JPH0420179B2 - - Google Patents
Info
- Publication number
- JPH0420179B2 JPH0420179B2 JP21347383A JP21347383A JPH0420179B2 JP H0420179 B2 JPH0420179 B2 JP H0420179B2 JP 21347383 A JP21347383 A JP 21347383A JP 21347383 A JP21347383 A JP 21347383A JP H0420179 B2 JPH0420179 B2 JP H0420179B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- sandblasting
- weight
- support
- pattern layer
- 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
Links
- 238000005488 sandblasting Methods 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 29
- 239000011342 resin composition Substances 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 23
- 238000012546 transfer Methods 0.000 claims description 22
- 229920002635 polyurethane Polymers 0.000 claims description 16
- 239000004814 polyurethane Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000004291 polyenes Chemical class 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 46
- -1 polytetramethylene Polymers 0.000 description 21
- 229920002678 cellulose Polymers 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 239000001913 cellulose Substances 0.000 description 13
- 235000010980 cellulose Nutrition 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000013461 design Methods 0.000 description 8
- 229920001451 polypropylene glycol Polymers 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 4
- 229920000623 Cellulose acetate phthalate Polymers 0.000 description 4
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- 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 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229940081734 cellulose acetate phthalate Drugs 0.000 description 4
- 229920003086 cellulose ether Polymers 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- 125000003827 glycol group Chemical group 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 229920006305 unsaturated polyester Polymers 0.000 description 4
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical group OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical group O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- RBGUKBSLNOTVCD-UHFFFAOYSA-N 1-methylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C RBGUKBSLNOTVCD-UHFFFAOYSA-N 0.000 description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 239000002585 base Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- PVPBBTJXIKFICP-UHFFFAOYSA-N (7-aminophenothiazin-3-ylidene)azanium;chloride Chemical compound [Cl-].C1=CC(=[NH2+])C=C2SC3=CC(N)=CC=C3N=C21 PVPBBTJXIKFICP-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical group COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical group CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- CKKQLOUBFINSIB-UHFFFAOYSA-N 2-hydroxy-1,2,2-triphenylethanone Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C(=O)C1=CC=CC=C1 CKKQLOUBFINSIB-UHFFFAOYSA-N 0.000 description 1
- RZCDMINQJLGWEP-UHFFFAOYSA-N 2-hydroxy-1,2-diphenylpent-4-en-1-one Chemical compound C=1C=CC=CC=1C(CC=C)(O)C(=O)C1=CC=CC=C1 RZCDMINQJLGWEP-UHFFFAOYSA-N 0.000 description 1
- DIVXVZXROTWKIH-UHFFFAOYSA-N 2-hydroxy-1,2-diphenylpropan-1-one Chemical compound C=1C=CC=CC=1C(O)(C)C(=O)C1=CC=CC=C1 DIVXVZXROTWKIH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 108010076830 Thionins Proteins 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 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
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000001761 ethyl methyl cellulose Substances 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical group CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- DASJFYAPNPUBGG-UHFFFAOYSA-N naphthalene-1-sulfonyl chloride Chemical compound C1=CC=C2C(S(=O)(=O)Cl)=CC=CC2=C1 DASJFYAPNPUBGG-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
- B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
- B24C1/04—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods for treating only selected parts of a surface, e.g. for carving stone or glass
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/12—Production of screen printing forms or similar printing forms, e.g. stencils
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0044—Mechanical working of the substrate, e.g. drilling or punching
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
- H05K3/0079—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the method of application or removal of the mask
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Decoration By Transfer Pictures (AREA)
Description
本発明はサンドブラスト用マスク転写材、さら
に詳しくいえば、被加工基材への転写が可能であ
つて、十分なサンドブラスト耐性を有し、かつそ
の表面が粘着性を有しているために、接着剤を用
いることなく被加工基材へ貼着することが可能
な、繊細な図柄をもつサンドブラスト用マスクパ
ターン層を有したサンドブラスト用マスク転写材
に関するものである。
ガラス、石材、陶磁器、木材、合成樹脂、金
属、皮革などの表面にサンドブラストにより彫刻
などを施す際に、通常非彫刻面を保護するための
マスクが用いられる。
従来、このサンドブラスト用マスクを用いる場
合、手加工によりゴムや紙などからパターンを有
するマスクを作り、これを被加工基材に接着剤を
用いて貼着していたが、この方法では手間がかか
る上に繊細な図柄を有するマスクを得ることがで
きなかつた。
したがつて、このような欠点を改善するため
に、最近感光性樹脂を用いたサンドブラスト用マ
スクを使用する方法が各種提案されている。例え
ば被加工基材上に直接感光性樹脂層を設け、画像
露光、現像を行つてパターンを有するマスクを作
成する方法(特公昭46−35681号公報)が提案さ
れている。しかしながら、この方法においては、
曲面加工が困難である上に、被加工基材が大きい
場合には、多大の労力を必要とするなどの欠点が
ある。
また、支持体フイルム上に感光性樹脂によるマ
スクパターン層を形成させて成るマスク転写材を
被加工基材に貼着して転写する方法(特開昭53−
99258号公報)が提案されている。しかしながら、
この方法においては、前記の方法における欠点が
ある程度改善されるものの、該支持体フイルム上
に接着剤層が設けられていないために、マスクパ
ターン層作成における現像工程などで点や線など
の細かい硬化した樹脂層が該支持体フイルムから
脱落してしまうという問題があり、その上被加工
基材に該転写材を貼着したのち、その支持体フイ
ルムを剥離する際に、該支持体フイルムと硬化物
との貼着力のために、細かい図柄のマスクパター
ン層が被加工基材から脱離し、繊細な図柄の加工
には使用することができないという問題がある。
また、この提案においては、使用しうる感光性樹
脂組成物として、不飽和ポリエステルをポリマー
成分として含むものが例示され、このものは光硬
化量の調節により硬化状態で表面に粘着性をもた
せうるので、接着剤なしで被加工基材に貼着する
ことができると説明されている。しかしながら、
前記したように、この粘着性のために、支持体フ
イルムを剥離する際に、繊細な図柄のマスクパタ
ーン層の脱離が生じ、また、この粘着性のレベル
では、被加工基材に対して十分な接着効果を得る
ことができないために、サンドブラスト中にマス
クの剥離が起り、実際的には接着剤を用いて被加
工基材に貼着しなければならないという問題があ
る。
また、接着剤層を有する支持体上に感光性樹脂
によるマスクパターン層を形成したのち、該支持
体側を接着剤を用いて被加工基材に貼着する方法
(特開昭55−96270号公報)が提案されている。し
かしながら、この方法においては、該支持体をサ
ンドブラストで破壊除去するのに長時間を要する
上に、接着剤を用いて被加工基材へ貼着するため
に手間がかかるという欠点がある。
さらに、支持体フイルム上に感光性樹脂で形成
されたマスクパターン層を有するマスク転写材に
おいて、該支持体フイルムとマスクパターン層と
の間に、該フイルムとは剥離可能で、押圧により
被加工基材と密着し、かつサンドブラストにより
破壊される性質を有する中間被膜を設ける方法
(実開昭55−89555号公報)が提案されている。し
かしながら、この方法においては、該中間被膜の
粘着性が強いと、支持体フイルムとの剥離抵抗が
大きくなつて、該転写材を被加工基材に貼着した
のち、該支持体フイルムを剥離する際に、マスク
パターン層の一部が剥落するという問題が生じ、
また、該中間被膜を押圧によつて被加工基材に密
着させて転写材を貼着するので、図柄によつてマ
スクパターン層中の透孔部分が狭く、このような
貼り付けは困難であるし、その上サンドブラスト
により、最初に該中間被膜が破壊されて貼着の効
果がなくなり、次いでマスクが剥離するという問
題がある。
本発明者らは、このような問題を解決し、接着
剤を用いずに被加工基材へ貼着するこができ、そ
の上繊細な図柄でも該被加工基材に極めて正確に
加工しうるサンドブラスト用マスク転写材を提供
すべく鋭意研究を重ねた結果、支持体の上に特定
の性質を有する保持層を設け、該保持層の上に、
特定の組成を有する感光性樹脂組成物から得ら
れ、かつ所定のサンドブラスト耐性及び被加工基
材との接着性を有する硬化物から成るサンドブラ
スト用マスクパターン層を設けたものによりその
目的を達成しうることを見出し、この知見に基づ
いて本発明を完成するに至つた。
すなわち、本発明は、(A)(イ)一般式
B(XA)oXB′ ……(I)
〔式中のXはウレタン残基、Aはポリエーテル、
ポリエステル、ポリエーテルポリエステルブロツ
クコポリマー、ポリジエン、ポリエン又はこれら
の混合物、Bは一般式
The present invention relates to a mask transfer material for sandblasting, and more specifically, it is capable of being transferred to a substrate to be processed, has sufficient sandblasting resistance, and has an adhesive surface, so that it is adhesive. The present invention relates to a sandblasting mask transfer material having a sandblasting mask pattern layer with a delicate design, which can be attached to a processed substrate without using an agent. When sandblasting is used to engrave the surface of glass, stone, ceramics, wood, synthetic resin, metal, leather, etc., a mask is usually used to protect the non-engraved surface. Conventionally, when using this sandblasting mask, a mask with a pattern was made by hand from rubber or paper, and then attached to the substrate to be processed using adhesive, but this method is time-consuming. It was not possible to obtain a mask with delicate designs on the top. Therefore, in order to improve these drawbacks, various methods have recently been proposed using sandblasting masks made of photosensitive resin. For example, a method has been proposed (Japanese Patent Publication No. 46-35681) in which a photosensitive resin layer is directly provided on a substrate to be processed, imagewise exposed and developed to create a mask having a pattern. However, in this method,
In addition to being difficult to process curved surfaces, it also requires a great deal of labor when the substrate to be processed is large. Furthermore, there is also a method of attaching and transferring a mask transfer material, which is formed by forming a mask pattern layer of a photosensitive resin on a support film, onto a substrate to be processed (Japanese Unexamined Patent Application Publication No. 1989-1999-1).
99258) has been proposed. however,
In this method, although the drawbacks of the above methods are improved to some extent, since an adhesive layer is not provided on the support film, fine hardening of points and lines during the development process in creating the mask pattern layer, etc. There is a problem that the cured resin layer falls off from the support film, and furthermore, when the support film is peeled off after adhering the transfer material to the substrate to be processed, the resin layer and the hardened resin layer may fall off from the support film. There is a problem in that the mask pattern layer with a fine design detaches from the substrate to be processed due to the adhesive strength with objects, and it cannot be used for processing delicate designs.
Furthermore, in this proposal, as a photosensitive resin composition that can be used, one containing unsaturated polyester as a polymer component is exemplified, and this can be made to have adhesiveness on the surface in the cured state by adjusting the amount of photocuring. , it is explained that it can be attached to the workpiece substrate without adhesive. however,
As mentioned above, due to this tackiness, when the support film is peeled off, the mask pattern layer with delicate designs comes off. Since a sufficient adhesion effect cannot be obtained, the mask peels off during sandblasting, and there is a problem in that the mask must actually be attached to the substrate to be processed using an adhesive. In addition, a method in which a mask pattern layer made of photosensitive resin is formed on a support having an adhesive layer, and then the support side is attached to a substrate to be processed using an adhesive (Japanese Patent Laid-Open No. 55-96270) ) has been proposed. However, this method has disadvantages in that it takes a long time to destroy and remove the support by sandblasting, and it takes time and effort to attach it to the substrate to be processed using an adhesive. Furthermore, in a mask transfer material having a mask pattern layer formed of a photosensitive resin on a support film, there is a space between the support film and the mask pattern layer that is removable from the film and that allows the substrate to be processed to be A method has been proposed (Japanese Utility Model Application No. 55-89555) in which an intermediate film is provided which adheres closely to the material and has the property of being destroyed by sandblasting. However, in this method, if the adhesiveness of the intermediate film is strong, the peeling resistance from the support film becomes large, and after the transfer material is attached to the substrate to be processed, the support film is peeled off. At this time, a problem arises in which part of the mask pattern layer peels off.
In addition, since the transfer material is attached by pressing the intermediate film into close contact with the substrate to be processed, the through holes in the mask pattern layer are narrow depending on the design, making it difficult to attach in this way. Moreover, there is a problem in that sandblasting first destroys the intermediate coating, rendering the adhesion ineffective and then causing the mask to peel off. The present inventors have solved these problems, and have developed a method that can be attached to a workpiece base material without using an adhesive, and can also be processed extremely accurately on the workpiece base material even with delicate designs. As a result of extensive research in order to provide a mask transfer material for sandblasting, a retention layer with specific properties was provided on the support, and on the retention layer,
This objective can be achieved by providing a sandblasting mask pattern layer made of a cured product obtained from a photosensitive resin composition having a specific composition and having a predetermined sandblasting resistance and adhesion to the substrate to be processed. Based on this finding, we have completed the present invention. That is, the present invention provides (A) (a) general formula B (XA) o XB' ... (I) [in the formula, X is a urethane residue, A is a polyether,
Polyester, polyether polyester block copolymer, polydiene, polyene or mixture thereof, B is the general formula
【式】(た
だし、Zは水素原子又はメチル基、Yは(−CH2)−
n1O−、[Formula] (where Z is a hydrogen atom or a methyl group, Y is (-CH 2 )-
n1 O-,
【式】又は(−CH2CH2O)−n 3
、m1は1〜6、m2及びm3はそれぞれ1〜15で
ある)で示される化合物、B′は一般式
[Formula] or (-CH 2 CH 2 O)- n 3 , m 1 is 1 to 6, m 2 and m 3 are each 1 to 15), B' is a general formula
【式】(ただし、Z、Yは前記と
同じ意味をもつ)、RO又はROY(ただしRは炭素
数1〜8のアルキル基、Yは前記と同じ意味をも
つ)で示される化合物、nは1〜10である〕
で表わされる不飽和ポリウレタン50〜98重量部、
(ロ)エチレン性不飽和化合物2〜50重量部、及び(ハ)
(イ)成分と(ロ)成分との和に対して0.05〜10重量%の
光重合開始剤を主成分として含有して成る感光性
樹脂組成物から得られ、かつ20℃における被加工
基材に対する剥離抵抗値300g/cm2以上、破断伸
度100%以上、100%モジユラス500Kg/cm2以下を
有する硬化物から成るサンドブラスト用マスクパ
ターン層、(B)該マスクパターン層を保持する支持
体、及び(C)前記のマスクパターン層と支持体との
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を提供する
ものである。
本発明の転写材におけるサンドブラスト用マス
クパターン層を形成するために用いる感光性樹脂
組成物において、(イ)成分として用いる不飽和ポリ
ウレタンは、次の一般式()
B(XA)oXB′ ……(I)
〔式中のX、A、B、B′及びnは前記と同じ意
味をもつ)
で表わされる化合物であつて、式中のXとして
は、例えばトルイレンジイソシアネート残基、ヘ
キサメチレンジイソシアネート残基などが挙げら
れ、Aとしては、例えばポリエチレングリコール
残基、ポリプロピレングリコール残基、ポリテト
ラメチレングリコール残基、ポリエチレングリコ
ールポリプロピレングリコール残基、ポリプロピ
レングリコールアジペート残基、ポリブタジエ
ン、水添化ポリブタジエンなどが挙げられる。ま
たBとしては、例えば2−ヒドロキシエチルメタ
クリレート、2−ヒドロキシプロピルメタクリレ
ート、ポリプロピレングリコールメタクリレー
ト、ポリエチレングリコールメタクリレート又は
これらのアクリレート類などが、B′としては、
例えばエタノール残基、プロパノール残基、ヘキ
サノール残基、オクタノール残基、ポリエチレン
グリコールモノエチルエーテル残基、ポリプロピ
レングリコールモノメチルエーテル残基などが挙
げられる。
この不飽和ポリウレタンは、これを含有して成
る組成物の硬化物が十分な表面粘着性を有し、か
つ十分なサンドブラスト耐性を有するためには、
1分子中に二重結合が平均して1.5〜1.9個あるも
のが好ましく、またその数平均分子量が5000〜
50000、特に10000〜30000の範囲内にあるものが、
表面粘着性、耐ブラスト性及び未硬化状態の取り
扱い性などの点で好適である。
本発明に係る感光性樹脂組成物に(ロ)成分として
用いるエチレン性不飽和化合物としては、例えば
アクリル酸、メタクリル酸又はこれらのエステル
類、例えばアルキル、シクロアルキル、テトラヒ
ドロフルフリル、アリル、グリシジル、ヒドロキ
シアルキルアクリレートやそれらのメタクリレー
ト、アルキレングリコール、ポリアルキレングリ
コールのモノ、ジアクリレートやそれらのメタク
リレート、ペンタエリスリトールテトラアクリレ
ートやそのメタクリレートなど;アクリルアミ
ド、メタクリルアミド又はこれらの誘導体、例え
ばN−メチロールアクリルアミドやそのメタクリ
ルアミド、N,N′−アルキレンビスアクリルア
ミドやそのメタクリルアミド、ジアセトンアクリ
ルアミドやそのメタクリルアミドなど;付加重合
可能な不飽和単量体、例えばスチレン、ビニルト
ルエン、ジビニルベンゼン、ジアリルフタレー
ト、トリアリルシアヌレート、ビニルアセテー
ト、アクリロニトリルなど;不飽和ポリエステ
ル;アルキツド樹脂;ヒドロキシアルキルアクリ
レートやそのメタクリレートなどの活性水素を有
する付加重合可能な単量体で改質されたポリウレ
タンのような不飽和ポリウレタンなどが挙げられ
る。
本発明においては、前記(イ)成分の不飽和ポリウ
レタンと(ロ)成分のエチレン性不飽和化合物の配合
割合は、前者が50〜98重量部、後者が2〜50重量
部の範囲にあることが必要である。この範囲を外
れると、得られた硬化物は所望の表面粘着性やサ
ンドブラスト耐性が得られない。また、該不飽和
ポリウレタンに対する該エチレン性不飽和化合物
の比率が高くなると、硬化物の表面粘着性が小さ
くなる傾向を示すので、この比率が高いときは、
エチレン性不飽和化合物として単官能の化合物を
多く用いることが好ましい。
また、感光性樹脂組成物に(ハ)成分として用いる
光重合開始剤としては、例えばベンゾイン、ベン
ゾインアルキルエステル、α−メチルベンゾイン
やそのアルキルエーテル、α−フエニルベンゾイ
ン、α−アリルベンゾイン、アンスラキノン、ク
ロロアンスラキノン、メチルアンスラキノン、エ
チルアンスラキノン、ベンジル、ジアセチル、ア
セトフエノン、ω−ブロモアセトフエノン、2,
2−ジメトキシフエニルアセトフエノン、α−ナ
フタレンスルホニルクロリド、ジフエニルジスル
フイド、エオシンやチオニンのような染料などが
挙げられる。
これらの光重合開始剤は、(イ)成分の不飽和ポリ
ウレタンと(ロ)成分のエチレン性不飽和化合物との
和に対して0.05〜10重量%の範囲で用いられる。
本発明においては、前記の不飽和ポリウレタ
ン、エチレン性不飽和化合物及び光重合開始剤を
主成分とする感光性樹脂組成物から得られる硬化
物は、十分なサンドブラスト耐性及び表面粘着性
を有するためには、20℃において被加工基材に対
し300g/cm2以上の剥離抵抗値を有し、また破断
伸度100%以上、100%モジユラス500Kg/cm2以下
を有することが必要である。この剥離抵抗値が
300g/cm2よりも低いとサンドブラストの際に剥
離を生じ、また破断伸度が100%未満、100%モジ
ユラスが500Kg/cm2未満ではパターン層が破壊さ
れ、十分なマスキングがなされない。
本発明の転写材において用いる支持体として
は、例えばポリプロピレン、ポリエステル、ポリ
塩化ビニル、ポリカーボネート、ポリスチレン、
ポリエチレンなどの合成樹脂フイルム、スチール
やアルミニウムのような金属シートなどが挙げら
れる。これらの支持体の厚みは50μ〜1mmの範囲
が好適である。この厚みが50μより薄いと支持体
に、いわゆるコシがなくなつて支持体としての働
きができにくくなり、また1mmより厚くなると取
り扱い作業性が悪くなつて好ましくない。
また、本発明の転写材において、支持体と前記
の感光性樹脂組成物の硬化物から成るサンドブラ
スト用マスクパターン層との間に介在させる保持
層は、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ことが必要であ
る。
この保持層は、支持体上にマスクパターン層を
形成させる際の未露光感光性樹脂組成物を洗い出
す工程において、細かい点や線の樹脂硬化物が該
支持体から脱離するのを防ぐためと、転写材を被
加工基材に貼り付けたのち、支持体を剥離する際
に、マスクパターン層が被加工基材から脱離しな
いようにする目的で設けられる。この保持層と支
持体との剥離抵抗値は、該支持体を剥離する際の
作業性の点から10g/cm以下であることが望まし
い。
この保持層には、例えばセルロースエーテルや
セルロースエステルなどのセルロース誘導体、ポ
リメタクリル酸メチルなどのアクリル樹脂、ポリ
スチレン、石油樹脂などが用いられるが、マスク
パターン層との接着性の点でセルロース誘導体が
特に優れている。また未硬化樹脂組成物の洗い出
し工程において、樹脂硬化物が脱離しないため
に、洗い出し液である水、アルカリ液、界面活性
剤水溶液などに不溶性であることが重要であり、
この観点からセルロース誘導体の中でも、特にエ
チルセルロース、メチルセルロースなどのアルキ
ルセルロース類、セルロースアセテート、セルロ
ースアセテートブチレートなどのセルロースモノ
カルボン酸エステル類が適している。この保持層
は、好ましくは0.5〜20μの厚さで用いられる。こ
の厚さが0.5μ未満では保持層としての機能が劣
り、また20μを超えると、このような保持層を設
けた支持体の製造が困難となつて経済的でない。
次に、本発明の転写材を製造する方法について
その1例を示すと、まず保護フイルムの表面に該
フイルムと剥離しやすく、かつ未露光感光性樹脂
組成物の洗い出し液に可溶な被膜を形成し、この
保護フイルムを該被膜が露出する状態で透明画像
担体上に設ける。該保護フイルムとしては、例え
ばポリプロピレン、ポリエステル、ポリエチレ
ン、ポリスチレン、ポリ塩化ビニル、ポリアミ
ド、酢酸セルロース、ポリカーボネートなどの透
明な合成樹脂フイルムが挙げられ、その厚みは通
常5〜50μのものが用いられる。これより厚い
と、該フイルム内での光の散乱により画像の再現
性が低下しこれより薄いと取り扱い性が悪くな
る。好ましくは9〜25μの厚さである。また、該
フイルムの酸素透過性が小さいと、形成されるサ
ンドブラスト用マスクパターン層の表面粘着性を
減少させる傾向を示すので、酸素透過量が30×
10-6g/24hr/m2/mm厚/cmHg(21℃)以上であ
るものが好ましい。この点からポリプロピレンフ
イルム、セルロースエステル系フイルム、ポリカ
ーボネートフイルム、ポリエチレンフイルム、ポ
リスチレンフイルムなどが適している。さらに取
扱い性を考慮するとポリプロピレンフイルムが最
も適している。
この保護フイルムの表面に設ける被膜は、該フ
イルムと剥離が容易であつて、未露光感光性樹脂
組成物の洗い出し液に可溶であることが必要であ
り、また、該フイルムとの剥離抵抗値は10g/cm
以下であることが好ましい。したがつて、この被
膜には、例えばヒドロキシル基含有セルロースエ
ーテル又はエステル、カルボキシル基含有セルロ
ースエーテル又はエステルなどのセルロース誘導
体、部分ケン化ポリ酢酸ビニルなどが使用可能で
ある。ヒドロキシル基含有セルロース誘導体とし
ては、例えばヒドロキシエチルセルロース、ヒド
ロキシプロピルセルロース、セルロースヒドロキ
シ酢酸エステルなどが、カルボキシル基含有セル
ロースエーテルとしては、例えばカルボキシメチ
ルセルロース、カルボキシエチルセルロースなど
が挙げられる。また、カルボキシル基含有セルロ
ースエステルとしては、セルロースと、ジ又はト
リカルボン酸などのポリカルボン酸、例えばコハ
ク酸、アジピン酸、セバシン酸、フタル酸、イソ
フタル酸、テレフタル酸、トリメリツト酸などと
の、あるいはこれらの一部を酢酸、プロピオン
酸、酪酸、安息香酸などのモノカルボン酸で置き
換えたものとのエステル化反応物が挙げられる。
また、これらのカルボン酸は塩の状態になつてい
てもよい。
前記以外のものでも洗い出し液に可溶で被膜性
を有するものであれば使用可能である。
また、これらの被膜材の酸素透過性が小さいと
露光過程で表面の硬化がよく進み、形成されるサ
ンドブラスト用マスクパターン層の粘着性が低下
するので好ましくなく、この点から酸素透過性の
高いセルロース誘導体が好ましい。このセルロー
ス誘導体の中でも、吸湿性が小さく、弱アルカリ
水溶液や界面活性剤水溶液に可溶なカルボキシル
基含有セルロース誘導体が好ましく、さらに好ま
しくはセルロースとポリカルボン酸及びモノカル
ボン酸とのエステルであり、特に入手の容易さか
らセルロースアセテートフタレートが最適であ
る。
この被膜の厚さは、通常0.1〜10μの範囲であ
る。これより厚いと画像の再現性が低下し、これ
より薄いと製造上厚みコントロールが難しく、ま
たピンホールなどが発生しやすくなる。好ましい
被膜の厚さは0.2〜5μの範囲である。
次に、前記の保護フイルムの被膜の上に感光性
樹脂組成物層を設け、さらにその上に、保持層を
設けた支持体を、該保持層が感光性樹脂組成物層
に接するようにラミネートする。次いで透明画像
担体を通して活性光線で画像露光を行つたのち、
透明画像担体を外し、さらに保護フイルムを剥離
して、未露光部を洗い出し、乾燥することによ
り、本発明の転写材が得られる。
この際、保護フイルムの被膜上に設ける感光性
樹脂組成物層の厚さは、通常0.05〜3mmの範囲で
ある。これより薄いと十分なサンドブラスト耐性
が得られず、またこれより厚いと解像力が悪くな
つて好ましくない。
また、画像露光に用いる活性光線の光源として
は、例えばアーク灯、水銀灯、キセノン灯、けい
光灯、紫外線発生装置、太陽光などが挙げられ
る。活性光源の波長としては200〜800mμ、好ま
しくは300〜500mμの範囲である。
さらに、未露光部の洗い出し液としては、例え
ば水、又は水酸化ナトリウム、炭酸ナトリウム、
酸性炭酸ナトリウム、ホウ酸ナトリウム、リン酸
ナトリウム、ケイ酸ナトリウム、トリエタノール
アミンなどのアルカリ水溶液、あるいはセツケ
ン、アルキルベンゼンスルホネート、アルキルス
ルホネート、アルキルアミンクロリド、ポリオキ
シアルキレングリコール、ポリオキシアルキレン
グリコールアルキルエーテル、ポリオキシアルキ
レングリコールアルキルエステル、ソルビタン脂
肪酸エステル、ポリオキシアルキレングリコール
ソルビタン脂肪酸エステルなどの界面活性剤水溶
液が挙げられる。また、乾燥は温風又は熱風の吹
きつけや、室温での放置などによつて行われる。
本発明のサンドブラスト用マスク転写材は、接
着剤を用いずに被加工基材に貼り付けることがで
き、その上サンドブラスト用マスクパターン層の
脱離を起さずに支持体を剥離することができ、繊
細な図柄でも極めて正確に被加工基材にサンドブ
ラスト加工ができる。
次に実施例によつて本発明をさらに詳細に説明
するが、本発明はこれらの例によつて何ら限定さ
れるものではない。
実施例 1
セルロースアセテートフタレートをメチルエチ
ルケトン/酢酸セロソルブ混合溶媒(重量比6/
1)に溶解させ、これを厚さ22μのポリプロピレ
ンフイルム上にバーコーターを用いてコーテイン
グすることにより、2μ厚さのセルロースアセテ
ートフタレート膜を有するポリプロピレンフイル
ムを得た。これをフイルムAとする。
また、エチルセルロースをメチルエチルケトン
に溶解させ、これを厚さ75μのポリエステルフイ
ルム上にバーコーターを用いてコーテイングし、
8μ厚のエチルセルロース層を有するポリエステ
ルフイルムを得た。これをフイルムBとする。
さらに、ポリプロピレングリコールアジペート
ジオール(数平均分子量2500)39重量部、ポリプ
ロピレングリコール(両末端にエチレンオキシド
合計10重量%付加させたもので、数平均分子量
2500)39重量部及びトルイレンジイソシアネート
6重量部を反応させて、両末端にイソシアネート
基を有するポリウレタンを得た。これに、15重量
部の2−ヒドロキシプロピルメタクリレートを反
応させて、両末端にメタクリレート基を有する不
飽和ポリウレタンを得た。この不飽和ポリウレタ
ンに、ポリプロピレングリコールモノメタクリレ
ート(数平均分子量550)20重量部、ジエチレン
グリコールジメタクリレート3重量部、2,2−
ジメトキシフエニルアセトフエノン1.5重量部、
2,6−ジ−t−ブチル−p−クレゾール0.1重
量部を添加混合して液状感光性樹脂組成物を得
た。
次に、厚さ10mmのガラス板上にポジフイルムを
置き、その上を前記フイルムAでセルロースアセ
テートフタレート膜がむき出しになるようにして
覆つた。さらに厚さ0.3mmのテフロン製スペーサ
ーを置き、前記のようにして調製した液状感光性
樹脂組成物を注いだ。次いで前記フイルムBをエ
チルセルロース膜が感光性樹脂組成物層と接する
ようにしてラミネートし、その上に10mm厚のガラ
ス板を置いて四端をクリツプで固定することによ
り厚みを制御した。
このようにして得た構成体を2KWの高圧水銀
灯から50cmの位置に置き、ポジフイルムを通して
80秒間露光した。次いでガラス板を外し、ポジフ
イルムに接していたフイルムAを剥離した。この
際の剥離抵抗はほとんどなく、小さな硬化樹脂部
分も脱離することはなかつた。次に2重量%の界
面活性剤(ライオン(株)製、ライポンF)水溶液を
0.8Kg/cm2の圧力で150秒間吹きつけることによ
り、未露光感光性樹脂組成物を洗い出した。この
ときも硬化樹脂が脱離することはなかつた。次い
で60℃で10分間乾燥することにより、サンドブラ
スト用マスク転写材を得た。このものを20℃に冷
却後、幅13mm、直径30mmのアルミニウム円柱の曲
面に両面接着テープで貼着し、ガラス板表面に
500g/cm2の力で4秒間押しつけたのち、30mm/
minのスピードで引き剥がし剥離抵抗値を測定し
たところ、600g/cmであつた。
次に、この転写材を厚さ7mmのガラス板に貼着
し、フイルムBを剥ぎ取つた。このとき剥離抵抗
はほとんどなかつた。次いでサイホン式サンドブ
ラスターを用い、研磨材としてアランダム#180
を3.5Kg/cm2の空気圧で全面に30秒間吹きつけて
彫刻を行つたところ、マスクがガラスより剥離す
ることがなく、目的とするパターンを彫刻するこ
とができた。
実施例 2
末端水酸基型水添化1,2−ポリブタジエン
(数平均分子量3000)86重量部、トルイレンジイ
ソシアネート6重量部とを反応させて、末端にイ
ソシアネート基を有するポリウレタンを得た。こ
れに15重量部の2−ヒドロキシプロピルメタクリ
レートを反応させて、末端にメタクリレート基を
有する不飽和ポリウレタンを得た。
この不飽和ポリウレタンにラウリルメタクリレ
ート20重量部、トリメチロールプロパントリメタ
クリレート2重量部、ジエチレングリコールジメ
タクリレート3重量部、2,2−ジメトキシフエ
ニルアセトフエノン1.5重量部、2,6−ジ−t
−ブチル−p−クレゾール0.1重量部を添加混合
し、液状感光性樹脂組成物を得た。
この感光性樹脂組成物を用い、実施例1と同様
にしてサンドブラスト用マスク転写材を得た。こ
のもののガラス板表面からの剥離抵抗値を実施例
1と同様にして測定したところ、650g/cmであ
つた。
この転写材をかこう岩表面に貼着したのち、フ
イルムBを剥ぎ取り、次いで直圧式サンドブラス
ターを用い、研磨材としてカーボランダム#200
を4Kg/cm2の空気圧で全面に50秒間吹きつけを行
つたところ、マスクが石材より剥離することな
く、目的のパターンを彫刻することができた。
比較例
無水マレイン酸2モル、イソフタル酸1モル、
トリエチレングリコール3モルを脱水縮合反応さ
せて、酸価23の不飽和ポリエステルを得た。この
不飽和ポリエステル70重量部、2−ヒドロキシエ
チルメタクリレート30重量部、ベンゾインイソブ
チルエーテル1重量部、2,6−ジ−t−ブチル
−p−クレゾール0.1重量部を混合溶解して液状
感光性樹脂組成物を得た。
この感光性樹脂組成物を用いて、現像液を1重
量%ホウ酸ナトリウム水溶液とする以外は、実施
例1と同様にしてサンドブラスト用マスク転写材
を作成した。これについて実施例1と同様にして
ガラス板からの剥離強度を測定したところ、100
g/cmと小さい値であつた。
これを用いて実施例1と同様にしてガラス板の
サンドブラスト加工を試みたが、途中でマスクが
ガラス板から剥離し、彫刻することはできなかつ
た。
参考例
実施例1及び2、比較例の感光性樹脂組成物
を、厚さ2mmのスペーサーを用いて片側を9μの
ポリエステルフイルムで覆つた2枚のガラス板の
間に樹脂とポリエステルフイルムが接するように
して成形し、20Wの紫外線けい光灯10本を並べた
光源の下方10cmの位置におき、片側から10分間露
光し、次いで成型体を反転させて最初とは反対の
側から10分間露光することにより、感光性樹脂硬
化シートを得た。このシートをJIS1号のダンベル
で打ち抜き、500mm/minのスピードで引張を行
い100%伸張時のモジユラスと破断伸度を測定し
た。
次に実施例1及び2、比較例で作成した各サン
ドブラスト用マスクの一点にアランダム#180を
5Kg/cm2の空気圧で吹きつけて破壊されるまでの
時間を測定した。
以上の結果を次表に示す。[Formula] (wherein Z and Y have the same meanings as above), RO or ROY (wherein R is an alkyl group having 1 to 8 carbon atoms, Y has the same meaning as above), n is 1 to 10] 50 to 98 parts by weight of unsaturated polyurethane,
(b) 2 to 50 parts by weight of an ethylenically unsaturated compound, and (c)
A substrate to be processed obtained from a photosensitive resin composition containing as a main component a photopolymerization initiator in an amount of 0.05 to 10% by weight based on the sum of components (a) and (b), and at 20°C. ( B) a support for holding the mask pattern layer; and (C) a retainer located between the mask pattern layer and the support, which adheres well to the mask pattern layer but is removable from the support and has the property of being destroyed by sandblasting. A sandblasting mask transfer material comprising layers is provided. In the photosensitive resin composition used to form the sandblasting mask pattern layer in the transfer material of the present invention, the unsaturated polyurethane used as component (a) has the following general formula () B(XA) o XB'... (I) A compound represented by [in the formula, X, A, B, B' and n have the same meanings as above], where X in the formula is, for example, a toluylene diisocyanate residue, hexamethylene diisocyanate Examples of A include polyethylene glycol residue, polypropylene glycol residue, polytetramethylene glycol residue, polyethylene glycol polypropylene glycol residue, polypropylene glycol adipate residue, polybutadiene, hydrogenated polybutadiene, etc. Can be mentioned. Further, as B, for example, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, polypropylene glycol methacrylate, polyethylene glycol methacrylate, or their acrylates, etc., and as B',
Examples include ethanol residue, propanol residue, hexanol residue, octanol residue, polyethylene glycol monoethyl ether residue, polypropylene glycol monomethyl ether residue, and the like. In order for the cured product of the composition containing this unsaturated polyurethane to have sufficient surface tackiness and sufficient sandblasting resistance,
It is preferable that there are 1.5 to 1.9 double bonds in one molecule on average, and the number average molecular weight is 5000 to 5000.
50000, especially those in the range 10000 to 30000,
It is suitable in terms of surface tackiness, blast resistance, and ease of handling in an uncured state. Examples of the ethylenically unsaturated compound used as component (b) in the photosensitive resin composition of the present invention include acrylic acid, methacrylic acid, or esters thereof, such as alkyl, cycloalkyl, tetrahydrofurfuryl, allyl, glycidyl, Hydroxyalkyl acrylates and their methacrylates, alkylene glycols, polyalkylene glycol mono- and diacrylates and their methacrylates, pentaerythritol tetraacrylate and their methacrylates, etc.; acrylamide, methacrylamide, or derivatives thereof, such as N-methylolacrylamide and its methacrylates Amide, N,N'-alkylenebisacrylamide and its methacrylamide, diacetone acrylamide and its methacrylamide, etc.; unsaturated monomers capable of addition polymerization, such as styrene, vinyltoluene, divinylbenzene, diallyl phthalate, triallyl cyanurate , vinyl acetate, acrylonitrile, etc.; unsaturated polyesters; alkyd resins; and unsaturated polyurethanes such as polyurethanes modified with addition-polymerizable monomers having active hydrogen such as hydroxyalkyl acrylates and their methacrylates. In the present invention, the blending ratio of the unsaturated polyurethane as the component (a) and the ethylenically unsaturated compound as the component (b) is in the range of 50 to 98 parts by weight of the former and 2 to 50 parts by weight of the latter. is necessary. Outside this range, the resulting cured product will not have the desired surface tackiness or sandblasting resistance. Furthermore, as the ratio of the ethylenically unsaturated compound to the unsaturated polyurethane increases, the surface tackiness of the cured product tends to decrease, so when this ratio is high,
It is preferable to use many monofunctional compounds as the ethylenically unsaturated compound. Examples of the photopolymerization initiator used as component (iii) in the photosensitive resin composition include benzoin, benzoin alkyl ester, α-methylbenzoin and its alkyl ether, α-phenylbenzoin, α-allylbenzoin, and anthraquinone. , chloroanthraquinone, methylanthraquinone, ethylanthraquinone, benzyl, diacetyl, acetophenone, ω-bromoacetophenone, 2,
Examples include 2-dimethoxyphenylacetophenone, α-naphthalenesulfonyl chloride, diphenyl disulfide, and dyes such as eosin and thionin. These photopolymerization initiators are used in an amount of 0.05 to 10% by weight based on the sum of the unsaturated polyurethane as component (a) and the ethylenically unsaturated compound as component (b). In the present invention, the cured product obtained from the photosensitive resin composition containing the above-mentioned unsaturated polyurethane, ethylenically unsaturated compound, and photopolymerization initiator as main components has sufficient sandblasting resistance and surface tackiness. It is necessary to have a peel resistance value of 300 g/cm 2 or more with respect to the substrate to be processed at 20° C., an elongation at break of 100% or more, and a 100% modulus of 500 Kg/cm 2 or less. This peel resistance value
If it is less than 300 g/cm 2 , peeling occurs during sandblasting, and if the elongation at break is less than 100% and the 100% modulus is less than 500 kg/cm 2 , the pattern layer will be destroyed and sufficient masking will not be achieved. Examples of the support used in the transfer material of the present invention include polypropylene, polyester, polyvinyl chloride, polycarbonate, polystyrene,
Examples include synthetic resin films such as polyethylene, and metal sheets such as steel and aluminum. The thickness of these supports is preferably in the range of 50 μm to 1 mm. If the thickness is less than 50 μm, the support loses its so-called stiffness, making it difficult to function as a support, and if it is thicker than 1 mm, handling efficiency becomes undesirable. In addition, in the transfer material of the present invention, the holding layer interposed between the support and the sandblasting mask pattern layer made of the cured product of the photosensitive resin composition adheres well to the mask pattern layer;
It is necessary that the support is releasable and has the property of being destroyed by sandblasting. This holding layer is used to prevent fine dots and lines of cured resin from detaching from the support during the process of washing out the unexposed photosensitive resin composition when forming a mask pattern layer on the support. , is provided for the purpose of preventing the mask pattern layer from detaching from the substrate to be processed when the support is peeled off after the transfer material is attached to the substrate to be processed. The peel resistance value between the holding layer and the support is desirably 10 g/cm or less from the viewpoint of workability when peeling the support. For this holding layer, for example, cellulose derivatives such as cellulose ether and cellulose ester, acrylic resins such as polymethyl methacrylate, polystyrene, petroleum resins, etc. are used, but cellulose derivatives are particularly preferred in terms of adhesiveness with the mask pattern layer. Are better. In addition, in the process of washing out the uncured resin composition, in order to prevent the cured resin from desorbing, it is important that it is insoluble in the washing liquid such as water, alkaline solution, or aqueous surfactant solution.
From this viewpoint, among cellulose derivatives, alkyl celluloses such as ethyl cellulose and methyl cellulose, and cellulose monocarboxylic acid esters such as cellulose acetate and cellulose acetate butyrate are particularly suitable. This retaining layer is preferably used in a thickness of 0.5 to 20 microns. If the thickness is less than 0.5 μm, the function as a retaining layer will be poor, and if it exceeds 20 μm, it will be difficult and uneconomical to manufacture a support provided with such a retaining layer. Next, an example of the method for producing the transfer material of the present invention will be described. First, a coating is applied to the surface of the protective film that is easily peeled from the film and is soluble in the washing solution of the unexposed photosensitive resin composition. This protective film is provided on a transparent image carrier with the coating exposed. Examples of the protective film include transparent synthetic resin films such as polypropylene, polyester, polyethylene, polystyrene, polyvinyl chloride, polyamide, cellulose acetate, and polycarbonate, and those having a thickness of usually 5 to 50 μm are used. If the film is thicker than this, the reproducibility of images will be lowered due to light scattering within the film, and if it is thinner than this, it will be difficult to handle. Preferably the thickness is 9 to 25 microns. In addition, if the oxygen permeability of the film is low, it tends to reduce the surface tackiness of the formed sandblasting mask pattern layer, so the oxygen permeability is 30×
It is preferable that it is 10 -6 g/24hr/m 2 /mm thickness/cmHg (21°C) or more. From this point of view, polypropylene film, cellulose ester film, polycarbonate film, polyethylene film, polystyrene film, etc. are suitable. Furthermore, considering ease of handling, polypropylene film is most suitable. The coating provided on the surface of this protective film needs to be easily peelable from the film and soluble in the washing solution of the unexposed photosensitive resin composition, and must have a peel resistance value from the film. is 10g/cm
It is preferable that it is below. Therefore, for this coating, for example, cellulose derivatives such as hydroxyl group-containing cellulose ethers or esters, carboxyl group-containing cellulose ethers or esters, partially saponified polyvinyl acetate, etc. can be used. Examples of hydroxyl group-containing cellulose derivatives include hydroxyethylcellulose, hydroxypropylcellulose, and cellulose hydroxyacetate, and examples of carboxyl group-containing cellulose ethers include carboxymethylcellulose and carboxyethylcellulose. In addition, the carboxyl group-containing cellulose ester may be a combination of cellulose and polycarboxylic acids such as di- or tricarboxylic acids, such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, or the like. Examples include esterification products in which a portion of the above is replaced with a monocarboxylic acid such as acetic acid, propionic acid, butyric acid, or benzoic acid.
Further, these carboxylic acids may be in the form of salts. Materials other than those mentioned above can also be used as long as they are soluble in the washing liquid and have film properties. In addition, if the oxygen permeability of these coating materials is low, the surface will harden rapidly during the exposure process and the adhesiveness of the formed sandblasting mask pattern layer will decrease, which is undesirable.From this point of view, cellulose with high oxygen permeability is Derivatives are preferred. Among these cellulose derivatives, carboxyl group-containing cellulose derivatives that have low hygroscopicity and are soluble in weak alkali aqueous solutions and surfactant aqueous solutions are preferred, and esters of cellulose and polycarboxylic acids and monocarboxylic acids are more preferred, especially esters of cellulose and polycarboxylic acids and monocarboxylic acids. Cellulose acetate phthalate is most suitable because of its easy availability. The thickness of this coating typically ranges from 0.1 to 10 microns. If it is thicker than this, the image reproducibility will deteriorate, and if it is thinner than this, it will be difficult to control the thickness in manufacturing, and pinholes will be more likely to occur. Preferred coating thicknesses range from 0.2 to 5 microns. Next, a photosensitive resin composition layer is provided on the protective film coating, and a support provided with a holding layer is laminated on top of the photosensitive resin composition layer so that the holding layer is in contact with the photosensitive resin composition layer. do. After imagewise exposure with actinic light through the transparent image carrier,
The transfer material of the present invention is obtained by removing the transparent image carrier, peeling off the protective film, washing out the unexposed areas, and drying. At this time, the thickness of the photosensitive resin composition layer provided on the protective film is usually in the range of 0.05 to 3 mm. If it is thinner than this, sufficient sandblasting resistance cannot be obtained, and if it is thicker than this, the resolution becomes poor, which is not preferable. In addition, examples of the active light source used for image exposure include arc lamps, mercury lamps, xenon lamps, fluorescent lamps, ultraviolet generators, and sunlight. The wavelength of the active light source is in the range of 200 to 800 mμ, preferably 300 to 500 mμ. Furthermore, as a washing liquid for the unexposed area, for example, water, sodium hydroxide, sodium carbonate,
Alkaline aqueous solutions such as acidic sodium carbonate, sodium borate, sodium phosphate, sodium silicate, and triethanolamine; Examples include aqueous solutions of surfactants such as oxyalkylene glycol alkyl esters, sorbitan fatty acid esters, and polyoxyalkylene glycol sorbitan fatty acid esters. Further, drying is performed by blowing warm air or hot air, or by leaving it at room temperature. The sandblasting mask transfer material of the present invention can be attached to a substrate to be processed without using an adhesive, and furthermore, the support can be peeled off without causing the sandblasting mask pattern layer to separate. , even delicate designs can be sandblasted onto the workpiece substrate with extreme precision. EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. Example 1 Cellulose acetate phthalate was dissolved in methyl ethyl ketone/cellosolve acetate mixed solvent (weight ratio 6/
1) and coated it on a 22μ thick polypropylene film using a bar coater to obtain a polypropylene film having a 2μ thick cellulose acetate phthalate film. This is called film A. In addition, ethyl cellulose was dissolved in methyl ethyl ketone, and this was coated on a 75μ thick polyester film using a bar coater.
A polyester film having an 8μ thick ethylcellulose layer was obtained. This is called film B. Furthermore, 39 parts by weight of polypropylene glycol adipate diol (number average molecular weight 2500), polypropylene glycol (with a total of 10 weight % of ethylene oxide added to both ends, number average molecular weight
2500) and 6 parts by weight of toluylene diisocyanate were reacted to obtain a polyurethane having isocyanate groups at both ends. This was reacted with 15 parts by weight of 2-hydroxypropyl methacrylate to obtain an unsaturated polyurethane having methacrylate groups at both ends. To this unsaturated polyurethane, 20 parts by weight of polypropylene glycol monomethacrylate (number average molecular weight 550), 3 parts by weight of diethylene glycol dimethacrylate, 2,2-
1.5 parts by weight of dimethoxyphenylacetophenone,
0.1 part by weight of 2,6-di-t-butyl-p-cresol was added and mixed to obtain a liquid photosensitive resin composition. Next, a positive film was placed on a glass plate having a thickness of 10 mm, and the positive film was covered with the film A so that the cellulose acetate phthalate film was exposed. Furthermore, a Teflon spacer with a thickness of 0.3 mm was placed, and the liquid photosensitive resin composition prepared as described above was poured into it. Next, the film B was laminated so that the ethyl cellulose membrane was in contact with the photosensitive resin composition layer, and a 10 mm thick glass plate was placed thereon and the four ends were fixed with clips to control the thickness. The structure obtained in this way was placed 50 cm from a 2KW high-pressure mercury lamp, and a positive film was passed through it.
Exposure was made for 80 seconds. Next, the glass plate was removed, and the film A that was in contact with the positive film was peeled off. At this time, there was almost no peeling resistance, and even a small portion of the cured resin did not come off. Next, a 2% by weight surfactant (Lipon F, manufactured by Lion Corporation) aqueous solution was added.
The unexposed photosensitive resin composition was washed out by spraying at a pressure of 0.8 Kg/cm 2 for 150 seconds. At this time, the cured resin did not come off. Next, a sandblasting mask transfer material was obtained by drying at 60° C. for 10 minutes. After cooling this material to 20℃, it was attached to the curved surface of an aluminum cylinder with a width of 13 mm and a diameter of 30 mm using double-sided adhesive tape, and then attached to the surface of a glass plate.
After pressing with a force of 500g/ cm2 for 4 seconds,
The peel resistance value was measured at a speed of 600 g/cm. Next, this transfer material was attached to a glass plate with a thickness of 7 mm, and the film B was peeled off. At this time, there was almost no peeling resistance. Next, use a siphon sandblaster and use Alundum #180 as the abrasive material.
When engraving was performed by spraying the mask over the entire surface for 30 seconds at an air pressure of 3.5 kg/cm 2 , the mask did not separate from the glass and the desired pattern could be engraved. Example 2 86 parts by weight of hydrogenated 1,2-polybutadiene with terminal hydroxyl groups (number average molecular weight 3000) and 6 parts by weight of toluylene diisocyanate were reacted to obtain a polyurethane having isocyanate groups at the terminals. This was reacted with 15 parts by weight of 2-hydroxypropyl methacrylate to obtain an unsaturated polyurethane having methacrylate groups at the ends. This unsaturated polyurethane contains 20 parts by weight of lauryl methacrylate, 2 parts by weight of trimethylolpropane trimethacrylate, 3 parts by weight of diethylene glycol dimethacrylate, 1.5 parts by weight of 2,2-dimethoxyphenylacetophenone, and 2,6-di-t.
0.1 part by weight of -butyl-p-cresol was added and mixed to obtain a liquid photosensitive resin composition. Using this photosensitive resin composition, a mask transfer material for sandblasting was obtained in the same manner as in Example 1. The peel resistance value of this product from the glass plate surface was measured in the same manner as in Example 1, and was found to be 650 g/cm. After adhering this transfer material to the surface of the granite, film B was peeled off, and then using a direct pressure sandblaster, carborundum #200 was used as an abrasive material.
When sprayed on the entire surface for 50 seconds at an air pressure of 4 kg/cm 2 , the desired pattern could be engraved without the mask peeling off from the stone. Comparative example: 2 moles of maleic anhydride, 1 mole of isophthalic acid,
An unsaturated polyester having an acid value of 23 was obtained by subjecting 3 moles of triethylene glycol to a dehydration condensation reaction. 70 parts by weight of this unsaturated polyester, 30 parts by weight of 2-hydroxyethyl methacrylate, 1 part by weight of benzoin isobutyl ether, and 0.1 part by weight of 2,6-di-t-butyl-p-cresol were mixed and dissolved to form a liquid photosensitive resin. I got something. Using this photosensitive resin composition, a sandblasting mask transfer material was prepared in the same manner as in Example 1, except that the developer was a 1% by weight sodium borate aqueous solution. Regarding this, when the peel strength from the glass plate was measured in the same manner as in Example 1, it was found that 100
The value was as small as g/cm. Using this, an attempt was made to sandblast a glass plate in the same manner as in Example 1, but the mask peeled off from the glass plate during the process, and engraving was not possible. Reference Example The photosensitive resin compositions of Examples 1 and 2 and Comparative Example were placed between two glass plates covered on one side with a 9 μm polyester film using a 2 mm thick spacer so that the resin and the polyester film were in contact with each other. By molding the product, placing it 10 cm below a line of 10 20W ultraviolet fluorescent lamps, exposing it to light from one side for 10 minutes, then turning the molded body over and exposing it to light from the opposite side for 10 minutes. A cured photosensitive resin sheet was obtained. This sheet was punched out using a JIS No. 1 dumbbell and stretched at a speed of 500 mm/min to measure the modulus at 100% elongation and elongation at break. Next, Alundum #180 was sprayed onto one point of each sandblasting mask prepared in Examples 1 and 2 and Comparative Example at an air pressure of 5 kg/cm 2 and the time until it was destroyed was measured. The above results are shown in the table below.
Claims (1)
ポリエステル、ポリエーテルポリエステルブロツ
クコポリマー、ポリジエン、ポリエン又はこれら
の混合物、Bは一般式【式】(た だし、Zは水素原子又はメチル基、Yは(−CH2)−
n1O−、【式】又は(−CH2CH2O)−n 3 、m1は1〜6、m2及びm3はそれぞれ1〜15で
ある)で示される化合物、B′は一般式
【式】(ただし、Z、Yは前記と 同じ意味をもつ)、RO又はROY(ただしRは炭素
数1〜8のアルキル基、Yは前記と同じ意味をも
つ)で示される化合物、nは1〜10である〕 で表わされる不飽和ポリウレタン50〜98重量部、
(ロ)エチレン性不飽和化合物2〜50重量部、及び(ハ)
(イ)成分と(ロ)成分との和に対して0.05〜10重量%の
光重合開始剤を主成分として含有して成る感光性
樹脂組成物から得られ、かつ20℃における被加工
基材に対する剥離抵抗値300g/cm2以上、破断伸
度100%以上、100%モジユラス500Kg/cm2以下を
有する硬化物から成るサンドブラスト用マスクパ
ターン層、(B)該マスクパターン層を保持するため
の支持体、及び(C)前記のマスクパターン層と支持
体との間に位置し、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。[Claims] 1 (A) (a) General formula B (XA) o XB' [In the formula, X is a urethane residue, A is a polyether,
Polyester, polyether polyester block copolymer, polydiene, polyene or a mixture thereof, B is the general formula [Formula] (where Z is a hydrogen atom or a methyl group, Y is (-CH 2 )-
n1 O-, [Formula] or (-CH 2 CH 2 O)- n 3 , m 1 is 1 to 6, m 2 and m 3 are each 1 to 15), B' is a general formula [Formula] (wherein Z and Y have the same meanings as above), RO or ROY (wherein R is an alkyl group having 1 to 8 carbon atoms, Y has the same meaning as above), n is 1 to 10] 50 to 98 parts by weight of unsaturated polyurethane,
(b) 2 to 50 parts by weight of an ethylenically unsaturated compound, and (c)
A substrate to be processed obtained from a photosensitive resin composition containing as a main component a photopolymerization initiator in an amount of 0.05 to 10% by weight based on the sum of components (a) and (b), and at 20°C. ( B) a support for holding the mask pattern layer; and (C) a material located between the mask pattern layer and the support, which adheres well to the mask pattern layer but is removable from the support and has the property of being destroyed by sandblasting. A sandblasting mask transfer material comprising a retention layer.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21347383A JPS60104939A (en) | 1983-11-14 | 1983-11-14 | Mask transfer material for sand blast |
US06/601,825 US4587186A (en) | 1982-05-13 | 1984-04-19 | Mask element for selective sandblasting and a method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21347383A JPS60104939A (en) | 1983-11-14 | 1983-11-14 | Mask transfer material for sand blast |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60104939A JPS60104939A (en) | 1985-06-10 |
JPH0420179B2 true JPH0420179B2 (en) | 1992-03-31 |
Family
ID=16639779
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21347383A Granted JPS60104939A (en) | 1982-05-13 | 1983-11-14 | Mask transfer material for sand blast |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60104939A (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0414798Y2 (en) * | 1985-07-10 | 1992-04-02 | ||
JP2828983B2 (en) * | 1988-02-18 | 1998-11-25 | 株式会社東芝 | Surface acoustic wave filter and method of manufacturing the same |
WO1992007303A1 (en) * | 1990-10-22 | 1992-04-30 | Aicello Chemical Co., Ltd. | Method of engraving with image mask and photosensitive laminate film for said image mask |
US5629132B1 (en) * | 1991-03-28 | 2000-02-08 | Aicello Chemical | Method for engraving and/or etching with image-carrying mask and photo-sensitive laminate film for use in making the mask |
US5518857A (en) * | 1991-03-28 | 1996-05-21 | Aicello Chemical Co., Ltd. | Image-carrying mask photo-sensitive laminate film for use in making an image carry mask |
JP4497862B2 (en) * | 2003-07-18 | 2010-07-07 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin laminate for sandblasting |
-
1983
- 1983-11-14 JP JP21347383A patent/JPS60104939A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS60104939A (en) | 1985-06-10 |
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