とは剥離可能であり、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
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
をこれに注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
、ベンゼンなどの有機溶剤、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、装置の腐蝕量
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 the film (Japanese Patent Publication No. 46-35681) involves sandwiching a liquid photosensitive resin composition between two transparent films, and exposing the patterned photomask to light to form a transparent film on the photomask side. Peel it off and remove the uncured part to form a design.
A method of bonding this side to the surface of the processed material and peeling off the film on the opposite side to form a pattern mask (Japanese Patent Laid-Open No. 53-99
258) etc. Next, a liquid photosensitive resin (100 χ modulus of photocuring liquid of 500 kg /
c4) is injected, exposed and developed to form an image mask consisting of a photocured photosensitive resin layer with through-holes corresponding to the design, and rubber glue is applied to this support side to adhere it to the processing material. (Japanese Unexamined Patent Publication No. 55-96270), a mask pattern layer made of a liquid photosensitive resin composition with a specified molecular structure and component performance, a support layer for holding the same, and a mask pattern layer. A mask transfer material for sandblasting consisting of a holding layer located between support layers, which adheres well to the mask pattern layer, but is removable from the support and has the property of being destroyed by sandblasting. JP-A-60-104939) and the like have been proposed. However, since a liquid photosensitive resin composition is used in either case, the resin composition must be injected into the composition 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 and developing these liquid photosensitive resin compositions after exposure, organic solvents such as acetone and benzene, alkaline aqueous solutions such as caustic soda and sodium borate, calcium chloride alcoholic solutions, and surfactant aqueous solutions such as neutral detergents are used. This is not only economically disadvantageous, but also causes various disadvantageous problems, such as health and safety problems for handlers, collection, wastewater treatment, and the effect on the amount of corrosion of equipment. become.
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、手間がかかって不便であり、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ー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剥離し
、加工不良の発生を招く原因となる。In addition, it is time-consuming and inconvenient to apply it to processed materials, especially those that require the use of adhesives. Compositions that exhibit surface adhesion and sandblasting resistance have been disclosed, but in all cases the adhesion is insufficient and the fine mask pattern peels off from the processed material during sandblasting, resulting in processing defects. This may cause
”° よ゛と る
本発明は、以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ているので、安全で経済
的であり、現像後のマスク面は熱圧着または塩類水溶液
によって強力な接着性を示し、接着剤なしで加工材料に
貼着、転写ができること；またマスクは保持層を設けて
いるため、微細な転写の際、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 has been developed in view of the above circumstances, and is suitable for manufacturing masks used when engraving the surfaces of processed materials such as glass, metals, and plastics. Elaborate images can be formed easily and accurately using photography; 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 latter mask surface exhibits strong adhesion by thermocompression bonding or salt aqueous solution, and can be attached and transferred to processed materials without adhesive; the mask also has a retaining layer, which provides support during fine transfer. It is an object of the present invention to provide a photosensitive laminated film for an engraving mask, which facilitates peeling of the body, eliminates positional deviation, and prevents minute spots from coming off during sandblasting, allowing accurate engraving.
量 、ｎ゛ るための−
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
感光性樹脂組成物を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よる彫食刻のレ
ジスト層を形成することにより、上記課題を解決するこ
とに成功した。In order to solve all of the above-mentioned drawbacks of the already known sandblasting masks, the present inventors have conducted various studies on photosensitive laminated films, and as a result, the present inventors have found that they are able to faithfully reproduce minute original images. can be reproduced. The above problem can be solved by applying a photosensitive resin composition that has photographic sensitivity and can be developed with water to a support provided with a mask image holding layer to form a resist layer for engraving by sandblasting or chemical liquid. succeeded in solving it.
すなわち、本発明の特徴は、（Ａ）支持体、（Ｂ）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
および（Ｃ）水現像の可能な感光性樹脂組成物層から成
る彫食刻マスク用感光性積層フィルムにある。That is, the present invention is characterized by an engraving comprising (A) a support, (B) an image mask holding layer as a film that can be peeled from the support, and (C) a water-developable photosensitive resin composition layer. Photosensitive laminated film for engraving masks.
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
０μ１１１〜５００μｍ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 thickness in the range of 0μ111 to 500μm is suitable because it has stiffness.
本発明の感光性積層フィルムにおいて、 （八）支持体
と（Ｃ）感光性樹脂組成物層との間に介在させる（Ｂ）
画像マスク保持層は、図柄画像が精密、微細な場合に加
工材料面に接着貼り付した後、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
のである。この画像マスク保持層は、サンドブラストや
介層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１〜１０μｍ厚
みの範囲が好ましい、また、（＾）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、（Ｃ）水現像のできる感光性樹脂
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, (8) (B) interposed between the support and (C) the photosensitive resin composition layer;
The image mask holding layer is adhesively attached to the surface of the processing material when the design image is precise and minute, and then the support is easily peeled off to eliminate misalignment. During sandblasting, it covers the entire image mask and holds fine spots. The purpose is to prevent the withdrawal of This image mask holding layer must be easily destroyed by sandblasting or the chemical solution used for the intermediate layer, and must have little resistance to engraving or etching.
The thickness of the film layer is 30 μm or less, preferably in the range of 1 to 10 μm, and (^) Although it is slightly adhered to the support, it does not peel off from the support during water development and sticks to the processing material. When the support is forcibly peeled off afterwards, it must be easily removable, so the adhesive strength with the (C) water-developable photosensitive resin composition layer is more important than the adhesive strength with the support material. A material with greater adhesive force may be used.
すなわち、ポリビニルアルコールとその誘導体、ポリビ
ニルブチラールエチルセルロース、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。That is, polyvinyl alcohol and its derivatives, cellulose derivatives such as polyvinyl butyral ethyl cellulose, cellulose acetate, and cellulose nitrate, and combinations of different materials with supports such as polyvinyl chloride, polystyrene, polyamide, etc., which are insoluble in water as a developer. , polymers that can form a self-retaining film are suitable.
この画像マスク保持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 holding layer, a coating film may be formed by preparing a coating material in which the above-mentioned film-forming polymer is dissolved in a solvent, coating it on one surface of the support, and drying it.
次に、（Ｃ）水現像のできる光架橋性組成物層の感光成
分としては、■水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（１−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４．４′−ビスアジドスチルベン−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。■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
バゾリウム基を導入したポリビニルアルコール水溶液に
ペンタ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、撹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樹脂組成物層を形成する。Next, (C) the photosensitive components of the water-developable photocrosslinkable composition layer include (1) a water-soluble polymer and a photocrosslinking agent, such as polyvinyl alcohol and a diazo resin (sulfuric acid of a formaldehyde condensate of 1-diazodiphenylamine); salt), polyvinylpyrrolidone and 4,4'-bisazidostilbene-2
, sodium 2'-disulfonate, polyvinyl methyl ether and mono(di)acryloxyethyl phosphate. (2) Water-soluble polymers having a photocrosslinkable group in the molecule, such as polyvinyl alcohol into which a stilbazolium group is introduced by acetalization, polyvinyl alcohol to which N-methylolacrylamide is added, and the like. ■ is one in which a photopolymerizable unsaturated compound and a photopolymerization initiator are compatible or dispersed in the photosensitive liquid of ■ or ■;
For example, 2-hydroxyethyl acrylate and sodium anthraquinone-2-sulfonate are dissolved in an aqueous solution of polyvinyl alcohol and diazo resin, and pentaerythritol triacrylate and benzophenone are added to an aqueous solution of polyvinyl alcohol into which a stilbazolium group has been introduced. , emulsification and dispersion by stirring, etc. Furthermore, for these photosensitive components, polyvinyl acetate, ethylene-vinyl acetate copolymer,
An aqueous composition obtained by mixing a polymer emulsion such as polystyrene or polyvinyl chloride with its plasticizer, fine powders such as silica or alumina, colorants such as dyes and pigments, and various additives such as surfactants. A dispersion liquid is prepared, and this is applied to the above-mentioned support film and dried to form (C) a water-developable photosensitive resin composition layer.
この層の厚さは、サンドブラスト加工の場合は、使用す
る研磨剤の粒度、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、また薬液による介層の
場合には、薬液の浸食性、濃度、浸漬時間に応じて適正
な厚みを選択すればよい。通常その厚みは０．０５〜２
０の範囲である。In the case of sandblasting, the thickness of this layer is selected depending on the particle size of the abrasive used, the jetting air pressure, and the depth of engraving (spraying time to the same place). An appropriate thickness may be selected depending on the erodibility, concentration, and immersion time. Usually its thickness is 0.05~2
It is in the range of 0.
さらに、詳しく本発明の彫食刻マスク用感光性積層フィ
ルムの使用方法を説明する。Furthermore, the method of using the photosensitive laminated film for engraving masks of the present invention will be explained in detail.
まず、原画ポジフィルムを感光性積層フィルムの（Ｃ）
水現像の可能な感光性樹脂組成物層面に密着し、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
みに応じた露光時間を設定して露光する。露光後、常温
の水に数分感浸漬けして非露光部を吸水膨潤させ、ブラ
シやスポンジを用いて軽くこすり、水をスプレーして、
洗い出しを完全に行って乾燥する。現像後の彫食刻マス
クを加工材料に接着する方法としては、画像マスク表面
を加工材料面に載せ、アイロンなどで熱着する方法もし
くは加工材料面またはマスク表面に無機塩類、例えば過
沃素酸ソーダ、塩化リチウム、臭化リチウム、硝酸リチ
ウム、塩化カルシウム、チオシアン酸アンモンニウム、
塩化亜鉛などの水溶性高分子を可溶化、膨潤する塩類の
稀釈水溶液を塗布し、画像マスクを圧着する方法を用い
ることができ、これらの方法によって加工材料面に画像
マスクを容易に貼着固定することが可能となる。その後
に、表面の支持体を剥離すれば、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。First, transfer the original positive film to the photosensitive laminated film (C).
A photosensitive film is produced using a normal printer exposure device that is in close contact with the water-developable photosensitive resin composition layer surface and has a 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. Set the exposure time according to the thickness and expose. After exposure, immerse the area in room temperature water for a few minutes to absorb water and swell the unexposed area, rub it lightly with a brush or sponge, and spray it with water.
Thoroughly wash and dry. After development, the etching mask can be bonded to the processing material by placing the image mask surface on the processing material surface and heat-bonding it with an iron, or by applying an inorganic salt, such as sodium periodate, to the processing material surface or the mask surface. , lithium chloride, lithium bromide, lithium nitrate, calcium chloride, ammonium thiocyanate,
A method can be used in which a dilute aqueous solution of salts that solubilizes and swells water-soluble polymers such as zinc chloride is applied, and the image mask is pressure-bonded.By these methods, the image mask can be easily attached and fixed to the surface of the processed material. It becomes possible to do so. Thereafter, when the surface support is peeled off, the surface of the image mask holding layer 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、フィルム状で露出、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（、加工材料に貼着できるため
便利である。As described above, since the photosensitive laminated film for engraving masks of the present invention can be exposed and developed in film form, 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２−程度は特に
困難な制約はないので、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, there are no particularly difficult restrictions on the size of the photosensitive film laminate, which is endless in the length direction and 2- or so in the width direction, so it can be fully applied to large-sized processed materials. Its practical value is extremely great.
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剤をノズルから噴射し、
マスクのない部分は研磨剤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剤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０．１〜２ ｍｍ）また、反対に
浅彫りの場合は膜厚は薄くともよい（例えば２０〜８０
μｌ１１）。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 abrasives such as diamond sand with various particle sizes from a nozzle.
The part without the mask is polished and engraved by the collision friction with the abrasive, and the part with the resist film is not polished because it absorbs the impact of the abrasive.The mask film thickness varies depending on the depth of the engraving, and in the case of deep engraving, it takes a long time. The film thickness is made thicker so that it can withstand the spray of water. (For example, 0.1 to 2 mm) On the other hand, in the case of shallow engraving, the film thickness may be thinner (for example, 20 to 80 mm).
μl11).
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、研磨剤の粒度によっておこなわれる。The depth of engraving is adjusted by the injection pressure, injection time, distance between the material to be processed 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、実施例を示して本発明の詳細な説明する。Hereinafter, the present invention will be described 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（信越化学工業製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ッン（昭和高分子
型ＥＶＡ Ａｎ−５０）１２０重量部、ジアゾ樹脂５重
量部、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、水現像の可能な感光性樹脂組成物液を
調製した。支持体としては７５μｍ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−１０４）をエチルアルコールとトルエン
１：１の混合溶媒に１０重量％で溶かした溶液を塗布乾
燥して、約５μ−のエチルセルロースの画像マスク保持
層を形成し、この面に水現像の可能な感光性樹脂組成物
を塗布、乾燥して感光層の厚さが８０ｕｓの感光性積層
フィルムを作製した。Example 1 A solution of 15 parts by weight of polyvinyl alcohol (PA-18 manufactured by Shin-Etsu Chemical Co., Ltd.) 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 added with ethylene-vinyl acetate at a solid concentration of 50% by weight. Add and mix 120 parts by weight of polymer emulsion (Showa polymer type EVA An-50), 5 parts by weight of diazo resin, 0.2 parts by weight of water-dispersible blue pigment, and 1 part by weight of polyoxyethylene lauryl phenyl ether nonionic activator. A water-developable photosensitive resin composition solution was prepared. A 75 μm polyester film was used as the support, and when forming the image mask holding layer, ethyl cellulose (manufactured by Dow Chemical Company, "ETCEL 5TD-104") was added to the support film in a mixed solvent of ethyl alcohol and toluene in a ratio of 1:1. A solution dissolved at 10% by weight is applied and dried to form an image mask holding layer of approximately 5 μm of ethyl cellulose.A water-developable photosensitive resin composition is applied to this surface and dried to determine the thickness of the photosensitive layer. A photosensitive laminated film with a length of 80 us was produced.
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、該積層フィルムの感光性フィルム
面に微細な図柄の原画ポジフィルムを密着させ、３に一
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、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°Ｃ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
および感光性樹脂組成物層間で全く剥離は起こらなかっ
た。To prepare a sandblasting engraving mask from this photosensitive laminated film, an original positive film with a fine pattern was brought into close contact with the photosensitive film surface of the laminated film, and exposed for 5 minutes from a distance of 1 m using a metal halide lamp. . Next, it was immersed in water at room temperature for about 3 minutes to absorb water and swell the non-exposed areas, and it was lightly rubbed with a sponge, developed, and dried with hot air at 50°C 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 resin composition layer.
次に、この画像マスクを８ｍｍ厚さのガラス板に１２０
℃に加熱したアイロンで圧着したところ、強力な接着貼
付けが得られた。その後、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 image mask was placed on a glass plate with a thickness of 120 mm.
When crimped with an iron heated to ℃, a strong adhesive was obtained. Thereafter, when the polyester film support was peeled off, the image mask holding layer and the polyester film support were easily peeled off, and the mask could be transferred without positional deviation.
このガラス板をサンドブラスト機内に設置し、アランダ
ム＃８０の研磨剤を圧縮空気圧４ ｋｇ ／ ｃｉにて
、口径３．６Ｍのノズルから約１０ｃｍ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損することがなく、ガ
ラス板は全く研磨されることがなかった。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秒間で約１鴫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。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。This glass plate was placed in a sandblasting machine, and an abrasive of Alundum #80 was sprayed at a compressed air pressure of 4 kg/ci from a distance of approximately 10 cm from a nozzle with a diameter of 3.6 M to perform abrasive engraving. Even after spraying for 30 seconds, the mask film did not peel or break, and the glass plate was not polished at all. On the other hand, in the area where there is no mask and the glass surface is covered only with the image mask holding layer, the polishing engraving progresses to a depth of about 1 depth in about 10 seconds.
An image faithful to the original was engraved. 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）にアセタール化
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
１５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（東亜合成化学製アロエツクスト８０３０
） １５重量部、ペンタエタスリトールトリアクリレー
ト１５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
を撹拌しながら添加して分散させた。さらに、この分散
液に５０重量％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水現像の可能な感光性
組成物液を調製した。Example 2 1.4% of N-methyl-γ-(p-formylstyryl)-pyridinium methosulfate 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. Acrylate oligomer (Aloext 8030 manufactured by Toagosei Kagaku Co., Ltd.
), 15 parts by weight of pentaetaethritol triacrylate, and 3 parts by weight of 2-chlorothioxanthone (Nippon Kayaku Kayacure CTX) as a photopolymerization initiator were added and dispersed with stirring. Furthermore, 55 parts by weight of a 50% by weight polyvinyl acetate aqueous emulsion (MA-6 manufactured by Hoechst Synthesis Co., Ltd.) and 0.2 parts by weight of a water-dispersible purple pigment were added and mixed to this dispersion to obtain a photosensitive material that can be developed in water. A composition liquid was prepared.
この感光液を実施例１で使用した７５μｍ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１００μ個の感光性積層フィルムを得
た。This photosensitive solution was applied onto the ethyl cellulose coated surface of the 75 μm polyester film used in Example 1 and dried to obtain a photosensitive laminated film having a photosensitive layer thickness of 100 μm.
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と同様な繰作により露光
、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こらなかった。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、この画像マスクを８１１ＩＩｌ厚さのガラス板に
貼り付けるに当り、過沃素酸ソーダの１％水溶液をガラ
ス板に塗布して、圧着したところ強固な接着が得られた
。その後、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塗布して約２分経過後水洗し、腐
食深度が５０μｍの画像を食刻することができた。この
際マスク表面の５μ層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。Next, when this image mask was attached to a glass plate having a thickness of 811 IIl, a 1% aqueous solution of sodium periodate was applied to the glass plate and pressure bonded, and strong adhesion was obtained. Thereafter, when the polyester film support was peeled off, the image mask holding layer and the polyester film were easily peeled off, and the mask could be transferred without any positional shift. When etching this glass plate, a 50% by weight aqueous hydrofluoric acid solution was applied to the mask surface, and after about 2 minutes, the mask was washed with water, and an image with a corrosion depth of 50 μm could be etched. At this time, it was found that the ethyl cellulose image mask holding layer with a thickness of 5 μm on the surface of the mask showed almost no resistance to the hydrofluoric acid solution, and that the entire mask was not attacked by the hydrofluoric acid at all.
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。After the etching was completed, the processed material was wetted with water to absorb water into the mask film, and the film was peeled off.
実施例３
実施例に記載したと同様の手順により、実施例１感光性
積層フィルムと同一の構成の積層フィルムを作製した。Example 3 A laminated film having the same structure as the photosensitive laminated film of Example 1 was produced by the same procedure as described in Example.
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１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
剥離することはなかった。Next, using an original positive film with a relatively large pattern, an image mask was prepared by performing exposure and development in the same manner as in Example 1. During the development process, the image mask portion did not peel off from the support.
加工材料として厚さ２ＩＩＩ１１の銅板を用い、この表
面に塩化リチウムの５％水溶液を塗布し、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、画像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 2III11 mm was used as the processing material. When a 5% aqueous solution of lithium chloride was applied to the surface of the plate and an image mask was attached by pressure, and the polyester film support was peeled off, only the image mask was transferred to the copper plate. Ta. 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, the image mask was not observed to peel off or become immersed in the ferric chloride solution. After etching was completed, the mask film was peeled off and removed.
Claims (1)
ルムとしての画像マスク保持層および（Ｃ）水現像の可
能な感光性樹脂組成物層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) An engraving characterized by comprising (A) a support, (B) an image mask holding layer as a film that can be peeled from the support, and (C) a water-developable photosensitive resin composition layer. Photosensitive laminated film for masks
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1211957A JPH0811365B2 (en) | 1989-08-17 | 1989-08-17 | Photosensitive laminated film for engraving mask |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1211957A JPH0811365B2 (en) | 1989-08-17 | 1989-08-17 | Photosensitive laminated film for engraving mask |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0379270A true JPH0379270A (en) | 1991-04-04 |
| JPH0811365B2 JPH0811365B2 (en) | 1996-02-07 |
Family
ID=16614503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1211957A Expired - Lifetime JPH0811365B2 (en) | 1989-08-17 | 1989-08-17 | Photosensitive laminated film for engraving mask |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0811365B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6140006A (en) * | 1998-06-15 | 2000-10-31 | The Chromaline Corporation | Integral membrane layer formed from a photosensitive layer in an imageable photoresist laminate |
| JP2001177136A (en) * | 1999-10-05 | 2001-06-29 | Fuji Electric Co Ltd | Method of manufacturing thin-film solar battery, and equipment of processing through hole and equipment of patterning the same by powder jetting method for thin-film substrate |
| WO2014061523A1 (en) * | 2012-10-19 | 2014-04-24 | 株式会社ミマキエンジニアリング | Sandblasting method |
| JP2014189904A (en) * | 2013-03-27 | 2014-10-06 | Yuji Yamada | Transfer method for performing low relief of image to metal surface by sand blast and etching |
| JP2017071202A (en) * | 2015-10-09 | 2017-04-13 | 株式会社アイセロ | Fine pattern transfer method to surface uneven article to be treated using film for uneven surface sticking |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5589555U (en) * | 1978-12-16 | 1980-06-20 | ||
| JPS56150512A (en) * | 1980-04-23 | 1981-11-21 | Teijin Ltd | Mat pattern forming method |
| JPS578074A (en) * | 1980-06-09 | 1982-01-16 | Hisao Yaginuma | Formation of three-dimensional carved design on surface of polygonal cylindrical member |
| JPS60104938A (en) * | 1982-05-13 | 1985-06-10 | Asahi Chem Ind Co Ltd | Mask transferring material for working surface of solid |
-
1989
- 1989-08-17 JP JP1211957A patent/JPH0811365B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5589555U (en) * | 1978-12-16 | 1980-06-20 | ||
| JPS56150512A (en) * | 1980-04-23 | 1981-11-21 | Teijin Ltd | Mat pattern forming method |
| JPS578074A (en) * | 1980-06-09 | 1982-01-16 | Hisao Yaginuma | Formation of three-dimensional carved design on surface of polygonal cylindrical member |
| JPS60104938A (en) * | 1982-05-13 | 1985-06-10 | Asahi Chem Ind Co Ltd | Mask transferring material for working surface of solid |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6140006A (en) * | 1998-06-15 | 2000-10-31 | The Chromaline Corporation | Integral membrane layer formed from a photosensitive layer in an imageable photoresist laminate |
| JP2001177136A (en) * | 1999-10-05 | 2001-06-29 | Fuji Electric Co Ltd | Method of manufacturing thin-film solar battery, and equipment of processing through hole and equipment of patterning the same by powder jetting method for thin-film substrate |
| WO2014061523A1 (en) * | 2012-10-19 | 2014-04-24 | 株式会社ミマキエンジニアリング | Sandblasting method |
| JP2014083607A (en) * | 2012-10-19 | 2014-05-12 | Mimaki Engineering Co Ltd | Sand blast method |
| JP2014189904A (en) * | 2013-03-27 | 2014-10-06 | Yuji Yamada | Transfer method for performing low relief of image to metal surface by sand blast and etching |
| JP2017071202A (en) * | 2015-10-09 | 2017-04-13 | 株式会社アイセロ | Fine pattern transfer method to surface uneven article to be treated using film for uneven surface sticking |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0811365B2 (en) | 1996-02-07 |
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