JPH0227674B2 - ZUGARAOJUSURUHYOJISOCHOGAIKOHANSHABOSHIBANOYOBISONOSEIZOHOHO - Google Patents
ZUGARAOJUSURUHYOJISOCHOGAIKOHANSHABOSHIBANOYOBISONOSEIZOHOHOInfo
- Publication number
- JPH0227674B2 JPH0227674B2 JP8104884A JP8104884A JPH0227674B2 JP H0227674 B2 JPH0227674 B2 JP H0227674B2 JP 8104884 A JP8104884 A JP 8104884A JP 8104884 A JP8104884 A JP 8104884A JP H0227674 B2 JPH0227674 B2 JP H0227674B2
- Authority
- JP
- Japan
- Prior art keywords
- transparent
- pattern
- photosensitive resin
- resin composition
- plate
- 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 - Lifetime
Links
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- 239000011342 resin composition Substances 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 19
- 230000002265 prevention Effects 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 23
- 239000000203 mixture Substances 0.000 description 18
- 239000010410 layer Substances 0.000 description 17
- -1 polypropylene Polymers 0.000 description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000000975 dye Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000004040 coloring Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000006224 matting agent Substances 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
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- 239000011347 resin Substances 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- 238000012719 thermal polymerization Methods 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 4
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- 239000002253 acid Substances 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 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
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000000986 disperse dye Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 2
- 229940081735 acetylcellulose Drugs 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical group 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 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
- 229920002601 oligoester Polymers 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical class C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
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- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 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
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- FSAONUPVUVBQHL-UHFFFAOYSA-N 1,3-bis(4-azidophenyl)prop-2-en-1-one Chemical compound C1=CC(N=[N+]=[N-])=CC=C1C=CC(=O)C1=CC=C(N=[N+]=[N-])C=C1 FSAONUPVUVBQHL-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- HWEONUWVYWIJPF-OWOJBTEDSA-N 1-azido-4-[(e)-2-(4-azidophenyl)ethenyl]benzene Chemical compound C1=CC(N=[N+]=[N-])=CC=C1\C=C\C1=CC=C(N=[N+]=[N-])C=C1 HWEONUWVYWIJPF-OWOJBTEDSA-N 0.000 description 1
- MVPFPGOWZLIWRV-UHFFFAOYSA-N 1-azido-4-[[3-[(4-azidophenyl)methylidene]cyclohexylidene]methyl]benzene Chemical compound C1=CC(N=[N+]=[N-])=CC=C1C=C(CCC1)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MVPFPGOWZLIWRV-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
- QYXHDJJYVDLECA-UHFFFAOYSA-N 2,5-diphenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=C(C=2C=CC=CC=2)C(=O)C=C1C1=CC=CC=C1 QYXHDJJYVDLECA-UHFFFAOYSA-N 0.000 description 1
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- QKTWWGYCVXCKOJ-UHFFFAOYSA-N 2-methoxy-1-(2-methoxyphenyl)-2-phenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1OC QKTWWGYCVXCKOJ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
- 229940076442 9,10-anthraquinone Drugs 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
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- 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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical compound CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
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- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-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
- QUWBSOKSBWAQER-UHFFFAOYSA-N [C].O=C=O Chemical compound [C].O=C=O QUWBSOKSBWAQER-UHFFFAOYSA-N 0.000 description 1
- XUGUHTGSMPZQIW-UHFFFAOYSA-N [[4-(4-diazonioiminocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-ylidene]hydrazinylidene]azanide Chemical group C1=CC(N=[N+]=[N-])=CC=C1C1=CC=C(N=[N+]=[N-])C=C1 XUGUHTGSMPZQIW-UHFFFAOYSA-N 0.000 description 1
- HEQKAHLJBJHDPR-UHFFFAOYSA-N [[4-[2-carboxy-2-(4-diazonioiminocyclohexa-2,5-dien-1-ylidene)ethylidene]cyclohexa-2,5-dien-1-ylidene]hydrazinylidene]azanide Chemical compound C=1C=C(N=[N+]=[N-])C=CC=1C(C(=O)O)=CC1=CC=C(N=[N+]=[N-])C=C1 HEQKAHLJBJHDPR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- HXBPYFMVGFDZFT-UHFFFAOYSA-N allyl isocyanate Chemical compound C=CCN=C=O HXBPYFMVGFDZFT-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 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
- 238000000149 argon plasma sintering Methods 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
- CHFBCXOSLARLKB-UHFFFAOYSA-N bis(4-azidophenyl)methanone Chemical compound C1=CC(N=[N+]=[N-])=CC=C1C(=O)C1=CC=C(N=[N+]=[N-])C=C1 CHFBCXOSLARLKB-UHFFFAOYSA-N 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
- 230000000903 blocking effect Effects 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004043 dyeing Methods 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
- 125000003700 epoxy group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 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
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000036211 photosensitivity Effects 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
- 239000004033 plastic Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Optical Elements Other Than Lenses (AREA)
- Illuminated Signs And Luminous Advertising (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Description
【発明の詳細な説明】
本発明は、例えば発光ダイオード等の表示管の
画像面上に重ねて使用し、不透明部と不透明な縞
又は格子模様を有する透明部とにより構成されて
いる所定の図柄を表出せしめると共に、入射する
外光の遮光及び表示管からの光の可視角調節を行
う機械的強度の優れた図柄を有する表示装置用外
光反射防止板及びその製造方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for displaying a predetermined pattern, which is used to overlap the image plane of a display tube such as a light emitting diode, and is composed of an opaque part and a transparent part having opaque stripes or a checkered pattern. The present invention relates to an external light reflection prevention plate for a display device, which has a pattern with excellent mechanical strength, which allows external light to be exposed, blocks incident external light, and adjusts the visible angle of light from a display tube, and a method for manufacturing the same.
最近、例えば自動車の運転席回りに取り付けら
れている種々な表示灯や表示灯付のスイツチ類に
入射する外光の遮光及び可視角調節のための図柄
を有する表示装置用外光反射防止板が使用される
ようになつてきた。 Recently, anti-reflection panels for display devices have been developed that have patterns to block external light from entering various indicator lights and switches with indicator lights installed around the driver's seat of automobiles and to adjust the viewing angle. It has come to be used.
その製造方法として特公昭47―43845号に、円
板状の透明層と不透明層とを交互に貼り合わせ積
層してロール状とした後、ロール面に沿つて削り
出して縞模様を有する膜状体を得、更にその表面
に図柄を印刷する方法が示されている。しかしな
がらこの方法では印刷工程も含め工程が煩雑であ
る。 The manufacturing method is described in Japanese Patent Publication No. 47-43845, in which disc-shaped transparent layers and opaque layers are alternately laminated and laminated to form a roll, and then cut out along the roll surface to form a film with a striped pattern. A method for obtaining a body and further printing a design on its surface is shown. However, this method involves complicated steps including the printing step.
本発明者らは上記従来技術の欠点なく簡単な工
程で図柄を有する表示装置用外光反射防止板を製
造する方法を提供することを目的に種々検討を重
ねた。そして特願昭56―73422号〜特願昭56―
73424号に開示されているような外光反射防止板、
すなわち透明な縞又は格子模様を有する透明画像
担体を通した光で感光性樹脂を露光硬化させて縞
又は格子状のレリーフを透明基板の全面に形成さ
せた外光反射防止板を得、その透明基板上に図柄
を印刷して検討したが、使用個所、例えば表示灯
の上から指で押すスイツチなどの場合に強度が必
ずしも充分でない欠点があつた。そして更に検討
を続けた結果、上記透明画像担体に透明部と不透
明部とから図柄を表わし、その不透明に予め透明
な縞又は格子模様を設けておくときは、得られた
板には露光硬化して形成された広い幅の面部と縞
又は格子状の線状部とから図柄が表わされていて
全体として機械的に非常に強固な外光反射防止板
の得られることを究明して本発明を完成した。 The present inventors have conducted various studies with the aim of providing a method of manufacturing an external light reflection prevention plate for a display device having a pattern through a simple process without the drawbacks of the prior art described above. And patent application No. 73422 - 1984 -
An external light antireflection plate as disclosed in No. 73424,
That is, by exposing and curing a photosensitive resin with light that has passed through a transparent image carrier having transparent stripes or a checkered pattern, an external light antireflection plate is obtained in which a striped or checkered relief is formed on the entire surface of a transparent substrate. A study was carried out by printing a pattern on a board, but there was a drawback that the strength was not necessarily sufficient in the places where it was used, for example, in the case of a switch that was pressed with a finger from above an indicator light. As a result of further studies, it was found that when a pattern is expressed on the transparent image carrier by a transparent part and an opaque part, and a transparent stripe or checkered pattern is provided on the opaque part in advance, the resulting plate is exposed to light and hardened. It was discovered that an external light reflection prevention plate can be obtained that has a pattern formed from a wide surface area and striped or lattice-like linear areas, and is mechanically very strong as a whole. completed.
すなわち本発明は、透明板、感光性樹脂組成物
によつて形成された図柄を表わすレリーフ層及び
透明板がこの順に積層されており、該図柄が不透
明部と不透明な縞又は格子模様を有する透明部と
により構成されていることを特徴とする図柄を有
する表示装置用外光反射防止板と、この図柄を有
する表示装置用外光反射防止板を製造するため
の、透明部と透明な縞又は格子模様を有する不透
明部とにより図柄が表わされている透明画像担体
と感光性樹脂組成物層と透明基板との少なくとも
３層をこの順に積層し、該透明画像担体を通して
活性光線を照射することにより該感光性樹脂組成
物を露光し、次いで該透明画像担体と該感光性樹
脂組成物の非露光部分とを除去する工程を経て得
られる着色されたレリーフ部の上面に透明板を貼
り合わせることを特徴とする図柄を有する表示装
置用外光反射防止板の製造方法とに関するもので
ある。 That is, the present invention provides a transparent plate, a relief layer representing a pattern formed by a photosensitive resin composition, and a transparent plate, which are laminated in this order, and the pattern has an opaque part and an opaque stripe or checkered pattern. A transparent part and a transparent stripe or Laminating at least three layers in this order: a transparent image carrier having a pattern represented by an opaque part having a checkered pattern, a photosensitive resin composition layer, and a transparent substrate, and irradiating actinic rays through the transparent image carrier. bonding a transparent plate to the upper surface of the colored relief portion obtained through a step of exposing the photosensitive resin composition to light and then removing the transparent image carrier and the unexposed portion of the photosensitive resin composition; The present invention relates to a method of manufacturing an external light reflection prevention plate for a display device having a pattern characterized by:
以下、図面によつて本発明を詳細に説明する。 Hereinafter, the present invention will be explained in detail with reference to the drawings.
第１図及び第２図はそれぞれ本発明方法で使用
する透明画像担体の例を示す図、第３図及び第４
図はそれぞれ第１図及び第２図の透明画像担体を
使用して製造した図柄を有する表示装置用外光反
射防止板の正面図、第５図は第３図中のＡ―Ａ線
断面図、第６図及び第７図はそれぞれ図柄を有す
る表示装置用外光反射防止板の他の例を示す正面
図である。 1 and 2 are diagrams showing examples of transparent image carriers used in the method of the present invention, and FIGS. 3 and 4 respectively.
The figures are a front view of an external light reflection prevention plate for a display device having a pattern manufactured using the transparent image carriers shown in FIGS. 1 and 2, respectively, and FIG. 5 is a cross-sectional view taken along the line AA in FIG. 3. , FIG. 6, and FIG. 7 are front views showing other examples of external light reflection prevention plates for display devices each having a pattern.
本発明方法を実施して本発明に係る図柄を有す
る表示装置用外光反射防止板を製造するには、先
ず第１図、第２図の如き透明部１ａと透明な縞又
は格子模様１b′を有する不透明部１ｂとより図柄
が表わされている透明画像担体１を準備する。担
体１の図柄の形状は透明部１ａと不透明部１ｂと
の境界を輪郭として形成されているのであり、担
体の図柄そのものは第１図の如く不透明部１ｂで
あつても、第２図の如く透明部１ａであつても、
いずれでも良い。上記縞又は格子模様１b′の寸法
は、その幅w1（格子の場合は格子を構成する縞の
幅）が20〜500μ、縞と縞との間隔w2（縞と縞との
間の不透明部分の幅）が20〜1000μが適当であ
る。この透明画像担体用のベースとしては、例え
ば銀塩像による写真製版用ネガフイルム、活性光
線に対して実質的に透明であるプラスチツクフイ
ルム、透明ガラス等が示され、このベースの面に
上記に従い印刷等により図柄を設ける。 In order to manufacture an external light reflection prevention plate for a display device having a pattern according to the present invention by carrying out the method of the present invention, first, a transparent portion 1a and a transparent striped or checkered pattern 1b' as shown in FIGS. 1 and 2 are prepared. A transparent image carrier 1 having an opaque portion 1b having a pattern representing a pattern is prepared. The shape of the pattern on the carrier 1 is formed using the border between the transparent part 1a and the opaque part 1b as an outline, and even if the pattern itself is in the opaque part 1b as shown in Fig. 1, it is formed as shown in Fig. 2. Even if it is the transparent part 1a,
Either is fine. The dimensions of the striped or lattice pattern 1b' are as follows: the width w 1 (in the case of a lattice, the width of the stripes constituting the lattice) is 20 to 500μ, the interval between the stripes w 2 (the opacity between the stripes) Appropriately, the width of the part is 20 to 1000μ. The base for this transparent image carrier includes, for example, a negative film for photolithography with a silver salt image, a plastic film that is substantially transparent to actinic light, a transparent glass, etc., and the surface of this base is printed according to the above-mentioned method. A pattern is provided by etc.
このようにして準備された透明画像担体１と感
光性樹脂組成物（以下、組成物と言うことがあ
る）層と透明基板２との少なくとも３層をこの順
に積層する。透明基板２としては、透明なガラ
ス，ポリメチルメタクリレート，ポリスチレン，
ポリ塩化ビニル，ポリカーボネート，ポリプロピ
レン，ポリエチレンテレフタレート（PET）、ア
セチルセルロース，ポリ塩化ビニリデン，ポリエ
チレン酢酸ビニル，ポリアクリロニトリル，ポリ
アミド，ポリビニルアルコール等が挙げられ、そ
の厚みは通常１〜10mmのものであるが、プラスチ
ツクの場合にはその厚みが20μ以上、好ましくは
50μ以上のフイルム又はシートも用いることがで
きる。これらのうち、透明なガラス，ポリメチル
メタクリレート，ポリカーボネート，ポリエチレ
ンテレフタレート等が取扱い性の点で好ましい
感光性樹脂の詳細は後記する。 At least three layers of the thus prepared transparent image carrier 1, photosensitive resin composition (hereinafter sometimes referred to as composition) layer, and transparent substrate 2 are laminated in this order. As the transparent substrate 2, transparent glass, polymethyl methacrylate, polystyrene,
Examples include polyvinyl chloride, polycarbonate, polypropylene, polyethylene terephthalate (PET), acetyl cellulose, polyvinylidene chloride, polyethylene vinyl acetate, polyacrylonitrile, polyamide, polyvinyl alcohol, etc., and the thickness is usually 1 to 10 mm. In the case of plastic, the thickness is 20μ or more, preferably
Films or sheets of 50μ or more can also be used. Among these, transparent glass, polymethyl methacrylate, polycarbonate, polyethylene terephthalate, etc. are preferred from the viewpoint of ease of handling. Details of the photosensitive resin will be described later.
このような透明基板２、組成物及び透明画像担
体１を積層する方法としては、透明基板２の所定
面上に好ましくは厚みが40〜2000μとなるように
組成物を層状に塗布又は該組成物のシートを接着
した後、透明画像担体１を上記組成物上に密着配
置する。又は、これとは逆に透明画像担体１に組
成物層を積層した後、透明基板２を密着配置して
もよく、更には透明基板２と透明画像担体１とを
厚み規正用スペーサーを用いて一定間隔を設けて
配置し、この間隔に液状もしくは溶融した組成物
を注入してもよい。上記の積層は必ずしも上記の
３層だけに限られず、例えば次のように積層して
もよい。 A method for laminating the transparent substrate 2, the composition, and the transparent image carrier 1 is to apply the composition in a layered manner onto a predetermined surface of the transparent substrate 2 so that the thickness is preferably 40 to 2000μ, or to coat the composition After adhering the sheet, transparent image carrier 1 is placed in close contact with the above composition. Alternatively, on the contrary, after laminating the composition layer on the transparent image carrier 1, the transparent substrate 2 may be placed in close contact with each other. They may be arranged at regular intervals and a liquid or molten composition may be injected into these intervals. The above lamination is not necessarily limited to the above three layers, and may be laminated as follows, for example.
組成物と透明画像担体１とを画像再現性の点か
ら密着配置することが好ましいが、組成物が液状
又は固状であつても表面が粘着性を有する場合に
は透明画像担体１と組成物との間に透明プラスチ
ツクフイム、例えばポリプロピレンフイルム，ポ
リカーボネートフイルム，ポリエチレンテレフタ
レートフイルム，アセチルセルロースフイルム，
ポリビニルアルコールフイルム，セロハン等の中
間層を設けることは透明画像担体１の保護や照射
後の透明画像担体１と組成物層との接着を防止す
る効果を有するので有効である。 It is preferable to place the composition and the transparent image carrier 1 in close contact with each other from the viewpoint of image reproducibility, but even if the composition is liquid or solid, if the surface is sticky, the transparent image carrier 1 and the composition may be placed in close contact with each other. A transparent plastic film such as polypropylene film, polycarbonate film, polyethylene terephthalate film, acetyl cellulose film,
Providing an intermediate layer such as polyvinyl alcohol film or cellophane is effective because it protects the transparent image carrier 1 and prevents adhesion between the transparent image carrier 1 and the composition layer after irradiation.
このようにして得られた積層体の透明画像担体
１を通して活性光線を照射すると、透明部１ａ及
び不透明部１ｂ中の透明な縞又は格子模様１b′を
透過した活性光線により、組成物の該当部分だけ
が露光され硬化する（このように硬化した部分を
露光部と言う）。活性光線としてはアーク灯、水
銀灯、キセノンランプ、紫外線用螢光灯、太陽光
などが用いられる。 When actinic light is irradiated through the transparent image carrier 1 of the laminate thus obtained, the actinic light that has passed through the transparent stripes or checkered pattern 1b' in the transparent part 1a and the opaque part 1b will cause the corresponding part of the composition to Only the exposed area is exposed and cured (the area that is cured in this way is called the exposed area). As active light, arc lamps, mercury lamps, xenon lamps, ultraviolet fluorescent lamps, sunlight, etc. are used.
露光が終了すれば、次いで透明画像担体１と組
成物の非露光部分とを除去することにより現像す
る。組成物の非露光部分を取り除く方法として
は、公知の方法、例えば露光を終了し透明画像担
体１を取り除いた版を現像される版画を外側にし
てドラム又は平板に取り付け現像液をスプレーに
よつて該版画に吹き付けて非露光部分を洗い出す
方法又は現像液中にブラシを浸し、このブラシで
非露光部分を除去する方法により行われる。 Once the exposure is completed, the transparent image carrier 1 and the unexposed portions of the composition are removed and developed. The unexposed portion of the composition can be removed by a known method, for example, by attaching the plate from which the exposure has been completed and the transparent image carrier 1 has been removed to a drum or flat plate with the developed print facing outward, and spraying a developing solution on the plate. This is carried out by spraying onto the print to wash out the unexposed areas, or by dipping a brush in a developer and removing the unexposed areas with the brush.
このようにして、第３図、第４図及び第５図に
示される如く、透明基板２上に、透明画像担体１
の透明部１ａ及び不透明部１ｂ中の透明な縞又は
格子模様１b′にそれぞれ対応して硬化した露光部
により広い幅を有する不透明な面部３ａと透明な
縞又は格子状の線状部３b′とから成るレリーフ３
が形成される。このようなレリーフ３の寸法上の
好ましい例は、第５図の如く線状部３b′の縞の幅
（格子の場合は格子を構成する縞の幅）をW1、縞
と縞との間隔をW2、感光樹脂像３の高さをＨと
すると、高さＨは好ましくは40〜2000μ、更に好
ましくは200〜1200μ幅W1は好ましくは20〜500μ、
特に好ましくは100〜300μ、間隔W2は20〜1000μ、
特に好ましくは200〜600μであり、幅／間隔＝1/
５〜1/1、間隔／高さ＝1/0.6〜1/2が好ましく、間
隔／高さ＝1/0.85〜1/2が特に好ましい。 In this way, as shown in FIGS. 3, 4, and 5, the transparent image carrier 1 is placed on the transparent substrate 2.
An opaque surface part 3a and a transparent striped or grid-like linear part 3b' having a wider width due to the hardened exposed part correspond to the transparent striped or checkered pattern 1b' in the transparent part 1a and the opaque part 1b, respectively. Relief 3 consisting of
is formed. A preferable example of the dimensions of such a relief 3 is as shown in FIG . is W2 , and the height of the photosensitive resin image 3 is H, the height H is preferably 40 to 2000μ, more preferably 200 to 1200μ, and the width W1 is preferably 20 to 500μ,
Particularly preferably 100 to 300μ, the interval W2 is 20 to 1000μ,
Particularly preferably 200 to 600 μ, width/spacing = 1/
5 to 1/1, interval/height = 1/0.6 to 1/2 is preferred, and interval/height = 1/0.85 to 1/2 is particularly preferred.
本発明方法においては、上記のようにして得ら
れたレリーフ３を形成する露光部を最終的に着色
されたものにするための着色処理を含んでいる。
この着色処理としては次に説明する如き方法があ
る。一つの着色処理方法は顔料又は染料の適当量
を予め感光性樹脂組成物に添加しておくことによ
り、露光、現像により得られる露光部を既に着色
されたものとする方法である。他の着色処理方法
は、露光、現像後に露光部を染料により染色する
方法である。染料としては、例えばカチオン染
料、分散染料、反応性染料、含金属染料が用いら
れるが、感光性樹脂組成物との相溶性及び染料の
吸収特性より選択するのが好ましく、染料の吸収
特性としては紫外部300〜400nmの吸収が小さく、
可視部400〜700nmに大きな吸収を持つものが好
ましい。また顔料に関しては感光性樹脂組成物中
での分散性が良いものを用い、またその添加量は
感光性樹脂組成物の感光特性を著しく低下させな
い程度にする必要がある。上記の如き着色処理を
施すことにより、レリーフ３を形成する露光部は
着色されたものとなる。 The method of the present invention includes a coloring process to finally color the exposed area forming the relief 3 obtained as described above.
As this coloring process, there are methods as described below. One coloring treatment method is to add an appropriate amount of a pigment or dye to a photosensitive resin composition in advance so that the exposed area obtained by exposure and development is already colored. Another coloring treatment method is to dye the exposed area with a dye after exposure and development. For example, cationic dyes, disperse dyes, reactive dyes, and metal-containing dyes are used as dyes, but they are preferably selected based on compatibility with the photosensitive resin composition and absorption characteristics of the dye. Absorption in the ultraviolet region of 300 to 400 nm is small,
It is preferable to have a large absorption in the visible region of 400 to 700 nm. As for the pigment, it is necessary to use one that has good dispersibility in the photosensitive resin composition, and the amount added must be such that it does not significantly deteriorate the photosensitivity properties of the photosensitive resin composition. By performing the coloring process as described above, the exposed areas forming the relief 3 become colored.
本発明方法においては、得られるレリーフ３の
側面に外光が反射して発生することのあるゴース
ト現象を防止するために、感光性樹脂組成物に予
め表面つや消し剤を添加混合しておく場合があ
る。表面つや消し剤としては、酸化チタン、雲
母、炭酸カルシウム、粉末ガラス（商品名；グラ
スバール、粒子径５〜15μ）、微粒子状シリカ
（商品名；サイロイド、エアロジルなどで粒子径
0.5〜20μ）アルミナ粉、クレー等があり、感光性
樹脂組成物への添加量は0.1〜20重量％、好まし
くは0.5〜10重量％である。この添加量が0.1重量
％未満では、ゴースト現象防止の効果がなく、ま
た20重量％を超えると添加量のわりに表面を粗面
化する効果が少なく、レリーフ３の透明度も不良
となり光の散乱によるレリーフ３の解像度の低下
がある。表面つや消し剤の添加量は上記範囲内に
おいてレリーフ３の表面が反射率測定方法により
反射率20％以下となるように選定されると一層好
ましい。これら表面つや消し剤のうち、粒子状シ
リカが分散性、光屈折率等の点から好ましい表面
つや消し剤である。また、レリーフ３の染色処理
に使用される染色は通常染料でも良いが、耐候性
の面より含金属分散染料が好ましい。 In the method of the present invention, a surface matting agent may be added and mixed in advance to the photosensitive resin composition in order to prevent a ghost phenomenon that may occur due to external light being reflected on the side surface of the relief 3 obtained. be. Surface matting agents include titanium oxide, mica, calcium carbonate, powdered glass (product name: Glass Bar, particle size 5-15μ), fine particulate silica (product name: Thyroid, Aerosil, etc.)
(0.5-20μ) alumina powder, clay, etc., and the amount added to the photosensitive resin composition is 0.1-20% by weight, preferably 0.5-10% by weight. If the amount added is less than 0.1% by weight, there will be no effect of preventing ghost phenomenon, and if it exceeds 20% by weight, the effect of roughening the surface will be small compared to the amount added, and the transparency of the relief 3 will also be poor, due to light scattering. There is a decrease in the resolution of relief 3. It is more preferable that the amount of the surface matting agent added is selected within the above range so that the surface of the relief 3 has a reflectance of 20% or less as measured by a reflectance measuring method. Among these surface matting agents, particulate silica is a preferred surface matting agent in terms of dispersibility, optical refractive index, and the like. Further, the dye used for the dyeing treatment of the relief 3 may be a normal dye, but a metal-containing disperse dye is preferable from the viewpoint of weather resistance.
次に本発明方法で使用する感光性樹脂組成物に
ついて説明する。 Next, the photosensitive resin composition used in the method of the present invention will be explained.
感光性樹脂組成物の代表に、エチレン重合性不
飽和基を有するプレポリマーと必要によりエチレ
ン性不飽和単量体、光重合増感剤、熱重合禁止剤
とから成る組成物がある。上記プレポリマーとし
ては、不飽和ポリエステル，不飽和ポリウレタ
ン，オリゴエステルアクリレート類、不飽和ポリ
アミド，不飽和ポリイミド，不飽和ポリエーテ
ル、不飽和ポリ（メタ）アクリレート及びこれら
の各種変性体、炭素―炭素二重結合を有する各種
ゴム化合物等を例示することができる。これらの
プレポリマーの数平均分子量は実質的に500以上
であるものを用いるのが一般的である。 A typical photosensitive resin composition is a composition comprising a prepolymer having an ethylenically polymerizable unsaturated group and, if necessary, an ethylenically unsaturated monomer, a photopolymerization sensitizer, and a thermal polymerization inhibitor. The above prepolymers include unsaturated polyesters, unsaturated polyurethanes, oligoester acrylates, unsaturated polyamides, unsaturated polyimides, unsaturated polyethers, unsaturated poly(meth)acrylates, and various modified products thereof, and carbon-carbon dioxide. Examples include various rubber compounds having multiple bonds. These prepolymers generally have a number average molecular weight of substantially 500 or more.
更に具体例を示すと、不飽和ポリエステル及び
アルキツドとしては例えばマレイン酸、フマル
酸、イクコン酸のような不飽和二塩基酸又はその
酸無水物とエチレングリコール，プロピレングリ
コール、ジエチレングリコール、トリエチレング
リコール、グリセリン，トリメチロールプロパ
ン，ペンタエリトリツト、末端水酸基を有する
１，４―ポリブタジエン，水添又は非水添１，２
―ポリブタジエン、ブタジエン―スチレン共重合
体、ブタジエン―アクリロニトリル共重合体など
の多価アルコールとのポリエステル、前記酸成分
の一部をコハク酸，アジピン酸，フタル酸，イソ
フタル酸，無水フタル酸，トリメリツト酸などの
飽和多塩基酸に置き換えたポリエステルあるいは
乾性油脂肪酸又は半乾燥性油脂肪酸で変性したポ
リエステルなどが、不飽和ポリウレタンとして
は、すなわち２個以上の末端水酸基を有するポリ
オールとポリイソシアネートから誘導されたウレ
タン基を介して連結した化合物の末端イソシアネ
ート基あるいは水酸基を利用して付加重合性不飽
和基を導入したもの、例えば前記した多価アルコ
ール，ポリエステルポリオール，ポリエーテルポ
リオールなどのポリオール末端水酸基を有する、
１，４―ポリブタジエン，水添又は非水添１，２
―ポリブタジエン、ブタジエン―スチレン共重合
体、ブタジエン―アクリロニトリル共重合体とト
ルイレンジイソシアネート，ジフエニルメタン―
４，4′―ジイソシアネート、ヘキサメチレンイソ
シアネートなどのポリイソシアネートとのポリウ
レタンの末端イソシアネートあるいは水酸基の反
応性を利用して不飽和基を導入したもの、すなわ
ち、前記した不飽和カルボン酸又はそのエステル
のうち水酸基、カルボキシル基、アミノ基などの
活性水素を有する化合物とイソシアネートとの反
応により不飽和基を導入したり、カルボキシル基
を有するものと水酸基との反応により不飽和基を
導入した化合物又は前記の不飽和ポリエステルを
ポリイソシアネートで連結した化合物などが、オ
リゴエステルアクリレート類としては、すなわち
多塩基酸と多価アルコールのエステル反応系にア
クリル酸又はメタクリル酸を共存させて、共縮合
させそれぞれのモル比を調整して分子量200〜
5000程度としたもの、例えばアジピン酸、フタル
酸、イソフタル酸又は酸無水物などとエチレング
リコール、プロピレングリコール、ジエチレング
リコール、トリエチレングリコール、グリセリ
ン、トリメチロールプロパン，ペンタエリトリツ
トなどの多価アルコールとのエステル反応系にア
クリル酸又はメタクリル酸を共存させて縮合させ
たもの、エポキシアクリレート類、例えば多価ア
ルコール，多価フエノール又はポリフエノールと
エピクロルヒドリン又はアルキレンオキシドと重
縮合反応により得られるエポキシ基を有する化合
物とアクリル酸又はメタクリル酸とのエステル，
側鎖に付加重合性炭素―炭素二重結合を有する高
分子化合物、例えばポリビニルアルコール，セル
ロースのような水酸基を持つ高分子化合物と不飽
和カルボン酸又はその酸無水物とを反応させて得
られる化合物や、アクリル酸又はメタクリル酸の
重合体又は共重合体のようなカルボキシル基を持
つ高分子化合物に、不飽和アルコール，グリシジ
ルアクリレート又はメタクリレートをエステル結
合させたもの、無水マレイン酸を含有する共重合
体とアリルアルコール；ヒドロキシアルキルアク
リレート又はメタクリレートとの反応物など、グ
リシジルアクリレート又はメタクリレートを共重
合成分として含有する共重合体とアクリル酸又は
メタクリレ酸との反応物などを挙げることができ
る。また、各種ゴム化合物としては、（）１，
４―ポリブタジエン、１，２―ポリブタジエン，
ブタジエン―スチレン共重合体、ブタジエン―ア
クリロニトリル共重合体、EPDN（）上記（）
の水酸化物、イソブチレン―イソプレン共重合
体、エチレンプロピレン共重体そして（）に示
される各種ゴム以上の化合物に公知の技術により
エチレン性不飽和基を導入した不飽和変性ゴム等
を例示できる。（）の化合物はそのままでも使
用できるが、その不飽和基を導入するには、末端
官能基を有する各種ゴム化合物を用いるのが便利
である。また、１，２―ポリブタジエンセグメン
トを有するゴム化合物の場合は該化合物に無水マ
レイン酸類を付加することにより、該不飽和基を
容易に導入できる。 To give more specific examples, unsaturated polyesters and alkyds include unsaturated dibasic acids such as maleic acid, fumaric acid, and iconic acid, or their acid anhydrides, and ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and glycerin. , trimethylolpropane, pentaerythritol, 1,4-polybutadiene with terminal hydroxyl groups, hydrogenated or non-hydrogenated 1,2
- Polyesters with polyhydric alcohols such as polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and some of the above acid components are succinic acid, adipic acid, phthalic acid, isophthalic acid, phthalic anhydride, trimellitic acid Examples of unsaturated polyurethanes include polyesters substituted with saturated polybasic acids such as polyesters or polyesters modified with drying oil fatty acids or semi-drying oil fatty acids; Addition-polymerizable unsaturated groups are introduced using terminal isocyanate groups or hydroxyl groups of compounds connected via urethane groups, for example, polyols such as the aforementioned polyhydric alcohols, polyester polyols, and polyether polyols having terminal hydroxyl groups.
1,4-polybutadiene, hydrogenated or non-hydrogenated 1,2
-Polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer and toluylene diisocyanate, diphenylmethane-
4,4'-diisocyanate, hexamethylene isocyanate, and other polyisocyanates into which unsaturated groups are introduced using the terminal isocyanate or hydroxyl group reactivity of polyurethane, i.e., among the above-mentioned unsaturated carboxylic acids or their esters. Compounds into which an unsaturated group is introduced by reacting a compound having active hydrogen such as a hydroxyl group, carboxyl group, or amino group with an isocyanate, or a compound into which an unsaturated group is introduced by reacting a compound having a carboxyl group with a hydroxyl group, or the unsaturated group mentioned above. Oligoester acrylates, such as compounds in which saturated polyesters are linked with polyisocyanate, are cocondensed by co-condensing acrylic acid or methacrylic acid in an ester reaction system of polybasic acid and polyhydric alcohol. Adjust the molecular weight to 200~
5000, for example, esters of adipic acid, phthalic acid, isophthalic acid, or acid anhydrides, and polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, glycerin, trimethylolpropane, and pentaerythritol. Those condensed in the presence of acrylic acid or methacrylic acid in the reaction system, epoxy acrylates, such as polyhydric alcohols, polyphenols, or polyphenols, and compounds having epoxy groups obtained by polycondensation reaction with epichlorohydrin or alkylene oxide. Esters with acrylic acid or methacrylic acid,
A compound obtained by reacting a polymer compound with an addition-polymerizable carbon-carbon double bond in its side chain, such as a polymer compound with a hydroxyl group such as polyvinyl alcohol or cellulose, with an unsaturated carboxylic acid or its acid anhydride. and polymer compounds with carboxyl groups, such as polymers or copolymers of acrylic acid or methacrylic acid, to which unsaturated alcohols, glycidyl acrylates or methacrylates are ester-bonded, and copolymers containing maleic anhydride. and allyl alcohol; a reaction product of hydroxyalkyl acrylate or methacrylate; a reaction product of a copolymer containing glycidyl acrylate or methacrylate as a copolymerization component and acrylic acid or methacrylic acid; and the like. In addition, various rubber compounds include ()1,
4-polybutadiene, 1,2-polybutadiene,
Butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, EPDN () above ()
hydroxide, isobutylene-isoprene copolymer, ethylene propylene copolymer, and unsaturated modified rubbers in which ethylenically unsaturated groups are introduced into compounds of the various rubbers shown in () by known techniques. The compound () can be used as is, but in order to introduce the unsaturated group, it is convenient to use various rubber compounds having a terminal functional group. Further, in the case of a rubber compound having a 1,2-polybutadiene segment, the unsaturated group can be easily introduced by adding maleic anhydride to the compound.
上記以外のプレポリマーとして、エチレン性二
重結合の付加以外の機構により光重合する該二重
結合を含有しない化合物例えば、水可溶性ナイロ
ン，ポリビニルアルコール及びその誘導体を用い
ても一向に差し支えない。 As prepolymers other than those mentioned above, there is no problem in using compounds that do not contain double bonds and are photopolymerized by a mechanism other than the addition of ethylenic double bonds, such as water-soluble nylon, polyvinyl alcohol, and derivatives thereof.
エチレン性不飽和単量体としては、公知の種々
の化合物を使用できるが、このような化合物の例
としては、アクリル酸，メタクリル酸のような不
飽和カルボン酸又はそのエステル、例えばアルキ
ル―，シクロアルキル―，ハロゲン化アルキル
―，アルコキシアルキル―，ヒドロキシアルキル
―，アミノアルキル―，テトラヒドロフルフリル
―，アリル―，グリシジル―，ベンジル―，フエ
ノキシ―などの各基を有するアクリレート及びメ
タクレート，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のモノ又はジアクリレート
及びメタクリレート，トリメチロールプロパント
リアクリレート及びメタクリレート，ペンタエリ
トリツトテトラアクリレート及びメタクリレート
など、アクリルアミド，メタクリルアミド又はそ
の誘導体、例えばアルキル，ヒドロキシアルキル
でＮ―置換又はＮ，N′―置換したアクリルアミ
ド及びメタクリルアミド，ジアセトンアクリルア
ミド及びメタクリルアミド，Ｎ，N′―アルキレ
ンビスアクリルアミド及びメタクリルアミドな
ど、アリル化合物、例えばアリルアルコール，ア
リルイソシアネート，ジアリルフタレート，トリ
アリルシアヌレートなど、マレイン酸，無水マレ
イン酸，フマル酸又はそのエステル、例えばアル
キル，ハロゲン化アルキル，アルコキシアルキル
のモノ又はジマレエート及びフマレートなど、そ
の他の不飽和化合物例えばスチレン，ビニルトル
エン，ジビニルベンゼン，Ｎ―ビニルカルバゾー
ル，Ｎ―ビニルピロリドンなどを挙げることがで
きる。またこれらの単量体の一部をアジド系化合
物例えば４，4′―ジアジドスチルベン，Ｐ―フエ
ニレン―ビスアジド，４，4′―ジアジドベンゾフ
エノン，４，4′―ジアドジドフエニルメタン，
４，4′―ジアジドカルコン，２，６―ジ（4′―ア
ジドベンザル）―シクロヘキサン，４，4′―ジア
ジドスチルベン―α―カルボン酸，４，4′―ジア
ジドジフエニル，４，４―ジアジドスチルベン―
２，2′―ジスルホン酸ソーダなどに置き換えるこ
とができる。これらの単量体はプレポリマー100
重量部に対し、０〜200重量部の範囲で添加すれ
ばよい。 Various known compounds can be used as the ethylenically unsaturated monomer, and examples of such compounds include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, or esters thereof, such as alkyl-, cyclo-, Acrylates and methacrylates, alkylene glycols, and polyesters containing groups such as alkyl, halogenated alkyl, alkoxyalkyl, hydroxyalkyl, aminoalkyl, tetrahydrofurfuryl, allyl, glycidyl, benzyl, and phenoxy. Mono- or diacrylates and methacrylates of oxyalkylene glycols, trimethylolpropane triacrylates and methacrylates, pentaerythritate tetraacrylates and methacrylates, acrylamide, methacrylamide or derivatives thereof, such as N-substituted with alkyl, hydroxyalkyl or N,N' Allyl compounds such as allyl alcohol, allyl isocyanate, diallyl phthalate, triallyl cyanurate, maleic acid, Maleic anhydride, fumaric acid or esters thereof, such as mono- or dimaleates and fumarates of alkyl, alkyl halides, alkoxyalkyl, other unsaturated compounds such as styrene, vinyltoluene, divinylbenzene, N-vinylcarbazole, N-vinylpyrrolidone etc. can be mentioned. Some of these monomers may also be converted into azide compounds such as 4,4'-diazidostilbene, P-phenylene-bisazide, 4,4'-diazidobenzophenone, 4,4'-diazidophenylmethane. ，
4,4'-Diazidochalcone, 2,6-di(4'-azidobenzal)-cyclohexane, 4,4'-diazidostilbene-α-carboxylic acid, 4,4'-diazidodiphenyl, 4,4 -Diazidostilbene-
It can be replaced with sodium 2,2'-disulfonate, etc. These monomers are prepolymer 100
It may be added in a range of 0 to 200 parts by weight.
光重合増感剤としては公知の種々の光増感剤を
使用し得る。このようなものとして、例えばベン
ゾインやベンゾインエチルエーテル，ベンゾイン
―ｎ―プロピルエーテル，ベンゾイン―イソプロ
ピルエーテル，ベンゾインイソブチル―エーテル
などのベンゾインアルキルエーテル類、２，2′―
ジメトキシ―２―フエニルアセトフエノン，ベン
ゾフエノン，ベンジル，ジアセチル，ジフエニル
スルフイド，エオシン，チオニン，９，10―アン
トラキノン，２―エチル―９，10―アントラキノ
ン，ミヒラーケトンなどがあり、組成物に対し
て、0.001〜10重量％の範囲で使用することがで
きる。熱重合禁止剤として、ハイドロキノン，モ
ノ第三ブチルハイドロキノン，ベンゾキノン，
２，５―ジフエニル―Ｐ―ベンゾキノン，ピクリ
ン酸，ジ―Ｐ―フルオロフエニルアミン，Ｐ―メ
トキシフエノール，２，６―ジ第三ブチル―Ｐ―
クレゾールなどを挙げることができる。これらの
熱重合禁止剤は、熱重合反応（暗反応）を防止す
るものであることが望ましい。したがつて、熱重
合禁止剤の添加量は、プレポリマーと架橋剤との
総量に対し、0.005〜5.0重量％の範囲であること
が望ましい。その他特公昭46―29525号公報に示
されるポリエンとポリチオールと光増感剤とより
成る組成物も有用である。 As the photopolymerization sensitizer, various known photosensitizers can be used. Examples of such substances include benzoin, benzoin alkyl ethers such as benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2'-
Dimethoxy-2-phenylacetophenone, benzophenone, benzyl, diacetyl, diphenyl sulfide, eosin, thionine, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, Michler's ketone, etc. On the other hand, it can be used in a range of 0.001 to 10% by weight. As a thermal polymerization inhibitor, hydroquinone, mono-tert-butylhydroquinone, benzoquinone,
2,5-diphenyl-P-benzoquinone, picric acid, di-P-fluorophenylamine, P-methoxyphenol, 2,6-di-tert-butyl-P-
Examples include cresol. It is desirable that these thermal polymerization inhibitors prevent thermal polymerization reactions (dark reactions). Therefore, it is desirable that the amount of the thermal polymerization inhibitor added is in the range of 0.005 to 5.0% by weight based on the total amount of the prepolymer and the crosslinking agent. In addition, compositions comprising polyenes, polythiols, and photosensitizers as disclosed in Japanese Patent Publication No. 46-29525 are also useful.
上記説明の感光性樹脂組成物を使用し、前記説
明の如く透明画像担体１と感光性樹脂組成物層と
透明基板２との少なくとも３層の積層、露光硬
化、現像及び着色処理を行うことにより、露光部
の着色された表示装置用外光反射防止板が得られ
る。かかる方法で得られる表示装置用外光反射防
止板には、第３図の如くレリーフ３の線状部３
b′が図柄の部分を占め、その他の部分が面部３ａ
となつているもの、また逆に、第４図の如くレリ
ーフ３の面部３ａが図柄の部分を占め、その他の
部分が線状部３b′となつているものがある。そし
て線状部３b′として第３図の如き横縞、第４図の
如き横縞、第６図の如き縦縞、第７図の如き格子
など種々の態様を採らせることができる。このよ
うにして得られる表示装置用外光反射防止板に第
５図の如く、そのレリーフ３の透明基板２とは反
対側に更に透明板４を貼り合わせる。透明板４の
貼り合わせにより、機械的強度を一層増すことが
できる。透明板４としては先に示した透明基板２
として使用される諸材料を使用することができ
る。レリーフ３と透明板４と貼り合わせるための
接着剤としては、ニトリルゴム系，ポリエステル
系，シアノアクリレート系，エポキシ系，酢ビ共
重合系，合成ゴム系，アクリル系，クロロプレン
系，ウレタン系，シラン化合物が挙げれる。 By using the photosensitive resin composition described above, and performing the lamination of at least three layers of the transparent image carrier 1, the photosensitive resin composition layer, and the transparent substrate 2, exposure curing, development, and coloring treatment as described above. , an external light antireflection plate for a display device whose exposed portion is colored is obtained. The external light reflection prevention plate for a display device obtained by this method has a linear portion 3 of a relief 3 as shown in FIG.
b' occupies the pattern part, and the other part is the surface part 3a
On the other hand, as shown in FIG. 4, there are some in which the surface part 3a of the relief 3 occupies the pattern part, and the other parts are linear parts 3b'. The linear portion 3b' can take various forms such as horizontal stripes as shown in FIG. 3, horizontal stripes as shown in FIG. 4, vertical stripes as shown in FIG. 6, and lattice as shown in FIG. As shown in FIG. 5, a transparent plate 4 is further bonded to the external light reflection prevention plate for a display device thus obtained on the opposite side of the relief 3 from the transparent substrate 2. By bonding the transparent plates 4 together, the mechanical strength can be further increased. As the transparent plate 4, the transparent substrate 2 shown earlier is used.
Materials used as such can be used. Adhesives for bonding the relief 3 and the transparent plate 4 include nitrile rubber, polyester, cyanoacrylate, epoxy, vinyl acetate copolymer, synthetic rubber, acrylic, chloroprene, urethane, and silane. Examples include compounds.
これらは、使用するレリーフの材質、透明板４
の種類によつて適宜、選択して使用される。これ
らのうち、ウレタン系，ポリエステル系，エポキ
シ系の接着剤が好ましく、特に透明板４としてポ
リエチレンテレフタレートフイルム（PET）を
用いた場合は、ウレタン系接着剤が好ましい。貼
り合わせる方法としては、厚さ0.05〜５mmの透明
板４に接着剤を平滑に塗布、又はレリーフ３表面
に接着剤を塗布し、レリーフ３表面と接着剤層と
が接するようにしてラミネーターで熱圧着する方
法が挙げられる。 These are the material of the relief used, the transparent plate 4
It is selected and used as appropriate depending on the type. Among these, urethane-based adhesives, polyester-based adhesives, and epoxy-based adhesives are preferred, and particularly when polyethylene terephthalate film (PET) is used as the transparent plate 4, urethane-based adhesives are preferred. The method of bonding is to apply the adhesive smoothly to the transparent plate 4 with a thickness of 0.05 to 5 mm, or to apply the adhesive to the surface of the relief 3, and heat it with a laminator so that the surface of the relief 3 and the adhesive layer are in contact with each other. An example is a method of crimping.
以上、本発明に係る図柄を有する表示装置用外
光反射防止板の製造方法は、透明部と透明な縞又
は格子模様を有する不透明部とから巧みに図柄を
構成した透明画像担体と感光性樹脂とを使用する
ことにより、透明基板を加えて少なくともこれら
を３層に形成する積層と、露光と、現像と、着色
処理と、透明板の貼り合わせという非常に簡単な
操作により本発明に係る透明板、感光性樹脂組成
物によつて形成された図柄を表わすレリーフ層及
び透明板がこの順に積層されており、該図柄が不
透明部と不透明な縞又は格子模様を有する透明部
とにより構成されている図柄を有する表示装置用
外光反射防止板を製造することができる。 As described above, the method for manufacturing an external light antireflection plate for a display device having a pattern according to the present invention includes a transparent image carrier having a pattern skillfully constructed from a transparent part and an opaque part having a transparent stripe or checkered pattern, and a photosensitive resin. By using a transparent substrate, the transparent substrate according to the present invention can be produced by a very simple operation of adding a transparent substrate to form at least three layers, exposing, developing, coloring, and bonding the transparent plates. A plate, a relief layer representing a pattern formed from a photosensitive resin composition, and a transparent plate are laminated in this order, and the pattern is composed of an opaque part and a transparent part having opaque stripes or a checkered pattern. It is possible to manufacture an external light reflection prevention plate for a display device having a pattern similar to the above.
そして得られる図柄を有する表示装置用外光反
射防止板は、着色されたレリーフ部において、斜
めからの入射光に対して、入射光側の透明基板を
透過した光を直接に及び／又は反対側の透明基板
に達したところからの反射光を遮光することによ
り外光反射防止能を有しており、一方内部表示管
からの斜めの光は着色されたレリーフ部において
遮光されるため、外光反射防止板を透過する光の
広がりは、リレーフの高さと間隔隔により定まる
可視角の範囲内に制御される。 The external light antireflection plate for a display device having the obtained pattern can be used to directly transmit light that has passed through the transparent substrate on the incident light side and/or to the opposite side in the case of obliquely incident light in the colored relief part. It has the ability to prevent external light reflection by blocking the reflected light that reaches the transparent substrate of the display tube, while the diagonal light from the internal display tube is blocked by the colored relief part, so external light is prevented. The spread of light passing through the anti-reflection plate is controlled within the visible angle range determined by the height and spacing of the reliefs.
（可視角θ＝2tan-1W2／Ｈ）
また、レリーフ自体が図柄を構成していてレリ
ーフには幅の広い面部を有し且つ両面を透明基板
と透明板により保護されていることにより、機械
的強度は非常に高い。従つて信号機，図柄を有す
るデイスプレイなどの他、表示灯付きの押しボタ
ン式スイツチなどの如き機械的強度を必要とする
使用にも充分に耐えることができる。 (Visible angle θ = 2tan -1 W 2 /H) In addition, the relief itself constitutes a pattern, and the relief has a wide surface and is protected on both sides by a transparent substrate and a transparent plate. Mechanical strength is very high. Therefore, it can sufficiently withstand uses that require mechanical strength, such as traffic lights, displays with patterns, and push-button switches with indicator lights.
以下、実施例により本発明方法を更に説明す
る。 The method of the present invention will be further explained below with reference to Examples.
実施例 １
プロピレングリコール，ジエチレングリコー
ル，アジピン酸，フマル酸，イソフタル酸をモル
比0.12／0.38／0.24／0.14／0.12の割合で縮合させ
て得た不飽和ポリエステル樹脂（酸価30）100部
に、ジエチレングリコールジメタクリレート12
部、テトラエチレングリコールジメタクリレート
30部、２―ヒドロキシエチルメタクリレート12
部、ジアセトンアクリルアミド６部、ベンゾイン
イソブチルエーテル２部、４―ターシヤリーブチ
ルカテコール0.03部を加え感光性樹脂組成物を
得、更に、この組成物に微粉末シリカ５部を加え
てつや消し剤含有感光性樹脂組成物を製造した。
次いで透明なガラス板上に、第１図の如き透明な
幅100μの縞200μ間隔で有する不透明部で図柄そ
のものを構成し、その他は透明部である透明画像
担体と、厚さ20μのポリプロピレンフイルムをこ
の順に重ね合わせた上に上記つや消し剤含有感光
性樹脂組成物を注ぎ、この組成物上に接着剤〔ア
ドコートAD―335A＋硬化剤ADFJ（東洋モート
ン社製）〕を平滑に塗布したPETフイルムを該樹
脂組成物と接触するように覆つた。Example 1 Diethylene glycol was added to 100 parts of an unsaturated polyester resin (acid value 30) obtained by condensing propylene glycol, diethylene glycol, adipic acid, fumaric acid, and isophthalic acid at a molar ratio of 0.12/0.38/0.24/0.14/0.12. Dimethacrylate 12
Part, tetraethylene glycol dimethacrylate
30 parts, 2-hydroxyethyl methacrylate 12
1 part, 6 parts of diacetone acrylamide, 2 parts of benzoin isobutyl ether, and 0.03 parts of 4-tert-butylcatechol were added to obtain a photosensitive resin composition, and further, 5 parts of finely powdered silica was added to this composition to obtain a photosensitive resin composition containing a matting agent. A synthetic resin composition was produced.
Next, on a transparent glass plate, as shown in Fig. 1, the pattern itself is composed of opaque areas having transparent stripes of 100 µm in width at 200 µm intervals, and the other parts are transparent image carriers and a polypropylene film with a thickness of 20 µm. The above photosensitive resin composition containing a matting agent is poured onto the layers stacked in this order, and a PET film on which an adhesive [Adcoat AD-335A + hardener ADFJ (manufactured by Toyo Morton Co., Ltd.)] is smoothly coated is placed on top of the photosensitive resin composition. It was covered so as to be in contact with the resin composition.
この際、樹脂層の厚みが200μになるようにス
ペーサーで調整した。このように組立てられた組
立体の透明画像担体側より、3KWの超高圧水銀
灯により透明画像担体側を通じて80秒間露光して
縞模様に光硬化させた。露光終了後、透明画像担
体及びポリプロピレンフイルムを取り除いた後、
液温40〜45℃の弱アルカリ溶液をスプレー方式に
より吹き付けて非露出部の樹脂組成物の除去を行
つた。この非露光除去後の版を水洗した後、後露
光（照射光量1000mJ／cm2）及び乾燥（50℃，10
分）を行い、次いで70〜80℃に加温した0.5重量
％の分散染料〔Lanyl Black BG（住友化学(株)
製）〕を含んだ湯浴中に10分間浸漬して染色をし、
更に水洗及び乾燥（50℃，10分）を行つた。これ
に接着剤〔アドコートAD―335A＋硬化剤ADFJ
（東洋モートン社製）〕を平滑に塗布したPETフ
イルムをレリーフ表面と接着剤層が接するように
してラミネータで熱圧着して、第３図の如き図柄
そのものを構成する線状部とその他の面部とから
成るレリーフの両面にPETフイルムを設けられ
た図柄を有する表示装置用外光反射防止板を製造
した。このものは充分な光遮光効果と機械的強度
を有するものであつた。 At this time, the thickness of the resin layer was adjusted to 200 μm using a spacer. The transparent image carrier side of the thus assembled assembly was exposed to light for 80 seconds using a 3 KW ultra-high pressure mercury lamp through the transparent image carrier side to form a striped pattern. After exposure, after removing the transparent image carrier and polypropylene film,
The resin composition in non-exposed areas was removed by spraying a weak alkaline solution at a liquid temperature of 40 to 45°C. After washing the unexposed plate with water, post-exposure (irradiation amount: 1000 mJ/cm 2 ) and drying (50℃, 10
0.5% by weight of disperse dye [Lanyl Black BG (Sumitomo Chemical Co., Ltd.)] was heated to 70-80°C.
dyed by soaking it in a hot water bath containing
Furthermore, it was washed with water and dried (50°C, 10 minutes). Add adhesive [Adcoat AD-335A + hardening agent ADFJ]
(manufactured by Toyo Morton Co., Ltd.)] is heat-pressed using a laminator so that the relief surface and the adhesive layer are in contact with each other, and the linear parts and other surface parts that make up the design itself are formed as shown in Figure 3. An external light antireflection plate for a display device was manufactured, which has a pattern consisting of a relief and PET films on both sides. This material had sufficient light shielding effect and mechanical strength.
第１図及び第２図はそれぞれ本発明方法で使用
する透明画像担体の例を示す図、第３図及び第４
図はそれぞれ第１図及び第２図の透明画像担体を
使用して製造した図柄を有する表示装置用外光反
射防止板の正面図、第５図は第３図中のＡ―Ａ線
断面図、第６図及び第７図はそれぞれ図柄を有す
る表示装置用外光反射防止板の他の例を示す正面
図である。
１……透明画像担体、１ａ……透明部、１ｂ…
…不透明部、１b′……不透明部中の透明な縞又は
格子模様、２……透明基板、３……レリーフ、３
ａ……面部、３b′……線状部、４……透明板、
w1……透明画像担体の透明な縞の幅、w2……透
明画像担体の透明な縞と縞との間隔、W1……レ
リーフの線状部の縞の幅、W2……レリーフの線
状部の縞と縞との間隔。
1 and 2 are diagrams showing examples of transparent image carriers used in the method of the present invention, and FIGS. 3 and 4 respectively.
The figures are a front view of an external light reflection prevention plate for a display device having a pattern manufactured using the transparent image carriers shown in FIGS. 1 and 2, respectively, and FIG. 5 is a cross-sectional view taken along the line AA in FIG. 3. , FIG. 6, and FIG. 7 are front views showing other examples of external light reflection prevention plates for display devices each having a pattern. 1...Transparent image carrier, 1a...Transparent part, 1b...
...opaque area, 1b'...transparent stripes or checkered pattern in the opaque area, 2...transparent substrate, 3...relief, 3
a... Surface part, 3b'... Linear part, 4... Transparent plate,
w 1 ... Width of the transparent stripes on the transparent image carrier, w 2 ... Distance between the transparent stripes on the transparent image carrier, W 1 ... Width of the stripes in the linear part of the relief, W 2 ... Relief The distance between stripes in the linear part of .
Claims (1)
た図柄を表わすレリーフ層及び透明板がこの順に
積層されており、該図柄が不透明部と不透明な縞
又は格子模様を有する透明部とにより構成されて
いることを特徴とする図柄を有する表示装置用外
光反射防止板。 ２ 透明部と透明な縞又は格子模様を有する不透
明部とにより図柄が表わされている透明画像担体
と感光性樹脂組成物層と透明基板との少なくとも
３層をこの順に積層し、該透明画像担体を通して
活性光線を照射することにより該感光性樹脂組成
物を露光し、次いで該透明画像担体と該感光性樹
脂組成物の非露光部分とを除去する工程を経て得
られる着色されたレリーフ部の上面に透明板を貼
り合わせることを特徴とする図柄を有する表示装
置用外光反射防止板の製造方法。[Scope of Claims] 1. A transparent plate, a relief layer representing a pattern formed from a photosensitive resin composition, and a transparent plate are laminated in this order, and the pattern has an opaque part and an opaque striped or checkered pattern. 1. An external light reflection prevention plate for a display device having a pattern, comprising a transparent part having a pattern. 2 At least three layers of a transparent image carrier having a pattern represented by a transparent part and an opaque part having transparent stripes or a checkered pattern, a photosensitive resin composition layer, and a transparent substrate are laminated in this order, and the transparent image The colored relief portion obtained through the steps of exposing the photosensitive resin composition by irradiating actinic light through the carrier, and then removing the transparent image carrier and the unexposed portion of the photosensitive resin composition. A method for manufacturing an external light antireflection plate for a display device having a pattern characterized by laminating a transparent plate on the top surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8104884A JPH0227674B2 (en) | 1984-04-24 | 1984-04-24 | ZUGARAOJUSURUHYOJISOCHOGAIKOHANSHABOSHIBANOYOBISONOSEIZOHOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8104884A JPH0227674B2 (en) | 1984-04-24 | 1984-04-24 | ZUGARAOJUSURUHYOJISOCHOGAIKOHANSHABOSHIBANOYOBISONOSEIZOHOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60125880A JPS60125880A (en) | 1985-07-05 |
| JPH0227674B2 true JPH0227674B2 (en) | 1990-06-19 |
Family
ID=13735530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8104884A Expired - Lifetime JPH0227674B2 (en) | 1984-04-24 | 1984-04-24 | ZUGARAOJUSURUHYOJISOCHOGAIKOHANSHABOSHIBANOYOBISONOSEIZOHOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0227674B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4877308A (en) | 1987-06-24 | 1989-10-31 | Asahi Kasei Kogyo Kabushiki Kaisha | Light shielding screen structure and a process for producing the same |
| JPH026987A (en) * | 1988-03-08 | 1990-01-11 | Fuji Electric Co Ltd | Front part decoration mechanism for electric equipment |
| JP4907958B2 (en) * | 2005-11-17 | 2012-04-04 | 信越ポリマー株式会社 | Peeping prevention body for display screen and manufacturing method thereof |
-
1984
- 1984-04-24 JP JP8104884A patent/JPH0227674B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60125880A (en) | 1985-07-05 |
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