WO2012060471A1 - Method for treating photosensitive silver halide material for hologram, and bleached phase hologram obtained using this treatment method - Google Patents
Method for treating photosensitive silver halide material for hologram, and bleached phase hologram obtained using this treatment method Download PDFInfo
- Publication number
- WO2012060471A1 WO2012060471A1 PCT/JP2011/076015 JP2011076015W WO2012060471A1 WO 2012060471 A1 WO2012060471 A1 WO 2012060471A1 JP 2011076015 W JP2011076015 W JP 2011076015W WO 2012060471 A1 WO2012060471 A1 WO 2012060471A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silver halide
- hologram
- bleaching
- wavelength
- treatment
- Prior art date
Links
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 117
- 239000004332 silver Substances 0.000 title claims abstract description 117
- -1 silver halide Chemical class 0.000 title claims abstract description 112
- 239000000463 material Substances 0.000 title claims abstract description 65
- 238000011282 treatment Methods 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000004061 bleaching Methods 0.000 claims abstract description 66
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 62
- 239000000839 emulsion Substances 0.000 claims abstract description 42
- 230000006641 stabilisation Effects 0.000 claims abstract description 21
- 238000011105 stabilization Methods 0.000 claims abstract description 21
- 238000002835 absorbance Methods 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000005540 biological transmission Effects 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 21
- 238000003672 processing method Methods 0.000 claims description 15
- 238000011161 development Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000000862 absorption spectrum Methods 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 238000005259 measurement Methods 0.000 claims description 5
- 230000007774 longterm Effects 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- 238000004847 absorption spectroscopy Methods 0.000 abstract 1
- 238000002235 transmission spectroscopy Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000975 dye Substances 0.000 description 14
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 14
- 108010010803 Gelatin Proteins 0.000 description 13
- 229920000159 gelatin Polymers 0.000 description 13
- 235000019322 gelatine Nutrition 0.000 description 13
- 235000011852 gelatine desserts Nutrition 0.000 description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000008273 gelatin Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- MKWYFZFMAMBPQK-UHFFFAOYSA-J sodium feredetate Chemical compound [Na+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O MKWYFZFMAMBPQK-UHFFFAOYSA-J 0.000 description 9
- 230000001235 sensitizing effect Effects 0.000 description 8
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 7
- 229910021612 Silver iodide Inorganic materials 0.000 description 7
- 229940045105 silver iodide Drugs 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 239000004848 polyfunctional curative Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000004373 Pullulan Substances 0.000 description 3
- 229920001218 Pullulan Polymers 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 230000002335 preservative effect Effects 0.000 description 3
- 235000019423 pullulan Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004153 Potassium bromate Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 2
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 2
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229940094037 potassium bromate Drugs 0.000 description 2
- 235000019396 potassium bromate Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- 229940116357 potassium thiocyanate Drugs 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- 150000003585 thioureas Chemical class 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 229920002085 Dialdehyde starch Polymers 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 1
- 235000019687 Lamb Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- UIZLQMLDSWKZGC-UHFFFAOYSA-N cadmium helium Chemical compound [He].[Cd] UIZLQMLDSWKZGC-UHFFFAOYSA-N 0.000 description 1
- 235000019981 calcium hexametaphosphate Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- CPBQJMYROZQQJC-UHFFFAOYSA-N helium neon Chemical compound [He].[Ne] CPBQJMYROZQQJC-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002545 isoxazoles Chemical class 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 229940062627 tribasic potassium phosphate Drugs 0.000 description 1
- 229940001496 tribasic sodium phosphate Drugs 0.000 description 1
- KRSIWAJXDVVKLZ-UHFFFAOYSA-H tricalcium;2,4,6,8,10,12-hexaoxido-1,3,5,7,9,11-hexaoxa-2$l^{5},4$l^{5},6$l^{5},8$l^{5},10$l^{5},12$l^{5}-hexaphosphacyclododecane 2,4,6,8,10,12-hexaoxide Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])(=O)O1 KRSIWAJXDVVKLZ-UHFFFAOYSA-H 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/40—Chemically transforming developed images
- G03C5/44—Bleaching; Bleach-fixing
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/04—Processes or apparatus for producing holograms
- G03H1/18—Particular processing of hologram record carriers, e.g. for obtaining blazed holograms
- G03H1/182—Post-exposure processing, e.g. latensification
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H2240/00—Hologram nature or properties
- G03H2240/10—Physical parameter modulated by the hologram
- G03H2240/11—Phase only modulation
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H2260/00—Recording materials or recording processes
- G03H2260/16—Silver halide emulsion
Definitions
- the present invention relates to a method for processing a silver halide photosensitive material for holograms, and to a bleached phase hologram which is excellent in light resistance obtained by the processing method and can obtain a high diffraction efficiency even after long-term storage.
- Silver halide photosensitive materials have the characteristics of high sensitivity and high resolution, and in recent years, researches on the use of silver halide emulsions as high-resolution recording photosensitive materials such as holograms have been conducted.
- photosensitive materials such as a dichromated gelatin photosensitive material, a photopolymer photosensitive material, and a thermoplastic photosensitive material are known as photosensitive materials used for hologram production. Since silver halide photosensitive materials have higher sensitivity and resolution than other photosensitive materials, they are used in various fields of display, medical, and anti-counterfeit printing (supervised by Junpei Uchiuchi, “Holographic Materials / Application Handbook ”, NTS Corporation, June 2007, first edition issued).
- a method for producing a hologram using a silver halide photosensitive material a method is known in which a laser light source is used to expose interference light between an object beam and a reference beam, and an amplitude hologram of developed silver is produced by development processing. . Furthermore, this amplitude hologram is used as a bleaching phase hologram by returning the silver developed by the bleaching process to silver halide again. With these treatments, a high diffraction efficiency and a bright hologram can be obtained. However, since the developed silver is returned to silver halide by the bleaching process, the stability of the produced hologram is likely to be deteriorated by light, the light resistance is deteriorated, and the diffraction efficiency is lowered. was there.
- JP-A-51-25135, JP-A-62-2279, and JP-A-10-149083 include silver chloride and odor. It has been proposed to convert photosensitive silver halides such as silver halide into silver iodide having high photostability. Although light stabilization processing by conversion to silver iodide is considered to be an excellent processing method in terms of work, a conventionally proposed processing method cannot produce a bleaching phase hologram having sufficient light resistance. In order to stably produce a bleaching phase hologram having a high diffraction efficiency even after long-term storage, further improvements are necessary.
- an object of the present invention is to provide a method for processing a silver halide photosensitive material for producing a bleached phase hologram that is excellent in light resistance and obtains high diffraction efficiency even after being stored for a long period of time, and its processing It is to provide a bleach phase hologram obtained by the method.
- a development processing step ethylenediaminetetraacetic acid (hereinafter sometimes referred to as “EDTA”) or After sequentially performing a bleaching treatment step using the salt as a bleaching treatment material, and performing a stabilization treatment step using an aqueous potassium iodide solution, the absorbance at a wavelength of 420 nm and the absorbance at a wavelength of 470 nm in a transmission absorption spectrum measurement
- EDTA ethylenediaminetetraacetic acid
- a bleaching phase hologram obtained by using the processing method described in 1 or 2 above.
- the silver halide photosensitive material for holograms used for the processing method of said 1 which has the photosensitive silver halide emulsion layer containing the silver halide grain whose average particle diameter is the range of 10-60 nm.
- a bleaching phase hologram having excellent light resistance and high diffraction efficiency even when stored for a long time can be produced.
- a stabilization processing method that can be immersed in an aqueous potassium iodide solution has been established. It can be used very advantageously in the production of bleached phase holograms.
- FIG. 1 is a particle size distribution diagram of a silver halide emulsion according to the present invention.
- FIG. 2 is a schematic view of a hologram recording apparatus according to the present invention.
- FIG. 3 is a schematic diagram of a fringe phase hologram interference fringe recording method and diffraction efficiency measurement method according to the present invention.
- FIG. 4 is a graph showing the results of a light resistance test of the bleaching phase hologram according to the present invention.
- FIG. 5 is a transmission absorption spectrum diagram of the bleaching phase hologram according to the present invention.
- FIG. 6 is a graph showing the effect of the rebleaching treatment on the diffraction efficiency after light degradation of the bleached phase hologram not subjected to the stabilization treatment according to the present invention.
- the present invention relates to a method for processing a silver halide photosensitive material for holograms and a bleached phase type hologram produced by the processing method.
- the silver halide photosensitive material for holograms comprises object light and reference light.
- the silver halide light-sensitive material can record at least one interference fringe, and has at least one silver halide emulsion layer on the support.
- a silver halide photosensitive material for hologram is usually a silver halide emulsion coated on a support, and is chemically sensitized or spectrally sensitized so as to be sensitive to the oscillation wavelength of laser light used for exposure recording. The ones with the are usually used.
- the support examples include a glass plate, an acrylic plate, a polyethylene terephthalate film, a polyethylene naphthalate film, a polystyrene film and a triacetyl cellulose film, which are usually used for silver halide photosensitive materials for holograms.
- a glass plate having no directionality, a polyethylene terephthalate film, or a polyethylene naphthalate film is preferred.
- the thickness of a support body can be suitably selected by a use and a usage method.
- the coated silver amount of the silver halide emulsion layer formed on the support is preferably in the range of 1 to 10 g / m 2 , and the amount of the dispersion medium such as gelatin to be coated is in the range of 1 to 10 g / m 2 . Is preferred.
- the silver / dispersion medium coating amount ratio is usually preferably in the range of 0.1 to 2.0.
- the coating thickness is usually preferably in the range of 3 to 12 ⁇ m.
- the silver halide grains contained in the silver halide emulsion layer can be prepared by a known production method. For example, a silver nitrate aqueous solution and a water-soluble halide aqueous solution in a gelatin aqueous solution in a single jet method, a double jet method, or a control double method. It can be mixed and manufactured using a jet method or the like. Among these, silver halides produced by the control double jet method are particularly preferable for controlling the grain size of silver halide.
- the outer shape of the silver halide grains contained in the silver halide emulsion according to the present invention is preferably a normal crystal, a cube, an octahedron, a rhomboid dodecahedron, a tetrahedron, and a rounded shape thereof.
- the average particle diameter is preferably 10 to 60 nm, and the emulsion containing silver halide grains having an average particle diameter of 30 to 50 nm is particularly preferable for producing the bleaching phase hologram having high diffraction efficiency of the present invention. .
- a silver halide emulsion mainly composed of grains having a particle size in the range of 40 to 45 nm produces a bleaching phase hologram that maintains the high diffraction efficiency of the present invention. This is true.
- the average grain size is smaller than 10 nm, the variation in the grain size of the silver halide grains in the silver halide emulsion is increased, which causes destabilization of the silver halide emulsion, and when the average grain size is larger than 60 nm. In some cases, the desired characteristics cannot be obtained due to light scattering by the particles.
- the average particle diameter of the silver halide grains means the diameter of the grains when the grains are spherical or approximate to a sphere, and when the grains are cubic, the diameter converted to a sphere can be obtained as the diameter.
- the Theory of the Photographic Process (The Theory of the World)” by CEK Mees & T. H. James. the photographic process), 3rd edition, pages 36 to 43, 1966, and can be obtained using a transmission electron microscope.
- the silver halide grains may be any of silver chloride, silver iodide, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like. Particularly preferred silver halide grains include silver bromide, silver iodobromide, silver chloroiodobromide, and silver chlorobromide.
- the silver halide emulsion can be spectrally sensitized with a sensitizing dye so as to match the oscillation wavelength of laser light used for exposure recording.
- a sensitizing dye examples include the cyanine dye, merocyanine dye, hemicyanine described in Masaaki Hayami, “Sensitive Dye—Mysterious Action and Various Functions”, published on October 17, 1997, pages 12 to 31. And dyes, styryl dyes and hemioxonol dyes. These sensitizing dyes may be used alone or in combination.
- the sensitizing dye is preferably dispersed and contained in the silver halide emulsion.
- the sensitizing dye can be added to the silver halide emulsion by a known addition method, for example, dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, water, acetone, pyridine or a mixed solvent thereof. Thereafter, a method of adding to a silver halide emulsion is mentioned. The timing of addition may be either during the preparation of the silver halide emulsion or after the preparation.
- the addition amount to the silver halide emulsion is preferably such that the sensitizing dye is contained in an amount of 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 ⁇ 2 mol per mol of silver in the silver halide grains.
- a dye that does not exhibit spectral sensitizing action itself may be added simultaneously or individually as a supersensitizing dye.
- the silver halide emulsion in the present invention can be chemically sensitized, and is added by adding a chemical sensitizer to the halogenated emulsion using a known method.
- the chemical sensitizer include sulfur sensitizers such as potassium thiocyanate, ammonium thiosulfate, sodium thiosulfate, hypo, thiourea compounds, tin (II) chloride, ascorbic acid and its derivatives, hydrazine derivatives, formamidine.
- sulfur sensitizers such as potassium thiocyanate, ammonium thiosulfate, sodium thiosulfate, hypo, thiourea compounds, tin (II) chloride, ascorbic acid and its derivatives, hydrazine derivatives, formamidine.
- reduction sensitizers such as sulfinic acid, silane compounds, and dimethylamine borane
- gold sensitizers such as chloroaurate.
- gelatin As a dispersion medium for protective colloid of silver halide grains, gelatin is preferably used.
- gelatin include acid-treated ones, alkali-treated ones, low-molecular gelatins having a low molecular fraction, and chemically-treated gelatins such as phthalated gelatin.
- pullulan derivatives such as acetylated pullulan and bi-charged pullulan
- hydrophilic properties such as albumin, casein, hydroxycellulose, carboxymethylcellulose, sodium alginate, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid and polyacrylamide
- the polymer can be used in combination with gelatin as a hydrophilic colloid or can be used alone.
- the silver halide photosensitive material for hologram used in the present invention includes chromium salts, aldehydes, N-methylol compounds, dioxane derivatives, active vinyl compounds, active halogen compounds, mucosates as hardeners on the silver halide emulsion layers.
- Use hardeners such as halogen acids, isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, carboxyl group-activated hardener alone or in combination of two or more. Can do.
- the silver halide emulsion layer of the silver halide light-sensitive material for hologram used in the present invention includes, in addition, Research Disclosure 17643 (issued in December 1978), Research Disclosure 18716 (December 1989), Research Disclosure 308119. (December 1989) can be used in the industry known additives and the like.
- silver halide photosensitive material for hologram used in the present invention
- a commercially available silver halide photosensitive material for hologram can also be used.
- Commercially available silver halide photosensitive materials for holograms include a silver halide photosensitive material for holograms manufactured by Konica Minolta Opto (trade name “P5600”), and a silver halide photosensitive material for holograms manufactured by Slavich ( Product names “PFG-01”, “PFG-03M”, “PFG-03C”), silver halide photosensitive materials for holograms manufactured by Colorholographics (trade names “BB640”, “BB520”, “BBVPan”) ]).
- an aqueous potassium iodide solution was used after exposure, a development processing step, a bleaching processing step using ethylenediaminetetraacetic acid or a salt thereof as a bleaching processing material. It is preferable to carry out a stabilization treatment step, followed by washing and drying treatment steps.
- Suitable laser beams include an Nd-YAG laser with a wavelength of 532 nm, an argon laser with a wavelength of 514.5 nm or 488 nm, a krypton ion laser with a wavelength of 647.1 nm, a helium-neon laser with a wavelength of 632.8 nm, a wavelength of 441.6 nm or 325 nm. Helium-cadmium laser and various semiconductor lasers.
- the developer used for the development processing is a processing solution mainly containing a developing agent that reduces silver ions
- the developing agent includes hydroquinone, p-aminophenol, N-methyl-p-aminophenol, P-aminophenols such as 2,4-diaminophenol, p-phenylenediamines, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazoline, 5,5-dimethyl Reducing agents such as 3-pyrazolidones such as -1-phenyl-3-pyrazolidone, catechol, phenidone, pyrogallol, ascorbic acid, and metol can be used.
- a preservative can be used in the developing solution.
- the preservative include sulfites such as sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite, metabisulfite, piperidinohexose concentrate. Reductons such as ductons can be mentioned.
- an alkali agent can be used in the developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic potassium phosphate, tribasic sodium phosphate, borate, acetoxime, 5- Examples include sulfosalicylic acid, phosphate, and carbonate.
- dissolution aids such as polyethylene glycol, sensitizers such as quaternary ammonium salts, silver sludge inhibitors such as sulfides, disulfide compounds and triazine compounds, antifoggants such as sodium bromide, potassium bromide and potassium iodide
- a chelating agent such as sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate, a development accelerator, a surfactant, a foam saving agent, a hardener, and the like can be appropriately added as necessary.
- the pH of the developer is adjusted to 8.0 to 12.0, and more preferably 9.0 to 11.5. Further, the temperature during the development processing is also important, and the processing is usually performed in the range of 10 to 45 ° C. More preferably, the immersion treatment is performed in the developer at a constant temperature in the range of 20 to 30 ° C.
- the development processing time is approximately 20 seconds to 4 minutes.
- an acidic solution that uses an acidic solution to shift the developer to the acidic side is used.
- it is treated with an acetic acid aqueous solution.
- an aqueous acetic acid solution is used, an aqueous solution having a concentration in the range of 0.5 to 5% by mass is used.
- the processing temperature in the stop processing is usually in the range of 10 to 45 ° C. as in the development processing. More preferably, the treatment is performed at a constant temperature in the range of 20 to 30 ° C.
- the bleaching solution after the development processing uses ethylenediaminetetraacetic acid or a salt thereof as a bleaching processing material.
- the salt of ethylenediaminetetraacetic acid include sodium ethylenediaminetetraacetate, ethylenediaminetetraacetic acid-iron (III) sodium, and the like.
- other bleaching treatment materials used for the bleaching treatment for example, sodium dichromate, parabenzoquinone, ferric nitrate and the like can be used.
- the bleaching solution appropriately contains a bleach accelerator such as a halogen compound, a thiourea derivative, and a thioether, a preservative, a pH buffer, a pH adjuster, and a chelating agent. be able to.
- the pH of the bleaching solution is 2.0 to 6.0, preferably 2.5 to 5.5.
- the bleaching treatment temperature is preferably in the range of 10 to 45 ° C., and the immersion treatment is preferably performed in the bleaching treatment solution, and more preferably the treatment temperature is in the range of 20 to 30 ° C. at a constant temperature.
- the processing time is approximately 20 seconds to 4 minutes.
- the treatment method of the present invention performs a stabilization treatment using an aqueous potassium iodide solution.
- a stabilization treatment of immersing in an aqueous potassium iodide solution is performed.
- the concentration of the aqueous potassium iodide solution is as follows: the thickness of the silver halide emulsion layer formed on the support of the silver halide photosensitive material for hologram used, the amount of silver contained in the silver halide emulsion, It is necessary to appropriately adjust the concentration of the stabilizing treatment solution, the treatment temperature, and the treatment time depending on the ratio of gelatin and the type of silver halide grains. For example, as shown in FIG.
- the condition that the absorbance at a wavelength of 420 nm corresponding to the absorption wavelength of silver iodide is 2 or more than the absorbance at a wavelength of 470 nm.
- the concentration is preferably 1.5 to 10% by mass, and the concentration range of 5 to 10% by mass is particularly preferable.
- the treatment time for immersing in the potassium iodide aqueous solution is in the range of 2 to 10 minutes, and the treatment temperature is usually in the range of 10 to 45 ° C. More preferably, the treatment is performed at a constant temperature within a treatment temperature range of 20 to 30 ° C.
- Stabilization treatment may not be able to obtain light resistance if the conditions are insufficient, and if the treatment is carried out excessively, interference fringes will be lost and diffraction efficiency will be reduced, resulting in a desirable bleached phase hologram. Disappear.
- the bleaching phase hologram produced by the above appropriate processing method has a difference between the absorbance at the wavelength of 420 nm and the absorbance at the wavelength of 470 nm of at least 2 and more preferably 2.5 or more when the transmission absorption spectrum is measured as described above. It becomes a bleaching phase hologram with a difference, and although it has a slightly yellowish color, a bright bleaching phase hologram that does not substantially absorb in the visible region having a wavelength of 450 nm or more can be produced.
- FIG. 2 shows a schematic diagram of an apparatus for exposure recording on the above-mentioned hologram silver halide photosensitive material
- FIG. 3 shows a recording method of a silver halide photosensitive material in which a silver halide emulsion is coated on a glass plate.
- the silver halide photosensitive material for hologram coated with the silver halide emulsion is placed at the position of the dry plate holder H 1 in FIG.
- the silver halide photosensitive material for hologram in which a silver halide emulsion is coated on a glass plate has a silver halide emulsion layer on the side on which recording light is incident.
- the laser beam of an Nd-YAG laser having a wavelength of 532 nm was divided into two light beams and incident at an intersecting angle of 32 °, and recording was performed with 1000 interference fringes / mm.
- Bleaching treatment was performed by immersing in a bleaching treatment solution prepared as an aqueous solution. After washing with water, 5 g of potassium iodide was dissolved in pure water and subjected to a stabilization treatment of immersing in an aqueous solution of 5% potassium iodide having a concentration of 100 ml for 10 minutes, followed by washing with water and drying to produce a bleached phase hologram.
- the absorbance at a wavelength of 420 nm and the absorbance at a wavelength of 470 nm there is a difference between the absorbance at a wavelength of 420 nm and the absorbance at a wavelength of 470 nm, that is, the absorbance at 420 nm of the absorption wavelength of silver iodide is at a wavelength of 470 nm.
- the bleaching phase hologram of the present invention is extremely useful for a bleaching phase hologram that may be slightly yellowish and does not stick to color. Further, the bleaching phase hologram having excellent light resistance according to the present invention can be used as a hologram recording original plate to be exposed and transferred to other recording materials.
- a bleaching phase hologram (Comparative Example 1: EDTA bleaching prescription) that is not subjected to a stabilization treatment with an aqueous potassium iodide solution after a bleaching treatment using ethylenediaminetetraacetic acid-sodium iron (III) as a bleaching treatment material;
- the processing methods EDTA bleaching + KI (potassium iodide) stabilization processing
- the bleaching processing materials are changed and the conventionally proposed bleaching shown below.
- Bleached phase holograms (Comparative Examples 2 to 5) treated with a treating agent were similarly evaluated.
- Comparative Example 1 EDTA bleaching formulation Ethylenediaminetetraacetic acid-iron (III) sodium 15 g Sodium hydrogen nitrate 15g Potassium bromide 15g Make up to 500 mL with pure water.
- Comparative Example 5 EDTA (KI) bleaching formulation Ethylenediaminetetraacetic acid-iron (III) sodium 15 g Sodium hydrogen sulfate 15g Potassium iodide 21.5g Make up to 500 ml with pure water.
- the bleaching phase holograms of the comparative examples all have a diffraction efficiency of less than 55% immediately after production (see Table 1), which is inferior to the bleaching phase hologram of the present invention that has been subjected to stabilization treatment. As shown, the diffraction efficiency after 300 hours when the light resistance test was performed was not sufficient.
- the thickness of the silver halide emulsion layer formed on the support of the silver halide photosensitive material for hologram used used, the amount of silver contained in the halide emulsion, the ratio of silver / dispersion medium, and silver halide grains
- the treatment conditions may be considered as appropriate, but a stabilization treatment with an aqueous potassium iodide solution is performed as a series of treatments following the bleaching treatment step using ethylenediaminetetraacetic acid-sodium iron (III) as a bleaching treatment material.
- the bleached phase hologram produced is a bleached phase hologram with excellent light resistance and high diffraction efficiency. It was confirmed to be a lamb.
- a bleaching phase hologram having excellent light resistance and high diffraction efficiency that can be stored for a long period of time can be obtained.
- a hologram used in various fields of display, medical, or anti-counterfeit printing, and furthermore, a high-efficiency hologram grating element, dichroic filter, dichroic mirror, hologram reflector, hologram condensing element / diffusion element Or as a color filtering element.
Abstract
The present invention addresses the problem of providing a method for treating a photosensitive silver halide material that is used to produce a bleached phase hologram which has excellent light resistance and by which high diffraction efficiency can be achieved even after long term storage, and providing a bleached phase hologram which is obtained using this treatment method, which has excellent light resistance and by which high diffraction efficiency can be achieved. The problem can be solved by providing a method for treating a photosensitive silver halide material for a hologram in order to obtain a bleached phase hologram in which the difference between absorbance at a wavelength of 420 nm and absorbance at a wavelength of 470 nm is 2 or higher in transmission/absorption spectrometry. The treatment method includes a step of exposing the photosensitive silver halide material for a hologram, which has a silver halide emulsion layer that contains a photosensitive silver halide emulsion on a support body, to light, carrying out developing treatment and then bleaching treatment using ethylenediaminetetraacetic acid or a salt thereof as a bleaching treatment material, and then carrying out a stabilization treatment step using an aqueous solution of potassium iodide.
Description
本発明は、ホログラム用ハロゲン化銀感光材料の処理方法、及びその処理方法によって得られる耐光性に優れ、長期間保存した後も高い回折効率の得られる漂白位相型ホログラムに関するものである。
The present invention relates to a method for processing a silver halide photosensitive material for holograms, and to a bleached phase hologram which is excellent in light resistance obtained by the processing method and can obtain a high diffraction efficiency even after long-term storage.
ハロゲン化銀感光材料は、高感度、高解像度という特徴をもち、近年、ホログラムなどの高解像度記録用感光材料として、ハロゲン化銀乳剤の用途研究が進められている。ホログラム作成に用いられる感光材料には、ハロゲン化銀感光材料のほかに、重クロム酸ゼラチン感光材料、フォトポリマー感光材料、サーモプラスチック感光材料などの感光材料が知られている。ハロゲン化銀感光材料は、その他の感光材料と比べて感度、解像度が高いことから、ディスプレー用、医療用、或いは偽造防止用印刷の各種分野で応用されている（辻内順平監修、『ホログラフィー材料・応用便覧』、株式会社エヌ・ティー・エス、２００７年６月第１版発行を参照）。
Silver halide photosensitive materials have the characteristics of high sensitivity and high resolution, and in recent years, researches on the use of silver halide emulsions as high-resolution recording photosensitive materials such as holograms have been conducted. In addition to the silver halide photosensitive material, photosensitive materials such as a dichromated gelatin photosensitive material, a photopolymer photosensitive material, and a thermoplastic photosensitive material are known as photosensitive materials used for hologram production. Since silver halide photosensitive materials have higher sensitivity and resolution than other photosensitive materials, they are used in various fields of display, medical, and anti-counterfeit printing (supervised by Junpei Uchiuchi, “Holographic Materials / Application Handbook ”, NTS Corporation, June 2007, first edition issued).
ハロゲン化銀感光材料を用いてホログラムを作製する方法としては、レーザー光源を使用し物体光と参照光との干渉光を露光し、現像処理によって現像銀の振幅ホログラムを作る方法が知られている。さらに、この振幅ホログラムは、漂白処理を行うことにより現像された銀を再びハロゲン化銀に戻すことで漂白位相型ホログラムとして使用している。これらの処理により、高い回折効率と明るいホログラムが得られる。しかし、漂白処理により現像銀がハロゲン化銀に戻されることによって、製作されたホログラムの安定性については、光による劣化を受け易くなり、耐光性が悪化し、回折効率の低下を伴うと言う問題があった。この問題を解決する手段の一つとして、例えば、特開昭５１−２５１３５号公報、特開昭６２−３２７９号公報、特開平１０−１４９０８３号公報に開示されている方法として、塩化銀や臭化銀などの感光性ハロゲン化銀を光安定性の高いヨウ化銀へ変換することが提案されている。ヨウ化銀への変換による光安定化処理は、作業的にも優れた処理方法と考えられるものの、従来から提案されている処理方法では、十分な耐光性を有する漂白位相型ホログラムが作製できず、長期間保存した後においても高い回折効率をもつ漂白位相型ホログラムを安定して作製するためには、更なる改良が必要であった。
As a method for producing a hologram using a silver halide photosensitive material, a method is known in which a laser light source is used to expose interference light between an object beam and a reference beam, and an amplitude hologram of developed silver is produced by development processing. . Furthermore, this amplitude hologram is used as a bleaching phase hologram by returning the silver developed by the bleaching process to silver halide again. With these treatments, a high diffraction efficiency and a bright hologram can be obtained. However, since the developed silver is returned to silver halide by the bleaching process, the stability of the produced hologram is likely to be deteriorated by light, the light resistance is deteriorated, and the diffraction efficiency is lowered. was there. As one of means for solving this problem, for example, methods disclosed in JP-A-51-25135, JP-A-62-2279, and JP-A-10-149083 include silver chloride and odor. It has been proposed to convert photosensitive silver halides such as silver halide into silver iodide having high photostability. Although light stabilization processing by conversion to silver iodide is considered to be an excellent processing method in terms of work, a conventionally proposed processing method cannot produce a bleaching phase hologram having sufficient light resistance. In order to stably produce a bleaching phase hologram having a high diffraction efficiency even after long-term storage, further improvements are necessary.
斯かる状況に鑑み、本発明の課題は、耐光性に優れ、長期間保存した後も高い回折効率が得られる漂白位相型ホログラムを作製するためのハロゲン化銀感光材料の処理方法、及びその処理方法によって得られる漂白位相型ホログラムを提供することにある。
In view of such a situation, an object of the present invention is to provide a method for processing a silver halide photosensitive material for producing a bleached phase hologram that is excellent in light resistance and obtains high diffraction efficiency even after being stored for a long period of time, and its processing It is to provide a bleach phase hologram obtained by the method.
本発明者等が鋭意研究し、検索したところ、下記構成によって本発明の課題を解決できることが判明した。
As a result of extensive research and search by the inventors, it has been found that the following problems can be solved by the following configuration.
１．支持体上に感光性ハロゲン化銀乳剤を含むハロゲン化銀乳剤層を有するホログラム用ハロゲン化銀感光材料を露光後、現像処理工程、エチレンジアミン四酢酸（以下、「ＥＤＴＡ」という場合もある。）またはその塩を漂白処理材料として用いる漂白処理工程を順次施した後に、ヨウ化カリウム水溶液を用いた安定化処理工程を施す工程を含む、透過吸収スペクトル測定における波長４２０ｎｍの吸光度と波長４７０ｎｍでの吸光度の差が２以上である漂白位相型ホログラムを得るためのホログラム用ハロゲン化銀感光材料の処理方法。
1. After exposing a silver halide photosensitive material for hologram having a silver halide emulsion layer containing a photosensitive silver halide emulsion on a support, a development processing step, ethylenediaminetetraacetic acid (hereinafter sometimes referred to as “EDTA”) or After sequentially performing a bleaching treatment step using the salt as a bleaching treatment material, and performing a stabilization treatment step using an aqueous potassium iodide solution, the absorbance at a wavelength of 420 nm and the absorbance at a wavelength of 470 nm in a transmission absorption spectrum measurement A method for processing a silver halide photosensitive material for holograms for obtaining a bleaching phase hologram having a difference of 2 or more.
２．ヨウ化カリウム水溶液の濃度が、濃度１．５乃至１０質量％であって、安定化処理工程の処理時間が、２乃至１０分の範囲である前記１記載のホログラム用ハロゲン化銀感光材料の処理法方法。
2. 2. The processing of a silver halide photosensitive material for hologram as described in 1 above, wherein the concentration of the potassium iodide aqueous solution is 1.5 to 10% by mass and the processing time of the stabilization processing step is in the range of 2 to 10 minutes. Law method.
３．前記１、２記載の処理方法を用いて得られる漂白位相型ホログラム。
3. A bleaching phase hologram obtained by using the processing method described in 1 or 2 above.
４．透過吸収スペクトル測定において、波長４２０ｎｍの吸光度と波長４７０ｎｍでの吸光度の差が２以上あり、かつ波長４５０ｎｍ以上の可視域に吸収を持たない前記３記載の漂白位相型ホログラム。
4). 4. The bleaching phase hologram according to 3 above, wherein, in transmission absorption spectrum measurement, the difference between the absorbance at a wavelength of 420 nm and the absorbance at a wavelength of 470 nm is 2 or more and has no absorption in the visible region of a wavelength of 450 nm or more.
５．平均粒径が１０乃至６０ｎｍの範囲であるハロゲン化銀粒子を含む感光性ハロゲン化銀乳剤層を有する前記１記載の処理方法に用いられるホログラム用ハロゲン化銀感光材料。
5). The silver halide photosensitive material for holograms used for the processing method of said 1 which has the photosensitive silver halide emulsion layer containing the silver halide grain whose average particle diameter is the range of 10-60 nm.
本発明により、耐光性に優れ、長期間保存しても高い回折効率を有する漂白位相型ホログラムを製造することができる。また、漂白位相型ホログラムの作製において、ハロゲン化銀感光材料の一連の処理方法の中で、ヨウ化カリウム水溶液に浸漬する安定化処理方法を確立できたことから、特に、明るさを要求される漂白位相型ホログラムの作製において極めて有利に用いることができる。
According to the present invention, a bleaching phase hologram having excellent light resistance and high diffraction efficiency even when stored for a long time can be produced. In addition, in the production of bleaching phase holograms, amongst a series of processing methods for silver halide light-sensitive materials, a stabilization processing method that can be immersed in an aqueous potassium iodide solution has been established. It can be used very advantageously in the production of bleached phase holograms.
既述したとおり、本発明は、ホログラム用ハロゲン化銀感光材料の処理方法及びその処理方法によって作製される漂白位相型ホログラムに関するものであり、ホログラム用ハロゲン化銀感光材料は、物体光と参照光の干渉縞を記録することができるハロゲン化銀感光材料であり、支持体に少なくとも１層のハロゲン化銀乳剤層を有する。
As described above, the present invention relates to a method for processing a silver halide photosensitive material for holograms and a bleached phase type hologram produced by the processing method. The silver halide photosensitive material for holograms comprises object light and reference light. The silver halide light-sensitive material can record at least one interference fringe, and has at least one silver halide emulsion layer on the support.
ホログラム用ハロゲン化銀感光材料は、通常、支持体上にハロゲン化銀乳剤が塗布されたものであり、露光記録に用いるレーザー光の発振波長に感度を有するように、化学増感、分光増感を施したものが通常用いられる。
A silver halide photosensitive material for hologram is usually a silver halide emulsion coated on a support, and is chemically sensitized or spectrally sensitized so as to be sensitive to the oscillation wavelength of laser light used for exposure recording. The ones with the are usually used.
支持体としては、ホログラム用ハロゲン化銀感光材料に通常用いられる、例えば、ガラス板、アクリル板、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリスチレンフィルム、トリアセチルセルロースフィルムなどが挙げられ、特に、光学異方性を持たないガラス板、ポリエチレンテレフタレートフィルム、又はポリエチレンナフタレートフィルムが好ましい。また、支持体の厚さは、用途、使用方法によって適宜選択できる。
Examples of the support include a glass plate, an acrylic plate, a polyethylene terephthalate film, a polyethylene naphthalate film, a polystyrene film and a triacetyl cellulose film, which are usually used for silver halide photosensitive materials for holograms. A glass plate having no directionality, a polyethylene terephthalate film, or a polyethylene naphthalate film is preferred. Moreover, the thickness of a support body can be suitably selected by a use and a usage method.
支持体上に塗布形成されるハロゲン化銀乳剤層の塗布銀量は、通常、１乃至１０ｇ／ｍ２の範囲が好ましく、塗布するゼラチンなどの分散媒体量は、１乃至１０ｇ／ｍ２の範囲が好ましい。また、銀／分散媒体塗布量比率は通常０．１乃至２．０の範囲が好ましい。塗布膜厚は通常３乃至１２μｍの範囲が好ましい。
The coated silver amount of the silver halide emulsion layer formed on the support is preferably in the range of 1 to 10 g / m 2 , and the amount of the dispersion medium such as gelatin to be coated is in the range of 1 to 10 g / m 2 . Is preferred. The silver / dispersion medium coating amount ratio is usually preferably in the range of 0.1 to 2.0. The coating thickness is usually preferably in the range of 3 to 12 μm.
ハロゲン化銀乳剤層に含まれるハロゲン化銀粒子は、公知の製造方法によって調製でき、例えば、硝酸銀水溶液と水溶性ハロゲン化物水溶液をゼラチン水溶液中にてシングルジェット法、ダブルジェット法、または、コントロールダブルジェット法等を用いて混合し製造することができる。このうち、コントロールダブルジェット法によって製造されたハロゲン化銀は、ハロゲン化銀の粒径を制御する上で特に好ましい。
The silver halide grains contained in the silver halide emulsion layer can be prepared by a known production method. For example, a silver nitrate aqueous solution and a water-soluble halide aqueous solution in a gelatin aqueous solution in a single jet method, a double jet method, or a control double method. It can be mixed and manufactured using a jet method or the like. Among these, silver halides produced by the control double jet method are particularly preferable for controlling the grain size of silver halide.
本発明に係るハロゲン化銀乳剤に含まれるハロゲン化銀粒子の外形は、正常晶であることが好ましく、立方体、八面体、菱形十二面体、十四面体、およびそれらが丸みを帯びた形状のものが好ましい。また、その平均粒径は１０乃至６０ｎｍのものが好ましく、平均粒径３０乃至５０ｎｍのハロゲン化銀粒子を含む乳剤は、本発明の高い回折効率を有する漂白位相型ホログラムを作製する上で特に好ましい。そして、ハロゲン化銀粒子の粒度分布を検討すると、粒径が４０乃至４５ｎｍの範囲の粒子が主要成分であるハロゲン化銀乳剤は、本発明の高い回折効率を維持する漂白位相型ホログラムを作製する上でこのましい。なお、平均粒径が１０ｎｍよりも小さくなると、ハロゲン化銀乳剤中のハロゲン化銀粒子の粒子サイズのばらつきが大きくなり、ハロゲン化銀乳剤の不安定化の原因となり、また、６０ｎｍよりも大きくなると、粒子による光散乱の影響により、所望の特性が得られない等の原因が生じる場合がある。
The outer shape of the silver halide grains contained in the silver halide emulsion according to the present invention is preferably a normal crystal, a cube, an octahedron, a rhomboid dodecahedron, a tetrahedron, and a rounded shape thereof. Are preferred. The average particle diameter is preferably 10 to 60 nm, and the emulsion containing silver halide grains having an average particle diameter of 30 to 50 nm is particularly preferable for producing the bleaching phase hologram having high diffraction efficiency of the present invention. . When the particle size distribution of the silver halide grains is examined, a silver halide emulsion mainly composed of grains having a particle size in the range of 40 to 45 nm produces a bleaching phase hologram that maintains the high diffraction efficiency of the present invention. This is true. When the average grain size is smaller than 10 nm, the variation in the grain size of the silver halide grains in the silver halide emulsion is increased, which causes destabilization of the silver halide emulsion, and when the average grain size is larger than 60 nm. In some cases, the desired characteristics cannot be obtained due to light scattering by the particles.
ここで、ハロゲン化銀粒子の平均粒径は、粒子が球状又は球に近似できる粒子の場合、粒子直径を意味し、粒子が立方体の場合は、球に換算した直径を粒径として求めることができ、例えば、シー・イー・ケー・ミーズ・アンド・ティー・エッチ・ジェームズ（Ｃ．Ｅ．Ｋ．Ｍｅｅｓ＆Ｔ．Ｈ．Ｊａｍｅｓ）著、『ザ・セオリー・オブ・ザ フォトグラフィック・プロセス（Ｔｈｅ Ｔｈｅｏｒｙ ｏｆ ｔｈｅ ｐｈｏｔｏｇｒａｐｈｉｃ ｐｒｏｃｅｓｓ）』、第３版、３６乃至４３頁、１９６６年を参照し、透過型電子顕微鏡を用いて求めることができる。
Here, the average particle diameter of the silver halide grains means the diameter of the grains when the grains are spherical or approximate to a sphere, and when the grains are cubic, the diameter converted to a sphere can be obtained as the diameter. For example, “The Theory of the Photographic Process (The Theory of the World)” by CEK Mees & T. H. James. the photographic process), 3rd edition, pages 36 to 43, 1966, and can be obtained using a transmission electron microscope.
また、ハロゲン化銀粒子は、塩化銀、ヨウ化銀、臭化銀、塩臭化銀、ヨウ臭化銀、塩ヨウ臭化銀など、何れでもよい。特に好ましいハロゲン化銀粒子としては、臭化銀、ヨウ臭化銀、塩ヨウ臭化銀、塩臭化銀が挙げられる。
The silver halide grains may be any of silver chloride, silver iodide, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like. Particularly preferred silver halide grains include silver bromide, silver iodobromide, silver chloroiodobromide, and silver chlorobromide.
ハロゲン化銀乳剤は、増感色素により、露光記録に用いるレーザー光の発振波長に合わせるように分光増感できる。用いる増感色素としては、例えば、速水正明監修、『感光色素−その不思議な作用と多彩な機能−』、１９９７年１０月１７日初版発行、１２乃至３１頁記載のシアニン色素、メロシアニン色素、ヘミシアニン色素、スチリル色素及びヘミオキソノール色素が挙げられる。これら増感色素は、単独で用いても複数を併用して用いてもよい。また、増感色素は、ハロゲン化銀乳剤中に分散含有させることが好ましい。ハロゲン化銀乳剤への増感色素の添加方法は、公知の添加方法により行うことができ、例えば、メチルアルコール、エチルアルコール、メチルセルソルブ、水、アセトン、ピリジン或いはこれらの混合溶媒に溶解させた後、ハロゲン化銀乳剤へ添加する方法が挙げられる。添加時期としては、ハロゲン化銀乳剤の調製時、または調製後のいずれであってもかまわない。また、ハロゲン化銀乳剤への添加量は、ハロゲン化銀粒子の銀１モル当り増感色素が１×１０−４乃至１×１０−２モル含有されるように添加するのが好ましい。増感色素と共に、それ自身は分光増感作用を示さない色素を強色増感色素として同時にあるいは個別に添加してもよい。
The silver halide emulsion can be spectrally sensitized with a sensitizing dye so as to match the oscillation wavelength of laser light used for exposure recording. Examples of the sensitizing dye to be used include the cyanine dye, merocyanine dye, hemicyanine described in Masaaki Hayami, “Sensitive Dye—Mysterious Action and Various Functions”, published on October 17, 1997, pages 12 to 31. And dyes, styryl dyes and hemioxonol dyes. These sensitizing dyes may be used alone or in combination. The sensitizing dye is preferably dispersed and contained in the silver halide emulsion. The sensitizing dye can be added to the silver halide emulsion by a known addition method, for example, dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, water, acetone, pyridine or a mixed solvent thereof. Thereafter, a method of adding to a silver halide emulsion is mentioned. The timing of addition may be either during the preparation of the silver halide emulsion or after the preparation. The addition amount to the silver halide emulsion is preferably such that the sensitizing dye is contained in an amount of 1 × 10 −4 to 1 × 10 −2 mol per mol of silver in the silver halide grains. Along with the sensitizing dye, a dye that does not exhibit spectral sensitizing action itself may be added simultaneously or individually as a supersensitizing dye.
また、本発明におけるハロゲン化銀乳剤には、化学増感を施すことができ、公知方法を用いて化学増感剤をハロゲン化乳剤に添加することにより行われる。化学増感剤としては、例えば、チオシアン酸カリウム、チオ硫酸アンモニウム、チオ硫酸ナトリウム、ハイポ、チオ尿素系化合物などの硫黄増感剤、塩化スズ（ＩＩ）、アスコルビン酸およびその誘導体、ヒドラジン誘導体、ホルムアミジンスルフィン酸、シラン化合物、ジメチルアミンボランなどの還元増感剤、塩化金酸塩などの金増感剤が挙げられる。
In addition, the silver halide emulsion in the present invention can be chemically sensitized, and is added by adding a chemical sensitizer to the halogenated emulsion using a known method. Examples of the chemical sensitizer include sulfur sensitizers such as potassium thiocyanate, ammonium thiosulfate, sodium thiosulfate, hypo, thiourea compounds, tin (II) chloride, ascorbic acid and its derivatives, hydrazine derivatives, formamidine. Examples thereof include reduction sensitizers such as sulfinic acid, silane compounds, and dimethylamine borane, and gold sensitizers such as chloroaurate.
ハロゲン化銀粒子の保護コロイド用分散媒体としては、ゼラチンを用いることが好ましい。ゼラチンは、酸処理したもの、アルカリ処理したもの、低分子画分の低分子ゼラチン、フタル化ゼラチンなど化学処理したゼラチンなどが挙げられる。また、ゼラチン以外にも、アセチル化プルラン、両荷電性プルランなどのプルラン誘導体、アルブミン、カゼイン、ヒドロキシセルロース、カルボキシメチルセルロース、アルギン酸ソーダ、ポリビニルアルコール、ポリアクリル酸、ポリメタクリル酸、ポリアクリルアミドなどの親水性高分子を親水性コロイドとして、ゼラチンと併用するか、或いは単独で使用することができる。
As a dispersion medium for protective colloid of silver halide grains, gelatin is preferably used. Examples of gelatin include acid-treated ones, alkali-treated ones, low-molecular gelatins having a low molecular fraction, and chemically-treated gelatins such as phthalated gelatin. Besides gelatin, pullulan derivatives such as acetylated pullulan and bi-charged pullulan, hydrophilic properties such as albumin, casein, hydroxycellulose, carboxymethylcellulose, sodium alginate, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid and polyacrylamide The polymer can be used in combination with gelatin as a hydrophilic colloid or can be used alone.
また、本発明に用いるホログラム用ハロゲン化銀感光材料には、ハロゲン化銀乳剤層へ硬膜剤として、クロム塩、アルデヒド類、Ｎ−メチロール化合物、ジオキサン誘導体、活性ビニル化合物、活性ハロゲン化合物、ムコハロゲン酸類、イソオキサゾール類、ジアルデヒド澱粉、２−クロロ−６−ヒドロキシトリアジニル化ゼラチン、カルボキシル基活性化型硬膜剤などの硬膜剤を単独、または２種以上を併用して用いることができる。
Further, the silver halide photosensitive material for hologram used in the present invention includes chromium salts, aldehydes, N-methylol compounds, dioxane derivatives, active vinyl compounds, active halogen compounds, mucosates as hardeners on the silver halide emulsion layers. Use hardeners such as halogen acids, isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, carboxyl group-activated hardener alone or in combination of two or more. Can do.
本発明に用いられるホログラム用ハロゲン化銀感光材料のハロゲン化銀乳剤層には、その他、リサーチ・ディスクロージャー １７６４３（１９７８年１２月発行）、リサーチ・ディスクロージャー １８７１６（１９８９年１２月）、リサーチ・ディスクロージャー ３０８１１９（１９８９年１２月）に記載の当業界公知の添加剤等を用いることができる。
The silver halide emulsion layer of the silver halide light-sensitive material for hologram used in the present invention includes, in addition, Research Disclosure 17643 (issued in December 1978), Research Disclosure 18716 (December 1989), Research Disclosure 308119. (December 1989) can be used in the industry known additives and the like.
また、本発明に用いるホログラム用ハロゲン化銀感光材料は、市販されているホログラム用ハロゲン化銀感光材料を用いることもできる。市販されているホログラム用ハロゲン化銀感光材料としては、コニカミノルタオプト社製造のホログラム用ハロゲン化銀感光材料（商品名『Ｐ５６００』）、スラビッチ（Ｓｌａｖｉｃｈ）社製造のホログラム用ハロゲン化銀感光材料（商品名『ＰＦＧ−０１』、『ＰＦＧ−０３Ｍ』、『ＰＦＧ−０３Ｃ』）、カラーホログラフィックス（Ｃｏｌｏｕｒｈｏｌｏｇｒａｐｈｉｃｓ）社製造のホログラム用ハロゲン化銀感光材料（商品名『ＢＢ６４０』、『ＢＢ５２０』、『ＢＢＶＰａｎ』）などが挙げられる。
Further, as the silver halide photosensitive material for hologram used in the present invention, a commercially available silver halide photosensitive material for hologram can also be used. Commercially available silver halide photosensitive materials for holograms include a silver halide photosensitive material for holograms manufactured by Konica Minolta Opto (trade name “P5600”), and a silver halide photosensitive material for holograms manufactured by Slavich ( Product names “PFG-01”, “PFG-03M”, “PFG-03C”), silver halide photosensitive materials for holograms manufactured by Colorholographics (trade names “BB640”, “BB520”, “BBVPan”) ]).
本発明に係るハロゲン化銀感光材料の処理方法としては、露光後、現像処理工程、エチレンジアミン四酢酸またはその塩を漂白処理材料として用いた漂白処理工程を施した後に、ヨウ化カリウム水溶液を用いた安定化処理工程を施し、水洗及び乾燥の処理工程を施すことによって行われることが好ましい。
As a processing method of the silver halide photosensitive material according to the present invention, an aqueous potassium iodide solution was used after exposure, a development processing step, a bleaching processing step using ethylenediaminetetraacetic acid or a salt thereof as a bleaching processing material. It is preferable to carry out a stabilization treatment step, followed by washing and drying treatment steps.
露光光源としては、位相の揃った可視域波長レーザー光を用いることができる。再生時に使用するレーザー光も露光時に使用したレーザー光を使用することができ、処理後のハロゲン化銀感光材料は未露光部が再生レーザー光を吸収することが無いように処理を行うことが必要である。適当なレーザー光としては、波長５３２ｎｍのＮｄ−ＹＡＧレーザー、波長５１４．５ｎｍまたは４８８ｎｍのアルゴンレーザー、波長６４７．１ｎｍのクリプトンイオンレーザー、波長６３２．８ｎｍのヘリウム−ネオンレーザー、波長４４１．６ｎｍまたは３２５ｎｍのヘリウム−カドミウムレーザー、各種半導体レーザーが挙げられる。
As the exposure light source, visible wavelength laser light having a uniform phase can be used. The laser beam used at the time of reproduction can also be the laser beam used at the time of exposure, and the processed silver halide photosensitive material needs to be processed so that the unexposed part does not absorb the reproduced laser beam It is. Suitable laser beams include an Nd-YAG laser with a wavelength of 532 nm, an argon laser with a wavelength of 514.5 nm or 488 nm, a krypton ion laser with a wavelength of 647.1 nm, a helium-neon laser with a wavelength of 632.8 nm, a wavelength of 441.6 nm or 325 nm. Helium-cadmium laser and various semiconductor lasers.
ここで、現像処理に用いられる現像液は、銀イオンを還元する現像主薬を主要成分とする処理液であり、現像主薬には、ヒドロキノン、ｐ−アミノフェノール、Ｎ−メチル−ｐ−アミノフェノール、２，４−ジアミノフェノールなどのｐ−アミノフェノール類、ｐ−フェニレンジアミン類、１−フェニル−３−ピラゾリドン、１−フェニル−４−メチル−４−ヒドロキシメチル−３−ピラゾリン、５，５−ジメチル−１−フェニル−３−ピラゾリドンなどの３−ピラゾリドン類、カテコール、フェニドン、ピロガロール類、アスコルビン酸、メトールなどの還元剤を使用することができる。これら現像主薬は単独で用いても２種以上を併用して用いてもよい。また、現像液には、保恒剤を用いることができ、保恒剤としては、亜硫酸ナトリウム、亜硫酸カリウム、亜硫酸アンモニウム、メタ重亜硫酸ナトリウムなどの亜硫酸塩、メタ重亜硫酸塩、ピペリジノヘキソースレダクトンなどのレダクトン類を挙げることができる。さらに、現像液にはアルカリ剤を用いることができ、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、第三リン酸カリウム、第三リン酸ナトリウム、硼酸塩、アセトオキシム、５−スルホサリチル酸、リン酸塩、炭酸塩などが挙げられる。その他、ポリエチレングリコールなどの溶解助剤、四級アンモニウム塩などの増感剤、スルフィド、ジスルフィド化合物、トリアジン化合物などの銀スラッジ防止剤、臭化ナトリウム、臭化カリウム、ヨウ化カリウムなどのカブリ防止剤、ヘキサメタリン酸ナトリウム、ヘキサメタリン酸カルシウム、ポリリン酸塩などのキレート剤、現像促進剤、界面活性剤、省泡剤、硬膜剤などを必要に応じて適宜添加することもできる。
Here, the developer used for the development processing is a processing solution mainly containing a developing agent that reduces silver ions, and the developing agent includes hydroquinone, p-aminophenol, N-methyl-p-aminophenol, P-aminophenols such as 2,4-diaminophenol, p-phenylenediamines, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazoline, 5,5-dimethyl Reducing agents such as 3-pyrazolidones such as -1-phenyl-3-pyrazolidone, catechol, phenidone, pyrogallol, ascorbic acid, and metol can be used. These developing agents may be used alone or in combination of two or more. In addition, a preservative can be used in the developing solution. Examples of the preservative include sulfites such as sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite, metabisulfite, piperidinohexose concentrate. Reductons such as ductons can be mentioned. Further, an alkali agent can be used in the developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic potassium phosphate, tribasic sodium phosphate, borate, acetoxime, 5- Examples include sulfosalicylic acid, phosphate, and carbonate. In addition, dissolution aids such as polyethylene glycol, sensitizers such as quaternary ammonium salts, silver sludge inhibitors such as sulfides, disulfide compounds and triazine compounds, antifoggants such as sodium bromide, potassium bromide and potassium iodide Further, a chelating agent such as sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate, a development accelerator, a surfactant, a foam saving agent, a hardener, and the like can be appropriately added as necessary.
現像液のｐＨは、８．０乃至１２．０に調製され、より好ましくは、９．０乃至１１．５の範囲とする。また、現像処理時の温度も重要であり、通常、１０乃至４５℃の範囲で処理する。より好ましくは、処理温度２０乃至３０℃の範囲で一定温度にて現像液中、浸漬処理することが望ましい。現像処理時間は概ね２０秒乃至４分の範囲で行う。
The pH of the developer is adjusted to 8.0 to 12.0, and more preferably 9.0 to 11.5. Further, the temperature during the development processing is also important, and the processing is usually performed in the range of 10 to 45 ° C. More preferably, the immersion treatment is performed in the developer at a constant temperature in the range of 20 to 30 ° C. The development processing time is approximately 20 seconds to 4 minutes.
現像処理を止めるための停止処理としては、酸性溶液を用いて現像液を酸性側にシフトさせる酸性溶液が用いられる。通常、酢酸水溶液を用いて処理する。酢酸水溶液を使用する場合、濃度は０．５乃至５質量％の範囲の水溶液を使用する。停止処理における処理温度も現像処理と同様に通常、１０乃至４５℃の範囲で処理する。より好ましくは、処理温度２０乃至３０℃の範囲で一定温度にて処理することが望ましい。
As the stopping process for stopping the developing process, an acidic solution that uses an acidic solution to shift the developer to the acidic side is used. Usually, it is treated with an acetic acid aqueous solution. When an aqueous acetic acid solution is used, an aqueous solution having a concentration in the range of 0.5 to 5% by mass is used. The processing temperature in the stop processing is usually in the range of 10 to 45 ° C. as in the development processing. More preferably, the treatment is performed at a constant temperature in the range of 20 to 30 ° C.
現像処理後の漂白処理液は、エチレンジアミン四酢酸またはその塩を漂白処理材料として用いる。エチレンジアミン四酢酸の塩としては、例えば、エチレンジアミン四酢酸ナトリウム、エチレンジアミン四酢酸−鉄（ＩＩＩ）ナトリウムなどを挙げることができる。なお、漂白処理に使用されるその他の漂白処理材料としては、例えば、重クロム酸ナトリウム、パラベンゾキノン、硝酸第二鉄なども用いることができる。
The bleaching solution after the development processing uses ethylenediaminetetraacetic acid or a salt thereof as a bleaching processing material. Examples of the salt of ethylenediaminetetraacetic acid include sodium ethylenediaminetetraacetate, ethylenediaminetetraacetic acid-iron (III) sodium, and the like. In addition, as other bleaching treatment materials used for the bleaching treatment, for example, sodium dichromate, parabenzoquinone, ferric nitrate and the like can be used.
なお、漂白処理液には、上記エチレンジアミン四酢酸またはその塩の他に、ハロゲン化合物、チオ尿素誘導体、チオエーテルなどの漂白促進剤、保恒剤、ｐＨ緩衝剤、ｐＨ調整剤、キレート剤を適宜含むことができる。漂白液のｐＨは２．０乃至６．０であり、好ましくは、２．５乃至５．５である。漂白処理温度は、１０乃至４５℃の範囲で漂白処理液中、浸漬処理するのが好ましく、より好ましくは、処理温度２０乃至３０℃の範囲で一定温度にて処理することが望ましい。処理時間は概ね２０秒乃至４分の範囲で行う。
In addition to the above-mentioned ethylenediaminetetraacetic acid or a salt thereof, the bleaching solution appropriately contains a bleach accelerator such as a halogen compound, a thiourea derivative, and a thioether, a preservative, a pH buffer, a pH adjuster, and a chelating agent. be able to. The pH of the bleaching solution is 2.0 to 6.0, preferably 2.5 to 5.5. The bleaching treatment temperature is preferably in the range of 10 to 45 ° C., and the immersion treatment is preferably performed in the bleaching treatment solution, and more preferably the treatment temperature is in the range of 20 to 30 ° C. at a constant temperature. The processing time is approximately 20 seconds to 4 minutes.
上記漂白処理の後、本発明の処理方法では、ヨウ化カリウム水溶液を用いた安定化処理をおこなう。具体的には、例えば、ヨウ化カリウム水溶液に浸漬する安定化処理をおこなう。ここで、ヨウ化カリウム水溶液の濃度としては、使用するホログラム用ハロゲン化銀感光材料の支持体上に塗布形成されたハロゲン化銀乳剤層の厚み、ハロゲン化銀乳剤に含まれる銀量、銀／ゼラチンの比率ならびにハロゲン化銀粒子の種類等によって、安定化処理溶液の濃度、処理温度、処理時間を適宜調整する必要がある。例えば、図５に示すとおり、安定化処理後の漂白位相型ホログラムの透過吸収スペクトル測定から、ヨウ化銀の吸収波長に相当する波長４２０ｎｍの吸光度が波長４７０ｎｍでの吸光度よりも２以上となる条件が特に望ましい。目安としては、濃度１．５乃至１０質量％とすることが好ましく、特に、５乃至１０質量％の濃度範囲がより好ましい範囲である。ヨウ化カリウム水溶液に浸漬する処理時間は、２乃至１０分の範囲で行い、処理温度は、通常、１０乃至４５℃の範囲内で処理する。より好ましくは、処理温度２０乃至３０℃の範囲内で一定温度にて処理することが望ましい。
After the bleaching treatment, the treatment method of the present invention performs a stabilization treatment using an aqueous potassium iodide solution. Specifically, for example, a stabilization treatment of immersing in an aqueous potassium iodide solution is performed. Here, the concentration of the aqueous potassium iodide solution is as follows: the thickness of the silver halide emulsion layer formed on the support of the silver halide photosensitive material for hologram used, the amount of silver contained in the silver halide emulsion, It is necessary to appropriately adjust the concentration of the stabilizing treatment solution, the treatment temperature, and the treatment time depending on the ratio of gelatin and the type of silver halide grains. For example, as shown in FIG. 5, from the measurement of the transmission absorption spectrum of the bleached phase hologram after the stabilization treatment, the condition that the absorbance at a wavelength of 420 nm corresponding to the absorption wavelength of silver iodide is 2 or more than the absorbance at a wavelength of 470 nm. Is particularly desirable. As a guideline, the concentration is preferably 1.5 to 10% by mass, and the concentration range of 5 to 10% by mass is particularly preferable. The treatment time for immersing in the potassium iodide aqueous solution is in the range of 2 to 10 minutes, and the treatment temperature is usually in the range of 10 to 45 ° C. More preferably, the treatment is performed at a constant temperature within a treatment temperature range of 20 to 30 ° C.
安定化処理は、その条件が不十分な場合、耐光性が得られない場合があり、また、処理をし過ぎると干渉縞が崩れ、回折効率の低下が起こり、望ましい漂白位相型ホログラムが得られなくなる。
Stabilization treatment may not be able to obtain light resistance if the conditions are insufficient, and if the treatment is carried out excessively, interference fringes will be lost and diffraction efficiency will be reduced, resulting in a desirable bleached phase hologram. Disappear.
以上の適切な処理方法によって作製される漂白位相型ホログラムは、上記のとおり透過吸収スペクトルを測定すると波長４２０ｎｍの吸光度と波長４７０ｎｍでの吸光度の差が少なくとも２以上、より好ましくは２．５以上の差がある漂白位相型ホログラムとなり、少し黄色味を帯びた色彩ではあるが、実質的に波長４５０ｎｍ以上の可視域に吸収を持たない明るい漂白位相型ホログラムを作製することができる。
The bleaching phase hologram produced by the above appropriate processing method has a difference between the absorbance at the wavelength of 420 nm and the absorbance at the wavelength of 470 nm of at least 2 and more preferably 2.5 or more when the transmission absorption spectrum is measured as described above. It becomes a bleaching phase hologram with a difference, and although it has a slightly yellowish color, a bright bleaching phase hologram that does not substantially absorb in the visible region having a wavelength of 450 nm or more can be produced.
本発明の実施の形態につき、以下、実施例に基づいて説明するけれども、本発明はこれら実施例にのみ限定されるものではない。
Embodiments of the present invention will be described below based on examples, but the present invention is not limited only to these examples.
＜ハロゲン化銀乳剤の調製＞
臭化カリウム０．２ｇ、ゼラチン９５ｇを含む水溶液１２００ｍＬを４０℃に保ち、その溶液中に攪拌しながら硝酸銀２９０ｇ含有する水溶液９６０ｍｌと臭化カリウム／ヨウ化カリウム混合液とを臭素イオン濃度（ｐＢｒ）を２．５５に電位制御しながらコントロールダブルジェット法により注入、混合した後、水洗脱塩処理を行いハロゲン化銀乳剤を得た。この乳剤について、透過型電子顕微鏡により観察・写真撮影を行いハロゲン化銀粒子の直径を測定して平均粒径及び粒度分布（個数％）を求めたところ、平均粒径が４５ｎｍ、粒度分布が２５~６５ｎｍの範囲にあることが確認された（粒度分布図を図１として示す）。 <Preparation of silver halide emulsion>
An aqueous solution (1200 mL) containing 0.2 g of potassium bromide and 95 g of gelatin was kept at 40 ° C., and 960 ml of an aqueous solution containing 290 g of silver nitrate and a mixed solution of potassium bromide / potassium iodide were mixed with the bromine ion concentration (pBr). Was injected and mixed by the control double jet method while controlling the potential to 2.55, and then washed with water and desalted to obtain a silver halide emulsion. This emulsion was observed and photographed with a transmission electron microscope and the diameter of the silver halide grains was measured to determine the average particle size and particle size distribution (number%). The average particle size was 45 nm and the particle size distribution was 25. It was confirmed to be in the range of ˜65 nm (particle size distribution diagram is shown as FIG. 1).
臭化カリウム０．２ｇ、ゼラチン９５ｇを含む水溶液１２００ｍＬを４０℃に保ち、その溶液中に攪拌しながら硝酸銀２９０ｇ含有する水溶液９６０ｍｌと臭化カリウム／ヨウ化カリウム混合液とを臭素イオン濃度（ｐＢｒ）を２．５５に電位制御しながらコントロールダブルジェット法により注入、混合した後、水洗脱塩処理を行いハロゲン化銀乳剤を得た。この乳剤について、透過型電子顕微鏡により観察・写真撮影を行いハロゲン化銀粒子の直径を測定して平均粒径及び粒度分布（個数％）を求めたところ、平均粒径が４５ｎｍ、粒度分布が２５~６５ｎｍの範囲にあることが確認された（粒度分布図を図１として示す）。 <Preparation of silver halide emulsion>
An aqueous solution (1200 mL) containing 0.2 g of potassium bromide and 95 g of gelatin was kept at 40 ° C., and 960 ml of an aqueous solution containing 290 g of silver nitrate and a mixed solution of potassium bromide / potassium iodide were mixed with the bromine ion concentration (pBr). Was injected and mixed by the control double jet method while controlling the potential to 2.55, and then washed with water and desalted to obtain a silver halide emulsion. This emulsion was observed and photographed with a transmission electron microscope and the diameter of the silver halide grains was measured to determine the average particle size and particle size distribution (number%). The average particle size was 45 nm and the particle size distribution was 25. It was confirmed to be in the range of ˜65 nm (particle size distribution diagram is shown as FIG. 1).
＜ホログラム用ハロゲン化銀感光材料の作製＞
得られたハロゲン化銀乳剤を適量とり、露光に用いるＮｄ−ＹＡＧレーザーの５３２ｎｍレーザー光に感度を有するようにシアニン色素、及びチオシアン酸カリウム、チオ硫酸アンモニウムを上記ハロゲン化銀乳剤へ添加し分光増感、化学増感を施した後、ガラス板に塗布して製膜し、ホログラム用ハロゲン化銀感光材料を作製した。 <Preparation of silver halide photosensitive material for hologram>
Spectral sensitization by taking an appropriate amount of the obtained silver halide emulsion and adding cyanine dye, potassium thiocyanate and ammonium thiosulfate to the above silver halide emulsion so as to be sensitive to 532 nm laser beam of Nd-YAG laser used for exposure. After chemical sensitization, the film was applied to a glass plate to form a silver halide photosensitive material for hologram.
得られたハロゲン化銀乳剤を適量とり、露光に用いるＮｄ−ＹＡＧレーザーの５３２ｎｍレーザー光に感度を有するようにシアニン色素、及びチオシアン酸カリウム、チオ硫酸アンモニウムを上記ハロゲン化銀乳剤へ添加し分光増感、化学増感を施した後、ガラス板に塗布して製膜し、ホログラム用ハロゲン化銀感光材料を作製した。 <Preparation of silver halide photosensitive material for hologram>
Spectral sensitization by taking an appropriate amount of the obtained silver halide emulsion and adding cyanine dye, potassium thiocyanate and ammonium thiosulfate to the above silver halide emulsion so as to be sensitive to 532 nm laser beam of Nd-YAG laser used for exposure. After chemical sensitization, the film was applied to a glass plate to form a silver halide photosensitive material for hologram.
＜ホログラムの露光記録＞
上記ホログラム用ハロゲン化銀感光材料への露光記録について装置の概略図を図２に示し、図３には、ガラス板にハロゲン化銀乳剤が塗布されたハロゲン化銀感光材料の記録方法を示す。なお、ハロゲン化銀乳剤を塗布したホログラム用ハロゲン化銀感光材料は、図２におけるＨ１の乾板ホルダーの位置に設置される。また図３において、ガラス板にハロゲン化銀乳剤が塗布されたホログラム用ハロゲン化銀感光材料は、記録光が入射する側にハロゲン化銀乳剤層が位置する。波長５３２ｎｍのＮｄ−ＹＡＧレーザーのレーザー光を２光束に分け交差角３２°で入射させ、干渉縞１０００本／ｍｍの記録を行った。 <Hologram exposure recording>
FIG. 2 shows a schematic diagram of an apparatus for exposure recording on the above-mentioned hologram silver halide photosensitive material, and FIG. 3 shows a recording method of a silver halide photosensitive material in which a silver halide emulsion is coated on a glass plate. The silver halide photosensitive material for hologram coated with the silver halide emulsion is placed at the position of the dry plate holder H 1 in FIG. In FIG. 3, the silver halide photosensitive material for hologram in which a silver halide emulsion is coated on a glass plate has a silver halide emulsion layer on the side on which recording light is incident. The laser beam of an Nd-YAG laser having a wavelength of 532 nm was divided into two light beams and incident at an intersecting angle of 32 °, and recording was performed with 1000 interference fringes / mm.
上記ホログラム用ハロゲン化銀感光材料への露光記録について装置の概略図を図２に示し、図３には、ガラス板にハロゲン化銀乳剤が塗布されたハロゲン化銀感光材料の記録方法を示す。なお、ハロゲン化銀乳剤を塗布したホログラム用ハロゲン化銀感光材料は、図２におけるＨ１の乾板ホルダーの位置に設置される。また図３において、ガラス板にハロゲン化銀乳剤が塗布されたホログラム用ハロゲン化銀感光材料は、記録光が入射する側にハロゲン化銀乳剤層が位置する。波長５３２ｎｍのＮｄ−ＹＡＧレーザーのレーザー光を２光束に分け交差角３２°で入射させ、干渉縞１０００本／ｍｍの記録を行った。 <Hologram exposure recording>
FIG. 2 shows a schematic diagram of an apparatus for exposure recording on the above-mentioned hologram silver halide photosensitive material, and FIG. 3 shows a recording method of a silver halide photosensitive material in which a silver halide emulsion is coated on a glass plate. The silver halide photosensitive material for hologram coated with the silver halide emulsion is placed at the position of the dry plate holder H 1 in FIG. In FIG. 3, the silver halide photosensitive material for hologram in which a silver halide emulsion is coated on a glass plate has a silver halide emulsion layer on the side on which recording light is incident. The laser beam of an Nd-YAG laser having a wavelength of 532 nm was divided into two light beams and incident at an intersecting angle of 32 °, and recording was performed with 1000 interference fringes / mm.
＜漂白位相型ホログラムへの処理方法＞
現像処理は、メトール２．５ｇ、アスコルビン酸２０ｇ、無水炭酸ナトリウム３０ｇ、水酸化ナトリウム３．５ｇ、臭化カリウム１ｇを純水に溶解して５００ｍｌとし、この水溶液を現像液として用い、メトール・アスコルビン酸現像処理を行った後、１．５％酢酸水溶液にて現像処理を停止させ、次いでエチレンジアミン四酢酸−鉄（ＩＩＩ）ナトリウム１５ｇ、硫酸水素ナトリウム１５ｇ、臭化カリウム１５ｇを純水に溶解し５００ｍｌの水溶液とした漂白処理液に浸漬することにより漂白処理を行った。水洗処理した後、ヨウ化カリウム５ｇを純水に溶解し１００ｍｌとした濃度５％ヨウ化カリウム水溶液に浸漬する安定化処理を１０分間行い、水洗、乾燥させ、漂白位相型ホログラムを作製した。 <Processing to bleach phase hologram>
In the development process, 2.5 g of metol, 20 g of ascorbic acid, 30 g of anhydrous sodium carbonate, 3.5 g of sodium hydroxide, and 1 g of potassium bromide were dissolved in pure water to make 500 ml, and this aqueous solution was used as a developing solution. After the acid development processing, the development processing is stopped with a 1.5% acetic acid aqueous solution, and then ethylenediaminetetraacetic acid-sodium iron (III) 15 g, sodium hydrogen sulfate 15 g, and potassium bromide 15 g are dissolved inpure water 500 ml. Bleaching treatment was performed by immersing in a bleaching treatment solution prepared as an aqueous solution. After washing with water, 5 g of potassium iodide was dissolved in pure water and subjected to a stabilization treatment of immersing in an aqueous solution of 5% potassium iodide having a concentration of 100 ml for 10 minutes, followed by washing with water and drying to produce a bleached phase hologram.
現像処理は、メトール２．５ｇ、アスコルビン酸２０ｇ、無水炭酸ナトリウム３０ｇ、水酸化ナトリウム３．５ｇ、臭化カリウム１ｇを純水に溶解して５００ｍｌとし、この水溶液を現像液として用い、メトール・アスコルビン酸現像処理を行った後、１．５％酢酸水溶液にて現像処理を停止させ、次いでエチレンジアミン四酢酸−鉄（ＩＩＩ）ナトリウム１５ｇ、硫酸水素ナトリウム１５ｇ、臭化カリウム１５ｇを純水に溶解し５００ｍｌの水溶液とした漂白処理液に浸漬することにより漂白処理を行った。水洗処理した後、ヨウ化カリウム５ｇを純水に溶解し１００ｍｌとした濃度５％ヨウ化カリウム水溶液に浸漬する安定化処理を１０分間行い、水洗、乾燥させ、漂白位相型ホログラムを作製した。 <Processing to bleach phase hologram>
In the development process, 2.5 g of metol, 20 g of ascorbic acid, 30 g of anhydrous sodium carbonate, 3.5 g of sodium hydroxide, and 1 g of potassium bromide were dissolved in pure water to make 500 ml, and this aqueous solution was used as a developing solution. After the acid development processing, the development processing is stopped with a 1.5% acetic acid aqueous solution, and then ethylenediaminetetraacetic acid-sodium iron (III) 15 g, sodium hydrogen sulfate 15 g, and potassium bromide 15 g are dissolved in
＜ホログラムの評価＞
作製した漂白位相型ホログラムについて、露光に用いた５３２ｎｍレーザー光により再生し、回折効率を求めたところ作製直後の回折効率は６３％と高い数値を示した。なお、回折効率は、照明光の強さを１００としたときの、再生光（１次光）の強さの割合を計算により求めた（図３、参照）。 <Evaluation of hologram>
The produced bleached phase hologram was reproduced with a 532 nm laser beam used for exposure and the diffraction efficiency was determined. As a result, the diffraction efficiency immediately after production was as high as 63%. The diffraction efficiency was obtained by calculating the ratio of the intensity of the reproduction light (primary light) when the intensity of the illumination light was 100 (see FIG. 3).
作製した漂白位相型ホログラムについて、露光に用いた５３２ｎｍレーザー光により再生し、回折効率を求めたところ作製直後の回折効率は６３％と高い数値を示した。なお、回折効率は、照明光の強さを１００としたときの、再生光（１次光）の強さの割合を計算により求めた（図３、参照）。 <Evaluation of hologram>
The produced bleached phase hologram was reproduced with a 532 nm laser beam used for exposure and the diffraction efficiency was determined. As a result, the diffraction efficiency immediately after production was as high as 63%. The diffraction efficiency was obtained by calculating the ratio of the intensity of the reproduction light (primary light) when the intensity of the illumination light was 100 (see FIG. 3).
＜耐光性試験＞
また、耐光性を評価するために、キセノンウェザーメーター（商品名『ＸＬ７５』、スガ試験機社製造）照度１１５ｋｌｕｘ（照射強度８４ｍＷ／ｍ２、３０℃、５０％ＲＨ）にて光照射し、回折効率の変化を測定したところ、図４に示すとおり、本発明の処理方法によって作製された漂白位相型ホログラムは３００時間後においても作製直後の回折効率をほぼ維持していることが分かった。 <Light resistance test>
In addition, in order to evaluate light resistance, a xenon weather meter (trade name “XL75”, manufactured by Suga Test Instruments Co., Ltd.) is irradiated with light at an illuminance of 115 klux (irradiation intensity: 84 mW / m 2 , 30 ° C., 50% RH), and diffraction. When the change in efficiency was measured, as shown in FIG. 4, it was found that the bleaching phase hologram produced by the processing method of the present invention almost maintained the diffraction efficiency immediately after production even after 300 hours.
また、耐光性を評価するために、キセノンウェザーメーター（商品名『ＸＬ７５』、スガ試験機社製造）照度１１５ｋｌｕｘ（照射強度８４ｍＷ／ｍ２、３０℃、５０％ＲＨ）にて光照射し、回折効率の変化を測定したところ、図４に示すとおり、本発明の処理方法によって作製された漂白位相型ホログラムは３００時間後においても作製直後の回折効率をほぼ維持していることが分かった。 <Light resistance test>
In addition, in order to evaluate light resistance, a xenon weather meter (trade name “XL75”, manufactured by Suga Test Instruments Co., Ltd.) is irradiated with light at an illuminance of 115 klux (irradiation intensity: 84 mW / m 2 , 30 ° C., 50% RH), and diffraction. When the change in efficiency was measured, as shown in FIG. 4, it was found that the bleaching phase hologram produced by the processing method of the present invention almost maintained the diffraction efficiency immediately after production even after 300 hours.
本発明の漂白位相型ホログラムについて、その透過吸収スペクトルを測定すると、波長４２０ｎｍの吸光度と波長４７０ｎｍでの吸光度の差が２以上あり、即ち、ヨウ化銀の吸収波長の４２０ｎｍにおける吸光度が波長４７０ｎｍの吸光度に対して２以上大きく、ヨウ化銀以外の化合物に由来する、例えば、波長４７０ｎｍに吸収をもつ化合物がほとんどない漂白位相型ホログラムとなり、少し黄色味を帯びた色彩ではあるが、実質的に波長４５０ｎｍ以上の可視域に吸収を持たない明るい漂白位相型ホログラムであることがわかった（図５、参照）。このことから、本発明の漂白位相型ホログラムは、少し黄色味を帯びていてもよい、色彩にこだわることのない漂白位相型ホログラムに極めて有用であると考えられる。また、本発明の耐光性に優れた漂白位相型ホログラムは、その他の記録材料に露光転写させるホログラム記録原板として利用することも可能である。
When the transmission absorption spectrum of the bleached phase hologram of the present invention is measured, there is a difference between the absorbance at a wavelength of 420 nm and the absorbance at a wavelength of 470 nm, that is, the absorbance at 420 nm of the absorption wavelength of silver iodide is at a wavelength of 470 nm. It becomes a bleached phase hologram that is larger than the absorbance by 2 or more and is derived from a compound other than silver iodide, for example, a compound having almost no absorption at a wavelength of 470 nm. It was found to be a bright bleached phase type hologram having no absorption in the visible region having a wavelength of 450 nm or more (see FIG. 5). From this, it is considered that the bleaching phase hologram of the present invention is extremely useful for a bleaching phase hologram that may be slightly yellowish and does not stick to color. Further, the bleaching phase hologram having excellent light resistance according to the present invention can be used as a hologram recording original plate to be exposed and transferred to other recording materials.
＜比較例＞
比較例として、エチレンジアミン四酢酸−鉄（ＩＩＩ）ナトリウムを漂白処理材料として用いた漂白処理の後に、ヨウ化カリウム水溶液による安定化処理を施さない漂白位相型ホログラム（比較例１：ＥＤＴＡ漂白処方）と、実施例１として記載の本発明のホログラム用感光材料の処理方法（ＥＤＴＡ漂白＋ＫＩ（ヨウ化カリウム）安定化処理）のうち、漂白処理材料を変更し、下記に示す従来から提案されている漂白処理剤によって処理した漂白位相型ホログラム（比較例２~５）について、同様に評価した。 <Comparative example>
As a comparative example, a bleaching phase hologram (Comparative Example 1: EDTA bleaching prescription) that is not subjected to a stabilization treatment with an aqueous potassium iodide solution after a bleaching treatment using ethylenediaminetetraacetic acid-sodium iron (III) as a bleaching treatment material; Of the processing methods (EDTA bleaching + KI (potassium iodide) stabilization processing) of the hologram photosensitive material of the present invention described in Example 1, the bleaching processing materials are changed and the conventionally proposed bleaching shown below. Bleached phase holograms (Comparative Examples 2 to 5) treated with a treating agent were similarly evaluated.
比較例として、エチレンジアミン四酢酸−鉄（ＩＩＩ）ナトリウムを漂白処理材料として用いた漂白処理の後に、ヨウ化カリウム水溶液による安定化処理を施さない漂白位相型ホログラム（比較例１：ＥＤＴＡ漂白処方）と、実施例１として記載の本発明のホログラム用感光材料の処理方法（ＥＤＴＡ漂白＋ＫＩ（ヨウ化カリウム）安定化処理）のうち、漂白処理材料を変更し、下記に示す従来から提案されている漂白処理剤によって処理した漂白位相型ホログラム（比較例２~５）について、同様に評価した。 <Comparative example>
As a comparative example, a bleaching phase hologram (Comparative Example 1: EDTA bleaching prescription) that is not subjected to a stabilization treatment with an aqueous potassium iodide solution after a bleaching treatment using ethylenediaminetetraacetic acid-sodium iron (III) as a bleaching treatment material; Of the processing methods (EDTA bleaching + KI (potassium iodide) stabilization processing) of the hologram photosensitive material of the present invention described in Example 1, the bleaching processing materials are changed and the conventionally proposed bleaching shown below. Bleached phase holograms (Comparative Examples 2 to 5) treated with a treating agent were similarly evaluated.
比較例１：ＥＤＴＡ漂白処方
エチレンジアミン四酢酸−鉄（ＩＩＩ）ナトリウム １５ｇ
硝酸水素ナトリウム １５ｇ
臭化カリウム １５ｇ
純水で５００ｍＬにする。 Comparative Example 1: EDTA bleaching formulation Ethylenediaminetetraacetic acid-iron (III) sodium 15 g
Sodium hydrogen nitrate 15g
Potassium bromide 15g
Make up to 500 mL with pure water.
エチレンジアミン四酢酸−鉄（ＩＩＩ）ナトリウム １５ｇ
硝酸水素ナトリウム １５ｇ
臭化カリウム １５ｇ
純水で５００ｍＬにする。 Comparative Example 1: EDTA bleaching formulation Ethylenediaminetetraacetic acid-iron (III) sodium 15 g
Sodium hydrogen nitrate 15g
Potassium bromide 15g
Make up to 500 mL with pure water.
比較例２：ヨウ素漂白処方
ヨウ素 １００ｍｇ
エチルアルコール １００ｍｌ
純水 ２５ｍｌ Comparative Example 2: Iodine bleaching formula Iodine 100mg
Ethyl alcohol 100ml
25 ml of pure water
ヨウ素 １００ｍｇ
エチルアルコール １００ｍｌ
純水 ２５ｍｌ Comparative Example 2: Iodine bleaching formula Iodine 100mg
Ethyl alcohol 100ml
25 ml of pure water
比較例３：臭素酸カリ漂白処方
エチレンジアミン四酢酸−鉄（ＩＩＩ）ナトリウム ２５ｇ
臭素酸カリウム ３ｇ
臭化カリウム １５ｇ
１％硫酸水溶液 １００ｍｌ
純水で１Ｌにする。 Comparative Example 3: Potassium bromate bleaching formula Ethylenediaminetetraacetic acid-iron (III) sodium 25 g
Potassium bromate 3g
Potassium bromide 15g
1% sulfuric acid aqueous solution 100ml
Make to 1 L with pure water.
エチレンジアミン四酢酸−鉄（ＩＩＩ）ナトリウム ２５ｇ
臭素酸カリウム ３ｇ
臭化カリウム １５ｇ
１％硫酸水溶液 １００ｍｌ
純水で１Ｌにする。 Comparative Example 3: Potassium bromate bleaching formula Ethylenediaminetetraacetic acid-iron (III) sodium 25 g
Potassium bromate 3g
Potassium bromide 15g
1% sulfuric acid aqueous solution 100ml
Make to 1 L with pure water.
比較例４：フェリシアン化カリ漂白処方
フェリシアン化カリウム ４５ｇ
ヨウ化カリウム ２５ｇ
純水で１Ｌにする。 Comparative Example 4: Potassium ferricyanide bleaching formula 45 g potassium ferricyanide
Potassium iodide 25g
Make to 1 L with pure water.
フェリシアン化カリウム ４５ｇ
ヨウ化カリウム ２５ｇ
純水で１Ｌにする。 Comparative Example 4: Potassium ferricyanide bleaching formula 45 g potassium ferricyanide
Potassium iodide 25g
Make to 1 L with pure water.
比較例５：ＥＤＴＡ（ＫＩ）漂白処方
エチレンジアミン四酢酸−鉄（ＩＩＩ）ナトリウム １５ｇ
硫酸水素ナトリウム １５ｇ
ヨウ化カリウム ２１．５ｇ
純水で５００ｍｌにする。 Comparative Example 5: EDTA (KI) bleaching formulation Ethylenediaminetetraacetic acid-iron (III) sodium 15 g
Sodium hydrogen sulfate 15g
Potassium iodide 21.5g
Make up to 500 ml with pure water.
エチレンジアミン四酢酸−鉄（ＩＩＩ）ナトリウム １５ｇ
硫酸水素ナトリウム １５ｇ
ヨウ化カリウム ２１．５ｇ
純水で５００ｍｌにする。 Comparative Example 5: EDTA (KI) bleaching formulation Ethylenediaminetetraacetic acid-iron (III) sodium 15 g
Sodium hydrogen sulfate 15g
Potassium iodide 21.5g
Make up to 500 ml with pure water.
比較例の漂白位相型ホログラムは、いずれも作製直後の回折効率は５５％を下回り（表１、参照）、安定化処理を行った本発明の漂白位相型ホログラムよりも劣り、また、図４に示すとおり、耐光性試験を行ったときの３００時間後の回折効率はいずれも十分な値が得られなかった。
The bleaching phase holograms of the comparative examples all have a diffraction efficiency of less than 55% immediately after production (see Table 1), which is inferior to the bleaching phase hologram of the present invention that has been subjected to stabilization treatment. As shown, the diffraction efficiency after 300 hours when the light resistance test was performed was not sufficient.
以上のことから、ホログラム用ハロゲン化銀感光材料を露光後、現像処理を行った後に、エチレンジアミン四酢酸−鉄（ＩＩＩ）ナトリウムを漂白処理材料として用いて漂白処理工程を行った後に、さらにヨウ化カリウム水溶液による安定化処理を行うことによって、作製後の回折効率が高く、その後、長期間保存した後に高い回折効率を維持した耐光性に優れた漂白位相型ホログラムを作製することができることがわかった。
From the above, after the exposure of the silver halide photosensitive material for hologram, after developing, after performing a bleaching step using ethylenediaminetetraacetic acid-iron (III) sodium as a bleaching material, further iodide It was found that by performing stabilization treatment with an aqueous potassium solution, it is possible to produce a bleaching phase hologram that has high diffraction efficiency after production, and then has excellent light resistance that maintains high diffraction efficiency after long-term storage. .
＜光劣化後の再漂白処理＞
比較例１に記載のエチレンジアミン四酢酸−鉄（ＩＩＩ）ナトリウムを漂白処理材料として用いた漂白処理の後に、ヨウ化カリウム水溶液による安定化処理を施さなかった漂白位相型ホログラムについては、作製直後の回折効率が５５％であったが、耐光性試験により、３６時間後には１７％の回折効率にまで低下してしまった（図４の比較例１に関するグラフ、および、露光時間０乃至３６時間の範囲の拡大図である図６、参照）。これは、既述したように、現像・漂白処理により現像銀がハロゲン化銀に変換され、安定化処理を施さなかったため、光劣化により再び現像銀となり、耐光性の悪化ならびに回折効率の低下を招いたと考えられる。 <Re-bleaching after photodegradation>
For the bleached phase hologram that was not subjected to stabilization treatment with an aqueous potassium iodide solution after bleaching treatment using ethylenediaminetetraacetic acid-iron (III) sodium as described in Comparative Example 1 as a bleaching treatment material, diffraction immediately after production was performed. Although the efficiency was 55%, it was reduced to a diffraction efficiency of 17% after 36 hours by the light resistance test (the graph relating to Comparative Example 1 in FIG. 4 and the exposure time range of 0 to 36 hours). FIG. 6 is an enlarged view of FIG. As described above, the developed silver is converted into silver halide by the development / bleaching process and is not subjected to the stabilization process. Therefore, the developed silver is again developed by the light deterioration, which deteriorates the light resistance and the diffraction efficiency. It is thought that he was invited.
比較例１に記載のエチレンジアミン四酢酸−鉄（ＩＩＩ）ナトリウムを漂白処理材料として用いた漂白処理の後に、ヨウ化カリウム水溶液による安定化処理を施さなかった漂白位相型ホログラムについては、作製直後の回折効率が５５％であったが、耐光性試験により、３６時間後には１７％の回折効率にまで低下してしまった（図４の比較例１に関するグラフ、および、露光時間０乃至３６時間の範囲の拡大図である図６、参照）。これは、既述したように、現像・漂白処理により現像銀がハロゲン化銀に変換され、安定化処理を施さなかったため、光劣化により再び現像銀となり、耐光性の悪化ならびに回折効率の低下を招いたと考えられる。 <Re-bleaching after photodegradation>
For the bleached phase hologram that was not subjected to stabilization treatment with an aqueous potassium iodide solution after bleaching treatment using ethylenediaminetetraacetic acid-iron (III) sodium as described in Comparative Example 1 as a bleaching treatment material, diffraction immediately after production was performed. Although the efficiency was 55%, it was reduced to a diffraction efficiency of 17% after 36 hours by the light resistance test (the graph relating to Comparative Example 1 in FIG. 4 and the exposure time range of 0 to 36 hours). FIG. 6 is an enlarged view of FIG. As described above, the developed silver is converted into silver halide by the development / bleaching process and is not subjected to the stabilization process. Therefore, the developed silver is again developed by the light deterioration, which deteriorates the light resistance and the diffraction efficiency. It is thought that he was invited.
ここで、光劣化により１７％までに回折効率の低下した比較例１の漂白位相型ホログラムを再度比較例１と同じ条件で漂白処理を行い回折効率の回復を試みたところ、作製直後の回折効率５５％まで回復せず、３９％と作製直後の回折効率の約７０％しか回復できなかった（図６、参照）。したがって、一旦、回折効率が低下した漂白位相型ホログラムの回折効率を回復させることは困難であり、従来の処理方法で作製した漂白位相型ホログラムでは、長時間の保存によって高い回折効率を維持することは難しいことがわかった。
Here, when the bleaching phase hologram of Comparative Example 1 whose diffraction efficiency was reduced to 17% due to light deterioration was again bleached under the same conditions as in Comparative Example 1, an attempt was made to restore the diffraction efficiency. It did not recover to 55%, and only 39%, which was about 70% of the diffraction efficiency immediately after fabrication, was recovered (see FIG. 6). Therefore, it is difficult to recover the diffraction efficiency of a bleached phase hologram whose diffraction efficiency has once decreased, and a bleached phase hologram produced by a conventional processing method can maintain high diffraction efficiency by long-term storage. Found it difficult.
以上のとおり、使用するホログラム用ハロゲン化銀感光材料の支持体上に塗布形成されたハロゲン化銀乳剤層の厚み、ハロゲン化乳剤に含まれる銀量、銀／分散媒体の比率ならびにハロゲン化銀粒子の種類等によって適宜処理条件を考える場合があっても、エチレンジアミン四酢酸−鉄（ＩＩＩ）ナトリウムを漂白処理材料として用いた漂白処理工程に続き一連の処理として、ヨウ化カリウム水溶液による安定化処理を十分に施すこと、つまり、作製した漂白位相型ホログラムの透過吸収スペクトルを測定したときに、ヨウ化銀の吸収波長に相当する波長４２０ｎｍの吸光度と波長４７０ｎｍでの吸光度の差が２以上となる条件にて処理を行えば、作製される漂白位相型ホログラムは耐光性の優れた、高い回折効率を有する漂白位相型ホログラムとなることが確認された。
As described above, the thickness of the silver halide emulsion layer formed on the support of the silver halide photosensitive material for hologram used, the amount of silver contained in the halide emulsion, the ratio of silver / dispersion medium, and silver halide grains Depending on the type of treatment, the treatment conditions may be considered as appropriate, but a stabilization treatment with an aqueous potassium iodide solution is performed as a series of treatments following the bleaching treatment step using ethylenediaminetetraacetic acid-sodium iron (III) as a bleaching treatment material. Apply sufficiently, that is, when the transmission absorption spectrum of the prepared bleach phase hologram is measured, a condition that the difference between the absorbance at a wavelength of 420 nm corresponding to the absorption wavelength of silver iodide and the absorbance at a wavelength of 470 nm is 2 or more The bleached phase hologram produced is a bleached phase hologram with excellent light resistance and high diffraction efficiency. It was confirmed to be a lamb.
叙上のごとく、本発明のハロゲン化銀感光材料の処理方法を用いることにより、長期間保存可能な耐光性に優れた、高い回折効率を有する漂白位相型ホログラムが得られ、この漂白位相型ホログラムはディスプレー用、医療用、或いは偽造防止用印刷の各種分野に用いられるホログラムとして、更には、高効率ホログラムグレーティング素子、二色性フィルター、二色性ミラー、ホログラムリフレクター、ホログラム集光素子・拡散素子、或いはカラーフィルタリング素子などとして極めて有用である。
As described above, by using the method for processing a silver halide photosensitive material of the present invention, a bleaching phase hologram having excellent light resistance and high diffraction efficiency that can be stored for a long period of time can be obtained. Is a hologram used in various fields of display, medical, or anti-counterfeit printing, and furthermore, a high-efficiency hologram grating element, dichroic filter, dichroic mirror, hologram reflector, hologram condensing element / diffusion element Or as a color filtering element.
Ｓ シャッター
Ｍ１、Ｍ２、Ｍ３ ミラー
ＯＢ 対物レンズ
ＣＬ コリメータレンズ
ＢＳ ビームスプリッター
Ｈ１ 乾板ホルダー S Shutter M1, M2, M3 Mirror OB Objective lens CL Collimator lens BS Beam splitter H1 Dry plate holder
Ｍ１、Ｍ２、Ｍ３ ミラー
ＯＢ 対物レンズ
ＣＬ コリメータレンズ
ＢＳ ビームスプリッター
Ｈ１ 乾板ホルダー S Shutter M1, M2, M3 Mirror OB Objective lens CL Collimator lens BS Beam splitter H1 Dry plate holder
Claims (5)
- 支持体上に感光性ハロゲン化銀乳剤を含むハロゲン化銀乳剤層を有するホログラム用ハロゲン化銀感光材料を露光後、現像処理工程、エチレンジアミン四酢酸またはその塩を漂白処理材料として用いる漂白処理工程を順次施した後に、ヨウ化カリウム水溶液を用いた安定化処理工程を施す工程を含む、透過吸収スペクトル測定における波長４２０ｎｍの吸光度と波長４７０ｎｍでの吸光度の差が２以上である漂白位相型ホログラムを得るためのホログラム用ハロゲン化銀感光材料の処理方法。 After exposing a silver halide photosensitive material for hologram having a silver halide emulsion layer containing a photosensitive silver halide emulsion on a support, a development processing step, and a bleaching processing step using ethylenediaminetetraacetic acid or a salt thereof as a bleaching processing material A bleaching phase hologram is obtained in which the difference between the absorbance at a wavelength of 420 nm and the absorbance at a wavelength of 470 nm in a transmission absorption spectrum measurement is 2 or more, including a step of performing a stabilization treatment step using an aqueous potassium iodide solution after sequential application. For processing a silver halide photosensitive material for hologram.
- ヨウ化カリウム水溶液の濃度が、濃度１．５乃至１０質量％であって、安定化処理工程の処理時間が、２乃至１０分の範囲である請求の範囲第１項記載のホログラム用ハロゲン化銀感光材料の処理法方法。 The silver halide for hologram according to claim 1, wherein the concentration of the potassium iodide aqueous solution is 1.5 to 10% by mass and the treatment time of the stabilization treatment step is in the range of 2 to 10 minutes. Method for processing photosensitive material.
- 請求の範囲第１項又は第２項記載の処理方法を用いて得られる漂白位相型ホログラム。 A bleached phase hologram obtained by using the processing method according to claim 1 or 2.
- 透過吸収スペクトル測定において、波長４２０ｎｍの吸光度と波長４７０ｎｍでの吸光度の差が２以上あり、かつ波長４５０ｎｍ以上の可視域に吸収を持たない請求の範囲第３項記載の漂白位相型ホログラム。 The bleached phase hologram according to claim 3, wherein, in transmission absorption spectrum measurement, the difference between the absorbance at a wavelength of 420 nm and the absorbance at a wavelength of 470 nm is 2 or more, and there is no absorption in the visible region of a wavelength of 450 nm or more.
- 平均粒径が１０乃至６０ｎｍの範囲であるハロゲン化銀粒子を含む感光性ハロゲン化銀乳剤層を有する請求の範囲第１項記載の処理方法に用いられるホログラム用ハロゲン化銀感光材料。 The silver halide photosensitive material for holograms used for the processing method of Claim 1 which has the photosensitive silver halide emulsion layer containing the silver halide grain whose average particle diameter is the range of 10-60 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012541922A JPWO2012060471A1 (en) | 2010-11-05 | 2011-11-04 | Method for processing silver halide photosensitive material for hologram, and bleached phase hologram obtained by the processing method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-248863 | 2010-11-05 | ||
| JP2010248863 | 2010-11-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2012060471A1 true WO2012060471A1 (en) | 2012-05-10 |
Family
ID=46024580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2011/076015 WO2012060471A1 (en) | 2010-11-05 | 2011-11-04 | Method for treating photosensitive silver halide material for hologram, and bleached phase hologram obtained using this treatment method |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPWO2012060471A1 (en) |
| WO (1) | WO2012060471A1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09251199A (en) * | 1996-03-15 | 1997-09-22 | Konica Corp | Silver halide photosensitive material for transmission type hologram and image forming method therefor |
| JPH103250A (en) * | 1996-06-14 | 1998-01-06 | Konica Corp | Silver halide photographic sensitive material for hologram and its processing method |
| JPH10123643A (en) * | 1996-10-21 | 1998-05-15 | Konica Corp | Silver halide photographic material for hologram |
| JPH10149084A (en) * | 1996-11-19 | 1998-06-02 | Konica Corp | Silver halide photosensitive material for hologram |
| JPH10149083A (en) * | 1996-11-18 | 1998-06-02 | Konica Corp | Silver halide photosensitive material for hologram |
| JP2004219435A (en) * | 2003-01-09 | 2004-08-05 | Konica Minolta Holdings Inc | Silver halide photographic sensitive material for hologram, hologram forming method, and hologram forming system |
-
2011
- 2011-11-04 WO PCT/JP2011/076015 patent/WO2012060471A1/en active Application Filing
- 2011-11-04 JP JP2012541922A patent/JPWO2012060471A1/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09251199A (en) * | 1996-03-15 | 1997-09-22 | Konica Corp | Silver halide photosensitive material for transmission type hologram and image forming method therefor |
| JPH103250A (en) * | 1996-06-14 | 1998-01-06 | Konica Corp | Silver halide photographic sensitive material for hologram and its processing method |
| JPH10123643A (en) * | 1996-10-21 | 1998-05-15 | Konica Corp | Silver halide photographic material for hologram |
| JPH10149083A (en) * | 1996-11-18 | 1998-06-02 | Konica Corp | Silver halide photosensitive material for hologram |
| JPH10149084A (en) * | 1996-11-19 | 1998-06-02 | Konica Corp | Silver halide photosensitive material for hologram |
| JP2004219435A (en) * | 2003-01-09 | 2004-08-05 | Konica Minolta Holdings Inc | Silver halide photographic sensitive material for hologram, hologram forming method, and hologram forming system |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2012060471A1 (en) | 2014-05-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS5851252B2 (en) | silver halide photographic emulsion | |
| US4025345A (en) | Method of preparing bleached phase hologram and a bleaching solution composition therefor | |
| JPS6014334B2 (en) | Shadow image forming method | |
| WO2012060471A1 (en) | Method for treating photosensitive silver halide material for hologram, and bleached phase hologram obtained using this treatment method | |
| JPS581408B2 (en) | Shin-halogen storage case | |
| JP2514316B2 (en) | Silver halide photographic material | |
| JPS62194248A (en) | Internal latent image type silver halide emulsion | |
| US4217405A (en) | Production of volume dielectric holograms | |
| JPH10149084A (en) | Silver halide photosensitive material for hologram | |
| JPS626251A (en) | Silver halide photographic sensitive material | |
| JPH10123643A (en) | Silver halide photographic material for hologram | |
| JP3531018B2 (en) | Method for producing silver halide photographic light-sensitive material | |
| JPH103250A (en) | Silver halide photographic sensitive material for hologram and its processing method | |
| JP2613406B2 (en) | Direct positive silver halide photographic material | |
| JPH09251199A (en) | Silver halide photosensitive material for transmission type hologram and image forming method therefor | |
| JPS63163453A (en) | Manufacture of hologram | |
| JP2654703B2 (en) | Direct positive image forming method | |
| JPH037091B2 (en) | ||
| JPH0690453B2 (en) | Direct positive image formation method | |
| JPH10149083A (en) | Silver halide photosensitive material for hologram | |
| JPH0320742B2 (en) | ||
| JPH0227329A (en) | Silver halide photographic paper | |
| JPS6014336B2 (en) | Shadow image forming method | |
| JP2007065188A (en) | Silver halide holographic photosensitive material, processing method therefor, bleaching liquid, and hologram | |
| JPS61260236A (en) | Silver halide photographic sensitive material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11838118 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 2012541922 Country of ref document: JP Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 11838118 Country of ref document: EP Kind code of ref document: A1 |