JP4880417B2 - Surface protection method for workpieces - Google Patents
Surface protection method for workpieces Download PDFInfo
- Publication number
- JP4880417B2 JP4880417B2 JP2006281257A JP2006281257A JP4880417B2 JP 4880417 B2 JP4880417 B2 JP 4880417B2 JP 2006281257 A JP2006281257 A JP 2006281257A JP 2006281257 A JP2006281257 A JP 2006281257A JP 4880417 B2 JP4880417 B2 JP 4880417B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- workpiece
- curable composition
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 44
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- 230000001681 protective effect Effects 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000012545 processing Methods 0.000 claims description 20
- 238000007650 screen-printing Methods 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 8
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- 239000003112 inhibitor Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
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- 238000005520 cutting process Methods 0.000 description 18
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- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 2
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- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 2
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- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- PSGCQDPCAWOCSH-BREBYQMCSA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C=C)C[C@@H]1C2(C)C PSGCQDPCAWOCSH-BREBYQMCSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229960002130 benzoin Drugs 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
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 150000001634 bornane-2,3-dione derivatives Chemical class 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- TZAMQIAPGYOUKF-UHFFFAOYSA-N diethoxyphosphoryl(phenyl)methanone Chemical compound CCOP(=O)(OCC)C(=O)C1=CC=CC=C1 TZAMQIAPGYOUKF-UHFFFAOYSA-N 0.000 description 1
- XVKKIGYVKWTOKG-UHFFFAOYSA-N diphenylphosphoryl(phenyl)methanone Chemical compound C=1C=CC=CC=1P(=O)(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 XVKKIGYVKWTOKG-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- MHCLJIVVJQQNKQ-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O MHCLJIVVJQQNKQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 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
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000002562 thickening agent Substances 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、いろいろな部材を加工するに際しての被加工物を切削屑などからの保護膜、インキ等で被加工物に塗装や印字加工するに際しての塗装や印字の不要な部分を保護するための仮固定用の表面保護膜（以下、単に「保護膜」とする）であり、また、それに好適な表面保護用硬化性組成物、並びにその表面保護用硬化性組成物からなる接着剤を用いた被加工部材の表面保護方法に関する。 The present invention provides a protective film for cutting workpieces when processing various members, a protective film from cutting scraps, and the like for protecting unnecessary portions of coating and printing when coating or printing on the workpiece with ink or the like. A surface protective film for temporary fixing (hereinafter, simply referred to as “protective film”), and a suitable surface protective curable composition and an adhesive made of the surface protective curable composition were used. The present invention relates to a method for protecting a surface of a workpiece.
金属板、金型、アルミサッシ、プラスチック板、半導体ウエハ、回路基板、セラミック、ガラスや石英などの光学部品、センサーなど電子、電気部品等の加工、特に切断、研削、研磨等の精密加工等に際して、被加工物の既加工面や回路、センサー部位など機能を有する部位を被覆することで、切削水によるダメージや切削屑等からの傷や汚染が生じたり、破損するのを防止し、部品を保護する仮固定用の表面保護材が広く使用されている。尚、表面保護材としては、フィルムやシートなどの基材上に粘着加工を施した感圧接着性シートが主に用いられている。 For processing metal plates, molds, aluminum sashes, plastic plates, semiconductor wafers, circuit boards, ceramics, optical parts such as glass and quartz, electronic and electronic parts such as sensors, especially precision processing such as cutting, grinding and polishing By covering the functional surfaces such as the processed surface, circuit and sensor part of the work piece, it is possible to prevent damage from cutting water, scratches and contamination from cutting waste, etc. A surface fixing material for temporary fixing to protect is widely used. In addition, as a surface protective material, the pressure sensitive adhesive sheet which gave the adhesive process on base materials, such as a film and a sheet | seat, is mainly used.
また、プリント配線版などの回路基板で用いられるメッキ処理工程においても、回路上でメッキが不要な部分には、メッキ液による汚染を防止する保護材として感圧接着シートを任意の形にカットしたものがマスキング材として使用されている。 Also, in the plating process used on circuit boards such as printed wiring boards, pressure sensitive adhesive sheets were cut into any shape as a protective material to prevent contamination by the plating solution in areas where plating is unnecessary on the circuit. Things are used as masking material.
また、電子、電器部品に限らず、様々な工業製品、例えばネームプレート、ロゴなどの各種銘板、計器の目盛り、装飾などに関して、塗装やさまざまな印字が各種印刷法によって行われているが、塗装や印字の不必要な部分がある場合も感圧接着性シートをその部分に貼り付けて、その後に塗装・印字加工を行われている。 In addition to electronic and electrical parts, various industrial products such as nameplates, various nameplates such as logos, instrument scales, decorations, etc. are painted and variously printed by various printing methods. Even when there is an unnecessary part for printing, a pressure-sensitive adhesive sheet is applied to the part, followed by painting and printing.
しかし、感圧接着シートを被加工材を加工する際の保護膜として用いた場合、昨今の部品の小型化、微細化にともない、貼り付け作業が頻雑になるとともに、貼り付け位置のわずかなずれで製品としての歩留まりや意匠性に不具合を生じる欠点があるし、部品に凹凸がある場合には、シートがその凹凸に追随できずに、加工中に剥がれを生じ、被加工材が汚染される場合がある。加えて、被加工品の形状に合わせて、感圧接着シートをカットしたものを使用しようとすると、そのカット品を製作するために高価な金型が必要になるなどコスト面でも欠点がある。 However, when the pressure-sensitive adhesive sheet is used as a protective film when processing a workpiece, the pasting work becomes more complicated and the pasting position is slightly smaller with the recent miniaturization and miniaturization of parts. There is a defect that causes a defect in the product yield and design properties due to misalignment, and if the part has irregularities, the sheet cannot follow the irregularities, causing peeling during processing and contaminating the workpiece. There is a case. In addition, if it is intended to use a material obtained by cutting a pressure-sensitive adhesive sheet in accordance with the shape of the workpiece, there is a disadvantage in terms of cost, for example, an expensive mold is required to produce the cut product.
これらの欠点を解決するために感圧シートとは別に、特定の有機溶剤やアルカリ水溶液によって除去する紫外線硬化性組成物を加工物面にスクリーン印刷法で塗布し紫外線硬化させることで被服し、マスキングする方法が検討されている（特許文献１〜３参照）が、アルカリ水溶液や有機溶剤を用いるため、洗浄処理工程が頻雑で、しかも作業環境的に問題があるし、また被加工物表面に微細な凹凸がある場合には、十分に有機溶剤が浸透できず、保護膜を完全に除去できず該被加工物の外観上問題が発生している。
金属板、金型、アルミサッシ、プラスチック板、半導体ウエハ、回路基板、セラミック、ガラスや石英などの光学部品、センサーなどの電子、電気部品等を加工する際にこれらの部材及び部材表面への切削水の進入や切削屑などによる傷や汚染から保護する保護膜、また、プリント配線板など回路基板で用いられるメッキ液による汚染を防止する保護膜、更に、電子、電器部品に限らず様々な工業製品、例えばネームプレート、ロゴなどの各種銘板、計器の目盛り、装飾品などについて塗装、印字加工時のマスキングに好適な一時的な保護膜として、作業性が良好な表面保護用の硬化性組成物が望まれている。加えて、加工後に保護膜を被加工物から剥離する際に、糊残りのない、環境的にも作業性にも優れた表面保護方法が望まれている。 Cutting metal members, molds, aluminum sashes, plastic plates, semiconductor wafers, circuit boards, ceramics, optical parts such as glass and quartz, electronic parts such as sensors, electrical parts, etc. Protective film to protect from scratches and contamination caused by water ingress and cutting waste, protective film to prevent contamination by plating solution used on circuit boards such as printed wiring boards, and various industries, not limited to electronic and electrical parts product, for example name plates, nameplates such as logos, instrument scale, ornaments such as for painting, suitable temporary protective film to the masking during printing processing, workability curable composition of excellent surface protection Is desired. In addition, when the protective film is peeled off from the workpiece after processing, there is a demand for a surface protection method that has no adhesive residue and is excellent in terms of environment and workability.
本発明者は、これらの課題を解決するためにいろいろ検討した結果、特定の（メタ）アクリルモノマーを含有する硬化性組成物が、被加工物を加工する際の表面保護膜に好適であること、更に、特定な粘度を有するものではスクリーン印刷法の適用を可能とすること、加えて、当該硬化性組成物からなる保護膜を用いるときに、被加工部材の加工時に於ける傷や汚れの発生が防止でき、しかも表面保護剥がれ残りのない特徴を有する被加工部材の表面保護方法が提供できることを見いだし本発明に至ったものである。 As a result of various investigations to solve these problems, the present inventors have found that a curable composition containing a specific (meth) acrylic monomer is suitable for a surface protective film when processing a workpiece. Furthermore, it is possible to apply a screen printing method to a material having a specific viscosity, and in addition, when using a protective film made of the curable composition, scratches and dirt in processing of a workpiece are processed. It has been found that a method for protecting a surface of a workpiece having characteristics that can be prevented from occurring and has no remaining surface protection peeling, has been achieved.
本発明は、以下の要旨を有するものである。
１．被加工部材の表面に下記（Ａ）、（Ｂ）、（Ｃ）及び（Ｅ）を含有する表面保護用硬化性組成物が硬化してなる保護膜を設け、被加工材を加工した後、前記保護膜を３０℃以上９０℃以下の温水に浸漬して被加工部材より剥離することを特徴とする被加工部材の表面保護方法。
（Ａ）分子の末端又は側鎖に１個以上の（メタ）アクリロイル基を有し、かつ、その分子量が５００以上であるポリイソプレン、
（Ｂ）（Ａ）以外の（メタ）アクリレート、
（Ｃ）光重合開始剤
（Ｅ）重合禁止剤
２．表面保護用硬化性組成物が、（Ａ）及び（Ｂ）成分の合計量１００質量部中（Ａ）を
２０〜９０質量部、（Ａ）及び（Ｂ）成分の合計量１００質量部中（Ｂ）を１０〜８０質
量部、（Ａ）及び（Ｂ）の合計１００質量部に対して（Ｃ）を０．１〜２０質量部含有す
ることを特徴とする１に記載の被加工部材の表面保護方法。
３．表面保護用硬化性組成物が、（Ｄ）無機充填材を含有することを特徴とする１〜２の
いずれかに記載の被加工部材の表面保護方法。
４．（Ｄ）無機充填材がシリカであることを特徴とする３に記載の被加工部材の表面保護
方法。
５．表面保護用硬化性組成物の粘度が５０００ｍＰａ・ｓ以上であることを特徴とする１
〜４のいずれかに記載の被加工部材の表面保護方法。
６．表面保護用硬化性組成物が、シクロペンタジエン骨格を含有する樹脂を含有すること
を特徴とする１〜５のいずれかに記載の被加工部材の表面保護方法。
７．表面保護用硬化性組成物が、極性有機溶媒を含有することを特徴とする１〜６のいず
れかに記載の被加工部材の表面保護方法。
８．被加工部材の表面に保護膜を設ける際に、スクリーン印刷法によることを特徴とす
る１〜７のいずれかに記載の被加工部材の表面保護方法。
The present invention has the following gist.
1. After providing a protective film formed by curing the surface-protecting curable composition containing the following (A), (B), (C) and (E) on the surface of the workpiece, and processing the workpiece, A method for protecting a surface of a workpiece, wherein the protective film is immersed in warm water of 30 ° C. or higher and 90 ° C. or lower and peeled off from the workpiece.
(A) polyisoprene having one or more (meth) acryloyl groups at the terminal or side chain of the molecule and having a molecular weight of 500 or more,
(B) (meth) acrylates other than (A),
(C) Photopolymerization initiator (E) Polymerization inhibitor
2 . In the curable composition for surface protection, 20 to 90 parts by mass of (A) in 100 parts by mass of the total amount of the components (A) and (B), and 100 parts by mass of the total amount of the components (A) and (B) ( 2. The workpiece according to 1 , wherein 0.1 to 20 parts by mass of (C) is contained with respect to 10 to 80 parts by mass of B) and 100 parts by mass of (A) and (B) in total. Surface protection method.
3 . The method for protecting a surface of a workpiece according to any one of 1 to 2 , wherein the curable composition for surface protection contains (D) an inorganic filler.
4 . (D) The method for protecting a surface of a workpiece according to 3 , wherein the inorganic filler is silica.
5 . 1 wherein the viscosity of the curable composition for surface protection is 5000 mPa · s or more.
Surface protecting method of the workpiece according to any one of 1 to 4.
6 . The method for protecting a surface of a workpiece according to any one of 1 to 5 , wherein the curable composition for surface protection contains a resin containing a cyclopentadiene skeleton.
7 . The method for protecting a surface of a workpiece according to any one of 1 to 6 , wherein the curable composition for surface protection contains a polar organic solvent.
8 . The method for protecting a surface of a workpiece according to any one of 1 to 7 , wherein a protective film is provided on the surface of the workpiece, by screen printing.
本発明の表面保護用硬化性組成物は、その組成故に光硬化性を有し、可視光または紫外線によって硬化するとともに、好ましい実施態様においては、スクリーン印刷法を適用可能な粘度を有するために、省力化、省エネルギー化、作業短縮の面で著しい効果が得られる。また、ほん発明の表面保護用硬化性組成物は、加工時に用いる切削水などに影響されない保護膜を提供できるので、切削水の進入や切削屑などによる傷や汚染の発生から被加工物の表面を保護することができるとともに、加工後の被加工物からの保護膜の剥離に際しては、糊残りがなく容易に剥離するので作業性に優れるという効果が得られる。更に、本発明の表面保護用硬化性組成物を用いた被加工部材の表面保護方法は、本発明の表面保護用硬化性組成物から得られる保護膜が、３０℃以上の温水、特に９０℃以下の温水に接触することで接着強度を低下させ、部材間の或いは部材と治具との接合力を低下する性質を有するので、容易に部材を回収できる特徴があり、従来公知技術に比べ、高価で、発火性の強い、或いは人体に有害なガスを発生する有機溶媒を用いる必要がないという格段の効果が得られる。The curable composition for surface protection of the present invention has photocurability because of its composition, is cured by visible light or ultraviolet light, and in a preferred embodiment, has a viscosity to which a screen printing method can be applied. Significant effects are obtained in terms of labor saving, energy saving, and work shortening. In addition, the curable composition for surface protection according to the present invention can provide a protective film that is not affected by cutting water used at the time of processing. In addition, when the protective film is peeled off from the workpiece after processing, there is no adhesive residue, and the film is easily peeled off, so that the workability is excellent. Furthermore, in the method for protecting the surface of the workpiece using the curable composition for surface protection of the present invention, the protective film obtained from the curable composition for surface protection of the present invention is warm water of 30 ° C. or higher, particularly 90 ° C. Since it has the property of reducing the adhesive strength by contacting the following hot water and reducing the bonding force between the members or between the member and the jig, there is a feature that the member can be easily recovered, compared to the conventionally known technology, A remarkable effect is obtained that it is not necessary to use an organic solvent that is expensive, strongly ignitable, or generates a gas harmful to the human body.
本発明で使用する（Ａ）分子の末端又は側鎖に１個以上の（メタ）アクリロイル基を有し、分子量が５００以上である（メタ）アクリレートとしては、１，２-ポリブタジエン末端ウレタン（メタ）アクリレート（例えば、日本曹達社製「ＴＥ−２０００」、「ＴＥＡ−１０００」）、前記水素添加物（例えば、日本曹達社製「ＴＥＡＩ−１０００」）、１，４−ポリブタジエン末端ウレタン（メタ）アクリレート（例えば、大阪有機化学社製「ＢＡＣ−４５」）、ポリイソプレン末端（メタ）アクリレート、ポリエステル系ウレタン（メタ）アクリート、ポリエーテル系ウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレート、ビスＡ型エポキシ（メタ）アクリレート（例えば、大阪有機化学社製「ビスコート＃５４０」、昭和高分子社製「ビスコートＶＲ−７７」）などの分子量５００以上のオリゴマー／ポリマーを末端又は側鎖に１個以上（メタ）アクロイル化した（メタ）アクリレートが例示される。尚、当該（メタ）アクリレートの分子量についてはスクリーン印刷法可能な粘度を確保する理由から５００以上であることが選択される。その上限について技術的に定める必要性はないものの表面保護用硬化性組成物としては作業性の観点で液状であることが好ましく、他の（メタ）アクレートモノマーへの溶解性の理由から１０００００以下のものが好ましい。 The (meth) acrylate having at least one (meth) acryloyl group at the terminal or side chain of the molecule (A) used in the present invention and having a molecular weight of 500 or more includes 1,2-polybutadiene-terminated urethane (meta ) Acrylate (for example, “TE-2000”, “TEA-1000” manufactured by Nippon Soda Co., Ltd.), the hydrogenated product (for example, “TEAI-1000” manufactured by Nippon Soda Co., Ltd.), 1,4-polybutadiene-terminated urethane (meth) Acrylate (for example, “BAC-45” manufactured by Osaka Organic Chemical Co., Ltd.), polyisoprene terminated (meth) acrylate, polyester urethane (meth) acrylate, polyether urethane (meth) acrylate, polyester (meth) acrylate, bis A type Epoxy (meth) acrylate (for example, “Biscoat # 540” manufactured by Osaka Organic Chemical Co., Ltd., Showa Examples thereof include (meth) acrylates in which one or more (meth) acroylated oligomers / polymers having a molecular weight of 500 or more such as “Biscoat VR-77” manufactured by Kobunshi Co., Ltd. are formed at the terminal or side chain. The molecular weight of the (meth) acrylate is selected to be 500 or more for the reason of securing a viscosity that can be screen-printed. Although there is no need to technically determine the upper limit, the curable composition for surface protection is preferably liquid from the viewpoint of workability, and is 100,000 or less for reasons of solubility in other (meth) acrylate monomers. Are preferred.
（Ａ）については、ポリブタジエン、ポリイソプレン、及び前２者の水素添加物からなる群から選ばれる１種以上であることが、表面保護用硬化性組成物の硬化体を温水に浸漬した時に被着物より当該硬化体が剥離する性質（以下、単に「剥離性」という）が助長されるので、好ましい。 Regarding (A), it is at least one selected from the group consisting of polybutadiene, polyisoprene, and the former two hydrogenated products when the cured product of the surface-protecting curable composition is immersed in warm water. This is preferable because the property of the cured body to peel from the kimono (hereinafter simply referred to as “peelability”) is promoted.
本発明において、（Ａ）分子の末端又は側鎖に１個以上の（メタ）アクリロイル基を有し、分子量が５００以上である（メタ）アクリレートの添加量は、（Ａ）と（Ｂ）の合計量１００質量部中、２０〜９０質量部が好ましい。２０質量部以上であれば剥離性が充分であるし、スクリーン印刷法可能な粘度が確保できる。また、９０質量部以下であれば、粘度上昇を生じて作業性が低下することがない。 In the present invention, (A) the addition amount of (meth) acrylate having one or more (meth) acryloyl groups at the end or side chain of the molecule and having a molecular weight of 500 or more is the ratio of (A) and (B). 20-90 mass parts is preferable in the total amount of 100 mass parts. If it is 20 parts by mass or more, the releasability is sufficient, and a viscosity capable of screen printing can be secured. Moreover, if it is 90 mass parts or less, a viscosity raise will be produced and workability | operativity will not fall.
（Ａ）分子の末端又は側鎖に１個以上の（メタ）アクリロイル基を有し、分子量が５００以上である（メタ）アクリレートは、疎水性のものが好ましい。水溶性の場合には、切削加工時に表面保護用硬化性組成物の硬化体が膨潤もしくは一部が溶解することにより位置ずれを起こし加工精度が劣る恐れがあるため好ましくないが、親水性であっても、その表面保護用硬化性組成物の硬化体が水によって大きく膨潤もしくは一部溶解することがなければ、使用しても差し支えない。 (A) The (meth) acrylate having one or more (meth) acryloyl groups at the end or side chain of the molecule and having a molecular weight of 500 or more is preferably hydrophobic. In the case of water solubility, it is not preferable because the cured product of the surface-protecting curable composition may swell or partially dissolve during cutting, which may cause positional displacement and inferior processing accuracy. However, the cured product of the curable composition for surface protection may be used as long as it is not greatly swollen or partially dissolved by water.
本発明で使用する（Ｂ）（Ａ）以外の（メタ）アクリレートとしては、単官能（メタ）アクリレートモノマーとして、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、フェニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニロキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、メトキシ化シクロデカトリエン（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、グリシジル（メタ）アクリレート、カプロラクトン変性テトラヒドロフルフリル（メタ）アクリレート、３−クロロ−２−ヒドロキシプロピル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、ｔ−ブチルアミノエチル（メタ）アクリレート、エトキシカルボニルメチル（メタ）アクリレート、フェノールエチレンオキサイド変性アクリレート、フェノール（エチレンオキサイド２モル変性）アクリレート、フェノール（エチレンオキサイド４モル変性）アクリレート、パラクミルフェノールエチレンオキサイド変性アクリレート、ノニルフェノールエチレンオキサイド変性アクリレート、ノニルフェノール（エチレンオキサイド４モル変性）アクリレート、ノニルフェノール（エチレンオキサイド８モル変性）アクリレート、ノニルフェノール（プロピレンオキサイド２．５モル変性）アクリレート、２−エチルヘキシルカルビトールアクリレート、エチレンオキシド変性フタル酸（メタ）アクリレ−ト、エチレンオキシド変性コハク酸（メタ）アクリレート、トリフロロエチル（メタ）アクリレート、アクリル酸、メタクリル酸、マレイン酸、フマル酸、ω−カルボキシ−ポリカプロラクトンモノ（メタ）アクリレート、フタル酸モノヒドロキシエチル（メタ）アクリレート、（メタ）アクリル酸ダイマー、β−（メタ）アクロイルオキシエチルハイドロジェンサクシネート、ｎ−（メタ）アクリロイルオキシアルキルヘキサヒドロフタルイミド等が挙げられる。 As (meth) acrylates other than (B) (A) used in the present invention, as monofunctional (meth) acrylate monomers, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3- Phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, ethoxycarbonylmethyl (meth) acrylate, phenol ethylene oxide modified acrylate, Nord (ethylene oxide 2 mol modified) acrylate, phenol (ethylene oxide 4 mol modified) acrylate, paracumylphenol ethylene oxide modified acrylate, nonylphenol ethylene oxide modified acrylate, nonylphenol (ethylene oxide 4 mol modified) acrylate, nonylphenol (ethylene oxide 8 mol) Modified) acrylate, nonylphenol (propylene oxide 2.5 mol modified) acrylate, 2-ethylhexyl carbitol acrylate, ethylene oxide modified phthalic acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, trifluoroethyl (meth) acrylate , Acrylic acid, methacrylic acid, maleic acid, fumaric acid, ω-carboxy-polycaprola Ton mono (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, (meth) acrylic acid dimer, β- (meth) acryloyloxyethyl hydrogen succinate, n- (meth) acryloyloxyalkyl hexahydrophthalimide, etc. Can be mentioned.
さらに２官能（メタ）アクリレートモノマーとして、１，３−ブチレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、２−エチル−２−ブチル−プロパンジオール（メタ）アクリレート、ネオペンチルグリコール変性トリメチロールプロパンジ（メタ）アクリレート、ステアリン酸変性ペンタエリストールジアクリレート、ポリプロピレングリコールジ（メタ）アクリレート、２，２−ビス（４−（メタ）アクリロキシジエトキシフェニル）プロパン、２，２−ビス（４−（メタ）アクリロキシプロポキシフェニル）プロパン、２，２−ビス（４−（メタ）アクリロキシテトラエトキシフェニル）プロパン等が挙げられ、３官能（メタ）アクリレートモノマーとしては、トメチロールプロパントリ（メタ）アクリレート、トリス［（メタ）アクリロイキシエチル］イソシアヌレート等が挙げられ、４官能以上の（メタ）アクリレートモノマーとしては、ジメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールエトキシテトラ（メタ）アクリレート、ジペンタエリストールペンタ（メタ）アクリレート、ジペンタエリストールヘキサ（メタ）アクリレート等が挙げられる Furthermore, as a bifunctional (meth) acrylate monomer, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, 1,9- Nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 2-ethyl-2-butyl-propanediol (meth) acrylate, neopentyl glycol modified trimethylolpropane di (Meth) acrylate, stearic acid modified pentaerythritol diacrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- ( (Meta) acryloxypro Xylphenyl) propane, 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) propane, and the like. Examples of the trifunctional (meth) acrylate monomer include tomethylolpropane tri (meth) acrylate, tris [(meta ) Acryloylethyl] isocyanurate, etc., and the tetrafunctional or higher (meth) acrylate monomers include dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate. , Dipentaerystol penta (meth) acrylate, dipentaerystol hexa (meth) acrylate, etc.
本発明で使用する（Ｂ）（Ａ）以外の（メタ）アクリレートは、（Ａ）成分同様に疎水性のものがより好ましく、水溶性の場合、加工時に切削水に表面保護用硬化性組成物からなる保護膜が膨潤することにより位置ずれもしくは剥がれを起こし、切削水の進入や切削屑などの傷や汚染され、加工精度が劣る恐れがあるため好ましくない。親水性であっても、その表面保護用硬化性組成物からなる保護膜が水によって大きく膨潤もしくは一部溶解することがなければ、使用しても差し支えない。 The (meth) acrylates other than (B) and (A) used in the present invention are more preferably hydrophobic as in the case of the component (A). When water-soluble, the curable composition for surface protection in cutting water during processing. The protective film made of swells is not preferable because it may be displaced or peeled off, and may be infiltrated with cutting water or damaged or contaminated with cutting waste, resulting in poor processing accuracy. Even if it is hydrophilic, it can be used as long as the protective film made of the curable composition for surface protection is not greatly swollen or partially dissolved by water.
本発明で使用する（Ｂ）（Ａ）以外の（メタ）アクリレートの添加量は、（Ａ）及び（Ｂ）成分の合計量１００質量部中、１０〜８０質量部が好ましい。１０質量部未満だと初期の接着性が低下す恐れがあり、８０質量部を越えると、剥離性が低下する恐れがある。 The addition amount of (meth) acrylate other than (B) (A) used in the present invention is preferably 10 to 80 parts by mass in 100 parts by mass of the total amount of components (A) and (B). If it is less than 10 parts by mass, the initial adhesiveness may be lowered, and if it exceeds 80 parts by mass, the peelability may be lowered.
また、前記（Ａ）及び（Ｂ）成分の配合組成に、（メタ）アクリロイルオキシエチルアシッドフォスフェート、ジブチル２−（メタ）アクリロイルオキシエチルアシッドフォスフェート、ジオクチル２−（メタ）アクリロイルオキシエチルフォスフェート、ジフェニル２−（メタ）アクリロイルオキシエチルフォスフェート、（メタ）アクリロイルオキシエチルポリエチレングリコールアシッドフォスフェート等のビニル基又は（メタ）アクリル基を有するリン酸エステルを併用することで、金属面への密着性をさらに向上させることができる。 In addition, the composition of the components (A) and (B) includes (meth) acryloyloxyethyl acid phosphate, dibutyl 2- (meth) acryloyloxyethyl acid phosphate, dioctyl 2- (meth) acryloyloxyethyl phosphate. , Diphenyl 2- (meth) acryloyloxyethyl phosphate, (meth) acryloyloxyethyl polyethylene glycol acid phosphate, etc. The property can be further improved.
本発明で使用される（Ｃ）光重合開始剤としては、可視光線や紫外線の活性光線により増感させて表面保護用硬化性組成物の光硬化を促進するために配合するものであり、公知の各種光重合開始剤が使用可能である。具体的にはベンゾフェノン及びその誘導体、ベンジル及びその誘導体、エントラキノン及びその誘導体、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタール等のベンゾイン誘導体、ジエトキシアセトフェノン、４−ｔ−ブチルトリクロロアセトフェノン等のアセトフェノン誘導体、２−ジメチルアミノエチルベンゾエート、ｐ−ジメチルアミノエチルベンゾエート、ジフェニルジスルフィド、チオキサントン及びその誘導体、カンファーキノン、７，７−ジメチル−２，３−ジオキソビシクロ［２．２．１］ヘプタン−１−カルボン酸、７，７−ジメチル−２，３−ジオキソビシクロ［２．２．１］ヘプタン−１−カルボキシ−２−ブロモエチルエステル、７，７−ジメチル−２，３−ジオキソビシクロ［２．２．１］ヘプタン−１−カルボキシ−２−メチルエステル、７，７−ジメチル−２，３−ジオキソビシクロ［２．２．１］ヘプタン−１−カルボン酸クロライド等のカンファーキノン誘導体、２−メチル−１−［４-（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１等のα−アミノアルキルフェノン誘導体、ベンゾイルジフェニルホスフィンオキサイド、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド、ベンゾイルジエトキシポスフィンオキサイド、２，４，６−トリメチルベンゾイルジメトキシフェニルホスフィンオキサイド、２，４，６−トリメチルベンゾイルジエトキシフェニルホスフィンオキサイド等のアシルホスフィンオキサイド誘導体等が挙げられる。光重合開始剤は１種又は２種以上を組み合わせて用いることができる。 The (C) photopolymerization initiator used in the present invention is blended to accelerate photocuring of the curable composition for surface protection by sensitizing with actinic light of visible light or ultraviolet light, and is publicly known. These various photopolymerization initiators can be used. Specifically, benzophenone and derivatives thereof, benzyl and derivatives thereof, enthraquinone and derivatives thereof, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin derivatives such as benzyl dimethyl ketal, diethoxyacetophenone, Acetophenone derivatives such as 4-t-butyltrichloroacetophenone, 2-dimethylaminoethyl benzoate, p-dimethylaminoethyl benzoate, diphenyl disulfide, thioxanthone and derivatives thereof, camphorquinone, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] Heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2 Bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2 2.1] Camphorquinone derivatives such as heptane-1-carboxylic acid chloride, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Α-aminoalkylphenone derivatives such as amino-1- (4-morpholinophenyl) -butanone-1, benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, 2, 4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, 2 Acylphosphine oxide derivatives such as 4,6-trimethylbenzoyl dichloride ethoxyphenyl phosphine oxide. A photoinitiator can be used 1 type or in combination of 2 or more types.
本発明で使用される（Ｃ）光重合開始剤の添加量は、（Ａ）及び（Ｂ）の合計１００質量部に対して、０．１〜２０質量部が好ましい。より好ましくは３〜２０質量部が好ましい。０．１質量部以上であれば硬化促進の効果が得られるし、２０質量部以下で十分な硬化速度を得ることができる。より好ましくは（Ｃ）成分を３質量部以上添加することで、光照射量に依存なく硬化可能となり、さらに表面保護用硬化性組成物の硬化体の架橋度が高くなり、切削加工時に位置ずれ等を起こさなくなる点や剥離性が向上する。 As for the addition amount of (C) photoinitiator used by this invention, 0.1-20 mass parts is preferable with respect to a total of 100 mass parts of (A) and (B). More preferably, 3-20 mass parts is preferable. If it is 0.1 part by mass or more, the effect of promoting curing can be obtained, and if it is 20 parts by mass or less, a sufficient curing rate can be obtained. More preferably, by adding 3 parts by mass or more of component (C), curing can be performed without depending on the amount of light irradiation, and the degree of cross-linking of the cured product of the curable composition for surface protection increases, resulting in misalignment during cutting. The point which does not raise | generate etc. and peelability improve.
本発明の表面保護用硬化性組成物にシクロペンタジエン骨格を含有する樹脂を併用することで表面硬化性を向上させることができる。シクロペンタジエン骨格を含有する樹脂は、Ｃ５留分から抽出されたシクロペンタジエンを主原料に製造された石油樹脂である。具体的には、日本ゼオン社製「クイントン１７００」、「クイントン１５００」、「クイントン１３２５」等が挙げられる。 Surface curability can be improved by using a resin containing a cyclopentadiene skeleton in combination with the curable composition for surface protection of the present invention. The resin containing a cyclopentadiene skeleton is a petroleum resin produced using cyclopentadiene extracted from a C5 fraction as a main raw material. Specific examples include “Quinton 1700”, “Quinton 1500”, and “Quinton 1325” manufactured by ZEON Corporation.
さらに本発明の表面保護硬化性組成物中に極性有機溶媒を共に用いることで保護膜が温水と接触して容易に膨潤したりして接着強度が低下する現象を確実に発現することができる。 Furthermore, by using a polar organic solvent together with the surface protective curable composition of the present invention, it is possible to reliably develop a phenomenon in which the protective film comes into contact with warm water and easily swells to lower the adhesive strength.
極性有機溶媒に関しては、その沸点が５０℃以上１３０℃以下であることが好ましい。沸点が前記範囲内の極性有機溶媒を選択する時には、硬化後の組成物が温水と接触して接着強度が低下する現象をより一層確実に発現することができるので好ましい。また、このような極性有機溶媒としては、例えば、アルコール、ケトン、エステル等が挙げられるが、発明者の検討結果に拠れば、このうちアルコールが好ましく選択される。 The polar organic solvent preferably has a boiling point of 50 ° C. or higher and 130 ° C. or lower. When a polar organic solvent having a boiling point within the above range is selected, it is preferable because a phenomenon that the cured composition comes into contact with warm water and the adhesive strength decreases can be more reliably exhibited. Examples of such a polar organic solvent include alcohols, ketones, esters, and the like. Of these, alcohols are preferably selected according to the results of investigations by the inventors.
アルコールとしては、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ-ブタノール、イソブタノール、第二ブタノール、第三ブタノール、ｎ−アミルアルコール、イソアミルアルコール、２−エチルブチルアルコール等が挙げられる。さらに、前記アルコールの中でも、好ましくは沸点が１２０℃以下であるメタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ-ブタノール、イソブタノール、第二ブタノール、第三ブタノールが好ましく、その中でもメタノ−ル、エタノール、イソプロパノール、ｎ-ブタノールが一層好ましい。 Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, 2-ethylbutyl alcohol and the like. Further, among the alcohols, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol having a boiling point of 120 ° C. or less are preferred, and among these, methanol, ethanol More preferred are isopropanol and n-butanol.
極性有機溶媒の添加量は、（Ａ）及び（Ｂ）の合計量１００質量部に対して、０．５〜３０質量部が好ましい。０．５質量部以上であれば剥離性が確保でき、３０質量部以下であれば、初期の接着性が低下する恐れもなく、表面保護用硬化性組成物の硬化体がフィルム状に剥離する。 As for the addition amount of a polar organic solvent, 0.5-30 mass parts is preferable with respect to 100 mass parts of total amounts of (A) and (B). If it is 0.5 parts by mass or more, releasability can be ensured, and if it is 30 parts by mass or less, the initial adhesiveness is not lowered, and the cured product of the curable composition for surface protection is peeled into a film. .
本発明の表面保護用硬化性組成物は、その貯蔵安定性向上のため少量の重合禁止剤を使用することができる。例えば重合禁止剤としては、メチルハイドロキノン、ハイドロキノン、２，２−メチレン−ビス（４−メチル−６−ターシャリーブチルフェノール）、カテコール、ハイドロキノンモノメチルエーテル、モノターシャリーブチルハイドロキノン、２，５−ジターシャリーブチルハイドロキノン、ｐ−ベンゾキノン、２，５−ジフェニル−ｐ−ベンゾキノン、２，５−ジターシャリーブチル−ｐ−ベンゾキノン、ピクリン酸、クエン酸、フェノチアジン、ターシャリーブチルカテコール、２−ブチル−４−ヒドロキシアニソール及び２，６−ジターシャリーブチル−ｐ−クレゾール等が挙げられる。 The curable composition for surface protection of the present invention can use a small amount of a polymerization inhibitor for improving the storage stability. For example, polymerization inhibitors include methylhydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol), catechol, hydroquinone monomethyl ether, monotertiarybutylhydroquinone, 2,5-ditertiarybutyl. Hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertiarybutyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary butylcatechol, 2-butyl-4-hydroxyanisole and Examples include 2,6-ditertiary butyl-p-cresol.
これらの重合禁止剤の使用量は、（Ａ）及び（Ｂ）の合計量１００質量部に対し、０．００１〜３質量部が好ましく、０．０１〜２質量部がより好ましい。０．００１質量部以上ならば十分な貯蔵安定性が得られるし、３質量部以下で接着性が低下しやすくなったり、未硬化になることもない。 The amount of these polymerization inhibitors used is preferably 0.001 to 3 parts by mass and more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B). If it is 0.001 part by mass or more, sufficient storage stability can be obtained, and if it is 3 parts by mass or less, the adhesiveness is not easily lowered or uncured.
本発明における（Ｄ）無機充填材としては、球状アルミナ、破砕アルミナ、酸化マグネシウム、酸化ベリリウム、酸化チタン等の酸化物類、窒化ホウ素、窒化ケイ素、窒化アルミニウム等の窒化物類、炭化ケイ素等の炭化物類、水酸化アルミニウム、水酸化マグネシウム等の水和金属類、銅、銀、鉄、アルミニウム、ニッケル等の金属充填材、チタン等の金属合金充填材、ダイヤモンド、カーボン等の炭素系充填材、石英、石英ガラス、溶融シリカ、球状シリカ、ヒュームドシリカ等のシリカ、珪砂、フォラストナイト、クレ−、タルク、炭酸カルシウム、ガラスビーズ、シラスバルーンなどがあり、これら無機質充填材は、１種または２種以上を使用することができる。これら無機質充填材のうち、容易に入手可能であり、表面保護用硬化性組成物の光硬化性を考慮すると、特にシリカが好ましく、より好ましくは、スクリーン印刷性を考慮すると乾式法シリカが最適である。 Examples of the inorganic filler (D) in the present invention include spherical alumina, crushed alumina, magnesium oxide, beryllium oxide, titanium oxide and other oxides, boron nitride, silicon nitride, aluminum nitride and other nitrides, silicon carbide, etc. Carbides, hydrated metals such as aluminum hydroxide and magnesium hydroxide, metal fillers such as copper, silver, iron, aluminum and nickel, metal alloy fillers such as titanium, carbon-based fillers such as diamond and carbon, There are silica, quartz glass, fused silica, spherical silica, fumed silica and the like, silica sand, forastonite, clay, talc, calcium carbonate, glass beads, shirasu balloon, etc., and these inorganic fillers are one kind or Two or more types can be used. Among these inorganic fillers, silica is particularly preferable in consideration of the photocurability of the surface-protecting curable composition, and more preferably dry method silica is more preferable in consideration of screen printability. is there.
乾式法シリカとは、結晶シリカ粉、溶融シリカ粉、球状シリカ粉及びヒュームドシリカ等のシリカ粉、俗称ホワイトカーボンのなかで、例えば、四塩化珪素を水素及び酸素存在下、１０００℃前後の高熱で熱分解により製造されたシリカであり、シリカ内部構造が安定しているため、粒子表面にシラノール基が剥き出しになっているシリカである。また、本発明では、乾式法シリカのうち、表面変性と分散性改良のためにシリカ表面に存在するシラノール基を有機珪素ハロゲン化物やアルコール類で反応させることによって処理し疎水化して得られる表面処理したシリカでも構わない。このような乾式シリカとしては、例えば、「アエロジル１３０」、「アエロジル２００」、「アエロジル３００」、「アエロジル３８０」、「アエロジルＲ９７２」（いずれも日本アエロジル社製）、「Ｃａｂ-Ｏ-Ｓｉｌ」（Ｇ．Ｌ．Ｃａｂｏｔ Ｃｏｒｐ．社製）、「ＤＣ Ｆｉｎｅ Ｓｌｉｃａ」（Ｄｏｗ Ｃｏｒｎｉｎｇ社製）、「Ｆｒａｎｓｉｌ ２５１」（Ｆａｒｎｓｏｌ社製）などが挙げられ、これら乾式シリカは、塗料や接着剤など塗布する場合、液だれしないように液体自身の構造粘性を高くする目的で汎用的に使用されており、これら乾式シリカを添加することでスクリーン印刷法な可能な粘度に容易に調整可能である。 Dry silica is crystalline silica powder, fused silica powder, spherical silica powder, fumed silica, or other silica powder, commonly known as white carbon. For example, silicon tetrachloride is heated at a high temperature around 1000 ° C. in the presence of hydrogen and oxygen. The silica is produced by pyrolysis of the silica, and the silica internal structure is stable, so that the silanol group is exposed on the particle surface. Further, in the present invention, surface treatment obtained by treating and hydrophobizing silanol groups present on the silica surface with organosilicon halides or alcohols for surface modification and dispersibility improvement in dry process silica. Silica that has been used may be used. Examples of such dry silica include “Aerosil 130”, “Aerosil 200”, “Aerosil 300”, “Aerosil 380”, “Aerosil R972” (all manufactured by Nippon Aerosil), “Cab-O-Sil”. (Manufactured by GL Cabot Corp.), “DC Fine Slica” (manufactured by Dow Corning), “Fransil 251” (manufactured by Farnsol), and the like. In this case, it is generally used for the purpose of increasing the structural viscosity of the liquid itself so that the liquid does not spill, and by adding these dry silicas, it can be easily adjusted to a viscosity that can be achieved by screen printing.
本発明の表面保護用硬化性組成物は、本発明の目的を損なわない範囲で、一般に使用されているアクリルゴム、ウレタンゴム、アクリロニトリル−ブタジエン−スチレンゴムなどの各種エラストマー、溶剤、増量材、補強材、可塑剤、増粘剤、染料、顔料、難燃剤、シランカップリング剤及び界面活性剤等の添加剤を使用してもよい。 The curable composition for surface protection of the present invention is a range of elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, solvents, fillers, reinforcements, etc. that are generally used within a range that does not impair the object of the present invention. Additives such as materials, plasticizers, thickeners, dyes, pigments, flame retardants, silane coupling agents and surfactants may be used.
本発明の表面保護用硬化性組成物の粘度としては、５０００ｍＰａ・ｓ以上が好ましい。５０００ｍＰａ・ｓ以上であるとスクリーン印刷法において液だれもなく、良好な保護膜を得ることができる。より好ましくは１００００ｍＰａ・ｓ以上であれば、スクリーン印刷法においてより良好な保護膜を得ることができる。また、粘度の上限については、当該硬化性組成物の用法に応じて適宜選択されるが、スクリーン印刷の場合には２００００００ｍＰａ・ｓ以下であることが好ましく、刷毛塗り等の場合には１０００００ｍＰａ・ｓ以下であることが好ましい。 As a viscosity of the curable composition for surface protection of this invention, 5000 mPa * s or more is preferable. When it is 5000 mPa · s or more, there is no liquid dripping in the screen printing method, and a good protective film can be obtained. More preferably, if it is 10,000 mPa · s or more, a better protective film can be obtained in the screen printing method. The upper limit of the viscosity is appropriately selected according to the usage of the curable composition, but is preferably 20000 mPa · s or less in the case of screen printing, and 100000 mPa · s in the case of brush coating or the like. The following is preferable.
また、本発明の表面保護方法は、被加工部材の表面に上記の表面保護用硬化性組成物からなる保護膜を設け、被加工材を加工した後、前記保護膜を被加工部材より剥離することを特徴とする被加工部材の表面保護方法である。これによりセラミック、ガラスや石英などの光学部品、センサーなどの電子、電気部品等の加工時に起きる切削水の進入や切削屑などによる被加工物の傷や汚染の発生から保護や、プリント配線版など回路基板で用いられるメッキ液による汚染を防止したり、ネームプレート、ロゴなどの各種銘板、計器の目盛り、装飾など塗装、印字加工時のマスキングするための好適な保護膜として機能することができる。 In the surface protection method of the present invention, a protective film made of the above-mentioned curable composition for surface protection is provided on the surface of the workpiece, and after processing the workpiece, the protective film is peeled off from the workpiece. This is a method for protecting a surface of a workpiece. This protects against the occurrence of scratches and contamination of the workpiece due to the ingress of cutting water and cutting debris that occur during processing of optical parts such as ceramics, glass and quartz, electronic and electrical parts such as sensors, and printed wiring boards It can function as a suitable protective film for masking at the time of coating and printing such as nameplates, logos and other nameplates, instrument scales, decorations, etc.
さらに本発明の表面保護方法は、被加工部材の表面に保護膜を設ける際に、刷毛塗り、各種コーティング法、スクリーン印刷法、ダンボ印刷法、スプレー法、ポッティング法、ディッピング法など任意の塗布方法が使用できるが、この中でもスクリーン印刷法を用いることがより好ましい。スクリーン印刷法は、孔版印刷の一種で、絹、ナイロン、テトロン等の繊維やステンレス鋼針金のスクリーンの目を利用した印刷法であり、凸版、平板、凹版、曲面にも印刷でき、いろんな分野で利用されている。スクリーン印刷法を用いることで、微細部分もずれなく上記の表面保護用硬化性組成物を塗布することが可能となり、作業性の点で好ましい。 Furthermore, the surface protection method of the present invention is applicable to any coating method such as brush coating, various coating methods, screen printing method, dumbo printing method, spray method, potting method, dipping method, etc., when a protective film is provided on the surface of the workpiece. Among them, it is more preferable to use the screen printing method. The screen printing method is a kind of stencil printing that uses silk, nylon, tetron, etc., and stainless steel wire screens, and can print on relief plates, flat plates, intaglio plates, and curved surfaces. It's being used. By using the screen printing method, it becomes possible to apply the above-mentioned curable composition for surface protection without shifting even a fine portion, which is preferable in terms of workability.
本発明は、保護膜を被加工材より剥離するに際して、適度に加熱した９０℃以下の温水を用いることで剥離性が短時間に達成でき、生産性の面から好ましい。前記温水の温度に関しては、３０℃〜８０℃、好ましくは４０〜８０℃、の温水を用いると短時間で硬化性組成物からなる保護膜が少し膨潤するかまたは軟化するため、保護膜と被加工物が容易に分離することができる。尚、保護膜と温水の接触の方法については、特に制限されず、温水中に保護膜を設けた被加工物ごとあるいは保護膜部分のみを浸漬してもよい。 In the present invention, when the protective film is peeled off from the workpiece, it is possible to achieve peelability in a short time by using moderately heated hot water of 90 ° C. or less, which is preferable from the viewpoint of productivity. Regarding the temperature of the warm water, when using warm water of 30 ° C. to 80 ° C., preferably 40 to 80 ° C., the protective film made of the curable composition is slightly swollen or softened in a short time. The workpiece can be easily separated. The method for contacting the protective film with the warm water is not particularly limited, and the workpiece or the protective film portion provided with the protective film may be immersed in the warm water.
本発明において、被加工物の材質には特に制限はない。このような材質として、例えば、アルミ、鉄、ＳＵＳ、ニッケル等の金属部材、ガラス部材、アルミナ、窒化アルミなどセラミックス部材、プラスチック部材、シリコン、サファイアなどウエハが挙げられる。本発明の被加工部材の表面保護方法は、ガラスレンズ、プラスチックレンズ、ガラスや石英などの光学部品、光ディスクの加工をはじめ、金属板、金型、アルミサッシ、プラスチック板、半導体ウエハ、回路基板、セラミック、やセンサーなどの電子、電気部品の加工に適用可能である。特に切削水の進入や切削屑などの傷や汚染から保護しなければならないレンズ・プリズムなどの光学ガラスの既加工面の保護、センサー部品や表面が凹凸のある回路基板等の被加工物の保護、プリント配線版など回路基板で用いられるメッキ液による汚染防止、電子、電器部品に限らず様々な工業製品に施されるネームプレート、ロゴなどの各種銘板、計器の目盛り、装飾など塗装、印字加工時のマスキングに有用である。 In the present invention, the material of the workpiece is not particularly limited. Examples of such materials include metal members such as aluminum, iron, SUS, and nickel, glass members, ceramic members such as alumina and aluminum nitride, plastic members, and wafers such as silicon and sapphire. The method of protecting the surface of the workpiece of the present invention includes processing of glass lenses, plastic lenses, optical parts such as glass and quartz, optical disks, metal plates, molds, aluminum sashes, plastic plates, semiconductor wafers, circuit boards, It can be applied to the processing of electronic and electrical parts such as ceramics and sensors. In particular, protection of already processed surfaces of optical glass such as lenses and prisms that must be protected from scratches and contamination of cutting water, cutting chips, etc., protection of workpieces such as sensor parts and circuit boards with uneven surfaces Prevention of contamination by plating solution used on circuit boards such as printed wiring boards, nameplates applied to various industrial products, not just electronic and electrical parts, various nameplates such as logos, instrument scales, decorations, painting, printing, etc. Useful for masking time.
（実施例１）
（Ａ）分子の末端又は側鎖に１個以上の（メタ）アクリロイル基を有し、分子量が５００以上である（メタ）アクリレートとして、クラレ社製「ＵＣ−２０３」（メタクロイル変性ポリイソプレン、以下「ＵＣ−２０３」と略す。）８０質量部、（Ｂ）（Ａ）以外の（メタ）アクリレートとしてジシクロペンテニルオキシエチルメタクリレート（ローム＆ハース社製「ＱＭ−６５７」、以下「ＱＭ」と略す。）２０質量部、（Ｃ）光重合開始剤として２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン（チバ・スペシャルティ・ケミカルズ社製「ＩＲＧＡＣＵＲＥ９０７」、以下「Ｉ−９０７」と略す。）（Ｄ）無機充填材として乾式法シリカである「アエロジルＲ９７２」（日本アエロジル社製）２部、重合禁止剤として２，２−メチレン−ビス（４−メチル−６−ターシャリーブチルフェノール）（以下「ＭＤＰ」と略す。）０．１質量部添加して表面保護用硬化性組成物を作成した。得られた表面保護硬化性組成物を使用して、以下に示す評価方法にて引張せん断接着強さの測定及び剥離試験を行った。それらの結果を表１に示す。
Example 1
(A) “UC-203” (methacryloyl-modified polyisoprene, manufactured by Kuraray Co., Ltd.) as a (meth) acrylate having one or more (meth) acryloyl groups at the terminal or side chain of the molecule and having a molecular weight of 500 or more. (Abbreviated as “UC-203”) 80 parts by mass, (B) (C) other than (A) dicyclopentenyloxyethyl methacrylate (Rohm & Haas “QM-657”, hereinafter abbreviated as “QM”) .) 20 parts by mass, (C) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“IRGACURE907” manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, (Hereinafter abbreviated as “I-907”) (D) “Aerosil R972” (produced by Nippon Aerosil Co., Ltd.) 2 which is a dry process silica as an inorganic filler. Then, 0.1 part by mass of 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol) (hereinafter abbreviated as “MDP”) was added as a polymerization inhibitor to prepare a curable composition for surface protection. . Using the obtained surface protective curable composition, the tensile shear bond strength was measured and the peel test was performed by the following evaluation methods. The results are shown in Table 1.
（評価方法）
粘度：Ｂ型粘度計を使用して、温度２３℃の条件下、作成した表面保護用硬化性組成物の粘度を測定した。
表面硬化性：耐熱パイレックス（商標登録）ガラス上に作成した表面保護用硬化性組成物をスクリーン印刷法により塗布厚みとして約７０μｍ塗布し、メタルハライドランプを使用したアイグラフィックス社製硬化装置により、３６５ｎｍの波長の積算光量２０００ｍＪ／ｃｍ２の条件にて硬化させた。その直後、表面硬化性を指触にて下記に示す判定基準で評価した。
○ ：タック無く良好
△ ：少しタックがある
×：べとつき、指先が汚染される
剥離性（１）：上記と同様に耐熱パイレックス（商標登録）ガラス上に表面保護用硬化性組成物を塗布し、メタルハライドランプを使用したアイグラフィックス社製硬化装置により、３６５ｎｍの波長の積算光量２０００ｍＪ／ｃｍ２の条件にて硬化させ、保護膜を形成させた剥離試験体を作成した。得られた試験体を、温水（８０℃）に浸漬し、耐熱パイレックス（商標登録）ガラスから保護膜が剥離する時間を測定した。
剥離性（２）：被着体としてポリカーボネートを用いた以外は、剥離性（１）と同様に保護膜を形成させた剥離試験体を作成した。得られた試験体を同様にポリカーボネートから保護膜が剥離する時間を測定した。
(Evaluation methods)
Viscosity : Using a B-type viscometer, the viscosity of the prepared curable composition for surface protection was measured under the condition of a temperature of 23 ° C.
Surface curability : A surface-protective curable composition prepared on heat-resistant Pyrex (registered trademark) glass was applied to a coating thickness of about 70 μm by a screen printing method, and 365 nm by a curing device manufactured by Eye Graphics using a metal halide lamp. Curing was performed under the condition of an integrated light quantity of 2000 mJ / cm 2 at the wavelength of. Immediately thereafter, the surface curability was evaluated by touch with the following criteria.
○: Good without tack △: Slightly tacky ×: Sticky and contaminated fingertip
Peelability (1) : In the same manner as described above, a surface-protective curable composition was applied onto heat-resistant Pyrex (registered trademark) glass, and an integrated amount of light having a wavelength of 365 nm was applied by a curing device manufactured by Igraphics Corporation using a metal halide lamp. A peel test body was formed by curing under the condition of 2000 mJ / cm 2 to form a protective film. The obtained specimen was immersed in warm water (80 ° C.), and the time for the protective film to peel from the heat-resistant Pyrex (registered trademark) glass was measured.
Peelability (2) : Except that polycarbonate was used as the adherend, a peel test specimen having a protective film formed in the same manner as the peelability (1) was prepared. Similarly, the time required for the protective film to peel from the polycarbonate was measured for the obtained specimen.
（実施例２〜１９）
表１、表２に示す種類の原材料を表１、表２に示す組成で使用した以外は実施例１と同様にして表面保護用硬化性組成物を作成した。得られた硬化性組成物について、実施例１と同様に引張せん断接着強さの測定及び剥離試験を行った。それらの結果を表１、２に示す
(Examples 2 to 19)
A curable composition for surface protection was prepared in the same manner as in Example 1 except that the raw materials of the types shown in Tables 1 and 2 were used in the compositions shown in Tables 1 and 2. About the obtained curable composition, the measurement of the tensile shear bond strength and the peeling test were performed similarly to Example 1. The results are shown in Tables 1 and 2.
（使用材料）
（Ａ）分子の末端又は側鎖に１個以上の（メタ）アクリロイル基を有し、分子量が５００以上である（メタ）アクリレート
ＴＥ−２０００：１，２-ポリブタジエン末端ウレタンメタクリレート（日本曹達社製「ＴＥ-２０００」、分子量２０００）
ＵＶ７０００Ｂ：ウレタンアクリレート（日本合成化学社製「紫光ＵＶ−７０００Ｂ」、分子量３５００）
ＵＶ３０００Ｂ：ポリエステル系ウレタンアクリレート（日本合成化学社製「紫光ＵＶ−３０００Ｂ」、分子量１８０００）
（Ｂ）（Ａ）以外の（メタ）アクリレート
Ｍ−１０１Ａ：フェノールエチレンオキサイド２モル変性アクリレート（東亞合成社製「アロニックスＭ−１０１Ａ」）
Ｍ−１４０：２−（１，２−シクロヘキサカルボキシイミド）エチルアクリレート（東亜合成社製「アロニックスＭ−１４０」）
ＩＢＸＡ：イソボルニルアクリレート（共栄社化学社製「ライトアクリレートＩＢ−ＸＡ」）
Ｒ−６８４：ジシクロテンタニルジアクリレート（日本化薬社製「ＫＡＹＡＲＡＤ Ｒ−６８４」）
その他成分
ＡＣＭＯ：アクロイルモルホリン（興人社製「ＡＣＭＯ」）
クイントン１７００：シクロペンタジエン樹脂（日本ゼオン社製「クイントン１７００」）
ＩＰＡ：イソプロピルアルコール
(Materials used)
(A) (Meth) acrylate TE-2000: 1,2-polybutadiene terminated urethane methacrylate (manufactured by Nippon Soda Co., Ltd. ) having one or more (meth) acryloyl groups at the terminal or side chain of the molecule and having a molecular weight of 500 or more . "TE-2000", molecular weight 2000)
UV7000B: urethane acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd. "purple light UV-7000B", molecular weight 3500)
UV3000B: Polyester urethane acrylate ("Nippon Gosei Kagaku""purple light UV-3000B", molecular weight 18000)
(B) (Meth) acrylates other than (A) M-101A: Phenolethylene oxide 2 mol modified acrylate (“Aronix M-101A” manufactured by Toagosei Co., Ltd.)
M-140: 2- (1,2-cyclohexacarboximide) ethyl acrylate (“Aronix M-140” manufactured by Toagosei Co., Ltd.)
IBXA: Isobornyl acrylate (“Light acrylate IB-XA” manufactured by Kyoeisha Chemical Co., Ltd.)
R-684: dicyclotentanyl diacrylate (“KAYARAD R-684” manufactured by Nippon Kayaku Co., Ltd.)
Other ingredients ACMO: Acroyl morpholine ("ACMO" manufactured by Kojin Co., Ltd.)
Quinton 1700: cyclopentadiene resin ("Quinton 1700" manufactured by Nippon Zeon)
IPA: isopropyl alcohol
（比較例１〜５）
表３に示す種類の原材料を表３に示す組成で使用した以外は実施例１と同様にして硬化性組成物を作成した。得られた硬化性組成物について、実施例１と同様に粘度測定した。実施例１と同様にスクリーン印刷法により表面硬化性及び剥離試験用の試験片の作成を行ったが比較例１〜５はいずれも粘度が低く、スクリーン印刷はできなかった。そこで、刷毛塗りにより被着体である耐熱パイレックス（登録商標）ガラスやポリカーボネート上に硬化性組成物を塗布し表面硬化性及び剥離試験を行った。それらの結果を表３に示す。
(Comparative Examples 1-5)
A curable composition was prepared in the same manner as in Example 1 except that the raw materials of the type shown in Table 3 were used in the composition shown in Table 3. The viscosity of the obtained curable composition was measured in the same manner as in Example 1. Although the test piece for surface curability and a peeling test was produced by the screen printing method like Example 1, all of Comparative Examples 1-5 had low viscosity, and screen printing was not able to be performed. Therefore, a curable composition was applied onto heat-resistant Pyrex (registered trademark) glass or polycarbonate as an adherend by brush coating, and surface curability and a peel test were performed. The results are shown in Table 3.
（使用材料）
（Ｂ）（Ａ）以外の（メタ）アクリレート
ＢＺ：ベンジルメタクリレート（共栄社化学社製「ライトエステルＢＺ」）
ＩＢＸ：イソボルニルメタクリレート（共栄社化学社製「ライトエステルＩＢ−Ｘ」）
２−ＨＥＭＡ：２-ヒドロキシエチルメタクリレート
ＭＴＥＧＭＡ：メトシキテトラエチレングリコールモノメタクリレート（新中村化学社製「ＮＫエステルＭ−９０Ｇ」）
(Materials used)
(B) (Meth) acrylate BZ other than (A) : benzyl methacrylate (“Eye ester BZ” manufactured by Kyoeisha Chemical Co., Ltd.)
IBX: isobornyl methacrylate (“Light Ester IB-X” manufactured by Kyoeisha Chemical Co., Ltd.)
2-HEMA: 2-hydroxyethyl methacrylate MTEGMA: methoxytetraethylene glycol monomethacrylate (“NK ester M-90G” manufactured by Shin-Nakamura Chemical Co., Ltd.)
その結果、実施例１〜１９の表面保護用硬化性組成物は、いずれもスクリーン印刷は可能であり、表面硬化性を確保するとともに、得られた保護膜はいずれもフィルム状で容易に剥離した。比較例１及び５の硬化性組成物からなる保護膜は、ガラス、ポリカーボネートいずれの被着体から剥離しなかった。また、比較例２及び４の硬化性組成物からなる保護膜は、温水に接触すると同時に溶解した。また比較例３の硬化性組成物からなる保護膜は、剥離試験した後に一部保護膜が残留した（糊のこり）。 As a result, all of the curable compositions for surface protection of Examples 1 to 19 can be screen-printed to ensure surface curability, and the obtained protective films were all film-like and easily peeled off. . The protective film consisting of the curable composition of Comparative Examples 1 and 5 did not peel off from the adherend of either glass or polycarbonate. Moreover, the protective film which consists of a curable composition of the comparative examples 2 and 4 melt | dissolved simultaneously with contact with warm water. Moreover, the protective film which consists of a curable composition of the comparative example 3 partially remained after the peeling test (glue paste).
本発明はレンズ、プリズムなどの光学ガラスの既加工面の保護、センサー部品や表面が凹凸のある回路基板等の被加工物の保護、プリント配線版など回路基板で用いられるメッキ液による汚染の防止用保護膜、電子、電器部品に限らず様々な工業製品に施されるネームプレート、ロゴなどの各種銘板、計器の目盛り、装飾など塗装、印字加工時のマスキングに有用である。 The present invention protects the processed surfaces of optical glass such as lenses and prisms, protects workpieces such as sensor parts and circuit boards with uneven surfaces, and prevents contamination by plating solutions used on circuit boards such as printed wiring boards. It is useful for masking during coating and printing, such as nameplates, logos, and other nameplates applied to various industrial products, as well as protective coatings, electronic and electrical parts.
Claims (8)
（Ａ）分子の末端又は側鎖に１個以上の（メタ）アクリロイル基を有し、かつ、その分子量が５００以上であるポリイソプレン、
（Ｂ）（Ａ）以外の（メタ）アクリレート、
（Ｃ）光重合開始剤
（Ｅ）重合禁止剤 After providing a protective film formed by curing the surface-protecting curable composition containing the following (A), (B), (C) and (E) on the surface of the workpiece, and processing the workpiece, A method for protecting a surface of a workpiece, wherein the protective film is immersed in warm water of 30 ° C. or higher and 90 ° C. or lower and peeled off from the workpiece.
(A) polyisoprene having one or more (meth) acryloyl groups at the terminal or side chain of the molecule and having a molecular weight of 500 or more,
(B) (meth) acrylates other than (A),
(C) Photopolymerization initiator (E) Polymerization inhibitor
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| JP2006281257A JP4880417B2 (en) | 2006-10-16 | 2006-10-16 | Surface protection method for workpieces |
| KR1020087013075A KR101447298B1 (en) | 2006-01-13 | 2007-01-11 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
| PCT/JP2007/050273 WO2007080936A1 (en) | 2006-01-13 | 2007-01-11 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
| CN201010622598XA CN102161732B (en) | 2006-01-13 | 2007-01-11 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
| CN200780002262.XA CN101370879B (en) | 2006-01-13 | 2007-01-11 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
| KR1020137014159A KR101320823B1 (en) | 2006-01-13 | 2007-01-11 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
| US12/159,231 US20080289750A1 (en) | 2006-01-13 | 2007-01-11 | Curable Resin Composition, Surface Protection Method, Temporary Fixation Method, and Separation Method |
| EP07706620A EP1972663A4 (en) | 2006-01-13 | 2007-01-11 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
| TW096101311A TWI405831B (en) | 2006-01-13 | 2007-01-12 | A hardening resin composition, a surface protection method, a temporary fixing method, and a peeling method |
| MYPI20082032A MY145362A (en) | 2006-01-13 | 2008-06-10 | Curable resin composition, surface-protecting method, temporary fixing method and removing method |
| US13/181,031 US8338526B2 (en) | 2006-01-13 | 2011-07-12 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
| US13/436,025 US8415425B2 (en) | 2006-01-13 | 2012-03-30 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
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| JP5020577B2 (en) * | 2006-09-14 | 2012-09-05 | 電気化学工業株式会社 | Method for removing protective film coated on workpiece |
| JP2010163594A (en) * | 2008-12-15 | 2010-07-29 | Hitachi Chem Co Ltd | Curable resin composition, curable resin film and plating method using the same |
| JP5724340B2 (en) * | 2010-12-06 | 2015-05-27 | 株式会社デンソー | Photo-curing drip-proof material |
| JP5778304B2 (en) * | 2014-02-28 | 2015-09-16 | 古河電気工業株式会社 | Resin composition for sealing electronic device and electronic device |
| JP5778303B2 (en) * | 2014-02-28 | 2015-09-16 | 古河電気工業株式会社 | Resin composition for sealing electronic device and electronic device |
| JP5901808B2 (en) | 2014-08-05 | 2016-04-13 | 古河電気工業株式会社 | Curable hygroscopic resin composition for sealing electronic device, sealing resin and electronic device |
| JP6471493B2 (en) * | 2014-12-25 | 2019-02-20 | 東洋インキＳｃホールディングス株式会社 | Active energy ray polymerizable resin composition and laminate |
| JPWO2018021351A1 (en) * | 2016-07-26 | 2019-05-16 | 日産化学株式会社 | Method for forming easily releasable protective resin film and easily releasable protective resin film forming composition |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6191270A (en) * | 1984-10-12 | 1986-05-09 | Sumitomo Electric Ind Ltd | Formation of coating film |
| JPS62151476A (en) * | 1985-12-26 | 1987-07-06 | Nitto Electric Ind Co Ltd | Tentative surface protection for metal plates |
| JPH05255631A (en) * | 1992-03-12 | 1993-10-05 | Hayakawa Rubber Co Ltd | Ultraviolet-curable ink composition, formation of cured coating films and use of ultraviolet-curable ink composition |
| JP2874482B2 (en) * | 1992-10-02 | 1999-03-24 | 日立化成工業株式会社 | Temporary surface protection method and resin composition used therefor |
| JP3346022B2 (en) * | 1994-03-29 | 2002-11-18 | 大日本インキ化学工業株式会社 | Resin composition and method for producing polybutadiene-containing urethane acrylate resin |
| JPH07286117A (en) * | 1994-04-20 | 1995-10-31 | Hitachi Chem Co Ltd | Photo-setting moistureproof insulating coating and production of moistureproof insulated electronic part |
| JPH09157336A (en) * | 1995-12-12 | 1997-06-17 | Dainippon Ink & Chem Inc | Resin composition, substrate impregnating material and coating material |
| JPH101523A (en) * | 1996-06-14 | 1998-01-06 | Japan Synthetic Rubber Co Ltd | Radiation-curable resin composition |
| JP4505875B2 (en) * | 1999-03-31 | 2010-07-21 | 株式会社吉野工業所 | Synthetic resin molded products with labels formed only by printing |
| JP2002069138A (en) * | 2000-08-28 | 2002-03-08 | Nippon Synthetic Chem Ind Co Ltd:The | Ultraviolet ray curing type resin composition and use thereof |
| JP2002155230A (en) * | 2000-11-20 | 2002-05-28 | Hitachi Chem Co Ltd | Photo-setting moistureproof and insulating coating and moistureproofed and insulated electronic part |
| JP2004035843A (en) * | 2002-07-08 | 2004-02-05 | Toagosei Co Ltd | Active energy beam-curable insulative covering material composition |
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