EP0212534B1 - Heat-developable colour-photographic recording material - Google Patents
Heat-developable colour-photographic recording material Download PDFInfo
- Publication number
- EP0212534B1 EP0212534B1 EP86111108A EP86111108A EP0212534B1 EP 0212534 B1 EP0212534 B1 EP 0212534B1 EP 86111108 A EP86111108 A EP 86111108A EP 86111108 A EP86111108 A EP 86111108A EP 0212534 B1 EP0212534 B1 EP 0212534B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- silver
- color
- recording material
- binder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000463 material Substances 0.000 title claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 54
- -1 silver halide Chemical class 0.000 claims description 49
- 229910052709 silver Inorganic materials 0.000 claims description 40
- 239000004332 silver Substances 0.000 claims description 40
- 239000011230 binding agent Substances 0.000 claims description 31
- 238000011161 development Methods 0.000 claims description 30
- 229920000159 gelatin Polymers 0.000 claims description 23
- 235000019322 gelatine Nutrition 0.000 claims description 23
- 239000004814 polyurethane Substances 0.000 claims description 22
- 229920002635 polyurethane Polymers 0.000 claims description 22
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 21
- 125000000129 anionic group Chemical group 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000001828 Gelatine Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 62
- 239000000975 dye Substances 0.000 description 51
- 239000000243 solution Substances 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 229920000728 polyester Polymers 0.000 description 25
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 23
- 239000000523 sample Substances 0.000 description 21
- 108010010803 Gelatin Proteins 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 19
- 239000008273 gelatin Substances 0.000 description 19
- 235000011852 gelatine desserts Nutrition 0.000 description 19
- 239000000839 emulsion Substances 0.000 description 16
- 150000003378 silver Chemical class 0.000 description 16
- CUUNWWCQMKJKRR-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid;hexane-1,1-diol Chemical compound OCC(C)(C)CO.CCCCCC(O)O.OC(=O)CCCCC(O)=O CUUNWWCQMKJKRR-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000009792 diffusion process Methods 0.000 description 14
- 125000000217 alkyl group Chemical class 0.000 description 13
- 238000000034 method Methods 0.000 description 13
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- 239000003973 paint Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 12
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- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 229940117969 neopentyl glycol Drugs 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
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- 238000005266 casting Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- CZLCEPVHPYKDPJ-UHFFFAOYSA-N guanidine;2,2,2-trichloroacetic acid Chemical compound NC(N)=N.OC(=O)C(Cl)(Cl)Cl CZLCEPVHPYKDPJ-UHFFFAOYSA-N 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000012992 electron transfer agent Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- NSFYPZRDTCJZAS-UHFFFAOYSA-M sodium;1-aminoethanesulfonate Chemical compound [Na+].CC(N)S([O-])(=O)=O NSFYPZRDTCJZAS-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- KPVMVJXYXFUVLR-UHFFFAOYSA-N 12-ethyltetradecan-1-amine Chemical compound CCC(CC)CCCCCCCCCCCN KPVMVJXYXFUVLR-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
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- 150000003839 salts Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical class C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 3
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical class C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 229920000084 Gum arabic Polymers 0.000 description 2
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- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
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- 239000010937 tungsten Substances 0.000 description 2
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- IBWXIFXUDGADCV-UHFFFAOYSA-N 2h-benzotriazole;silver Chemical compound [Ag].C1=CC=C2NN=NC2=C1 IBWXIFXUDGADCV-UHFFFAOYSA-N 0.000 description 1
- YLBAGJYQBOPFCD-UHFFFAOYSA-N 4-ethenyl-1-methyl-2h-pyridine Chemical compound CN1CC=C(C=C)C=C1 YLBAGJYQBOPFCD-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- 229940006015 4-hydroxybutyric acid Drugs 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical class CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- PUGUFBAPNSPHHY-UHFFFAOYSA-N 4-phenyl-1h-1,2,4-triazole-5-thione Chemical class SC1=NN=CN1C1=CC=CC=C1 PUGUFBAPNSPHHY-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
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- IZXSLAZMYLIILP-ODZAUARKSA-M silver (Z)-4-hydroxy-4-oxobut-2-enoate Chemical compound [Ag+].OC(=O)\C=C/C([O-])=O IZXSLAZMYLIILP-ODZAUARKSA-M 0.000 description 1
- NBYLLBXLDOPANK-UHFFFAOYSA-M silver 2-carboxyphenolate hydrate Chemical compound C1=CC=C(C(=C1)C(=O)O)[O-].O.[Ag+] NBYLLBXLDOPANK-UHFFFAOYSA-M 0.000 description 1
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- YRSQDSCQMOUOKO-KVVVOXFISA-M silver;(z)-octadec-9-enoate Chemical compound [Ag+].CCCCCCCC\C=C/CCCCCCCC([O-])=O YRSQDSCQMOUOKO-KVVVOXFISA-M 0.000 description 1
- RUVFQTANUKYORF-UHFFFAOYSA-M silver;2,4-dichlorobenzoate Chemical compound [Ag+].[O-]C(=O)C1=CC=C(Cl)C=C1Cl RUVFQTANUKYORF-UHFFFAOYSA-M 0.000 description 1
- OEVSPXPUUSCCIH-UHFFFAOYSA-M silver;2-acetamidobenzoate Chemical compound [Ag+].CC(=O)NC1=CC=CC=C1C([O-])=O OEVSPXPUUSCCIH-UHFFFAOYSA-M 0.000 description 1
- JRTHUBNDKBQVKY-UHFFFAOYSA-M silver;2-methylbenzoate Chemical compound [Ag+].CC1=CC=CC=C1C([O-])=O JRTHUBNDKBQVKY-UHFFFAOYSA-M 0.000 description 1
- OXOZKDHFGLELEO-UHFFFAOYSA-M silver;3-carboxy-5-hydroxyphenolate Chemical compound [Ag+].OC1=CC(O)=CC(C([O-])=O)=C1 OXOZKDHFGLELEO-UHFFFAOYSA-M 0.000 description 1
- UCLXRBMHJWLGSO-UHFFFAOYSA-M silver;4-methylbenzoate Chemical compound [Ag+].CC1=CC=C(C([O-])=O)C=C1 UCLXRBMHJWLGSO-UHFFFAOYSA-M 0.000 description 1
- CLDWGXZGFUNWKB-UHFFFAOYSA-M silver;benzoate Chemical group [Ag+].[O-]C(=O)C1=CC=CC=C1 CLDWGXZGFUNWKB-UHFFFAOYSA-M 0.000 description 1
- OIZSSBDNMBMYFL-UHFFFAOYSA-M silver;decanoate Chemical compound [Ag+].CCCCCCCCCC([O-])=O OIZSSBDNMBMYFL-UHFFFAOYSA-M 0.000 description 1
- MNMYRUHURLPFQW-UHFFFAOYSA-M silver;dodecanoate Chemical compound [Ag+].CCCCCCCCCCCC([O-])=O MNMYRUHURLPFQW-UHFFFAOYSA-M 0.000 description 1
- GXBIBRDOPVAJRX-UHFFFAOYSA-M silver;furan-2-carboxylate Chemical compound [Ag+].[O-]C(=O)C1=CC=CO1 GXBIBRDOPVAJRX-UHFFFAOYSA-M 0.000 description 1
- LTYHQUJGIQUHMS-UHFFFAOYSA-M silver;hexadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCC([O-])=O LTYHQUJGIQUHMS-UHFFFAOYSA-M 0.000 description 1
- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 description 1
- OHGHHPYRRURLHR-UHFFFAOYSA-M silver;tetradecanoate Chemical compound [Ag+].CCCCCCCCCCCCCC([O-])=O OHGHHPYRRURLHR-UHFFFAOYSA-M 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- MWASJOFAOJVIGL-UHFFFAOYSA-M sodium;2h-benzotriazole-4-carboxylate Chemical compound [Na+].[O-]C(=O)C1=CC=CC2=C1N=NN2 MWASJOFAOJVIGL-UHFFFAOYSA-M 0.000 description 1
- KQFAFFYKLIBKDE-UHFFFAOYSA-M sodium;ethanesulfonate Chemical compound [Na+].CCS([O-])(=O)=O KQFAFFYKLIBKDE-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
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- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/40—Development by heat ; Photo-thermographic processes
- G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
- G03C8/408—Additives or processing agents not provided for in groups G03C8/402 - G03C8/4046
-
- 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
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
-
- 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
- G03C1/00—Photosensitive materials
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/498—Photothermographic systems, e.g. dry silver
- G03C1/49836—Additives
- G03C1/49863—Inert additives, e.g. surfactants, binders
Definitions
- the invention relates to a color photographic recording material which can be developed by heat treatment and has at least one binder layer which is applied to a layer support and which contains light-sensitive silver halide and a non-diffusing coloring compound, the binder layer containing a synthetic polymer as binder.
- color-providing compound those which can be embedded in the layer of a photographic recording material in non-diffusing form and which, as a result of the development, are able to release a diffusible dye (color releaser).
- color releaser a diffusible dye
- the particular suitability of such color releasers is based on the fact that the imagewise released dyes can be transferred to special image-receiving layers with the formation of a brilliant color image which is not overlaid with disruptive image silver or silver halide and accordingly does not require any aftertreatment. Combining the heat development process with the color diffusion process thus results in an advantageous rapid process for producing colored images.
- a recording material suitable for this is described, for example, in DE-A-3 215 485.
- a recording material having a layer which contains a combination of silver halide, silver benzotriazole, a color releaser and guanidine trichloroacetate (base donor) in a hydrobene binder is exposed imagewise and then subjected to a heat treatment in contact with an image-receiving sheet, the imagewise released dye the image receiving sheet is transferred.
- the silver halide in each of these combinations being sensitive to a different spectral range of the light and, in accordance with its spectral sensitivity, containing a color releaser which releases a dye of a different color, usually a color that is complementary is the color of the light for which the silver halide in question has a predominant sensitivity.
- Such assignments can be arranged one above the other in different layers.
- the color images obtained with the known color photographic recording material which can be developed by heat treatment have rather low maximum color densities and high fog.
- the recording material also leaves something to be desired in terms of sensitivity.
- the application is therefore based on the object of specifying a color photographic recording material which can be developed by heat treatment and which is further improved in terms of the Dmin / Dmax variation and in terms of sensitivity.
- the present invention relates to a heat treatment-developable photographic recording material having at least one binder layer applied to a layer, which contains light-sensitive silver halide, optionally combined with a substantially non-light-sensitive silver salt, and at least one non-diffusing color-providing compound which, as a result of the development by heat treatment is able to release a diffusible dye, which is characterized in that the binder of said binder layer contains at least 30% by weight. consists of a polyurethane containing anionic groups.
- the color photographic recording material according to the invention contains, on a dimensionally stable support, at least one binder layer which contains, as essential components, a light-sensitive silver halide, optionally in combination with an essentially non-light-sensitive silver salt, and a non-diffusing color-imparting compound which can produce a diffusible dye through heat development.
- the light-sensitive silver halide can consist of silver chloride, silver bromide, silver iodide or mixtures thereof and a particle size between 0.01 and 2.0 ⁇ m. preferably have between 0.1 and 1.0 ⁇ m. It can be in the form of an unsensitized silver halide or it can also be chemically sensitized, e.g. B. with compounds of sulfur, selenium or tellurium, or with compounds of gold, platinum, palladium, rhodium or iridium, or with a reducing agent, such as. B. a tin halide, or a combination thereof.
- the silver halide can additionally be spectrally sensitized with known organic sensitizing dyes.
- the amount of light-sensitive silver halide in the respective layer can be between 0.01 and 2.0 g per m 2 , the actual amount of the silver halide used, due to its catalytic function (as exposed silver halide) in some embodiments, mainly in the lower part of the stated Area moved.
- the substantially non-light-sensitive silver salt can be, for example, a silver salt which is comparatively stable to light, e.g. B. act an organic silver salt.
- Suitable examples include the silver salts of aliphatic or aromatic carboxylic acids and the silver salts of nitrogen-containing heterocycles; also silver salts of organic mercapto compounds.
- Preferred examples of silver salts of aliphatic carboxylic acids are silver behenate, silver stearate, silver oleate, silver laurate, silver caprate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartrate, silver furoate, silver linolate, silver adipate, silver sebacate, silver succinate, silver acetate or silver acetate.
- the carboxylic acids on which these silver salts are based can be substituted, for example, by halogen atoms, hydroxyl groups or thioether groups.
- silver salts of aromatic carboxylic acids and other compounds containing carboxyl groups include silver benzoate, silver 3,5-dihydroxybenzoate, silver o-methylbenzoate, silver m-methylbenzoate, silver p-methylbenzoate, silver 2,4-dichlorobenzoate, silver acetamidobenzoate , Silver gallate, silver tannate, silver phthalate, silver terephthalate, silver salicylate, silver phenylacetate, silver pyromellitate, silver salts of 3-carboxymethyl-4-methyl-4-thiazolin-2-thione or similar heterocyclic compounds.
- Silver salts of organic mercaptans e.g. B.
- the silver salts of compounds having an imino group are also suitable.
- Preferred examples include the silver salts of benzotriazole and its derivatives, e.g. B. silver salts of alkyl and / or halogen-substituted benzotriazoles, such as. B. the silver salts of methylbenzotriazole, 5-chlorobenzotriazole and also the silver salts of 1,2,4-triazole, 1-H-tetrazole, carbazole, saccharin and silver salts of imidazole, benzimidazole and their derivatives.
- the application amount of essentially non-photosensitive silver salt according to the present invention is in the respective layer between 0.05 and 5 g per m 2 .
- the essentially non-light-sensitive silver salt and the light-sensitive silver halide can be present side by side as separate particles or in a combined form, which can be produced, for example, by treating a substantially non-light-sensitive silver salt in the presence of halide ions, the surface of which Particles of the essentially non-photosensitive silver salt are formed by double conversion (conversion) of photosensitive centers from photosensitive silver halide.
- halide ions the surface of which Particles of the essentially non-photosensitive silver salt are formed by double conversion (conversion) of photosensitive centers from photosensitive silver halide.
- conversion conversion
- the essentially non-light-sensitive silver salt serves as a reservoir for metal ions, which are reduced to elemental silver when heat is developed in the presence of a reducing agent under the catalytic influence of the imagewise exposed silver halide and thereby serve as an oxidizing agent (for the reducing agent present).
- Another essential component of the recording material according to the invention is at least one non-diffusing coloring compound which, as a result of a redox reaction taking place during development, is able to release a diffusible dye and which is referred to below as a color releasing agent.
- the dye releasers used according to the invention can be a variety of connection types, all of which are distinguished by a link which is redox-dependent in terms of their bond strength and which links a dye residue to a carrier residue containing a ballast residue.
- Redox-active carrier residues of the BALLAST-REDOX structure and corresponding color releasers are known in a wide variety of embodiments. A detailed description can be omitted here with regard to the above-mentioned overview article in the app. Chem. Lnt. Ed. Engl. 22 (1983) 191-209.
- redox-active carrier residues Some examples of redox-active carrier residues are listed below, by way of explanation only to which a dye residue is split off in accordance with an image-related oxidation or reduction:
- the groups enclosed in brackets are functional groups of the dye residue and are separated together with this from the remaining part of the carrier residue.
- the functional group can be a substituent which can have a direct influence on the absorption and, if appropriate, complex formation properties of the released dye.
- the functional group can also be separated from the chromophore of the dye by an intermediate link or a link.
- the functional group together with the intermediate member may also be of importance for the diffusion and pickling behavior of the released dye.
- Suitable intermediate members are, for example, alkylene or arylene groups.
- the residues of dyes of all dye classes are suitable as dye residues insofar as they are sufficiently diffusible to be able to diffuse from the light-sensitive layer of the light-sensitive material into an image-receiving layer.
- the dye residues can be provided with one or more alkali-solubilizing groups.
- Suitable alkali-solubilizing groups include carboxyl groups, sulfo groups, sulfonamide groups and aromatic hydroxyl groups.
- Such alkali-solubilizing groups can already be pre-formed in the dye releasers or can only result from the cleavage of the dye residue from the carrier residue containing ballast groups.
- Suitable dyes include: azo dyes, azomethine dyes, anthraquinone dyes, phthalocyanine dyes, indigoid dyes, triphenylmethane dyes, including those dyes that are complexed or complexable with metal ions.
- the residues of dye precursors are to be understood as the residues of those compounds which, in the course of photographic processing, in particular under the conditions of heat development, either by oxidation, by coupling, by complex formation or by exposure of an auxochromic group in a chromophoric system, for example by saponification, can be converted into dyes.
- Dye precursors in this sense can be leuco dyes, couplers or dyes that are converted into other dyes during processing. Unless a distinction is made between dye residues and the residues of dye precursors, the latter should also be understood below as dye residues.
- the color releasers can be present as oxidisable or couplable color releasers, in others as reducible color releasers.
- the dye is released from the oxidized or from the reduced form of the color releasing agent, negative or positive illumination is obtained from the original when conventional negative-working silver halide emulsions are used. You can therefore create positive or negative images by selecting suitable color releasing systems.
- DE-A-2 645 656 is described, for example, in DE-A-2 645 656 which is particularly suitable for the heat-developable recording materials according to the invention.
- the color splitter can be oxidized, then it is itself a reducing agent which, directly or indirectly, with the participation of electron transfer agents (electron transfer agent, ETA) through the imagewise exposed silver halide or through the essentially non-photosensitive silver salt under the catalytic action of the imagewise exposed Silver halide is oxidized.
- electron transfer agent electro transfer agent
- the paint releaser is reducible, then it is suitably used in combination with one; reducing agent present in a limited amount, a so-called electron donor compound or an electron donor precursor compound, which in this case is contained in the same binder layer in addition to the color releaser, the photosensitive silver halide and, if appropriate, the essentially non-photosensitive silver salt.
- reducing agent present in a limited amount, a so-called electron donor compound or an electron donor precursor compound, which in this case is contained in the same binder layer in addition to the color releaser, the photosensitive silver halide and, if appropriate, the essentially non-photosensitive silver salt.
- electron transfer agents can also prove to be advantageous in the case of the use of reducible color releasers in combination with electron donor compounds.
- the electron donor compound used in combination with a reducible color releasing agent also serves as a reducing agent for the silver halide, the essentially non-photosensitive silver salt and the color releasing agent. Because the essentially non-light-sensitive silver salt and the color releaser compete with each other to a certain extent in the oxidation of the electron donor compound, but the latter is in any case superior to the latter in the presence of exposed silver halide, the silver halide present becomes determinant for that in accordance with a previous imagewise exposure Image areas within which the color releaser is converted into its reduced form by the electron donor compound.
- the electron donor compound which is present in a limited amount, under the conditions of development, in the present case when the imagewise exposed color photographic material is heated, in accordance with the extent of the exposure under the catalytic effect of the latent image nuclei produced by exposure in the silver halide by the essentially non-light-sensitive silver salt and
- the light-sensitive silver halide oxidizes and is therefore no longer available for a reaction with the color releaser. This creates an image-like distribution of unused electron donor compound.
- electron donor compounds are disclosed in DE-A-2 947 425, DE-A-3 006 268, DE-A-3 130 842, DE-A-3 144 037, DE-A-3 217 877 and EP-A- 0 124 915 and Research Disclosure 24 305 (July 1984). It has been shown that the electron donor compounds mentioned also meet the requirements placed on them under the conditions of heat development and are therefore also suitable as electron donor compounds in the context of the present invention. Particularly suitable are those electron donor compounds that are formed in the layer from corresponding electron donor precursor compounds only under the conditions of heat development, i. H. Electron donor compounds that are only in a capped form in the recording material before development, in which they are practically ineffective. Under the conditions of heat development, the electron donor compounds, which are initially ineffective, are then converted into their effective form, for example by hydrolytically cleaving off certain protective groups. In the present case, the electron donor precursor compounds mentioned are also understood as electron donor compounds.
- the binder consists of at least 30% by weight of a polyurethane containing anionic groups.
- the remaining (up to 100% by weight. Missing) portion of the binder mainly consists of a conventional hydrophilic layer binder, mostly of natural origin, in particular gelatin.
- Binder compositions preferred according to the invention are mixtures of gelatin and a polyurethane containing anionic groups, the latter preferably being present in an amount between 50 and 95% by weight, based on the total amount of binder.
- the polyurethane mentioned can also be the sole binder.
- Water-insoluble compounds that can be added are gelatin-compatible plastic latices of polyacrylic acid esters and their copolymers and polyvinyl ethers or their copolymers.
- the compounds according to the invention can advantageously be combined with dispersions of water-insoluble polyethers of the type described in GB-A-1 053 568 or with dispersions of other water-insoluble compounds with a boiling point above 250 ° C.
- polyurethanes to be used according to the invention are distinguished by the fact that they contain chemically incorporated hydrophilic groups, in particular anionic groups, preferably sulfate, sulfonate or carboxylate groups.
- Suitable polyurethanes are, for example, those which contain an anionic group content of at least 5 milliequivalents per 100 g solid, preferably from 9 to 35 milliequivalents per 100 g solid.
- the polyurethanes are generally formed by the reaction (polyaddition) of polyisocyanates with compounds which contain several reactive hydrogen atoms.
- polyester polyacetals, polyethers, polyamides or polyesteramides, and such compounds with a lower molecular weight, the so-called chain extenders.
- the reactive hydrogen atoms are usually those of hydroxyl, amino or carboxyl groups.
- Common starting products for the production of polyurethanes are, for example, hydroxyl-containing polyesters, in particular linear polyesters with two terminal free hydroxyl groups.
- Particularly suitable polyisocyanates are diisocyanates, for example all aromatic and aliphatic diisocyanates, such as. B. 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyte diisocyanate, 1,3-phenylene diisocyanate.
- diisocyanates for example all aromatic and aliphatic diisocyanates, such as. B. 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyte diisocyan
- 1,4-phenylene diisocyanate the isomers of tolylene diisocyanate, optionally in a mixture, chlorinated and brominated diisocyanates, preferably the aliphatic diisocyanates, butane-1,4-diisocyanate, hexane-1,6-diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate as well as prepolymers containing isocyanate groups.
- the introduction of the anionic groups into the molecule of the polyurethanes can be achieved in that compounds which contain at least one active hydrogen atom and at least one anionic group or a group which can be converted into an anionic group are already present during the polyaddition reaction which leads to the polyurethanes . These latter compounds are incorporated into the polymer molecule by reaction with some of the isocyanate groups present. If the isocyanate groups present are not completely consumed in the production of the polyurethanes, the anionic groups can also be introduced by means of the compounds mentioned after the formation of the polyurethanes.
- the subsequent introduction of the anionic or anionizable groups can also be achieved in a known manner by reaction with compounds which have an alkylating or acylating function and can form an anionic group in the reaction concerned.
- compounds mostly have a cyclic structure; Dicarboxylic anhydrides, sulfones, lactones, epoxy carboxylic acids and cyclic sulfates are examples of this.
- the polyaddition can be carried out, for example, with the use of solvents, with low-boiling solvents such as acetone, ethanol, methanol, tert-butanol, methyl ethyl ketone, which may optionally contain a proportion of water, preferably being suitable.
- solvents with low-boiling solvents such as acetone, ethanol, methanol, tert-butanol, methyl ethyl ketone, which may optionally contain a proportion of water, preferably being suitable.
- Water can be used as a solvent for inorganic bases and the compounds having at least one hydrogen atom reacting with isocyanate groups and at least one anionic group, if appropriate without the addition of organic solvents.
- the resulting predominantly linear, high molecular weight anionic group-containing polyurethanes can be converted into the aqueous phase by adding water and the organic solvents can be removed simultaneously or subsequently. Dispersions are obtained in the form of latices or solutions. Processes for the preparation of suitable polyurethanes containing anionic groups are described, for example, in GB-A-1 076 688, US-A-3 479 310, US-A-4 108 814, US-4 092 286, DE-A-2 725 589 and DE-A-2 811 148.
- Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentylglycol polyester (OH number 63), 55 g of 1,6-hexanediisocyanate and 27.8 g of sodium 1,2-diaminoethane-N-pro-pansulfonate.
- Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 55 g of 1,6-hexanediisocyanate and 29.8 g of potassium 1,2-diaminoethane-N-propanesulfonate.
- Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentylglycol polyester, 30.6 g of 1,6-hexanediisocyanate and 31.9 g of a 20% aqueous sodium ethanesulfonate solution.
- Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 45.5 g of 1,6-hexanediisocyanate and 138.0 g of a 20% aqueous sodium aminoethanesulfonate solution.
- Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 44.2 g of 1,6-hexanediisocyanate and 92.0 g of a 20% aqueous sodium aminoethanesulfonate solution.
- Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 39.0 g of 1,6-hexanediisocyanate and 92.0 g of a 20% aqueous sodium aminoethanesulfonate solution.
- Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 32.6 g of 1,6-hexanediisocyanate and 46 g of a 20% aqueous sodium aminoethanesulfonate solution.
- Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 34.6 g of 1,6-hexanediisocyanate and 61.2 g of a 20% aqueous sodium aminoethanesulfonate solution.
- Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentylglycol polyester, 52.0 g of 1,6-hexanediisocyanate and 184.0 g of a 20% aqueous sodium aminoethanesulfonate solution.
- Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 42.0 g of 1,6-hexanediisocyanate, 12.9 g of diethylenetriamine, 12.5 g of succinic anhydride and 4.9 g of potassium hydroxide.
- Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 42.0 g of 1,6-hexanediisocyanate, 12.9 g of diethylenetriamine, 12.5 g of succinic anhydride and 6.3 g of potassium hydroxide.
- Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 38.0 g of 1,6-hexanediisocyanate and 14.9 g of potassium 1,2-diaminoethane-N-propanesulfonate.
- Polyaddition product made from 218.5 g adipic acid-hexanediol-neopentyl glycol polyester, 32.5 g of 1,6-hexanediisocyanate and 7.5 g of potassium 1,2-diaminoethane-N-propanesulfonate.
- Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 36.7 g of 1,6-hexanediisocyanate and 11.2 g of potassium 1,2-diaminoethane-N-propanesulfonate.
- Polyaddition product made from 106.3 g adipic acid-hexanediol-neopentyl glycol polyester (OH number 65.85), 128.5 g 1,6-hexane diisocyanate, 52.0 g neopentyl glycol and 29.8 g potassium 1,2-diaminoethane N-propane sulfonate.
- Polyaddition product made from 106.3 g adipic acid-hexanediol-neopentyl glycol polyester (OH number 65.85), 121.0 g of 1,6-hexane diisocyanate, 26.5 g of diethylene glycol, 26.0 g of neopentyl glycol and 29.8 g of potassium 1,2-diaminoethane-N-propanesulfonate.
- Polyaddition product made from 212.5 g adipic acid-hexanediol-neopentyl glycol polyester (OH number 65.85), 89.0 g of 1,6-hexane diisocyanate and 59.6 g of potassium 1,2-diaminoethane-N-propanesulfonate.
- Polyaddition product consisting of 212.5 g adipic acid-hexanediol-neopentylglycol polyester (OH number 65.85), 72.0 g of 1,6-hexane diisocyanate and 44.7 g of potassium 1,2-diaminoethane-N-propanesulfonate.
- Polyaddition product made from 250.0 g polypropylene glycol (OH number 56), 48.0 g 1,6-hexane diisocyanate and 29.8 g potassium 1,2-diaminoethane-N-propanesulfonate.
- the color photographic recording material can contain further constituents and auxiliary substances which are beneficial, for example, for carrying out the heat treatment and the color transfer which takes place in the process.
- these further constituents or auxiliary substances can be contained in a light-sensitive layer or in a non-sensitive layer.
- auxiliaries are, for example, auxiliary developers.
- ETA electron transfer agents
- auxiliary developers examples include hydroquinone, pyrocatechol, pyrogallol, hydroxylamine, ascorbic acid, 1-phenyl-3-pyrazolinone and their derivatives. Since the auxiliary developers have a catalytic function, it is not necessary for them to be present in stoichiometric amounts. In general, it is sufficient if they are present in the layer in amounts up to a maximum of 1/2 mol per mol of color releaser. Incorporation into the layer can take place, for example, from solutions in water-soluble solvents or in the form of aqueous dispersions which have been obtained using oil formers.
- auxiliaries are, for example, basic substances or compounds which are able to provide basic substances under the influence of the heat treatment.
- a suitable alkaline medium is created during the heat treatment in the light-sensitive layer and the adjacent layers in order to ensure the release of the diffusible dyes from the color releasers and their diffusion into the image-receiving layer.
- auxiliaries are, for example, compounds which are able to release water under the action of heat.
- inorganic salts containing water of crystallization come into question, e.g. B. Na 2 S0 4 -10H 2 0, NH4Fe (S04h.12H20, and also compounds of the sodium benzotriazolate type, which crystallize as a complex with various amounts of water (up to 24 mol H 2 0) and which in US-A-4 418 139 are described.
- the water released during heating favors the development and diffusion processes required for image formation.
- auxiliaries are, for example, the so-called thermal solvents or development and diffusion promotion agents, which are generally understood to mean non-hydrolyzable organic compounds which are solid or liquid under normal conditions, but in any case provide a liquid medium at the temperature of the heat treatment, in which the development and diffusion processes can run faster.
- Preferred examples of these include polyglycols as described, for example, in US-A-3,347,675, e.g. B. polyethylene glycol with an average molecular weight of 1500 to 20,000, derivatives of polyethylene oxide, such as its oleic acid ester, beeswax, monostearin, compounds with a high dielectric constant, which have a -S0 2 - or -CO group, such as. B.
- the development of the imagewise exposed color photographic recording material according to the invention comprises the partial steps of silver halide development, generation of an imagewise distribution of diffusible dyes and diffusion transfer of this imagewise distribution into the image receiving layer. It is initiated by subjecting the exposed recording material to a heat treatment in which the photosensitive binder layer is heated to an elevated temperature, e.g. B. is brought in the range of 80 to 250 ° C. This makes suitable ones in the recording material Conditions for the development processes including dye diffusion are created without the addition of a liquid medium, e.g. B. in the form of a developer bath. During development, diffusible dyes are released imagewise from the color releasers and transferred to an image-receiving layer which is either an integral part of the color photographic recording material according to the invention or is in contact with it at least during the development period.
- Image-wise silver development, dye release and color transfer take place synchronously in a one-step development process.
- the color image formation with the color photographic recording material according to the invention can also be carried out in a two-step development process, silver halide development and dye release taking place in a first step, followed by color image transfer in a second step from the light-sensitive part to an image receiving part brought into contact with it, e.g. . B. by heating to a temperature between 50 and 150 ° C, preferably to 70 to 90 ° C, in which case diffusion aids (solvents) can be applied externally before the lamination of the light-sensitive part and the image receiving part.
- diffusion aids solvents
- the image-receiving layer can accordingly be arranged on the same layer support as the light-sensitive element (single sheet material) or on a separate layer support (two-sheet material). It essentially consists of a binder which contains mordants for the determination of the diffusible dyes released from the non-diffusing paint releasers. Long-chain quaternary ammonium or phosphonium compounds, e.g. B. As described in US-A-3,271,147 and US-A-3,271,148.
- certain metal salts and their hydroxides which form poorly soluble compounds with the acid dyes, can also be used.
- polymeric mordants such as those described in DE-A-2 315 304, DE-A-2 631 521 or DE-A-2 941 818.
- the dye mordants are dispersed in the mordant layer in one of the usual hydrophilic binders, e.g. B. in gelatin, polyvinyl pyrrolidone, completely or partially hydrolyzed cellulose esters.
- some binders can also act as mordants, e.g. B.
- polymers of nitrogen-containing, optionally quaternary bases such as N-methyl-4-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, as described, for example, in US Pat. No. 2,484,430.
- Other useful binding agents are, for example, guanylhydrazone derivatives of alkyl vinyl ketone polymers, as described, for example, in US Pat. No. 2,882,156, or guanylhydrazone derivatives of acyl styrene polymers, as described, for example, in DE-A-2 009 498.
- other binders e.g. B. add gelatin.
- the image-receiving layer remains in layer contact with the light-sensitive element even after development is complete, there is usually an alkali-permeable, pigment-containing, light-reflecting image middle layer between them, which serves as an optical separation between negative and positive and serves as an aesthetically pleasing background for the positive color image.
- the binder-receiving layer is arranged between the support and the photosensitive element and is separated from the latter by a pre-formed light-reflecting layer, either the support must be transparent so that the color transfer image produced can be viewed through it, or the photosensitive element together with the light-reflecting layer of the image-receiving layer are removed to expose the latter.
- the image-receiving layer can, however, also be present as the top layer in an integral color photographic recording material, in which case the exposure is expediently carried out through the transparent layer support.
- emulsion 2 For spectral sensitization, parts of emulsion 2 (crude emulsion) were melted at 40 ° C., per mol of Ag with 4 x 10- 4 mol red sensitizer, 4 x 10- 4 mol green sensitizer or 8 x 10- 4 mol blue sensitizer, each in methanolic solution or slurry , added and digested in a closed vessel for about 70 min.
- Dispersant 1 (paint releasing agent C 1)
- Dispersant 2 (paint releasing agent M -1)
- Dispersant 3 (paint releasing agent M - 2)
- Dispersant 4 (paint releasing agent Y - 1)
- Dispersant 5 (auxiliary developer precursor compound)
- auxiliary developer precursor compound 62 g were dissolved in 120 g of diethyl laurylamide and 150 ml of ethyl acetate and dispersed in 612 g of 10% aqueous gelatin solution in the presence of 3.5 g of sodium dodecylbenzenesulfonate; and then the auxiliary solvent was removed as for Dispersate 1. Yield: 997 g of disperse 5
- the Ti0 2 layer can be dispensed with.
- the light-sensitive parts of non-inventive (comparison) and color photographic recording materials according to the invention for the color diffusion transfer process were produced as follows:
- dispersant 1 color releasing agent C -1
- disperse 5 auxiliary developer precursor compound
- 66 g of 20% gelatin 150 mg of mercury-II chloride dissolved in 30 ml of water and 3.2 g of guanidine trichloroacetate in 30 ml of water were added and the mixture was then brought to a final weight of 320 g with water.
- the solution was applied with a wet layer thickness of 100 ⁇ m to a layer support made of polyethylene terephthalate and covered with a 1% aqueous gelatin solution (wet layer thickness 40 ⁇ m) containing a hardening agent and rocked.
- the finished casting solution was applied with a wet layer thickness of 100 ⁇ m to a layer support made from polyethylene terephthalate and dried at 35 ° C. With a 1% aqueous gelatin solution containing a hardening agent was overlaid (wet layer thickness 40 microns) and dried.
- the samples produced according to Example 4 were exposed with a tungsten lamp, the exposure in the case of samples 1, 2, 4, 5 and 7 being carried out behind a transparent yellow filter with a density of 1.25.
- the intensity and duration of the exposure can be seen from Table 1.
- the samples were then dried to 110 ° C for development; the duration of this treatment is also shown in Table 1.
- the samples were then swollen in water for 10 s and laminated together with an image-receiving sheet (from Example 3) which had been swollen in water for 30 s and heated on a regulated heating bench at 75 ° C. for 2 minutes, then separated and then immediately dried. Sharp, brilliant color transfers were obtained on the image-receiving sheets.
- the Dmin and Dmax values are also shown in Table 1.
- Integral recording materials for the color diffusion transfer process consisting of the light-sensitive part and the image-receiving part were produced by applying the layer-coating solutions described below on a layer support made of polyethylene terephthalate.
- Samples 8, 9 and 10 were exposed to a tungsten lamp with 1000 lux through the transparent support for 10 s, in the case of samples 8 and 9 behind a transparent yellow filter with a density of 1.25. Then dry development was carried out for 60 s at 110 ° C. on a heating bench and the dry developed samples 8, 9 and 10 were only exposed to a water vapor atmosphere of 75 ° C. for 4 minutes. It was then dried briefly at room temperature. The Dmin and Dmax values obtained are shown in Table 2.
- the process variant described here does not require any processing baths; Rather, heat is sufficient and secondly water vapor, for example at 75 ° C. However, the second treatment step can also consist in swelling the (dry developed) recording material in water and then heating it to 75 ° C., for example on a heating bench.
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Description
Die Erfindung betrifft ein durch Wärmebehandlung entwickelbares farbfotografisches Aufzeichnungsmaterial mit mindestens einer auf einem Schichtträger aufgetragenen Bindemittelschicht, die lichtempfindliches Silberhalogenid und eine nichtdiffundierende farbgebende Verbindung enthält, wobei die Bindemittelschicht ein synthetisches Polymer als Bindemittel enthält.The invention relates to a color photographic recording material which can be developed by heat treatment and has at least one binder layer which is applied to a layer support and which contains light-sensitive silver halide and a non-diffusing coloring compound, the binder layer containing a synthetic polymer as binder.
Es ist bekannt, mittels geeigneter farbfotografischer Aufzeichnungsmaterialien farbige Bilder durch Wärmebehandlung herzustellen. Als farbgebende Verbindung eignen sich hierbei in besonderem Maße solche, die in nichtdiffundierender Form in die Schicht eines fotografischen Aufzeichnungsmaterials eingelagert werden können und als Folge der Entwicklung einen diffusionsfähigen Farbstoff freizusetzen vermögen (Farbabspalter). Die besondere Eignung solcher Farbabspalter beruht auf dem Umstand, daß die bildmäßig freigesetzten Farbstoffe auf besondere Bildempfangsschichten übertragen werden können unter Bildung eines brillanten Farbbildes, das nicht von störendem Bildsilber oder Silberhalogenid überlagert ist und dementsprechend keiner Nachbehandlung bedarf. Durch Kombination des Wärmeentwicklungsverfahrens mit dem Farbdiffusionsverfahren ergibt sich somit ein vorteilhaftes Schnellverfahren zur Herstellung farbiger Bilder. Ein hierfür geeignetes Aufzeichnungsmaterial ist beispielsweise beschrieben in DE-A-3 215 485.It is known to produce colored images by heat treatment using suitable color photographic recording materials. Particularly suitable as a color-providing compound are those which can be embedded in the layer of a photographic recording material in non-diffusing form and which, as a result of the development, are able to release a diffusible dye (color releaser). The particular suitability of such color releasers is based on the fact that the imagewise released dyes can be transferred to special image-receiving layers with the formation of a brilliant color image which is not overlaid with disruptive image silver or silver halide and accordingly does not require any aftertreatment. Combining the heat development process with the color diffusion process thus results in an advantageous rapid process for producing colored images. A recording material suitable for this is described, for example, in DE-A-3 215 485.
Nach dieser Veröffentlichung wird ein Aufzeichnungsmaterial mit einer Schicht, die in einem hydroben Bindemittel eine Kombination aus Silberhalogenid, Silberbenzotriazol, einem Farbabspalter und Guanidintrichloracetat (Basenspender) enthält, bildmäßig belichtet und anschließend in Kontakt mit einem Bildempfangsblatt einer Wärmebehandlung unterworfen, wobei der bildmäßig freigesetzte Farbstoff auf das Bildempfangsblatt übertragen wird. Für die Herstellung mehrfarbiger Bilder müssen mehrere solcher Kombinationen vorhanden sein, wobei das Silberhalogenid in jeder dieser Kombinationen für einen anderen Spektralbereich des Lichtes empfindlich ist und entsprechend seiner Spektralempfindlichkeit einen Farbabspalter zugeordnet enthält, der einen Farbstoff einer anderen Farbe freisetzt, meist einer Farbe, die komplementär ist zu der Farbe des Lichtes, für die das betreffende Silberhalogenid eine überwiegende Empfindlichkeit aufweist. Solche Zuordnungen können in verschiedenen Schichten übereinander angeordnet sein.According to this publication, a recording material having a layer which contains a combination of silver halide, silver benzotriazole, a color releaser and guanidine trichloroacetate (base donor) in a hydrobene binder is exposed imagewise and then subjected to a heat treatment in contact with an image-receiving sheet, the imagewise released dye the image receiving sheet is transferred. For the production of multicolored images, several such combinations must be present, the silver halide in each of these combinations being sensitive to a different spectral range of the light and, in accordance with its spectral sensitivity, containing a color releaser which releases a dye of a different color, usually a color that is complementary is the color of the light for which the silver halide in question has a predominant sensitivity. Such assignments can be arranged one above the other in different layers.
Die mit dem bekannten durch Wärmebehandlung entwickelbaren farbfotografischen Aufzeichnungsmaterial erhaltenen Farbbilder weisen ziemlich geringe maximale Farbdichten und hohe Schleier auf. Auch läßt das Aufzeichnungsmaterial hinsichtlich der Empfindlichkeit noch zu wünschen übrig.The color images obtained with the known color photographic recording material which can be developed by heat treatment have rather low maximum color densities and high fog. The recording material also leaves something to be desired in terms of sensitivity.
Der Anmeldung liegt daher die Aufgabe zugrunde ein durch Wärmebehandlung entwickelbares farbfotografisches Aufzeichnungsmaterial anzugeben, das hinsichtlich der Dmin/Dmax-Reiation und hinsichtlich der Empfindlichkeit weiter verbessert ist.The application is therefore based on the object of specifying a color photographic recording material which can be developed by heat treatment and which is further improved in terms of the Dmin / Dmax variation and in terms of sensitivity.
Gegenstand der vorliegenden Erfindung ist ein durch Wärmebehandlung entwickelbares fotografisches Aufzeichnungsmaterial mit mindestens einer auf einem Schichtträger aufgetragenen Bindemittelschicht, die lichtempfindliches Silberhalogenid, gegebenenfalls kombiniert mit einem im wesentlichen nicht lichtempfindlichen Silbersalz, und mindestens eine nicht diffundierende farbgebende Verbindung enthält, die als Folge der Entwicklung durch Wärmebehandlung einen diffusionsfähigen Farbstoff freizusetzen vermag, das dadurch gekennzeichnet ist, daß das Bindemittel der genannten Bindemittelschicht zu mindestens 30 Gew.-%. aus einem anionische Gruppen enthaltenden Polyurethan besteht.The present invention relates to a heat treatment-developable photographic recording material having at least one binder layer applied to a layer, which contains light-sensitive silver halide, optionally combined with a substantially non-light-sensitive silver salt, and at least one non-diffusing color-providing compound which, as a result of the development by heat treatment is able to release a diffusible dye, which is characterized in that the binder of said binder layer contains at least 30% by weight. consists of a polyurethane containing anionic groups.
Das erfindungsgemäße farbfotografische Aufzeichnungsmaterial enthält auf einem dimensionsstabilen Schichtträger mindestens eine Bindemittelschicht, die als wesentliche Bestandteile ein lichtempfindliches Silberhalogenid, gegebenenfalls in Kombination mit einem im wesentlichen nicht lichtempfindlichen Silbersalz, und eine nicht diffundierende farbgebende Verbindung enthält, die durch Wärmeentwicklung einen diffusionsfähigen Farbstoff liefern kann.The color photographic recording material according to the invention contains, on a dimensionally stable support, at least one binder layer which contains, as essential components, a light-sensitive silver halide, optionally in combination with an essentially non-light-sensitive silver salt, and a non-diffusing color-imparting compound which can produce a diffusible dye through heat development.
Das lichtempfindliche Silberhalogenid kann aus Silberchlorid, Silberbromid, Silberiodid oder deren Gemischen bestehen und eine Teilchengröße zwischen 0,01 und 2,0 um. vorzugsweise zwischen 0,1 und 1,0 µm aufweisen. Es kann als unsensibilisiertes Silberhalogenid vorliegen oder aber auch chemisch sensibilisiert sein, z. B. mit Verbindungen von Schwefel, Selen oder Tellur, oder mit Verbindungen von Gold, Platin, Palladium, Rhodium oder Iridium, oder mit einem Reduktionsmittel, wie z. B. einem Zinnhalogenid, oder einer Kombination davon. Darüber hinaus kann das Silberhalogenid noch zusätzlich mit bekannten organischen Sensibilisierungsfarbstoffen spektral sensibilisiert sein.The light-sensitive silver halide can consist of silver chloride, silver bromide, silver iodide or mixtures thereof and a particle size between 0.01 and 2.0 µm. preferably have between 0.1 and 1.0 µm. It can be in the form of an unsensitized silver halide or it can also be chemically sensitized, e.g. B. with compounds of sulfur, selenium or tellurium, or with compounds of gold, platinum, palladium, rhodium or iridium, or with a reducing agent, such as. B. a tin halide, or a combination thereof. In addition, the silver halide can additionally be spectrally sensitized with known organic sensitizing dyes.
Die Menge des lichtempfindlichen Silberhalogenids kann in der jeweiligen Schicht zwischen 0,01 und 2,0 g pro m2 betragen, wobei sich die tatsächliche Menge des eingesetzten Silberhalogenids wegen seiner katalytischen Funktion (als belichtetes Silberhalogenid) in manchen Ausführungsformen hauptsächlich im unteren Teil des angegebenen Bereiches bewegt.The amount of light-sensitive silver halide in the respective layer can be between 0.01 and 2.0 g per m 2 , the actual amount of the silver halide used, due to its catalytic function (as exposed silver halide) in some embodiments, mainly in the lower part of the stated Area moved.
Bei dem im wesentlichen nicht lichtempfindlichen Silbersalz kann es sich beispielsweise um ein gegenüber Licht vergleichsweise stabiles Silbersalz, z. B. ein organisches Silbersalz handeln. Zu geeigneten Beispielen hierfür zählen die Silbersalze aliphatischer oder aromatischer Carbonsäuren sowie die Silbersalze von stickstoffhaltigen Heterocyclen; ferner auch Silbersalze organischer Mercaptoverbindungen.The substantially non-light-sensitive silver salt can be, for example, a silver salt which is comparatively stable to light, e.g. B. act an organic silver salt. Suitable examples include the silver salts of aliphatic or aromatic carboxylic acids and the silver salts of nitrogen-containing heterocycles; also silver salts of organic mercapto compounds.
Bevorzugte Beispiele für Silbersalze aliphatischer Carbonsäuren sind Silberbehenat, Silberstearat, Silberoleat, Silberlaurat, Silbercaprat, Silbermyristat, Silberpalmitat, Silbermaleat, Silberfumarat, Silbertartrat, Silberfuroat, Silberlinolat, Silberadipat, Silbersebacat, Silbersuccinat, Silberacetat oder Silberbutyrat. Die diesen Silbersalzen zugrunde liegenden Carbonsäuren können beispielsweise durch Halogenatome, Hydroxylgruppen oder Thioethergruppen substituiert sein.Preferred examples of silver salts of aliphatic carboxylic acids are silver behenate, silver stearate, silver oleate, silver laurate, silver caprate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartrate, silver furoate, silver linolate, silver adipate, silver sebacate, silver succinate, silver acetate or silver acetate. The carboxylic acids on which these silver salts are based can be substituted, for example, by halogen atoms, hydroxyl groups or thioether groups.
Zu Beispielen für Silbersalze aromatischer Carbonsäuren und anderer carboxylgruppenhaltiger Verbindungen gehören Silberbenzoat, Silber-3,5-dihydroxybenzoat, Silber-o-methylbenzoat, Silber-m-methylbenzoat, Silber-p-methyl-benzoat, Silber-2,4-dichlorbenzoat, Silberacetamidobenzoat, Silbergallat, Silbertannat, Silberphthalat, Silberterephthalat, Silbersalicylat, Silberphenylacetat, Silberpyromellitat, Silbersalze von 3-Carboxymethyl-4-methyl-4-thiazolin-2-thion oder ähnlichen heterocyclischen Verbindungen. Geeignet sind ferner Silbersalze von organischen Mercaptanen, z. B. die Silbersalze von 3-Mercapto-4-phenyl-1,2,4-triazol, 2-Mercaptobenz-imidazol, 2- Mercaptobenzothiazol, 2-Mercaptobenzoxazol, 2-Mercaptooxadiazol, Mercaptotriazin, Thioglykolsäure, ferner die Silbersalze von Dithiocarbonsäuren, wie z. B. das Silbersalz von Dithioacetat.Examples of silver salts of aromatic carboxylic acids and other compounds containing carboxyl groups include silver benzoate, silver 3,5-dihydroxybenzoate, silver o-methylbenzoate, silver m-methylbenzoate, silver p-methylbenzoate, silver 2,4-dichlorobenzoate, silver acetamidobenzoate , Silver gallate, silver tannate, silver phthalate, silver terephthalate, silver salicylate, silver phenylacetate, silver pyromellitate, silver salts of 3-carboxymethyl-4-methyl-4-thiazolin-2-thione or similar heterocyclic compounds. Silver salts of organic mercaptans, e.g. B. the silver salts of 3-mercapto-4-phenyl-1,2,4-triazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptooxadiazole, mercaptotriazine, thioglycolic acid, and also the silver salts of dithiocarboxylic acids, such as e.g. B. the silver salt of dithioacetate.
Außerdem geeignet sind die Silbersalze von Verbindungen mit einer Iminogruppe. Zu bevorzugten Beispielen hierfür gehören die Silbersalze von Benzotriazol und dessen Derivaten, z. B. Silbersalze von alkyl-und/oder halogensubstituierten Benzotriazolen, wie z. B. die Silbersalze von Methylbenzotriazol, 5-Chlorbenzotriazol sowie auch die Silbersalze von 1,2,4-Triazol, 1-H-Tetrazol, Carbazol, Saccharin und Silbersalze von Imidazol, Benzimidazol und deren Derivaten.The silver salts of compounds having an imino group are also suitable. Preferred examples include the silver salts of benzotriazole and its derivatives, e.g. B. silver salts of alkyl and / or halogen-substituted benzotriazoles, such as. B. the silver salts of methylbenzotriazole, 5-chlorobenzotriazole and also the silver salts of 1,2,4-triazole, 1-H-tetrazole, carbazole, saccharin and silver salts of imidazole, benzimidazole and their derivatives.
Die Auftragsmenge an im wesentlichen nicht lichtempfindlichem Silbersalz gemäß der vorliegenden Erfindung liegt in der jeweiligen Schicht zwischen 0,05 und 5 g pro m2. Das im wesentlichen nicht lichtempfindliche Silbersalz und das lichtempfindliche Silberhalogenid können nebeneinander als getrennte Partikel vorliegen oder auch in einer kombinierten Form, die beispielsweise dadurch erzeugt werden kann, daß ein im wesentlichen nicht lichtempfindliches Silbersalz in Gegenwart von Halogenidionen behandelt wird, wobei sich auf der Oberfläche der Teilchen aus dem im wesentlichen nicht lichtempfindlichen Silbersalz durch doppelte Umsetzung (Konvertierung) lichtempfindliche Zentren aus lichtempfindlichem Silberhalogenid bilden. Hierzu ist zu verweisen auf US-A-3 457 075.The application amount of essentially non-photosensitive silver salt according to the present invention is in the respective layer between 0.05 and 5 g per m 2 . The essentially non-light-sensitive silver salt and the light-sensitive silver halide can be present side by side as separate particles or in a combined form, which can be produced, for example, by treating a substantially non-light-sensitive silver salt in the presence of halide ions, the surface of which Particles of the essentially non-photosensitive silver salt are formed by double conversion (conversion) of photosensitive centers from photosensitive silver halide. For this purpose, reference is made to US-A-3 457 075.
Das im wesentlichen nicht lichtempfindliche Silbersalz dient als Reservoir für Metallionen, die bei der Wärmeentwicklung in Gegenwart eines Reduktionsmittels unter dem katalytischen Einfluß des bildmäßig belichteten Silberhalogenids zu elementarem Silber reduziert werden und dabei selbst als Oxidationsmittel (für das vorhandene Reduktionsmittel) dienen.The essentially non-light-sensitive silver salt serves as a reservoir for metal ions, which are reduced to elemental silver when heat is developed in the presence of a reducing agent under the catalytic influence of the imagewise exposed silver halide and thereby serve as an oxidizing agent (for the reducing agent present).
Ein weiterer wesentlicher Bestandteil des erfindungsgemäßen Aufzeichnungsmaterials ist mindestens eine nicht diffundierende farbgebende Verbindung, die als Folge einer bei der Entwicklung stattfindenden Redoxreaktion einen diffusionsfähigen Farbstoff freizusetzen vermag und die im folgenden als Farbabspalter bezeichnet wird.Another essential component of the recording material according to the invention is at least one non-diffusing coloring compound which, as a result of a redox reaction taking place during development, is able to release a diffusible dye and which is referred to below as a color releasing agent.
Bei den erfindungsgemäß verwendeten Farbabspaltern kann es sich um eine Vielfalt von Verbindungstypen handeln, die sich sämtlich durch ein in seiner Bindungsfestigkeit redoxabhängiges Bindeglied auszeichnen, welches einen Farbstoffrest mit einem einen Ballastrest enthaltenden Trägerrest verknüpft.The dye releasers used according to the invention can be a variety of connection types, all of which are distinguished by a link which is redox-dependent in terms of their bond strength and which links a dye residue to a carrier residue containing a ballast residue.
In diesem Zusammenhang ist auf eine zusammenfassende Darstellung des Sachgebiets in Angew. Chem. lnt. Ed. Engl. 22 (1983),191 - 209 zu verweisen, in der die wichtigsten der bekannten Systeme beschrieben sind.In this context, a summary of the subject area in Angew. Chem. Lnt. Ed. Engl. 22 (1983), 191-209, in which the most important of the known systems are described.
Als besonders vorteilhaft erweisen sich hierbei redoxaktive Farbabspalter der Formel
- BALLAST - REDOX - FARBSTOFF,
- worin bedeuten
- BALLAST einen Ballastrest
- REDOX eine redoxaktive Gruppe, d. h. eine Gruppe die unter den Bedingungen der alkalischen Entwicklung oxidierbar oder reduzierbar ist und je nachdem, ob sie im oxidierten oder im reduzierten Zustand vorliegt, in unterschiedlichem Ausmaß einer Eliminierungsreaktion, einer nukleophilen Verdrängungsreaktion, einer Hydrolyse oder einer sonstigen Spaltungsreaktion unterliegt mit der Folge, daß der Rest FARB-STOFF abgespalten wird, und
- FARBSTOFF den Rest eines diffusionsfähigen Farbstoffes, z. B. eines Gelb-, Purpur- oder Blaugrünfarbstoffes, oder den Rest eines Farbstoffvorläufers.
- BALLAST - REDOX - DYE,
- in what mean
- BALLAST a ballast remnant
- REDOX is a redox-active group, i.e. a group that is oxidizable or reducible under the conditions of alkaline development and, depending on whether it is in the oxidized or in the reduced state, is subject to different degrees to an elimination reaction, a nucleophilic displacement reaction, a hydrolysis or another cleavage reaction with the result that the rest of DYE is split off, and
- DYE the rest of a diffusible dye, e.g. B. a yellow, purple or cyan dye, or the rest of a dye precursor.
Als Ballastreste sind solche Reste anzusehen, die es ermöglichen, die erfindungsgemäßen Farbabspalter in den üblicherweise bei fotografischen Materialien verwendeten hydrophilen Kolloiden diffusionsfest einzulagern. Hierzu sind vorzugsweise organische Reste geeignet, die im allgemeinen geradkettige oder verzweigte aliphatische Gruppen mit im allgemeinen 8 bis 20 C-Atomen und gegebenenfalls auch carbocyclische oder heterocyclische gegebenenfalls aromatische Gruppen enthalten. Mit dem übrigen Molekülteil sind diese Reste entweder direkt oder indirekt, z. B. über eine der folgenden Gruppen verbunden:
- -NHCO-, NHS02-, -NR-, wobei R Wasserstoff oder Alkyl bedeutet, -O- oder -S-. Zusätzlich kann der Ballastrest auch wasserlöslichmachende Gruppen enthalten, wie z. B. Sulfogruppen oder Carboxylgruppen, die auch in anionischer Form vorliegen können. Da die Diffusionseigenschaften von der Molekülgröße der verwendeten Gesamtverbindung abhängen, genügt es in bestimmten Fällen, z. B. wenn das verwendete Gesamtmolekül groß genug ist, als Ballastreste auch kürzerkettige Reste zu verwenden.
- -NHCO-, NHS0 2 -, -NR-, where R is hydrogen or alkyl, -O- or -S-. In addition, the ballast residue can also contain water-solubilizing groups, such as. B. sulfo groups or carboxyl groups, which may also be in anionic form. Since the diffusion properties depend on the molecular size of the total compound used, it is sufficient in certain cases, e.g. B. if the total molecule used is large enough to use short-chain residues as ballast residues.
Redoxaktive Trägerreste der Struktur BALLAST-REDOX- und entsprechende Farbabspalter sind in den verschiedensten Ausführungsformen bekannt. Auf eine detaillierte Darstellung kann an dieser Stelle verzichtet werden im Hinblick auf den genannten übersichtartikel im Angew. Chem. lnt. Ed. Engl. 22 (1983) 191 - 209.Redox-active carrier residues of the BALLAST-REDOX structure and corresponding color releasers are known in a wide variety of embodiments. A detailed description can be omitted here with regard to the above-mentioned overview article in the app. Chem. Lnt. Ed. Engl. 22 (1983) 191-209.
Lediglich zur Erläuterung sind im folgenden einige Beispiele für redoxaktive Trägerreste aufgeführt, von denen ein Farbstoffrest nach Maßgabe einer bildmäßig stattgefundenen Oxidation oder Reduktion abgespalten wird:
Die in Klammern eingeschlossenen Gruppen sind funktionelle Gruppen des Farbstoffrestes und werden zusammen mit diesem vom zurückbleibenden Teil des Trägerrestes abgetrennt. Bei der funktionellen Gruppe kann es sich um einen Substituenten handeln, der einen unmittelbaren Einfluß auf die Absorptions- und gegebenenfalls Komplexbildungseigenschaften des freigesetzten Farbstoffes ausüben kann. Die funktionelle Gruppe kann andererseits aber auch von dem Chromophor des Farbstoffes durch ein Zwischenglied oder Verknüpfungsglied getrennt sein. Die funktionelle Gruppe kann schließlich auch gegebenenfalls zusammen mit dem Zwischenglied von Bedeutung sein für das Diffusions- und Beizverhalten des freigesetzten Farbstoffes. Geeignete Zwischenglieder sind beispielsweise Alkylen- oder Arylengruppen.The groups enclosed in brackets are functional groups of the dye residue and are separated together with this from the remaining part of the carrier residue. The functional group can be a substituent which can have a direct influence on the absorption and, if appropriate, complex formation properties of the released dye. On the other hand, the functional group can also be separated from the chromophore of the dye by an intermediate link or a link. Finally, the functional group together with the intermediate member may also be of importance for the diffusion and pickling behavior of the released dye. Suitable intermediate members are, for example, alkylene or arylene groups.
Als Farbstoffreste sind grundsätzlich die Reste von Farbstoffen aller Farbstoffklassen geeignet, soweit sie genügend diffusionsfähig sind, um aus der lichtempfindlichen Schicht des lichtempfindlichen Materials in eine Bildempfangsschicht diffundieren zu können. Zu diesem Zweck können die Farbstoffreste mit einer oder mehreren alkalilöslichmachenden Gruppen versehen sein. Als alkalilöslichmachende Gruppen sind unter anderem geeignet Carboxylgruppen, Sulfogruppen, Sulfonamidgruppen sowie aromatische Hydroxylgruppen. Solche alkalilöslichmachende Gruppen können in den Farbabspaltern bereits vorgebildet sein oder erst aus der Abspaltung des Farbstoffrestes von dem mit Ballastgruppen behafteten Trägerrest resultieren. An geeigneten Farbstoffen sind zu erwähnen: Azofarbstoffe, Azomethinfarbstoffe, Anthrachinonfarbstoffe, Phtalocyaninfarbstoffe, indigoide Farbstoffe, Triphenylmethanfarbstoffe, einschließlich solcher Farbstoffe, die mit Metallionen komplexiert oder komplexierbar sind.In principle, the residues of dyes of all dye classes are suitable as dye residues insofar as they are sufficiently diffusible to be able to diffuse from the light-sensitive layer of the light-sensitive material into an image-receiving layer. For this purpose, the dye residues can be provided with one or more alkali-solubilizing groups. Suitable alkali-solubilizing groups include carboxyl groups, sulfo groups, sulfonamide groups and aromatic hydroxyl groups. Such alkali-solubilizing groups can already be pre-formed in the dye releasers or can only result from the cleavage of the dye residue from the carrier residue containing ballast groups. Suitable dyes include: azo dyes, azomethine dyes, anthraquinone dyes, phthalocyanine dyes, indigoid dyes, triphenylmethane dyes, including those dyes that are complexed or complexable with metal ions.
Unter den Resten von Farbstoffvorläufern sind die Reste solcher Verbindungen zu verstehen, die im Laufe der fotografischen Verarbeitung, insbesondere unter den Bedingungen der Wärmeentwicklung, sei es durch Oxidation, sei es durch Kupplung, durch Komplexbildung oder durch Freilegung einer auxochromen Gruppen in einem chromophoren System, beispielsweise durch Verseifung, in Farbstoffe übergeführt werden. Farbstoffvorläufer in diesem Sinn können sein Leukofarbstoffe, Kuppler oder auch Farbstoffe, die im Laufe der Verarbeitung in andere Farbstoffe umgewandelt werden. Sofern nicht eine Unterscheidung zwischen Farbstoffresten und den Resten von Farbstoffvorläufern von wesentlicher Bedeutung ist, sollen letztere im folgenden auch unter der Bezeichnung Farbstoffreste verstanden werden.The residues of dye precursors are to be understood as the residues of those compounds which, in the course of photographic processing, in particular under the conditions of heat development, either by oxidation, by coupling, by complex formation or by exposure of an auxochromic group in a chromophoric system, for example by saponification, can be converted into dyes. Dye precursors in this sense can be leuco dyes, couplers or dyes that are converted into other dyes during processing. Unless a distinction is made between dye residues and the residues of dye precursors, the latter should also be understood below as dye residues.
Geeignete Farbabspalter sind beispielsweise beschrieben in:
- US-A-3 227 550, US-A-3 443 939, US-A-A-3 443 940,
- DE-A-1 930 215, DE-A-2 242 762, DE-A-2 402 900,
- DE-A-2 406 664, DE-A-2 505 248, DE-A-2 543 902,
- DE-A-2 613 005, DE-A-2 645 656, DE-A-2 809 716,
- DE-A-2 823159, BE-A-861 241, EP-A-0 004 399,
- EP-A-0 004 400, DE-A-3 008 588, DE-A-3 014 669,
- GB-A-8 012 242.
- US-A-3 227 550, US-A-3 443 939, US-AA-3 443 940,
- DE-A-1 930 215, DE-A-2 242 762, DE-A-2 402 900,
- DE-A-2 406 664, DE-A-2 505 248, DE-A-2 543 902,
- DE-A-2 613 005, DE-A-2 645 656, DE-A-2 809 716,
- DE-A-2 823159, BE-A-861 241, EP-A-0 004 399,
- EP-A-0 004 400, DE-A-3 008 588, DE-A-3 014 669,
- GB-A-8 012 242.
Die Farbabspalter können in manchen Ausführungsformen des erfindungsgemäßen Wärmeentwicklungsverfahrens als oxidierbare oder kupplungsfähige Farbabspalter, in anderen als reduzierbare Farbabspalter vorliegen. Je nach dem, ob der Farbstoff aus der oxidierten oder aus der reduzierten Form der Farbabspalter freigesetzt wird, erhält man bei Vewendung üblicher negativ arbeitender Silberhalogenidemulsionen von der Vorlage eine negative oder positive Ablichtung. Man kann daher nach Wunsch durch Auswahl geeigneter Farbabspaltersysteme positive oder negative Bilder herstellen.In some embodiments of the heat development method according to the invention, the color releasers can be present as oxidisable or couplable color releasers, in others as reducible color releasers. Depending on whether the dye is released from the oxidized or from the reduced form of the color releasing agent, negative or positive illumination is obtained from the original when conventional negative-working silver halide emulsions are used. You can therefore create positive or negative images by selecting suitable color releasing systems.
Für die erfindungsgemäßen wärmeentwickelbaren Aufzeichnungsmaterialien besonders geeignete oxidierbare Farbabspalter sind beispielsweise in DE-A-2 645 656 beschrieben.DE-A-2 645 656 is described, for example, in DE-A-2 645 656 which is particularly suitable for the heat-developable recording materials according to the invention.
Wenn der Farbspalter oxidierbar ist, dann stellt er selbst ein Reduktionsmittel dar, das unmittelbar oder mittelbar unter Mitwirkung von Elektronenübertragungsmitteln (elektron transfer agent, ETA) durch das bildmäßig belichtete Silberhalogenid bzw. durch das im wesentlichen nicht lichtempfindliche Silbersalz unter der katalytischen Einwirkung des bildmäßig belichteten Silberhalogenids oxidiert wird. Hierbei entsteht eine bildmäßige Differenzierung hinsichtlich der Fähigkeit, den diffusionsfähigen Farbstoff freizusetzen. Wenn andererseits der Farbabspalter reduzierbar ist, dann verwendet man ihn zweckmäßig in Kombination mit einem ; in begrenzter Menge vorliegenden Reduktionsmittel, einer sogenannten Elektronendonorverbindung oder einer Elektronendonorvorläuferverbindung, die in diesem Fall neben dem Farbabspalter, dem lichtempfindlichen Silberhalogenid und gegebenenfalls dem im wesentlichen nicht lichtempfindlichen Silbersalz in der gleichen Bindemittelschicht enthalten ist. Auch im Fall der Verwendung von reduzierbaren Farbabspaltern in Kombination mit Elektronendonorverbindungen kann sich die Mitwirkung von Elektronenübertragungsmitteln als günstig erweisen.If the color splitter can be oxidized, then it is itself a reducing agent which, directly or indirectly, with the participation of electron transfer agents (electron transfer agent, ETA) through the imagewise exposed silver halide or through the essentially non-photosensitive silver salt under the catalytic action of the imagewise exposed Silver halide is oxidized. This creates a pictorial differentiation in terms of the ability to release the diffusible dye. If, on the other hand, the paint releaser is reducible, then it is suitably used in combination with one; reducing agent present in a limited amount, a so-called electron donor compound or an electron donor precursor compound, which in this case is contained in the same binder layer in addition to the color releaser, the photosensitive silver halide and, if appropriate, the essentially non-photosensitive silver salt. The use of electron transfer agents can also prove to be advantageous in the case of the use of reducible color releasers in combination with electron donor compounds.
Für die Erzeugung positiver Farbbilder von positiven Vorlagen (Original) bei Verwendung negativ arbeitender Silberhalogenidemulsionen eignet sich beispielsweise ein erfindungsgemäßes Aufzeichnungsmaterial, das reduzierbare Farbabspalter der folgenden Formel enthält:
- R1 Alkyl oder Aryl;
- R2 Alkyl, Aryl oder eine Gruppierung, die zusammen mit R3 einen ankondensierten Ring vervollständigt;
- R3 Wasserstoff, Alkyl, Aryl, Hydroxyl, Halogen wie Chlor oder Brom, Amino, Alkylamino, Dialkylamino einschließlich cyclischer Aminogruppen (wie Piperidino, Morpholino), Acylamino, Alkylthio, Alkoxy, Aroxy, Sulfo, oder eine Gruppierung, die zusammen mit R2 einen ankondensierten Ring vervollständigt;
- R4 Alkyl;
- R5 Alkyl oder vorzugsweise Wasserstoff,
- R 1 is alkyl or aryl;
- R 2 is alkyl, aryl or a group which together with R 3 completes a fused ring;
- R 3 is hydrogen, alkyl, aryl, hydroxyl, halogen such as chlorine or bromine, amino, alkylamino, dialkylamino including cyclic amino groups (such as piperidino, morpholino), acylamino, alkylthio, alkoxy, aroxy, sulfo, or a group together with R 2 completed a condensed ring;
- R4 alkyl;
- R5 is alkyl or preferably hydrogen,
und wobei mindestens einer der Reste R1 bis R4 einen Ballastrest enthält.and wherein at least one of the radicals R 1 to R 4 contains a ballast radical.
Die in Kombination mit einem reduzierbaren Farbabspalter verwendete Elektronendonorverbindung dient gleichermaßen als Reduktionsmittel für das Silberhalogenid, das im wesentlichen nicht lichtempfindliche Silbersalz und den Farbabspalter. Dadurch, daß das im wesentlichen nicht lichtempfindliche Silbersalz und der Farbabspalter bei der Oxidation der Elektronendonorverbindung gewissermaßen miteinander in Konkurrenz treten, ersteres dem letzteren aber jedenfalls in Gegenwart von belichtetem Silberhalogenid hierbei überlegen ist, wird das vorhandene Silberhalogenid nach Maßgabe einer vorausgegangenen bildmäßigen Belichtung bestimmend für die Bildbereiche, innerhalb derer der Farbabspalter durch die Elektronendonorverbindung in seine reduzierte Form überführt wird.The electron donor compound used in combination with a reducible color releasing agent also serves as a reducing agent for the silver halide, the essentially non-photosensitive silver salt and the color releasing agent. Because the essentially non-light-sensitive silver salt and the color releaser compete with each other to a certain extent in the oxidation of the electron donor compound, but the latter is in any case superior to the latter in the presence of exposed silver halide, the silver halide present becomes determinant for that in accordance with a previous imagewise exposure Image areas within which the color releaser is converted into its reduced form by the electron donor compound.
Die in begrenzter Menge vorliegende Elektronendonorverbindung wird unter den Bedingungen der Entwicklung, im vorliegenden Fall beim Erwärmen des bildmäßig belichteten farbfotografischen Aufzeichnungsmaterials, nach Maßgabe des Ausmaßes der Belichtung unter der katalytlischen Wirkung der durch Belichtung in dem Silberhalogenid erzeugten Latentbildkeime durch das im wesentlichen nicht lichtempfindliche Silbersalz und das lichhtempfindliche Silberhalogenid oxidiert und steht folglich nicht mehr für eine Reaktion mit dem Farbabspalter zur Verfügung. Hierbei entsteht gleichsam eine bildmäßige Verteilung an nicht verbrauchter Elektronendonorverbindung.The electron donor compound, which is present in a limited amount, under the conditions of development, in the present case when the imagewise exposed color photographic material is heated, in accordance with the extent of the exposure under the catalytic effect of the latent image nuclei produced by exposure in the silver halide by the essentially non-light-sensitive silver salt and The light-sensitive silver halide oxidizes and is therefore no longer available for a reaction with the color releaser. This creates an image-like distribution of unused electron donor compound.
Als Elektronendonorverbindung sind beispielsweise nicht oder nur wenig diffundierende Derivate des Hydrochinons, des Benzisoxazolons, des p-Aminophenols oder der Ascorbinsäure (z. B. Ascorbylpalmitat) beschrieben worden (DE-A-2 809 716).Derivatives of hydroquinone, benzisoxazolone, p-aminophenol or ascorbic acid (e.g. ascorbyl palmitate) which have not or only little diffusing have been described as electron donor compounds (DE - A-2 809 716).
Weitere Beispiele für Elektronendonorverbindungen sind aus DE-A-2 947 425, DE-A-3 006 268, DE-A-3 130 842, DE-A-3 144 037, DE-A-3 217 877 und EP-A-0 124 915 und Research Disclosure 24 305 (Juli 1984) bekannt. Es hat sich gezeigt, daß die genannten Elektronendonorverbindungen auch unter den Bedingungen der Wärmeentwicklung den an sie gerichteten Anforderungen genügen und daher auch als Elektronendonorverbindungen im Rahmen der vorliegenden Erfindung geeignet sind. Besonders geeignet sind solche Elektronendonorverbindungen, die erst unter den Bedingungen der Wärmeentwicklung in der Schicht aus entsprechenden Elektronendonorvorläuferverbindungen gebildet werden, d. h. Elektronenndonorverbindungen, die in dem Aufzeichnungsmaterial vor der Entwicklung nur in einer verkappten Form vorliegen, in der sie praktisch unwirksam sind. Unter den Bedingungen der Wärmeentwicklung werden dann die zunächst unwirksamen Elektronendonorverbindungen in ihre wirksame Form überführt, indem beispielsweise bestimmte Schutzgruppen hydrolytisch abgespalten werden. Im vorliegenden Fall werden auch die erwähnten Elektronendonorvorläuferverbindungen als Elektronendonorverbindung verstanden.Further examples of electron donor compounds are disclosed in DE-A-2 947 425, DE-A-3 006 268, DE-A-3 130 842, DE-A-3 144 037, DE-A-3 217 877 and EP-A- 0 124 915 and Research Disclosure 24 305 (July 1984). It has been shown that the electron donor compounds mentioned also meet the requirements placed on them under the conditions of heat development and are therefore also suitable as electron donor compounds in the context of the present invention. Particularly suitable are those electron donor compounds that are formed in the layer from corresponding electron donor precursor compounds only under the conditions of heat development, i. H. Electron donor compounds that are only in a capped form in the recording material before development, in which they are practically ineffective. Under the conditions of heat development, the electron donor compounds, which are initially ineffective, are then converted into their effective form, for example by hydrolytically cleaving off certain protective groups. In the present case, the electron donor precursor compounds mentioned are also understood as electron donor compounds.
Die genannten wesentlichen Bestandteile des bei dem erfindungsgemäßen Verfahren verwendeten Aufzeichnungsmaterials, nämlich das lichtempfindliche Silberhalogenid, das gegebenenfalls vorhandene im wesentlichen nicht lichtempfindliche reduzierbare Silbersalz und der Farbabspalter, gegebenenfalls in Kombination mit einer Elektronendonoverbindung liegen nebeneinander in einer gemeinsamen Bindemittelphase vor. Nach vorliegender Erfindung besteht das Bindemittel zu mindestens 30 Gew.-% aus einem anionische Gruppen enthaltenden Polyurethan. Der restliche (bis zu 100 Gew.-%. fehlende) Anteil des Bindemittels besteht überwiegend aus einem üblichen hydrophilen Schichtbindemittel meist natürlicher Herkunft, insbesondere Gelatine. Erfindungsgemäß bevorzugte Bindemittelzusammensetzungen sind Gemische aus Gelatine und einem anionische Gruppen enthaltenden Polyurethan, wobei das letztere vorzugsweise in einer Menge zwischen 50 und 95 Gew.-%, bezogen auf die gesamte Bindemittelmenge vorhanden ist. Das genannte Polyurethan kann aber auch das alleinige Bindemittel darstellen.The above-mentioned essential constituents of the recording material used in the process according to the invention, namely the light-sensitive silver halide, the possibly non-light-sensitive reducible silver salt and the color releaser, optionally in combination with an electron donor compound, are present side by side in a common binder phase. According to the present invention, the binder consists of at least 30% by weight of a polyurethane containing anionic groups. The remaining (up to 100% by weight. Missing) portion of the binder mainly consists of a conventional hydrophilic layer binder, mostly of natural origin, in particular gelatin. Binder compositions preferred according to the invention are mixtures of gelatin and a polyurethane containing anionic groups, the latter preferably being present in an amount between 50 and 95% by weight, based on the total amount of binder. The polyurethane mentioned can also be the sole binder.
Zur Einstellung einer gewünschten Gießviskosität können den Gießlösungen weiterhin hochmolekulare wasserlösliche oder wasserunlösliche Verbindungen, sogenannte Verdickungsmittel zugesetzt werden, beispielsweise in einer Menge von bis zu 5 Gew.-%, bezogen auf die Gesamtmenge an Bindemittel. Als hochmolekulare wasserlösliche Verbindungen sind zu nennen:
- Polyvinylpyrrolidon, Polyvinylmethylether, Polyvinylalkohol, Polyacryl- und methacrylsäsure,
- Polyvinyl pyrrolidone, polyvinyl methyl ether, polyvinyl alcohol, polyacrylic and methacrylic acid,
Wasserunlösliche Verbindungen, die zugesetzt werden können, sind gelatineverträgliche Kunststofflatices von Polyacrylsäureestern und deren Mischpolymerisaten und Polyvinylethern bzw. deren Mischpolymerisaten. Außerdem lassen sich die erfindungsgemäßen Verbindungen mit Vorteil mit Dispersionen wasserunlöslicher PoIyether der in GB-A-1 053 568 beschriebenen Art oder mit Dispersionen anderer wasserunlöslicher Verbindungen mit einem Siedepunkt oberhalb von 250° C kombinieren.Water-insoluble compounds that can be added are gelatin-compatible plastic latices of polyacrylic acid esters and their copolymers and polyvinyl ethers or their copolymers. In addition, the compounds according to the invention can advantageously be combined with dispersions of water-insoluble polyethers of the type described in GB-A-1 053 568 or with dispersions of other water-insoluble compounds with a boiling point above 250 ° C.
Die erfindungsgemäß zu verwendenden Polyurethane zeichnen sich dadurch aus, daß sie chemisch eingebaute hydrophile Gruppen, insbesondere anionische Gruppen enthalten, vorzugsweise Sulfat-, Sulfonat-oder Carboxylatgruppen. Geeignete Polyurethane sind beispielsweise solche, die einen Gehalt an anionischen Gruppen von mindestens 5 Milliäquivalent pro 100 g Feststoff, vorzugsweise von 9 bis 35 Milliäquivalent pro 100 g Feststoff enthalten.The polyurethanes to be used according to the invention are distinguished by the fact that they contain chemically incorporated hydrophilic groups, in particular anionic groups, preferably sulfate, sulfonate or carboxylate groups. Suitable polyurethanes are, for example, those which contain an anionic group content of at least 5 milliequivalents per 100 g solid, preferably from 9 to 35 milliequivalents per 100 g solid.
Die Polyurethane entstehen im allgemeinen durch Reaktion (Polyaddition) von Polyisocyanaten mit Verbindungen, die mehrere reaktionsfähige Wasserstoffatome enthalten. Bei letzteren unterscheidet man zwischen Verbindungen, die bereits eine gewisse Molekülgröße, z. B. ein Molekulargewicht von mindestens 300 aufweisen, wobei es sich meistens um Präkondensate, z. B. Polyester, Polyacetale, Polyether, Polyamide oder Polyesteramide handelt, und solchen Verbindungen mit geringerem Molekulargewicht, den sogenannten Kettenverlängerungsmitteln. Bei den reaktionsfähigen Wasserstoffatomen handelt es sich in der Regel um solche von Hydroxyl-, Amino- oder Carboxylgruppen. Gebräuchliche Ausgangsprodukte für die Herstellung von Polyurethanen sind beispielsweise hydroxylgruppenhaltige Polyester, insbesondere lineare Polyester mit zwei endständigen freien Hydroxylgruppen.The polyurethanes are generally formed by the reaction (polyaddition) of polyisocyanates with compounds which contain several reactive hydrogen atoms. In the latter, a distinction is made between compounds that already have a certain molecular size, e.g. B. have a molecular weight of at least 300, which are mostly precondensates, for. As polyester, polyacetals, polyethers, polyamides or polyesteramides, and such compounds with a lower molecular weight, the so-called chain extenders. The reactive hydrogen atoms are usually those of hydroxyl, amino or carboxyl groups. Common starting products for the production of polyurethanes are, for example, hydroxyl-containing polyesters, in particular linear polyesters with two terminal free hydroxyl groups.
Als Polyisocyanate eignen sich insbesondere Diisocyanate, beispielsweise alle aromatischen und aliphatischen Diisocyanate, wie z. B. 1,5-Naphthylendiiso-cyanat, 4,4'-Diphenytmethandiisocyanat, 4,4'-Diphenyldimethylmethandiisocyanat, Di- und Tetraalkyldiphenylmethandiisocyanat, 4,4'-Dibenzytdiisocyanat, 1,3-Phenylendiisocyanat. 1,4-Phenylendiisocyanat, die Isomeren des Toluylendiisocyanats, gegebenenfalls in Mischung, chlorierte und bromierte Diisocyanate, vorzugsweise die aliphatischen Diisocyanate, Butan-1,4-diisocyanat, Hexan-1,6-diisocyanat, Dicyclohexylmethandiisocyanat, Cyclohexan-1,4-diisocyanat sowie auch Isocyanatgruppen enthaltende Präpolymere.Particularly suitable polyisocyanates are diisocyanates, for example all aromatic and aliphatic diisocyanates, such as. B. 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyte diisocyanate, 1,3-phenylene diisocyanate. 1,4-phenylene diisocyanate, the isomers of tolylene diisocyanate, optionally in a mixture, chlorinated and brominated diisocyanates, preferably the aliphatic diisocyanates, butane-1,4-diisocyanate, hexane-1,6-diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate as well as prepolymers containing isocyanate groups.
Die Einführung der anionischen Gruppen in das Molekül der Polyurethane kann dadurch erreicht werden, daß bereits während der Polyadditionsreaktion, die zu den Polyurethanen führt, Verbindungen zugegen sind, die mindestens ein aktives Wasserstoffatom und mindestens eine anionische Gruppe oder eine in eine anionische Gruppe überführbare Gruppe enthalten. Diese letzteren Verbindungen werden dabei durch Reaktion mit einem Teil der vorhandenen Isocyanatgruppen in das Polymermolekül eingebaut. Soweit bei der Herstellung der Polyurethane die vorhandenen lsocyanatgruppen nicht vollständig verbraucht werden, kann die Einführung der anionischen Gruppen mittels der genannten Verbindungen auch im Anschluß an die Bildung der Polyurethane erfolgen. Wenn das Polyurethan alkylierbare oder acylierbare Gruppen enthält, kann die nachträgliche Einführung der anionischen oder anionisierbaren Gruppen in bekannter Weise auch durch Reaktion mit Verbindungen erreicht werden, die eine alkylierende oder acylierende Funktion aufweisen und bei der betreffenden Reaktion eine anionische Gruppe bilden können. Solche Verbindungen haben meist cyclische Struktur; Dicarbonsäureanhydride, Sulfone, Lactone, Epoxycarbonsäuren und cyclische Sulfate sind Beispiele hierfür.The introduction of the anionic groups into the molecule of the polyurethanes can be achieved in that compounds which contain at least one active hydrogen atom and at least one anionic group or a group which can be converted into an anionic group are already present during the polyaddition reaction which leads to the polyurethanes . These latter compounds are incorporated into the polymer molecule by reaction with some of the isocyanate groups present. If the isocyanate groups present are not completely consumed in the production of the polyurethanes, the anionic groups can also be introduced by means of the compounds mentioned after the formation of the polyurethanes. If the polyurethane contains alkylatable or acylatable groups, the subsequent introduction of the anionic or anionizable groups can also be achieved in a known manner by reaction with compounds which have an alkylating or acylating function and can form an anionic group in the reaction concerned. Such compounds mostly have a cyclic structure; Dicarboxylic anhydrides, sulfones, lactones, epoxy carboxylic acids and cyclic sulfates are examples of this.
Die Polyaddition kann beispielsweise unter Mitverwendung von Lösungsmitteln durchgeführt werden, wobei niedrigsiedende Lösungsmittel wie beispielsweise Aceton, Ethanol, Methanol, tert.-Butanol, Methylethylketon vorzugsweise geeignet sind, die gegebenenfalls anteilig Wasser enthalten können. Als Lösungsmittel für anorganische Basen sowie die Verbindungen mit mindestens einem mit Isocyanatgruppen reagierenden Wasserstoffatom und mindestens einer anionischen Gruppe kann Wasser gegebenenfalls ohne Zusätze organischer Lösungsmittel verwendet werden.The polyaddition can be carried out, for example, with the use of solvents, with low-boiling solvents such as acetone, ethanol, methanol, tert-butanol, methyl ethyl ketone, which may optionally contain a proportion of water, preferably being suitable. Water can be used as a solvent for inorganic bases and the compounds having at least one hydrogen atom reacting with isocyanate groups and at least one anionic group, if appropriate without the addition of organic solvents.
Die entstehenden, überwiegend linearen, hochmolekularen anionische Gruppen enthaltenden Polyurethane können durch Zugabe von Wasser in die wäßrige Phase überführt und die organischen Lösungsmittel gleichzeitig oder anschließend entfernt werden. Man erhält Dispersionen in Form von Latices oder Lösungen. Verfahren zur Herstellung geeigneter anionische Gruppen enthaltender Polyurethane sind beispielsweise beschrieben in GB-A-1 076 688, US-A-3 479 310, US-A-4 108 814, US-4 092 286, DE-A-2 725 589 und DE-A-2 811 148.The resulting predominantly linear, high molecular weight anionic group-containing polyurethanes can be converted into the aqueous phase by adding water and the organic solvents can be removed simultaneously or subsequently. Dispersions are obtained in the form of latices or solutions. Processes for the preparation of suitable polyurethanes containing anionic groups are described, for example, in GB-A-1 076 688, US-A-3 479 310, US-A-4 108 814, US-4 092 286, DE-A-2 725 589 and DE-A-2 811 148.
Polyadditionsprodukt aus 218,5 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester (OH-Zahl 63), 55 g 1,6-Hexandiisocyanat und 27,8 g Natrium-1,2-diaminoethan-N-pro-pansulfonat.Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentylglycol polyester (OH number 63), 55 g of 1,6-hexanediisocyanate and 27.8 g of sodium 1,2-diaminoethane-N-pro-pansulfonate.
Polyadditionsprodukt aus 218,5 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester, 55 g 1,6-Hexandiisocyanat und 29,8 g Kalium-1,2-diaminoethan-N-propansulfonat.Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 55 g of 1,6-hexanediisocyanate and 29.8 g of potassium 1,2-diaminoethane-N-propanesulfonate.
Polyadditionsprodukt aus 218,5 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester, 30,6 g 1,6-Hexandiisocyanat und 31,9 g einer 20 %-igen wäßrigen Natriumethansulfonat-Lösung.Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentylglycol polyester, 30.6 g of 1,6-hexanediisocyanate and 31.9 g of a 20% aqueous sodium ethanesulfonate solution.
Polyadditionsprodukt aus 218,5 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester, 45,5 g 1,6-Hexandiisocyanat und 138,0 g einer 20 %-igen wäßrigen Natriumaminoethansulfonat-Lösung.Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 45.5 g of 1,6-hexanediisocyanate and 138.0 g of a 20% aqueous sodium aminoethanesulfonate solution.
Polyadditionsprodukt aus 218,5 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester, 44,2 g 1,6-Hexandiisocyanat und 92,0 g einer 20 %-igen wäßrigen Natriumaminoethansulfonat-Lösung.Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 44.2 g of 1,6-hexanediisocyanate and 92.0 g of a 20% aqueous sodium aminoethanesulfonate solution.
Polyadditionsprodukt aus 218,5 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester, 39,0 g 1,6-Hexandiisocyanat und 92,0 g einer 20 %-igen wäßrigen Natriumaminoethansulfonat-Lösung.Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 39.0 g of 1,6-hexanediisocyanate and 92.0 g of a 20% aqueous sodium aminoethanesulfonate solution.
Polyadditionsprodukt aus 218,5 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester, 32,6 g 1,6-Hexandiisocyanat und 46 g einer 20 %-igen wäßrigen Natriumaminoethansulfonat-Lösung.Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 32.6 g of 1,6-hexanediisocyanate and 46 g of a 20% aqueous sodium aminoethanesulfonate solution.
Polyadditionsprodukt aus 218,5 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester, 34,6 g 1,6-Hexandiisocyanat und 61,2 g einer 20 %-igen wäßrigen Natriumaminoethansulfonat-Lösung.Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 34.6 g of 1,6-hexanediisocyanate and 61.2 g of a 20% aqueous sodium aminoethanesulfonate solution.
Polyadditionsprodukt aus 218,5 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester, 52,0 g 1,6-Hexandiisocyanat und 184,0 g einer 20 %-igen wäßrigen Natriumaminoethansulfonat-Lösung.Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentylglycol polyester, 52.0 g of 1,6-hexanediisocyanate and 184.0 g of a 20% aqueous sodium aminoethanesulfonate solution.
Polyadditionsprodukt aus 218,5 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester, 42,0 g 1,6-Hexandiisocyanat, 12,9 g Diethylentriamin, 12,5 g Succinanhydrid und 4,9 g Kaliumhydroxid.Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 42.0 g of 1,6-hexanediisocyanate, 12.9 g of diethylenetriamine, 12.5 g of succinic anhydride and 4.9 g of potassium hydroxide.
Polyadditionsprodukt aus 218,5 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester, 42,0 g 1,6-Hexandiisocyanat, 12,9 g Diethylentriamin, 12,5 g Succinanhydrid und 6,3 g Kaliumhydroxid.Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 42.0 g of 1,6-hexanediisocyanate, 12.9 g of diethylenetriamine, 12.5 g of succinic anhydride and 6.3 g of potassium hydroxide.
Polyadditionsprodukt aus 218,5 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester, 38,0 g 1,6-Hexandiisocyanat und 14,9 g Kalium-1,2-diaminoethan-N-propansulfonat.Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 38.0 g of 1,6-hexanediisocyanate and 14.9 g of potassium 1,2-diaminoethane-N-propanesulfonate.
Polyadditionsprodukt aus 218,5 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester, 32,5 g 1,6-Hexandiisocyanat und 7,5 g Kalium-1,2-diaminoethan-N-propansulfonat.Polyaddition product made from 218.5 g adipic acid-hexanediol-neopentyl glycol polyester, 32.5 g of 1,6-hexanediisocyanate and 7.5 g of potassium 1,2-diaminoethane-N-propanesulfonate.
Polyadditionsprodukt aus 218,5 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester, 36,7 g 1,6-Hexandiisocyanat und 11,2 g Kalium-1,2-diaminoethan-N-propansulfonat.Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 36.7 g of 1,6-hexanediisocyanate and 11.2 g of potassium 1,2-diaminoethane-N-propanesulfonate.
Polyadditionsprodukt aus 106,3 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester (OH-Zahl 65,85), 128,5 g 1,6-Hexandiisocyanat, 52,0 g Neopentylglykol und 29,8 g Kalium-1,2-diaminoethan-N-propansulfonat.Polyaddition product made from 106.3 g adipic acid-hexanediol-neopentyl glycol polyester (OH number 65.85), 128.5 g 1,6-hexane diisocyanate, 52.0 g neopentyl glycol and 29.8 g potassium 1,2-diaminoethane N-propane sulfonate.
Polyadditionsprodukt aus 106,3 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester (OH-Zahl 65,85), 250,0 g 1,6-Hexandiisocyanat, 53,0 g Diethylenglykol, 52,0 g Neopentylglykol und 29,8 g Kalium-1,2-diaminoethan-N-propansulfonatPolyaddition product made from 106.3 g adipic acid-hexanediol-neopentyl glycol polyester (OH number 65.85), 250.0 g of 1,6-hexane diisocyanate, 53.0 g of diethylene glycol, 52.0 g of neopentyl glycol and 29.8 g of potassium 1,2-diaminoethane-N-propanesulfonate
Polyadditionsprodukt aus 106,3 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester (OH-Zahl 65,85), 121,0 g 1,6-Hexandiisocyanat, 26,5 g Diethylenglykol, 26,0 g Neopentylglykol und 29,8 g Kalium-1,2-diaminoethan-N-propansulfonat.Polyaddition product made from 106.3 g adipic acid-hexanediol-neopentyl glycol polyester (OH number 65.85), 121.0 g of 1,6-hexane diisocyanate, 26.5 g of diethylene glycol, 26.0 g of neopentyl glycol and 29.8 g of potassium 1,2-diaminoethane-N-propanesulfonate.
Polyadditionsprodukt aus 212,5 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester (OH-Zahl 65,85), 89,0 g 1,6-Hexandiisocyanat und 59,6 g Kalium-1,2-diaminoethan-N-propansulfonat.Polyaddition product made from 212.5 g adipic acid-hexanediol-neopentyl glycol polyester (OH number 65.85), 89.0 g of 1,6-hexane diisocyanate and 59.6 g of potassium 1,2-diaminoethane-N-propanesulfonate.
Polyadditionsprodukt aus 212,5 g Adipinsäure-Hexandiol-Neopentylglykol-Polyester (OH-Zahl 65,85), 72,0 g 1,6-Hexandiisocyanat und 44,7 g Kalium-1,2-diaminoethan-N-propansulfonat.Polyaddition product consisting of 212.5 g adipic acid-hexanediol-neopentylglycol polyester (OH number 65.85), 72.0 g of 1,6-hexane diisocyanate and 44.7 g of potassium 1,2-diaminoethane-N-propanesulfonate.
Polyadditionsprodukt aus 250,0 g Polypropylenglykol (OH-Zahl 56), 48,0 g 1,6-Hexandiisocyanat und 29,8 g Kalium-1,2-diaminoethan-N-propansulfonat.Polyaddition product made from 250.0 g polypropylene glycol (OH number 56), 48.0 g 1,6-hexane diisocyanate and 29.8 g potassium 1,2-diaminoethane-N-propanesulfonate.
Über die bereits genannten wesentlichen Bestandteile hinaus kann das farbfotografische Aufzeichnungsmaterial weitere Bestandteile und Hilfsstoffe enthalten, die beispielsweise für die Durchführung der Wärmebehandlung und des hierbei erfolgenden Farbübertrages förderlich sind. Diese weiteren Bestandteile bzw. Hilfsstoffe können in einer lichtempfindlichen Schicht oder in einer nicht empfindlichen Schicht enthalten sein.In addition to the essential constituents already mentioned, the color photographic recording material can contain further constituents and auxiliary substances which are beneficial, for example, for carrying out the heat treatment and the color transfer which takes place in the process. These further constituents or auxiliary substances can be contained in a light-sensitive layer or in a non-sensitive layer.
Solche Hilfsstoffe sind beispielsweise Hilfsentwickler. Diese Hilfsentwickler haben im allgemeinen entwickelnde Eigenschaften für belichtetes Silberhalogenid; im vorliegenden Fall wirken sie sich in erster Linie förderlich auf die zwischen dem belichteten Silbersalz (= Silbersalz in Gegenwart von belichtetem Silberhalogenid) und dem Reduktionsmittel ablaufenden Reaktionen aus, wobei das Reduktionsmittel im Falle der Verwendung oxidierbarer Farbabspalter mit letzteren identisch ist, bzw. im Fall der Verwendung reduzierbarer Farbabspalter seinerseits mit dem Farbabspalter reagiert. Da diese Reaktion hauptsächlich in einem Übertrag von Elektronen bestehen, werden die Hilfsentwickler auch als Elektronenübertragungsmittel (electron transfer agent; ETA) bezeichnet.Such auxiliaries are, for example, auxiliary developers. These auxiliary developers generally have developing properties for exposed silver halide; In the present case, they primarily have a beneficial effect on the reactions taking place between the exposed silver salt (= silver salt in the presence of exposed silver halide) and the reducing agent, the reducing agent being identical to the latter when using oxidizable color releasers, or in the case the use of reducible paint releasers in turn reacts with the paint releasers. Since this reaction consists mainly of electron transfer, the auxiliary developers are also referred to as electron transfer agents (ETA).
Beispiele für geeignete Hilfsentwickler sind etwa Hydrochinon, Brenzkatechin, Pyrogallol, Hydroxylamin, Ascorbinsäure, 1-Phenyl-3-pyrazolinon und deren Derivate. Da die Hilfsentwickler gleichsam eine katalytische Funktion ausüben, ist es nicht erforderlich, daß sie in stöchiometrischen Mengen anwesend sind. Im allgemeinen reicht es aus, wenn sie in Mengen bis zu maximal 1/2 Mol pro Mol Farbabspalter in der Schicht vorhanden sind. Die Einarbeitung in die Schicht kann beispielsweise aus Lösungen in wasserlöslichen Lösungsmitteln oder in Form von wäßrigen Dispersionen, die unter Verwendung von Ölbildnern gewonnen wurden, erfolgen.Examples of suitable auxiliary developers include hydroquinone, pyrocatechol, pyrogallol, hydroxylamine, ascorbic acid, 1-phenyl-3-pyrazolinone and their derivatives. Since the auxiliary developers have a catalytic function, it is not necessary for them to be present in stoichiometric amounts. In general, it is sufficient if they are present in the layer in amounts up to a maximum of 1/2 mol per mol of color releaser. Incorporation into the layer can take place, for example, from solutions in water-soluble solvents or in the form of aqueous dispersions which have been obtained using oil formers.
Weitere Hilfsstoffe sind beispielsweise basische Stoffe oder Verbindungen, die unter dem Einfluß der Wärmebehandlung basische Stoffe zur Verfügung zu stellen vermögen. Hier sind beispielsweise zu erwähnen Natriumhydroxid, Kaliumhydroxid, Calziumhydroxid, Natriumcarbonat, Natriumacetat und organische Basen, insbesondere Amine wie Trialkylamine, Hydroxyalkylamine, Piperidin, Morpholin, Dialkylanilin, p-Toluidin, 2-Picolin, Guanidin und deren Salze, insbesondere Salze mit aliphatischen Carbonsäuren z. B. Trichloracetate. Durch Zurverfügungsstellung der basischen Stoffe wird bei der Wärmebehandlung in der lichtempfindlichen Schicht und den angrenzenden Schichten ein geeignetes alkalisches Medium geschaffen, um die Freisetzung der diffusionsfähigen Farbstoffe aus den Farbabspaltern und ihre Diffusion in die Bildempfangsschicht zu gewährleisten.Other auxiliaries are, for example, basic substances or compounds which are able to provide basic substances under the influence of the heat treatment. Sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium acetate and organic bases, in particular amines such as trialkylamines, hydroxyalkylamines, piperidine, morpholine, dialkylaniline, p-toluidine, 2-picoline, guanidine and their salts, in particular salts with aliphatic carboxylic acids, e.g. . B. Trichloroacetate. By providing the basic substances, a suitable alkaline medium is created during the heat treatment in the light-sensitive layer and the adjacent layers in order to ensure the release of the diffusible dyes from the color releasers and their diffusion into the image-receiving layer.
Weitere Hilfsstoffe sind beispielsweise Verbindungen, die unter der Einwirkung von Wärme Wasser freizusetzen vermögen. Hierfür kommen insbesondere Kristallwasser enthaltende anorganische Salze in Frage, z. B. Na2S04-10H20, NH4Fe(S04h.12H20, sowie auch Verbindungen vom Typ des Natriumbenztriazolats, die als Komplex mit verschiedenen Mengen Wasser (bis 24 mol H20) kristallisieren und die in US-A-4 418 139 beschrieben sind.Other auxiliaries are, for example, compounds which are able to release water under the action of heat. In particular, inorganic salts containing water of crystallization come into question, e.g. B. Na 2 S0 4 -10H 2 0, NH4Fe (S04h.12H20, and also compounds of the sodium benzotriazolate type, which crystallize as a complex with various amounts of water (up to 24 mol H 2 0) and which in US-A-4 418 139 are described.
Das bei der Erwärmung freigesetzte Wasser begünstigt die für die Bilderzeugung erforderlichen Entwicklungs- und Diffusionsvorgänge.The water released during heating favors the development and diffusion processes required for image formation.
Weitere Hilfsstoffe sind beispielsweise die sogenannten thermischen Lösungsmittel bzw. Entwicklungs- und Diffusionsförderungsmittel, worunter man im allgemeinen nicht hydrolysierbare organische Verbindungen versteht, die bei Normalbedingungen fest oder flüssig sind, jedenfalls aber bei der Temperatur der Wärmebehandlung ein flüssiges Medium liefern, in dem die Entwicklungs- und Diffusionsvorgänge schneller ablaufen können. Bevorzugte Beispiele hierfür umfassen Polyglykole, wie beispielsweise beschrieben in US-A-3 347 675, z. B. Polyethylenglykol mit einem durchschnittlichen Molekulargewicht von 1500 bis 20 000, Derivate von Polyethylenoxid, wie beispielsweise dessen Ölsäureester, Bienenwachs, Monostearin, Verbindungen mit einer hohen dielektrischen Konstante, die eine -S02- oder -CO-Gruppe aufweisen, wie z. B. Acetamid, Lactame, Succinamid, Ethylcarbamat, Harnstoff, Methylsulfonamid, Ethylencarbonat, ferner polare Substanzen, wie beschrieben in US-A-3 667 959, das Lacton von 4-Hydroxybuttersäure, Dimethylsulfoxid, Tetrahydrothiophen-1,1-dioxid und 1,10-Decandiol, Methylanisat, Biphenylsuberat usw., auch Wasser, Ethylenglykol, Glycerin und andere gut solubisierende Lösungsmittel.Other auxiliaries are, for example, the so-called thermal solvents or development and diffusion promotion agents, which are generally understood to mean non-hydrolyzable organic compounds which are solid or liquid under normal conditions, but in any case provide a liquid medium at the temperature of the heat treatment, in which the development and diffusion processes can run faster. Preferred examples of these include polyglycols as described, for example, in US-A-3,347,675, e.g. B. polyethylene glycol with an average molecular weight of 1500 to 20,000, derivatives of polyethylene oxide, such as its oleic acid ester, beeswax, monostearin, compounds with a high dielectric constant, which have a -S0 2 - or -CO group, such as. B. acetamide, lactams, succinamide, ethyl carbamate, urea, methylsulfonamide, ethylene carbonate, also polar substances, as described in US Pat. No. 3,667,959, the lactone of 4-hydroxybutyric acid, dimethyl sulfoxide, tetrahydrothiophene-1,1-dioxide and 1, 10-decanediol, methyl anisate, biphenyl suberate etc., also water, ethylene glycol, glycerin and other well-solubilizing solvents.
Die Entwicklung des bildmäßig belichteten erfindungsgemäßen farbfotografischen Aufzeichnungsmaterials umfaßt die Teilschritte Silberhalogenidentwicklung, Erzeugung einer bildmäßigen Verteilung diffusionsfähiger Farbstoffe und Diffusionsübertragung dieser bildmäßigen Verteilung in die Bildempfangsschicht. Sie wird dadurch eingeleitet, daß man das belichtete Aufzeichnungsmaterial einer Wärmebehandlung unterzieht, bei der die lichtempfindliche Bindemittelschicht für eine Zeit von etwa 0,5 bis 300 s auf eine erhöhte Temperatur, z. B. im Bereich von 80 bis 250°C, gebracht wird. Hierdurch werden in dem Aufzeichnungsmaterial geeignete Bedingungen für die Entwicklungsvorgänge einschließlich der Farbstoffdiffusion geschaffen, ohne daß es der Zufuhr eines flüssigen Mediums, z. B. in Form eines Entwicklerbades bedarf. Bei der Entwicklung werden aus den Farbabspaltern bildmäßig Diffusionsfähige Farbstoffe freigesetzt und auf eine Bildempfangsschicht übertragen, die entweder integraler Bestandteil des erfindungsgemäßen farbfotografischen Aufzeichnungsmaterials ist oder sich mit jenem zumindest während der Entwicklungszeit in Kontakt befindet.The development of the imagewise exposed color photographic recording material according to the invention comprises the partial steps of silver halide development, generation of an imagewise distribution of diffusible dyes and diffusion transfer of this imagewise distribution into the image receiving layer. It is initiated by subjecting the exposed recording material to a heat treatment in which the photosensitive binder layer is heated to an elevated temperature, e.g. B. is brought in the range of 80 to 250 ° C. This makes suitable ones in the recording material Conditions for the development processes including dye diffusion are created without the addition of a liquid medium, e.g. B. in the form of a developer bath. During development, diffusible dyes are released imagewise from the color releasers and transferred to an image-receiving layer which is either an integral part of the color photographic recording material according to the invention or is in contact with it at least during the development period.
Hierbei finden in einem Einschritt-Entwicklungsprozeß bildmäßige Silberentwicklung, Farbstofffreisetzung und Farbtransfer synchron statt.Image-wise silver development, dye release and color transfer take place synchronously in a one-step development process.
Darüber hinaus kann die Farbbilderzeugung mit dem erfindungsgemäßen farbfotografischen Aufzeichnungsmaterial auch in einem Zweischritt-Entwicklungsprozeß erfolgen, wobei in einem ersten Schritt die Silberhalogenidentwicklung und Farbstofffreisetzung stattfindet, worauf in einem zweiten Schritt die Farbbildübertragung aus dem lichtempfindlichen Teil auf einen damit in Kontakt gebrachten Bildempfangsteil erfolgt, z. B. durch Erhitzen auf eine Temperatur zwischen 50 und 150°C, vorzugsweise auf 70 bis 90°C, wobei in diesem Fall vor dem Laminieren von lichtempfindlichem Teil und Bildempfangsteil noch Diffusionshilfsmittel (Lösungsmittel) extern angetragen werden können.In addition, the color image formation with the color photographic recording material according to the invention can also be carried out in a two-step development process, silver halide development and dye release taking place in a first step, followed by color image transfer in a second step from the light-sensitive part to an image receiving part brought into contact with it, e.g. . B. by heating to a temperature between 50 and 150 ° C, preferably to 70 to 90 ° C, in which case diffusion aids (solvents) can be applied externally before the lamination of the light-sensitive part and the image receiving part.
Die Bildempfangsschicht kann demnach auf dem gleichen Schichtträger angeordnet sein wie das lichtempfindliche Element (Einzelblatt-Material) oder auf einem separaten Schichtträger (Zweiblatt-Material). Sie besteht im wesentlichen aus einem Bindemittel, das Beizmittel für die Festlegung der aus den nichtdiffundierenden Farbabspaltern freigesetzten diffusionsfähigen Farbstoffe enthält. Als Beizmittel für anionische Farbstoffe dienen vorzugsweise langkettige quaternäre Ammonium- oder Phosphoniumverbindungen, z. B. solche, wie sie beschrieben sind in US-A-3 271 147 und US-A-3 271 148.The image-receiving layer can accordingly be arranged on the same layer support as the light-sensitive element (single sheet material) or on a separate layer support (two-sheet material). It essentially consists of a binder which contains mordants for the determination of the diffusible dyes released from the non-diffusing paint releasers. Long-chain quaternary ammonium or phosphonium compounds, e.g. B. As described in US-A-3,271,147 and US-A-3,271,148.
Ferner können auch bestimmte Metallsalze und deren Hydroxide, die mit den sauren Farbstoffen schwerlösliche Verbindungen bilden, verwandt werden. Weiterhin sind hier auch polymere Beizmittel zu erwähnen, wie etwa solche, die in DE-A-2 315 304, DE-A-2 631 521 oder DE-A-2 941 818 beschrieben sind. Die Farbstoffbeizmittel sind in der Beizmittelschicht in einem der üblichen hydrophilen Bindemittel dispergiert z. B. in Gelatine, Polyvinylpyrrolidon, ganz oder partiell hydrolysierten Celluloseestern. Selbstverständlich können auch manche Bindemittel als Beizmittel fungieren, z. B. Polymerisate von stickstoffhaltigen, gegebenenfalls quaternären Basen, wie etwa von N-Methyl-4-vinylpyridin, 4-Vinyl-pyridin, 1-Vinylimidazol, wie beispielsweise beschrieben in US-A-2 484 430. Weitere brauchbare beizende Bindemittel sind beispielsweise Guanylhydrazonderivate von Alkylvinylketonpolymerisaten, wie beispielsweise beschrieben in der US-A-2 882 156, oder Guanylhydrazonderivate von Acylstyrolpolymerisaten, wie beispielsweise beschrieben in DE-A-2 009 498. Im allgemeinen wird man jedoch den zuletzt genannten beizenden Bindemitteln andere Bindemittel, z. B. Gelatine, zusetzen.Furthermore, certain metal salts and their hydroxides, which form poorly soluble compounds with the acid dyes, can also be used. Also to be mentioned here are polymeric mordants, such as those described in DE-A-2 315 304, DE-A-2 631 521 or DE-A-2 941 818. The dye mordants are dispersed in the mordant layer in one of the usual hydrophilic binders, e.g. B. in gelatin, polyvinyl pyrrolidone, completely or partially hydrolyzed cellulose esters. Of course, some binders can also act as mordants, e.g. B. Polymers of nitrogen-containing, optionally quaternary bases, such as N-methyl-4-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, as described, for example, in US Pat. No. 2,484,430. Other useful binding agents are, for example, guanylhydrazone derivatives of alkyl vinyl ketone polymers, as described, for example, in US Pat. No. 2,882,156, or guanylhydrazone derivatives of acyl styrene polymers, as described, for example, in DE-A-2 009 498. In general, however, other binders, e.g. B. add gelatin.
Sofern die Bildempfangsschicht auch nach vollendeter Entwicklung in Schichtkontakt mit dem lichtempfindlichen Element verbleibt, befindet sich zwischen ihnen in der Regel eine alkalidurchlässige pigmenthaltige lichtreflektierende Bildemittelschicht, die der optischen Trennung zwischen Negativ und Positiv und als ästhetisch ansprechender Bildhintergrund für das übertragende positive Farbbild dient. Falls die Bindempfangsschicht zwischen Schichtträger und lichtempfindlichem Element angeordnet ist und von letzterem durch eine vorgebildete lichtreflektierende Schicht getrennt ist, muß entweder der Schichtträger transparent sein, so daß das erzeugte Farbübertragsbild durch ihn hindurch betrachtet werden kann, oder das lichtempfindliche Element muß mitsamt der lichtreflektierenden Schicht von der Bildempfangsschicht entfernt werden, um letztere freizulegen. Die Bildempfangsschicht kann aber auch als oberste Schicht in einem integralen farbfotografischen Aufzeichnungsmaterial vorhanden sein, in welch letzterem Fall die Belichtung zweckmäßigerweise durch den transparenten Schichtträger vorgenommen wird.If the image-receiving layer remains in layer contact with the light-sensitive element even after development is complete, there is usually an alkali-permeable, pigment-containing, light-reflecting image middle layer between them, which serves as an optical separation between negative and positive and serves as an aesthetically pleasing background for the positive color image. If the binder-receiving layer is arranged between the support and the photosensitive element and is separated from the latter by a pre-formed light-reflecting layer, either the support must be transparent so that the color transfer image produced can be viewed through it, or the photosensitive element together with the light-reflecting layer of the image-receiving layer are removed to expose the latter. The image-receiving layer can, however, also be present as the top layer in an integral color photographic recording material, in which case the exposure is expediently carried out through the transparent layer support.
Herstellung der SilbersalzemulsionenPreparation of the silver salt emulsions
17,0 g AgNOg, gelöst in 200 ml 45°C warmem Wasser, wurden innerhalb von 2 min zu einer 45°C warmen Lösung von 20,0 g Gelatine in 1000 ml Wasser, die 13,0 g Benzotriazol (BTA) enthielt, unter Rühren zudosiert. Anschließend wurde 5 min nachgerührt. Mit 5 %-iger Na2C0S-Lösung wurde pH 5,0 eingestellt. Durch Zugabe von 20 ml einer 10 %-igen Polystyrolsulfonsäurelösung, Kühlung auf 25°C und Zugabe von 10 %-iger Schwefelsäure (bis pH 3,0 bis 3,5) wurde geflockt und anschließend dreimal mit je 1000 ml Wasser gewaschen. Das Flockulat wurde auf 45°C erwärmt, mit 5 %-iger Na2C03-Lösung auf pH 6,0 gestellt, mit 5 ml 1 %-iger wäßriger Phenollösung versetzt und durch Zugabe von Wasser auf ein Endgewicht von 435 g gebracht.17.0 g of AgNOg, dissolved in 200 ml of water at 45 ° C., became a 45 ° C. solution of 20.0 g of gelatin in 1000 ml of water which contained 13.0 g of benzotriazole (BTA) within 2 min. metered in with stirring. The mixture was then stirred for 5 minutes. The pH was adjusted to 5.0 with a 5% Na 2 C0 S solution. The mixture was flocculated by adding 20 ml of a 10% polystyrene sulfonic acid solution, cooling to 25 ° C. and adding 10% sulfuric acid (up to pH 3.0 to 3.5) and then washing three times with 1000 ml of water each time. The flocculate was heated to 45 ° C, with 5% Na 2 C0 3 solution at pH 6.0 made, mixed with 5 ml of 1% aqueous phenol solution and brought g by addition of water to a final weight of 435th
34,0 g AgN03 gelöst in 200 ml Wasser wurden innerhalb von 10 min zu einer 50°C warmen Lösung von 40,0 g Gelatine, 23,7 g KBr und 1,66 g KI zudosiert. Anschließend wurde 20 min bei 50°C nachgerührt und dann auf 35°C gekühlt. 40 ml einer 10 %-igen Polystyrolsulfonsäurelösung wurden zugetropft und dann wurde auf 20°C gekühlt. Durch Zugabe von 10 %-iger Schwefelsäure (bis pH 3,0 bis 3,5) wurde geflockt und dreimal mit je 700 ml Wasser gewaschen. Dann wurde auf 40°C erwärmt und mit 10 %-iger Natronlauge auf pH 6,0 gestellt. Endgewicht 1171 g.34.0 g of AgN0 3 dissolved in 200 ml of water were metered in over the course of 10 min to a 50 ° C. solution of 40.0 g of gelatin, 23.7 g of KBr and 1.66 g of KI. The mixture was then stirred at 50 ° C for 20 min and then cooled to 35 ° C. 40 ml of a 10% polystyrene sulfonic acid solution was added dropwise and then it was cooled to 20 ° C. The mixture was flocculated by adding 10% sulfuric acid (up to pH 3.0 to 3.5) and washed three times with 700 ml of water each. The mixture was then heated to 40 ° C. and adjusted to pH 6.0 with 10% sodium hydroxide solution. Final weight 1171 g.
Zur Spektralsensibilisierung wurden Teile der Emulsion 2 (Rohemulsion) bei 40° C aufgeschmolzen, pro mol Ag mit 4 x 10-4 mol Rotsensibilisator, 4 x 10-4 mol Grünsensibilisator oder 8 x 10-4 mol Blausensibilisator, jeweils in methanolischer Lösung oder Anschlämmung, versetzt und ca. 70 min in einem geschlossenen Gefäß digeriert.For spectral sensitization, parts of emulsion 2 (crude emulsion) were melted at 40 ° C., per mol of Ag with 4 x 10- 4 mol red sensitizer, 4 x 10- 4 mol green sensitizer or 8 x 10- 4 mol blue sensitizer, each in methanolic solution or slurry , added and digested in a closed vessel for about 70 min.
Es wurden folgende Spektralsensibilisatoren verwendet.The following spectral sensitizers were used.
Rotsensibilisator:
Grünsensibilisator:
Blausensibilisator
Herstellung der DispergateManufacture of the Dispergate
50 g Farbabspalter C - 1 wurden in einer Mischung aus 50 g Trikresylphosphat, 50 g Tetrahydrofuran, 200 ml Ethylacetat mit 50 g 20 %-iger wäßriger Lösung von KHC03 gelöst und in Gegenwart von 2,6 g Natriumdodecylbenzolsulfonat in 330 g 10 %-iger wäßriger Gelatinelösung dispergiert, und anschließend wurden die Hilfslösungsmittel in einer Unterdruckapparatur mit entspanntem Wasserdampf entfernt. Ausbeute: 957 g Dispergat 150 g of color releaser C - 1 were dissolved in a mixture of 50 g of tricresyl phosphate, 50 g of tetrahydrofuran, 200 ml of ethyl acetate with 50 g of 20% aqueous solution of KHC0 3 and in the presence of 2.6 g of sodium dodecylbenzenesulfonate in 330 g of 10% - dispersed aqueous gelatin solution, and then the auxiliary solvents were removed in a vacuum apparatus with relaxed steam. Yield: 957 g of dispersant 1
50 g Farbabspalter M - 1 wurden in 25 g Diethyllaurylamid und 150 ml Ethylacetat gelöst und wie Dispergat 1 weiterbehandelt. Ausbeute: 834 g Dispergat 250 g of color releasing agent M-1 were dissolved in 25 g of diethyl laurylamide and 150 ml of ethyl acetate and further treated like disperse 1. Yield: 834 g of dispersant 2
31 g Farbabspalter M - 2 wurden in 15,5 g Diethyllaurylamid mit 100 ml Ethylacetat gelöst, in Gegenwart von 1,55 g Natriumdodecylbenzolsulfonat in 205 g 10 %-iger wäßriger Gelatinelösung dispergiert und anschließend wie in Dispergat 1 weiterbehandelt. Ausbeute: 1028 g Dispergat 331 g of color releaser M-2 were dissolved in 15.5 g of diethyl laurylamide with 100 ml of ethyl acetate, dispersed in 205 g of 10% strength aqueous gelatin solution in the presence of 1.55 g of sodium dodecylbenzenesulfonate and then further treated as in dispersant 1. Yield: 1028 g of dispersant 3
50 g Farbabspalter Y - 1 wurden in 25 g Diethyllaurylamid und 150 ml Ethylacetat gelöst und dann wie Dispergat 1 weiterbehandelt. Ausbeute: 821 g Dispergat 450 g of color releasing agent Y-1 were dissolved in 25 g of diethyl laurylamide and 150 ml of ethyl acetate and then further treated like disperse 1. Yield: 821 g of dispersant 4
62 g Hilfsentwicklervorläuferverbindung wurden in 120 g Diethyllaurylamid und 150 ml Ethylacetat gelöst und in Gegenwart von 3,5 g Natriumdodecylbenzolsulfonat in 612 g 10 %-iger wäßriger Gelatinelösung dispergiert; und anschließend wurde wie bei Dispergat 1 das Hilfslösungsmittel entfernt. Ausbeute: 997 g Dispergat 562 g of auxiliary developer precursor compound were dissolved in 120 g of diethyl laurylamide and 150 ml of ethyl acetate and dispersed in 612 g of 10% aqueous gelatin solution in the presence of 3.5 g of sodium dodecylbenzenesulfonate; and then the auxiliary solvent was removed as for Dispersate 1. Yield: 997 g of disperse 5
Es wurden folgende Verbindungen verwendet:
- Farbabspalter C -1
- Farbabspalter M - 1
- Farbabspalter M - 2
- Farbabspalter Y -1
- Paint releaser C -1
- Paint releaser M - 1
- Paint releaser M - 2
- Paint splitter Y -1
Hilfsentwicklervorläuferverbindung
Der Bildempfangsteil eines fotografischen Aufzeichnungsmaterials für das Farbdiffusionsübertragungsverfahren wurde dadurch hergestellt, daß auf einen transparenten Schichtträger aus Polyethylenterephthalat folgende Schichten nacheinander aufgetragen wurden. Die Mengenangaben beziehen sich dabei jeweils auf 1 m2.
- 1. Eine lichtreflektierende Schicht mit 20 g Ti02 und 2 g Gelatine.
- 2. Eine Beizschicht mit 2 g Polyurethanbeize aus 4,4'-Diphenylmethandiisocyanat und N-Ethyldiethanolamin, quaterniert mit Epichlorhydrin gemäß DE-A-2 631 521, Beispiel 1, und 2 g Gelatine.
- 3. Schutzschicht aus 1 g Gelatine. (Mit dieser Schutzschicht wird gleichzeitig Härtungsmittel mit aufgetragen).
- 1. A light reflecting layer with 20 g Ti0 2 and 2 g gelatin.
- 2. A pickling layer with 2 g of polyurethane pickle made from 4,4'-diphenylmethane diisocyanate and N-ethyldiethanolamine, quaternized with epichlorohydrin according to DE-A-2 631 521, Example 1, and 2 g of gelatin.
- 3. Protective layer made of 1 g gelatin. (This protective layer also applies hardening agent).
Bei Verwendung von barytiertem Papier als Schichtträger kann auf die Ti02-Schicht verzichtet werden.When using baryta paper as layer support, the Ti0 2 layer can be dispensed with.
Die lichtempfindlichen Teile von nicht erfindungsgemäßen (Vergleich) und erfindungsgemäßen farbfotografischen Aufzeichnungsmaterialien für das Farbdiffusionsübertragungsverfahren wurden wie folgt hergestellt:The light-sensitive parts of non-inventive (comparison) and color photographic recording materials according to the invention for the color diffusion transfer process were produced as follows:
32,0 g Emulsion 2, rotsensibilisiert und 45,6 g Emulsion 1 wurden bei 40° C aufgeschmolzen und mit 8 ml 4 %- iger wäßriger Lösung von Triton® X 100 versetzt.32.0 g of emulsion 2, sensitized to red, and 45.6 g of emulsion 1 were melted at 40 ° C. and mixed with 8 ml of 4% strength aqueous solution of Triton® X 100.
Hersteller: Rohm & Haas Company, PhiladelphiaManufacturer: Rohm & Haas Company, Philadelphia
Dann wurden 18,5 g Dispergat 1 (Farbabspalter C -1), 6,7 g Dispergat 5 (Hilfsentwicklervorläuferverbindung) und 66 g 20 %-ige Gelatine zugefügt und aufgeschmolzen. 150 mg Quecksilber-II-chlorid gelöst in 30 ml Wasser und 3,2 g Guanidintrichloracetat in 30 ml Wasser wurden zugefügt und dann wurde mit Wasser auf ein Endgewicht von 320 g eingestellt. Die Lösung wurde mit einer Naßschichtdicke von 100 µm auf einen Schichtträger aus Polyethylenterephthalat aufgetragen und mit einer ein Härtungsmittel enthaltenden 1 %- igen wäßrigen Gelatinelösung (Naßschichtdicke 40 µm) überschichtet und gerocknet.Then 18.5 g of dispersant 1 (color releasing agent C -1), 6.7 g of disperse 5 (auxiliary developer precursor compound) and 66 g of 20% gelatin were added and melted. 150 mg of mercury-II chloride dissolved in 30 ml of water and 3.2 g of guanidine trichloroacetate in 30 ml of water were added and the mixture was then brought to a final weight of 320 g with water. The solution was applied with a wet layer thickness of 100 μm to a layer support made of polyethylene terephthalate and covered with a 1% aqueous gelatin solution (wet layer thickness 40 μm) containing a hardening agent and rocked.
Herstellung in gleicher Weise wie Probe 1, jedoch unter Verwendung von 32,0 g Emulsion 2, grünsensibilisiert, und 17,2 g Dispergat 2 (Farbabspalter M -1).Preparation in the same way as sample 1, but using 32.0 g of emulsion 2, green-sensitized, and 17.2 g of disperse 2 (color releaser M -1).
Herstellung in gleicher Weise wie Probe 1 jedoch unter Verwendung von 32,0 g Emulsion 2, blausensibilisiert, und 15,3 g Dispergat 4 (Farbabspalter Y - 1)..Preparation in the same way as sample 1, but using 32.0 g of emulsion 2, blue-sensitized, and 15.3 g of disperse 4 (color releasing agent Y-1).
Die Proben 1 bis 3 sind nicht erfindungsgemäße Aufzeichnungsmaterialien, die zum Vergleich mitgetestet wurden; das Bindemittel besteht zu 100 % aus Gelatine. Die Herstellung der erfindungsgemäßen Aufzeichnungsmaterialien ist nachstehend beschrieben (Proben 4 bis 7). Das dabei verwendete Polyurethan ist eine 30 %-ige wäßrige netzmittelfreie Dispersion eines anionischen Polyesterpolyurethans, das aus
- 84,1 % Polyester, aus Adipinsäure, 1,6-Hexandiol und Neopentylglykol (Molverhältnis 30 : 22 : 12) OH-Zahl: 66,6; Molgewicht 1600-1700
- 13,1 % Hexamethylendiisocyanat, und
- 2,7 % N-Aminoethyltaurin
- 84.1% polyester, from adipic acid, 1,6-hexanediol and neopentyl glycol (molar ratio 30:22:12) OH number: 66.6; Molecular weight 1600-1700
- 13.1% hexamethylene diisocyanate, and
- 2.7% N-aminoethyl taurine
erhalten worden war; Gehalt an -S03Na-Gruppen 1,93 %.had been preserved; Content of -S0 3 Na groups 1.93%.
24,0 g 2,5 %-ige wäßrige Lösung von Natrosol wurden mit 108 ml Wasser und 8 ml einer 4 %-igen wäßrigen Lösung von Triton® X 100 homogenisiert. 6,7 g Dispergat 5, 18,5 g Dispergat 1 (Farbabspalter C - 1), 45,6 g Emulsion 1 und 32,0 g Emulsion 2, rotsensibilisiert, wurden zugefügt und aufgeschmolzen. Dann wurden langsam 3,2 g Guanidintrichloracetat in 30 ml Wasser zugefügt und schließlich 44,0 g der beschriebenen 30 %- igen Polyurethanlösung, worauf das Ganze homogenisiert wurde. Die fertige Gießlösung wurde mit einer Naßschichtdicke von 100 µm auf einen Schichtträger aus Polyethylenterephthalat aufgetragen und bei 35°C getrocknet. Mit einer 1 %-igen wäßrigen Gelatinelösung, die ein Härtungsmittel enthielt wurde überschichtet (Naßschichtdicke 40 µm) und getrocknet.24.0 g of 2.5% aqueous solution of Natrosol were homogenized with 108 ml of water and 8 ml of a 4% aqueous solution of Triton® X 100. 6.7 g of disperse 5, 18.5 g of disperse 1 (color releaser C-1), 45.6 g of emulsion 1 and 32.0 g of emulsion 2, red-sensitized, were added and melted. Then 3.2 g of guanidine trichloroacetate in 30 ml of water were added slowly and finally 44.0 g of the 30% polyurethane solution described, whereupon the whole was homogenized. The finished casting solution was applied with a wet layer thickness of 100 μm to a layer support made from polyethylene terephthalate and dried at 35 ° C. With a 1% aqueous gelatin solution containing a hardening agent was overlaid (wet layer thickness 40 microns) and dried.
Herstellung in gleicher Weise wie Probe 4, jedoch unter Verwendung von 32,0 g Emulsion 2, grünsensibilisiert, und 17,2 g Dispergat 2 (Farbabspalter M -1).Preparation in the same way as sample 4, but using 32.0 g of emulsion 2, green-sensitized, and 17.2 g of disperse 2 (color releaser M -1).
Herstellung in gleicher Weise wie Probe 4, jedoch unter Verwendung von 32,0 g Emulsion 2, blausensibilisiert, und 15,3 g Dispergat 4 (Farbabspalter Y - 1).Preparation in the same way as sample 4, but using 32.0 g of emulsion 2, blue-sensitized, and 15.3 g of disperse 4 (color releasing agent Y-1).
Herstellung in gleicher Weise wie Probe 4, jedoch unter Verwendung von 89 ml Wasser zur Homogenisierung der Natrosollösung (statt 108 ml); sowie 32,0 g Emulsion 2, grünsensibilisiert und 37,8 g Dispergat 3 (Farbabspalter M - 2).Preparation in the same way as sample 4, but using 89 ml of water to homogenize the Natrosol solution (instead of 108 ml); and 32.0 g of emulsion 2, green-sensitized and 37.8 g of dispersant 3 (color releaser M-2).
Die nach Beispiel 4 hergestellten Proben wurden mit einer Wolframlampe belichtet, wobei die Belichtung im Falle der Proben 1, 2, 4, 5 und 7 hinter einem transparenten Gelbfilter mit einer Dichte von 1,25 vorgenommen wurde. Intensität und Dauer der Belichtung ist aus Tabelle 1 ersichtlich. Anschließend wurden die Proben zur Entwicklung trocken auf 110°C erhitzt; die Dauer dieser Behandlung ist ebenfalls aus Tabelle 1 ersichtlich. Dann wurden die Proben 10 s in Wasser gequollen und mit einem Bildempfangsblatt (aus Beispiel 3), das in Wasser 30 s gequollen worden war, zusammen laminiert und auf einer geregelten Heizbank 2 min auf 75°C erhitzt, dann getrennt und anschließend sofort getrocknet. Es wurden auf den Bildempfangsblättern scharfe brillante Farbüberträge erhalten. Die Dmin- und Dmax-Werte sind aus Tabelle 1 ebenfalls ersichtlich.The samples produced according to Example 4 were exposed with a tungsten lamp, the exposure in the case of samples 1, 2, 4, 5 and 7 being carried out behind a transparent yellow filter with a density of 1.25. The intensity and duration of the exposure can be seen from Table 1. The samples were then dried to 110 ° C for development; the duration of this treatment is also shown in Table 1. The samples were then swollen in water for 10 s and laminated together with an image-receiving sheet (from Example 3) which had been swollen in water for 30 s and heated on a regulated heating bench at 75 ° C. for 2 minutes, then separated and then immediately dried. Sharp, brilliant color transfers were obtained on the image-receiving sheets. The Dmin and Dmax values are also shown in Table 1.
Aus Tabelle 1 ist zu ersehen, daß sich bei den erfindungsgemäßen Aufzeichnungsmaterialien eine starke Reduzierung der Entwicklungszeit ergibt, sowie eine deutliche Verbesserung der Empfindlichkeit um etwa den Faktor f = 80. Außerdem sind die Schleierwerte Dmin stark reduziert bei gleichzeitiger Verbesserung der Dmax-Werte. Wenn bei den Vergleichsproben das als Stabilisator wirkende Quecksilber-II-chlorid weggelassen wird, erhält man praktisch nur noch Farbschleier, jedoch praktisch keine Diskriminierung zwischen Dmin und Dmax.
Aus lichtempfindlichem Teil und Bildempfangsteil bestehende integrale Aufzeichnungsmaterialien für das Farbdiffusionsübertragungsverfahren wurden hergestellt durch Auftragen der nachstehend beschriebenen Schichtgießlösungen auf einen Schichtrräger aus Polyethylenterephthalat.Integral recording materials for the color diffusion transfer process consisting of the light-sensitive part and the image-receiving part were produced by applying the layer-coating solutions described below on a layer support made of polyethylene terephthalate.
1. 165 ml Wasser wurden bei 40°C mit 9 g Guanidin-trichloracetat in 60 ml Wasser und 6 ml einer 4 %-igen wäßrigen Lösung von Triston® X 100 versetzt und mit 60 g 20 %-iger Gelatine aufgeschmolzen.1. 165 ml of water were mixed at 40 ° C with 9 g of guanidine trichloroacetate in 60 ml of water and 6 ml of a 4% aqueous solution of Triston® X 100 and melted with 60 g of 20% gelatin.
Naßschichtdicke 50 µm.
- 2. 1,5 %-ige wäßrige Gelatinelösung mit Härtungsmittel. Naßschichtdicke 40 um.
- 3. Gießlösung wie bei Probe 4, jedoch ohne Guanidintrichloracetat. Naßschichtdicke 100 um; (Trocknung bei 35°C)
- 4. Wie Schicht 2
- 5. Dispersion von 50 g Ti02 in 250 g 2 %-iger wäßriger Gelatinelösung. Naßschichtdicke 60 µm.
- 6. Gießlösung wie für Beizsohicht in Beispiel 3. Naßschichtdicke 70 µm.
- 7 Wie Schicht 2, jedoch Naßschichtdicke 60 µm.
- 2. 1.5% aqueous gelatin solution with hardening agent. Wet film thickness 40 µm.
- 3. Casting solution as for sample 4, but without guanidine trichloroacetate. Wet film thickness 100 µm; (Drying at 35 ° C)
- 4. Like layer 2
- 5. Dispersion of 50 g of TiO 2 in 250 g of 2% aqueous gelatin solution. Wet layer thickness 60 µm.
- 6. Casting solution as for pickling in Example 3. Wet layer thickness 70 microns.
- 7 Like layer 2, but with a wet layer thickness of 60 µm.
Herstellung in gleicher Weise wie Probe 8, wobei aber für die Schicht 3 eine Gießlösung wie bei Probe 5, jedoch ohne Guanidin-trichloracetat verwendet wurde.Production in the same way as sample 8, but using a casting solution for layer 3 as for sample 5, but without guanidine trichloroacetate.
Herstellung in gleicher Weise wie bei Probe 8, wobei aber für Schicht 3 eine Gießlösung wie bei Probe 6, jedoch ohne Guanidin-trichloracetat verwendet wurde.Production in the same way as for sample 8, but using a casting solution for layer 3 as for sample 6, but without guanidine trichloroacetate.
Die Proben 8, 9 und 10 wurden mit einer Wolframlampe mit 1000 Lux durch den transparenten Träger 10 s belichtet, im Fall der Proben 8 und 9 hinter einem transparenten Gelbfilter der Dichte 1,25. Dann wurde 60 s bei 110°C auf einer Heizbank trocken entwickelt und die trocken entwickelten Proen 8, 9 und 10 4 min nur einer Wasserdampfatmosphäre von 75°C ausgesetzt. Anschließend wurde bei Raumtemperatur kurz getrocknet. Die erhaltenen Dmin- und Dmax-Werte sind aus Tabelle 2 ersichtlich. Die hier beschriebene Verfahrensvariante benötigt keinerlei Verarbeitungsbäder; es genügt vielmehr erstens Wärme und zweitens Wasserdampf beispielsweise von 75°C. Der zweite Behandlungsschritt kann aber auch darin bestehen, daß das (trocken entwickelte) Aufzeichnungsmaterial in Wasser gequollen und anschließend beispielsweise auf einer Heizbank auf 75° C erwärmt wird.
Claims (4)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3530156 | 1985-08-23 | ||
DE19853530156 DE3530156A1 (en) | 1985-08-23 | 1985-08-23 | COLOR PHOTOGRAPHIC RECORDING MATERIAL DEVELOPABLE BY HEAT TREATMENT |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0212534A2 EP0212534A2 (en) | 1987-03-04 |
EP0212534A3 EP0212534A3 (en) | 1987-12-16 |
EP0212534B1 true EP0212534B1 (en) | 1989-01-04 |
Family
ID=6279190
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86111108A Expired EP0212534B1 (en) | 1985-08-23 | 1986-08-12 | Heat-developable colour-photographic recording material |
Country Status (4)
Country | Link |
---|---|
US (1) | US4810628A (en) |
EP (1) | EP0212534B1 (en) |
JP (1) | JPS6250754A (en) |
DE (2) | DE3530156A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3768246D1 (en) * | 1987-01-16 | 1991-04-04 | Agfa Gevaert Nv | IMAGE RECEIVING MATERIAL FOR USE IN DIFFUSION TRANSFER REVERSE PROCESSES. |
DE3708307A1 (en) * | 1987-03-14 | 1988-09-22 | Agfa Gevaert Ag | COLOR PHOTOGRAPHIC RECORDING MATERIAL FOR THE COLOR DIFFUSION TRANSFER METHOD |
US5084331A (en) * | 1989-01-23 | 1992-01-28 | International Business Machines Corporation | Electroerosion recording medium of improved corrosion resistance |
US5176947A (en) * | 1990-12-07 | 1993-01-05 | International Business Machines Corporation | Electroerosion printing plates |
JP3794706B2 (en) * | 1995-07-18 | 2006-07-12 | アグフア−ゲヴエルト・ナームローゼ・フエンノートシヤツプ | Photothermographic recording material |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1472746B2 (en) * | 1965-03-17 | 1977-02-17 | Agfa-Gevaert Ag, 5090 Leverkusen | PHOTOGRAPHIC RECORDING MATERIAL |
DE2537935A1 (en) * | 1974-08-27 | 1976-03-18 | Canon Kk | LIGHT-SENSITIVE MATERIAL DEVELOPED BY HEATING |
JPS59229556A (en) * | 1983-06-13 | 1984-12-24 | Konishiroku Photo Ind Co Ltd | Heat developable color photosensitive element |
-
1985
- 1985-08-23 DE DE19853530156 patent/DE3530156A1/en not_active Withdrawn
-
1986
- 1986-08-12 EP EP86111108A patent/EP0212534B1/en not_active Expired
- 1986-08-12 DE DE8686111108T patent/DE3661660D1/en not_active Expired
- 1986-08-13 US US06/896,406 patent/US4810628A/en not_active Expired - Fee Related
- 1986-08-22 JP JP61195702A patent/JPS6250754A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
DE3530156A1 (en) | 1987-03-05 |
DE3661660D1 (en) | 1989-02-09 |
US4810628A (en) | 1989-03-07 |
JPS6250754A (en) | 1987-03-05 |
EP0212534A2 (en) | 1987-03-04 |
EP0212534A3 (en) | 1987-12-16 |
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