US3076808A - Anthrapyridone dye developers - Google Patents
Anthrapyridone dye developers Download PDFInfo
- Publication number
- US3076808A US3076808A US150661A US15066161A US3076808A US 3076808 A US3076808 A US 3076808A US 150661 A US150661 A US 150661A US 15066161 A US15066161 A US 15066161A US 3076808 A US3076808 A US 3076808A
- Authority
- US
- United States
- Prior art keywords
- anthrapyridone
- dye
- dihydroxyphenyl
- image
- ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- XBNVWXKPFORCRI-UHFFFAOYSA-N 2h-naphtho[2,3-f]quinolin-1-one Chemical compound C1=CC=CC2=CC3=C4C(=O)CC=NC4=CC=C3C=C21 XBNVWXKPFORCRI-UHFFFAOYSA-N 0.000 title description 29
- 239000000975 dye Substances 0.000 description 69
- -1 silver halide Chemical class 0.000 description 53
- 239000000203 mixture Substances 0.000 description 33
- 239000000839 emulsion Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 29
- 229910052709 silver Inorganic materials 0.000 description 29
- 239000004332 silver Substances 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 20
- 230000008569 process Effects 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 18
- 238000012545 processing Methods 0.000 description 16
- 238000010992 reflux Methods 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 108010010803 Gelatin Proteins 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 229920000159 gelatin Polymers 0.000 description 8
- 239000008273 gelatin Substances 0.000 description 8
- 235000019322 gelatine Nutrition 0.000 description 8
- 235000011852 gelatine desserts Nutrition 0.000 description 8
- 238000007363 ring formation reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 6
- 239000012346 acetyl chloride Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000005213 imbibition Methods 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000397 acetylating effect Effects 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000001000 anthraquinone dye Substances 0.000 description 4
- 150000004056 anthraquinones Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- 229910001864 baryta Inorganic materials 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- XCZKKZXWDBOGPA-UHFFFAOYSA-N 2-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=CC=CC=2)=C1 XCZKKZXWDBOGPA-UHFFFAOYSA-N 0.000 description 2
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- GAMPNQJDUFQVQO-UHFFFAOYSA-N acetic acid;phthalic acid Chemical compound CC(O)=O.OC(=O)C1=CC=CC=C1C(O)=O GAMPNQJDUFQVQO-UHFFFAOYSA-N 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 125000005518 carboxamido group Chemical group 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000001429 visible spectrum Methods 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- AQRBGHFSBWVHRO-UHFFFAOYSA-N 14-azatetracyclo[7.7.1.02,7.013,17]heptadeca-1(16),2,4,6,9(17),10,12,14-octaen-8-one Chemical compound C1=CC(C(=O)C=2C3=CC=CC=2)=C2C3=CC=NC2=C1 AQRBGHFSBWVHRO-UHFFFAOYSA-N 0.000 description 1
- VCDRVIPFMGTABC-UHFFFAOYSA-N 2-amino-3-(2-phenylethyl)benzene-1,4-diol Chemical compound NC=1C(=C(O)C=CC1O)CCC1=CC=CC=C1 VCDRVIPFMGTABC-UHFFFAOYSA-N 0.000 description 1
- ZLERQXKTMQQSSX-UHFFFAOYSA-N 2-amino-3-phenoxybenzene-1,4-diol Chemical compound NC=1C(=C(O)C=CC1O)OC1=CC=CC=C1 ZLERQXKTMQQSSX-UHFFFAOYSA-N 0.000 description 1
- SLLRRZRKLDZNAV-UHFFFAOYSA-N 2-amino-3-phenylbenzene-1,4-diol Chemical compound NC=1C(=C(O)C=CC1O)C1=CC=CC=C1 SLLRRZRKLDZNAV-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- 244000186140 Asperula odorata Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 235000008526 Galium odoratum Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000010022 Myron Substances 0.000 description 1
- 241001439614 Myron Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- SBXKRBZKPQBLOD-UHFFFAOYSA-N aminohydroquinone Chemical compound NC1=CC(O)=CC=C1O SBXKRBZKPQBLOD-UHFFFAOYSA-N 0.000 description 1
- BKNBVEKCHVXGPH-UHFFFAOYSA-N anthracene-1,4,9,10-tetrol Chemical compound C1=CC=C2C(O)=C3C(O)=CC=C(O)C3=C(O)C2=C1 BKNBVEKCHVXGPH-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000007257 deesterification reaction Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- FYAFBPSCUASJMG-UHFFFAOYSA-N ethyl(methyl)azanium;bromide Chemical compound [Br-].CC[NH2+]C FYAFBPSCUASJMG-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- XNERWVPQCYSMLC-UHFFFAOYSA-N phenylpropiolic acid Chemical compound OC(=O)C#CC1=CC=CC=C1 XNERWVPQCYSMLC-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical compound OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000000837 restrainer Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/02—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic ring being only condensed in peri position
- C09B5/14—Benz-azabenzanthrones (anthrapyridones)
-
- 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
- G03C8/02—Photosensitive materials characterised by the image-forming section
- G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
- G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
- G03C8/12—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors characterised by the releasing mechanism
- G03C8/14—Oxidation of the chromogenic substances
- G03C8/16—Oxidation of the chromogenic substances initially diffusible in alkaline environment
- G03C8/18—Dye developers
Definitions
- Another object is to provide novel processes and compositions for the development of silver halide emulsions, in which the novel silver halide developing agent is capable of developing an exposed silver halide emulsion and imparting a reversed or. positive colored image of the developed image to a superposed image-receiving material.
- the invention accordingly comprises the processes involving the several steps and the relation and order of one or more of such steps with respect to each ofthe others, and the products and compositions possessing the features, properties and. the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
- the objects of this invention may be accomplished by the use of certain novel, dyes which have the ability to develop an exposed silver halide emulsion; thus these novel described hereindyes; may be referred to as dye developers. dyes or dye developerswill be further after.
- the dye the-photographic processes and compositions disclosed herein are particularly useful in the treatment of an exposed s1lver halide emulsion,,whereby a positive dye image may be imparted toanother element, herein referred to asan image-carryingv or imagereceiving element.
- a photosensitive element containing a silver exposed and wetted with a liquid processing composition for example, by immersing, coating, spraying, flowing, etc., in the dark, photosensitive element superposed prior to, during or DCving element.
- sensitive element contains a the liquid processing composition is ap lied to the photosensitive element in a element is brought into superposed position with an imageinto superposed relationship halide emulsion is.
- the liquid processing composition permeates the emulsion to provide a solution of dye developer substantially uniformly distributed therein.
- the oxidation product of the dye developer is immobilized or precipitated in situ with the developed silver, thereby prodistribution of unoxidized dye d veloper dissolved in the liquid processing composition.
- This immobilization is apparently due, at least in part, to a change. in the solubility characteristics ofthe dye developer upon oxidation, and especially as regards its solubility in alkaline solutions.
- the image-receiving layer receives a depthwise diffusion, the emulsion, of unoxidized dye developer, without appreciably disturbing the imagewise distribution thereof, 7 reversed or positive, colored image of the developed or negative image.
- the image-receiving element may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developed. Imbibition periods of. approximately one minute have been found to give good results, but this contact period may be adjusted where necessary to compensate for variations in temperature or other conditions.
- the desired positive image isrevealed by separating the image-receiving layer from the silver halide emulsion at the end of the imbibition period.
- the dye developers of this invention may be utilized in the photosensitive element, for example in, on or behind the silver halide emulsion, or they may be utilized in the image-receiving element orin the liquid processing comosition.
- a coating or layer of the dye developer is placed behind the silver halide emulsion, i.e.,. on the side of the emulsion adapted to be located most distant from the photographed subject when the emulsion is exposed and preferably also adapted to be most distant from the image-receiving layer when in superposed relationship therewith. Placing the dye developer behind the emulsion layer, as in the preferred embodiment, has the advantage of providing increased also minimizes any light-filtering action by the colored dye developer.
- the layer of dye developer may be applied by using a coating solution containing, e.g., about 0.5 to 8%, byweight, of the dye developer. Similar concentrations may be used if the dye developer is utilized as a component ofv the liquid processing composition; In an especially useful mode of disposing the dye developers in the photosensitive elements, the dye developer is dissolved in a water-immiscible solvent and then dispersed inla gelatin coating solution.
- the liquid processing composition is to be applied to the emulsion by being. spread thereon, preferably in a relatively thin, uniform layer,,it may also include a viscosityincreasing compound constituting film-forming material of the type which, when spreadover a water-absorbent base, will form a relatively firm and relatively stable film.
- a preferred film-forming material is a high molecular weight polymer such as a polymeric, water'soluble ether inert to an alkali solution, as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose.
- Other films-forming materials orthickening agents whose ability an anthrapyridone, that is, a 3-azabenzanthrone, nucleus to V1 ich is attached at least one and preferably not more than two organic groups capable of functioning as silver halide developing groups.
- novel dye developers of the present invention cornprise anthrapyridone dyes characterized in that they contain at least one group of the formula:
- Z may be substituted by halogen, alkoxy, alkyl, etc., radicals.
- amino as used herein is amino and arylatnino groups.
- the developing group comprises a benzenoid deradicals such as alkylene radicals, ene radicals such as ethylene, isopropylene, etc.; sulfonamide; sulfamyl; carboxarnido; carbarnyl; arylene radicals such as phenylene, etc; aralkylene radicals such as phenethyl, etc; acyl radicals such as etc.; divalent radicals which contain both hetero and carbon atoms as constituent components, as for example,
- the anthrapyridone dye developers may be represented by the formula:
- R R R R R R may be 1-Z, hydrogen, aryl, alkyl and preferably lower alkyl,
- R may be Y-Z, hydrogen, alkyl and preferabl lower alkyl, aryl or aralkyl;
- each such group Y Z may be the same or different.
- anthrapyridone dye developers within'the preferred group which have a 6-alkylamino or 6-arylarnino substituent, are magenta dye developers 40 having exceptionally good spectral,characteristics, since they absorponly a minimal amount of light which ideally should be transmitted.
- these dye developers are particularly useful in multicolor products and processes such are described in the aforementioned US. Patent No. 2,983,686.
- those analogues having a 6-ary1- amino substituent have been found to possess unusually good stability.
- the alkylarnino 3 or arylamino substituent may in turn be substituted, as l illustrated in the above-named compounds, and may, for N example, contain a developing function.
- the anthrapyridone dye developers of this invention may be prepared by methods similar to those used to prepare anthrapyridone dyes.
- the anthrapyridone dye developers may be synthesized by cyclization of 1-acetarnidoanthraquinones, the acetyl group of which may be unsubstituted or substituted, for example, preferably substituted with a halogen group such as chlorine, by ester condensations with anthraquinones having a primary or secondary amino group alpha to a carbonyl group, e.g., l-arninoanthraquinone, or by cyclization of suitably substituted benzoic acids, e.g., m-carboxyanilides or phenylpropiolic acid, phenylpropionic acid or phenylpropargylio acid.
- the desired developer group or groups X may be introduced before or after formation of the anthrapyridone nucleus, as illustrated in Examples 1 and 2, respectively. It will be apparent that various groups may be substituted before or after formation of the anthrapyridone nucleus for the purpose of modifying the color, solubility, or other properties.
- One preferred method of preparing the aforementioned anthrapyridone dye developers wherein the desired developer group or groups is introduced prior to formation of the anthrapyridone nucleus comprises condensing an anthraquinone dye having at least one group of the formula:
- H -l ⁇ r-Y-z wherein Y and Z have the same significance as previously set forth; substituted on the anthraquinone nucleus in u-position to a carbonyl group with an ester selected from the group consisting of acetoacetic, malonic and cyanoacetio esters.
- ester condensations are preferably effected in the presence of a suitable catalyst, as for ex ample, a mixture of sodium acetate and cuprous chloride.
- Another preferred method of preparing anthrapyridone dye developers wherein the desired developer group or groups is introduced prior to formation of the anthrapyridone nucleus comprises acetylating an anthraquinone dye developer having a secondary amino group, such as the aforementioned substituent wherein Z is an ortho or dihydroxyphenyl radical, substituted on the anthraquinone nucleus in a position a, to a carbonyl group and then internally condensing the acetylated compound to effect cyclization thereof to form the anthrapyridone.
- the acetylation may be accomplished, for example, by refluxing the anthraquinone dye developer with acetyl chloride.
- this treatment concurrently acetylates the developing group.
- the cyclization may be carried out, for example, by refluxing with an alkaline solution in an inert atmosphere, such as under a blanket of nitrogen.
- the acetylated developer group is hydrolyzed to the free developer during this cyclization.
- a preferred method of preparing the aforementioned anthrapyridone dye developers wherein the desired develg oper group or groups is introduced subsequent to formation of the anthrapyridone nucleus comprises reacting an anthrapyridone dye having a nitro or halogen group substitutcd in position 6 with a compound of the formula:
- Y has the same significance as previously noted, X represents a primary or secondary amino group, and Z represents a protected developer group, e.g., 2',5-diacyloxyphenyl, etc.
- Another method of preparing the aforementioned anthrapyridone dye developers comprises effecting a condensation reaction between an anthrapyridone dye having substituted thereon one or more sulfonyl chloride and/ or acid chloride groups and a compound within the lastmentioned formula.
- Amino-hydroquinone, amino-phenyl-hydroquinone, and amino-phenyl-sulfonyl-hydroquinone, etc. which may be prepared by known chemical reactions.
- anthrapyridone dye developers may be prepared by effecting a condensation reaction between an anthrapyridone dye having substituted thereon one or more primary and/or secondary amino groups and a compound of the formula:
- Y and Z have the same significance as previously noted and W represents an acid chloride or sulfonyl chloride group.
- the protected derivatives of. Z- set forth in formula X--Y-Z may be prepared by the selective acylation of Z according to the procedure disclosed" in the copending US. application of Milton Green and Helen P. Husek, Serial'No. 612,063, filed September 25, 1956, and which was abandoned in favor of Serial No. 805,673, filed April 13, 1961, now US. Patent No. 3,0l9j,254.
- the protected derivatives of Z set forth in formula W--Y--Z may be prepared by conventional acylation of Z according to procedures Well known to the art. After reaction and prior to use as a photographic dye developer, the acyloxy groups may be removed by deesterification as, for example, by hydrolysis in the presence. of alkali.
- Example 2 24.2 g. (.10 mole) of leucoquinizarin, 60.0 g. (.225 mole) of amino-phenethyl-hydroquinone hydrochloride, 12.4 g. (.2 mole) of boric acid, 21.0 g. (.25 mole) of sodium bicarbonate, and 250 ml. of methyl Cellosolvewere mixed together and refluxed under a blanket of nitrogen for about 20 hours with stirring. 24.6 g. (.1 mole) of, practical grade chloranil was then added and refluxing was continued until oxidation was complete. The mixture was then cooled, filtered, and the filtrate poured into excess dilute hydrochloric acid to yield a precipitate.
- NED-@CHFCHPQ of nitrogen in 50 ml. of methyl Cellosolve A nitrogendeaerated solution of 5.6 g. (.1 mole) of potassium hydroxide in 20 ml. of methyl Cellosolve and ml. of water was added under nitrogen over a period of 3 minutes. Reflux was then continued for an additional 7 minutes, after which the solution was cooled for minutes and 10 ml. of acetic acid was added. The solution was then poured into 1 1. of dilute acetic acid to precipitate out a magenta solid, which was filtered off and dried to yield .1 g. of crude product. Purification by chromatography yielded 1.55 g.
- Example 4 A mixture of 24.0 g. (.10 mole) of quinizarin, 60.0 g. (.226 mole) of amino-phenethyl-hydroquinone hydrochloride, 12.4 g. (.20 mole) of sodium bicarbonate and 21.0 g. of boric acid in 250 ml. of pyridine was refluxed under nitrogen for about 48 hours until no further change in the visible spectrum was observed. The mixture was then cooled under an atmosphere of nitrogen and filtered. The filtrate was poured into a large volume of an excess of cold dilute hydrochloric acid with vigorous stirring. The precipitate was filtered oh and dried to yield 43 g. or" 4 [4 p-(2",5"-dihydroxyphenyl)ethyl]-anilino-1-hydroxy-anthraquinone, having the following structural formula:
- the rinsings were also filtered and the filtrates were then combined and precipitated into about 3 l. of hexane.
- the precipitate was filtered oil and vacuum dried to yield 6.7 g. of acetylated anthraquinone product.
- 4 g. of this product was refluxed in 40 ml. of methyl Cellosolve under a blanket of nitrogen.
- a deaerated solution of 3.92 g. (.07 mole) of potassium hydroxide in 4 ml. of water was then added under nitrogen during a one minute period. The reflux was continued for another 4 minutes, then the mixture was cooled, acidified with acetic acid and precipitated into cold dilute hydrochloric acid with vigorous stirring.
- Example A photosensitive element is prepared by coating a gelatin coated, film base with a solution comprising:
- a silver iodobromide emulsion is applied.
- the photosensitive element is exposed and an aqueous liquid processing composition comprising:
- the image-receiving element comprises a cellulose acetate-coated baryta paper which has. been coated with a 6% aqueous polyvinyl alcoholsolutionl After an imbibition period of approximately one minute, the image-receiving element is separated and is found to contain a reddishpinlc, positive image of the photographed subject matter.
- Example 7 A photosensitive element was prepared by coating a gelatin subcoated cellulose; acetate film base with a solution comprising 0.25 g. of 3-[fi-(2,5-dihydroxyphenyl)-amethyl ⁇ ethyl 6 [4f ,8 (2",5" dihydroxyphenyD- ethyll-anilino-anthrapyridone, dissolved in 10 cc. of a solution of 4% cellulose acetate hydrogen phthalate in a 50:50mixture, by volume, of methanol and tetrahydrofuran. After this coating dried, a green-sensitive silver iodobromide. emulsion was applied and allowed to dry. This. photosensitiveelement was exposed and brought into superposed relationship with an image-receiving element as an aqueous composition comprising:
- the image-receiving element comprised a 2:1 mixture by weight of polyvinyl alcohol and pol -4-vinylpyridine on a baryta paper support. After an imbibition period of approximately one minute, the image-receiving element was separated and contained a magenta positive image.
- Hydroxyethyl cellulose (high viscosity) [commercially available from Hercules Powder 00., under the trade name Natrosol 250] g 3.5 Sodium thiosulfate g 1.2 Benzotriazole -g 1.5 N-benzyl-e-picolinium bromide g 2.3
- The. image-receiving element comprised a 2:1 mixture by weight of polyvinyl alcohol and poly-4-vinylpyridine on a baryta paper support. After an imbibition period of approximately one minute, the image-receiving elementwas separated and contained a magentapositive image.
- the dye developers may, for example, be dispersed in a layer of gelatin in lieu of the procedures described in the aforementioned photographic examples.
- This dispersion may be made by procedures known in, the art.
- the dispersion may be made by dissolving the dye developer in a suitable organic solvent or mixtureof solvents and agitating this solution in a Waring Blender with an aqueous gelatin solution and. a suitable dispersing agent.
- the resulting dispersion may be. diluted, if desired, and coated onto a gelatin subcoated. film base in the manner heretofore described.
- the dye developers of this invention are also useful in integral multilayer photosensitive. elements for use in multicolor diffusion transfer processes.
- photosensitive elements mention may be made of the photosensitive elements disclosed and claimed in the copending- US. application of Edwin H. Land and Howard G. Rogers, Serial No. 565,135, filed February 13,
- a suitable arran ement of this type comprises a support carrying a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having as sociated therewith, respectively, a cyan dye developer, at magenta dye developer and a yellow dye developer.
- the dye developers are disposed in separate alkali-permeable layers behind the photosensitive silver halide emulsion stratum with which they are associated.
- the photosensitive elements within the scope of this invention may be used in roll film units which contain a plurality of photosensitive frames.
- the photosensitive elements or this invention are especially useful in composite roll film intended for use in a Polaroid Land Camera, sold by Polaroid Corporation, Cambridge 39, Massachusetts, or a similar camera structure such, for example, as the camera forming the subject matter of U.S. Patent No. 2,435,717, issued to Edwin H. Land on February 10, 1948.
- such composite roll films comprise a photosensitive roll, a roll of image-receiving material and a plurality of pods containing an aqueous alkaline processing solution.
- the rolls and pods are so associated with each other that, upon processing, the photosensitive element my be superposed on the image-receiving element and the pods may be ruptured to spread the aqueous alkaline processing solution between the superposed elements.
- the nature and construction of the pods used in such units are well known to the art. See, for example, US. Patents Nos. 2,543,181 and 2,634,886, issued to Edwin E. Land.
- the liquid processing composition may contain one or more auxiliary or accelerating silver halide developing agents, such as p-methylaminophenol (Metol); 2,4-diaminophenol (Amidol); benzylarninophenol', hydroquinone; a substituted hydroquinone such as toluhydroquinone, phenylhydroquinone, or 4'-methylphenylhydroquinone; or a 3-pyrazolidone such as l-phenyl-3-pyrazolidone.
- auxiliary or accelerating silver halide developing agents such as p-methylaminophenol (Metol); 2,4-diaminophenol (Amidol); benzylarninophenol', hydroquinone; a substituted hydroquinone such as toluhydroquinone, phenylhydroquinone, or 4'-methylphenylhydroquinone; or a 3-pyrazolidone such as l-phenyl-3-pyrazolid
- the dye developers of this invention may be used also in conventional photographic processes, such as tray or tank development of conventional photosensitive films, plates or papers to obtain black-and-white, monochromatic or toned prints or negatives.
- a developer composition suitable for such use may comprise an aqueous solution of approximately 1-2% of the dye developer, 1% sodium hydroxide, 2% sodium sulfite and 0.05% potassium bromide.
- any unreacted dye developer is Washed out of the photosensitive element, preferably with an alkaline washing medium or other medium in which the unreacted dye developer is soluble.
- the expression toned is used to designate photographic images wherein the silver is retained with the precipitated dye whereas monochromatic is intended to designate dye images free of silver.
- the dye developers of this medium are seli-sufiicient to provide the desired color image and do not depend upon coupling reactions to produce the desired color. They thus provide a complete departure from conventional photographic color processes in which id the color is produced bya coupling reaction between a color former or coupler and the oxidized developing agent, as well as so-called auto-coupling processes in which color is obtained by a reaction or the oxidized developing agent with unoxidized developing agent.
- the inventive concepts herein set forth are adaptable for multicolor work by the use of special photographic materials, for example, film materials of the type containing two or more photosensitized elements associated with an appropriate number of imagerecciving elements and adapted to be treated with one or more liquid processing compositions, appropriate dye developers suitable to impart the desired subtractive colors being incorporated in the photosensitized elements or in the liquid processing compositions. Examples of such photographic materials are disclosed in U.S. Patent No. 2,647,049 to Edwin H. Land.
- image-receiving materials examples include nylon, e.g., N-methoxymethyl-polyhexamethyiene adipamide, polyvinyl alcohol, and gelatin, particularly polyvinyl alcohol or gelatin containing a dye mordant such as polyl-vinylpyridine.
- the image-receiving element also may contain a development restrainer, e.g., l-phenyl-5-mercaptotetrazole, as disclosed in the copending application of Howard G. Rogers and Harriet W. Lutes, Serial No. 50,849, filed August 22, 1960.
- novel compounds herein disclosed are also suitable for use as dyes for textile fibres, such as nylon.
- R is selected from the group consisting of hydrogen and acetyl; R is selected from the group consisting of benzene and naphthalene snuclei substituted by two groups the group consisting of hydrogen and --Y--Z; Y is a divalent organic linking group selected from the group con sisting of lower alkylene, phenylene, and
- lower alkylene Z is an aryl nucleus selected from the group consisting of benzene and naphthaleen nuclei substituted by two groups selected from the group consisting of hydroxyl and amino groups, one of said groups being substituted in one of the ortho and para positions with respect to the other of said groups so as to be capable of developing an exposed silver halide emulsion and at least one of said R and R is -Y--Z.
Description
3,076,808 srramomt nrnnnvnrornas and to Elkan R. Blout, Belmont, Sidney Kasman, Arlington,
Myron 5. Simon, Mass, assrgnors Polaroid Corporation, Cambridge, Mass, a corporation of Delaware No-Drawing. Filed Nov-.7, 1961, Ser. No. 150,661
9 Claims- (Cl. 260-278) This invention relates to photography and more. particularly to products, compositions. and processes for. the
development. of photosensitive silver halide elements.
It is one object of the presentinvention to provide novel processes and compositions for the development of silver halide emulsions, in which novel colored silver halide developing agents are used.
Another object is to provide novel processes and compositions for the development of silver halide emulsions, in which the novel silver halide developing agent is capable of developing an exposed silver halide emulsion and imparting a reversed or. positive colored image of the developed image to a superposed image-receiving material.
Further objects are to provide said novel silver halide developing agents, and novel products, processes and compositions suitable for use in preparing monochromatic and multichromatic photographic images by the employment of said novel silver halide developing agents.
Other objects, of the invention will in part be obvious and will in part appearv hereinafter.
The invention accordingly comprises the processes involving the several steps and the relation and order of one or more of such steps with respect to each ofthe others, and the products and compositions possessing the features, properties and. the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
The objects of this invention may be accomplished by the use of certain novel, dyes which have the ability to develop an exposed silver halide emulsion; thus these These novel described hereindyes; may be referred to as dye developers. dyes or dye developerswill be further after.
The dye the-photographic processes and compositions disclosed herein are particularly useful in the treatment of an exposed s1lver halide emulsion,,whereby a positive dye image may be imparted toanother element, herein referred to asan image-carryingv or imagereceiving element.
US. Patent No. 2,983,606, issued May 9, 1961, to Howard G. Rogers, discloses diffusion transfer processes wherein. a. photographic negative material,v such as a photogra hic element comprising an exposed silver halide emulsion, is developed in the dye developer to impart to an image-receiving layer a reversed orpositive dye image. of the developed image by permeating into said emulsion a suitable liquid processing composition and bringing said emulsion with an appropriate imagereceiving layer. The inventive concepts herein set forthprovid'enovel. dye developers which may be advantageously used in such processes.
in carrying out the process of this invention, a photosensitive element containing a silver exposed and wetted with a liquid processing composition, for example, by immersing, coating, spraying, flowing, etc., in the dark, photosensitive element superposed prior to, during or ceiving element. sensitive element contains a the liquid processing composition is ap lied to the photosensitive element in a element is brought into superposed position with an imageinto superposed relationship halide emulsion is.
contrast in the positive image, and
vi'ding an imagewise to provide a United States Patt1tQffiC PM 2. receiving element. The liquid processing composition permeates the emulsion to provide a solution of dye developer substantially uniformly distributed therein. As the exposed silver halide emulsion is developed, the oxidation product of the dye developer is immobilized or precipitated in situ with the developed silver, thereby prodistribution of unoxidized dye d veloper dissolved in the liquid processing composition. This immobilization is apparently due, at least in part, to a change. in the solubility characteristics ofthe dye developer upon oxidation, and especially as regards its solubility in alkaline solutions. It may also be due, in part, to a tanning effect on the emulsion by the oxidized developing agen At least part of this imagewise distribution of unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer. The image-receiving layer receives a depthwise diffusion, the emulsion, of unoxidized dye developer, without appreciably disturbing the imagewise distribution thereof, 7 reversed or positive, colored image of the developed or negative image. The image-receiving element may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developed. Imbibition periods of. approximately one minute have been found to give good results, but this contact period may be adjusted where necessary to compensate for variations in temperature or other conditions. The desired positive image isrevealed by separating the image-receiving layer from the silver halide emulsion at the end of the imbibition period.
The dye developers of this invention may be utilized in the photosensitive element, for example in, on or behind the silver halide emulsion, or they may be utilized in the image-receiving element orin the liquid processing comosition. In a preferred embodiment, a coating or layer of the dye developer is placed behind the silver halide emulsion, i.e.,. on the side of the emulsion adapted to be located most distant from the photographed subject when the emulsion is exposed and preferably also adapted to be most distant from the image-receiving layer when in superposed relationship therewith. Placing the dye developer behind the emulsion layer, as in the preferred embodiment, has the advantage of providing increased also minimizes any light-filtering action by the colored dye developer. in this preferred embodiment, the layer of dye developer may be applied by using a coating solution containing, e.g., about 0.5 to 8%, byweight, of the dye developer. Similar concentrations may be used if the dye developer is utilized as a component ofv the liquid processing composition; In an especially useful mode of disposing the dye developers in the photosensitive elements, the dye developer is dissolved in a water-immiscible solvent and then dispersed inla gelatin coating solution.
The liquid processing composition which is used in the processes herein disclosed comprises at least an aqueous solution of an alkaline compound, for example, diethylamine, sodium hydroxide or sodium carbonate, and may contain the dye developer. in some instances, it may contain an additional silver halide developing agent. the liquid processing composition is to be applied to the emulsion by being. spread thereon, preferably in a relatively thin, uniform layer,,it may also include a viscosityincreasing compound constituting film-forming material of the type which, when spreadover a water-absorbent base, will form a relatively firm and relatively stable film. A preferred film-forming material is a high molecular weight polymer such as a polymeric, water'soluble ether inert to an alkali solution, as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose. Other films-forming: materials orthickening agents whose ability an anthrapyridone, that is, a 3-azabenzanthrone, nucleus to V1 ich is attached at least one and preferably not more than two organic groups capable of functioning as silver halide developing groups.
1 to novel dye developers of the present invention cornprise anthrapyridone dyes characterized in that they contain at least one group of the formula:
an exposed silver halide emulsion.
In addition to the substituents which provide the silver halide developing function, Z may be substituted by halogen, alkoxy, alkyl, etc., radicals. The term amino as used herein is amino and arylatnino groups.
general, the developing group comprises a benzenoid deradicals such as alkylene radicals, ene radicals such as ethylene, isopropylene, etc.; sulfonamide; sulfamyl; carboxarnido; carbarnyl; arylene radicals such as phenylene, etc; aralkylene radicals such as phenethyl, etc; acyl radicals such as etc.; divalent radicals which contain both hetero and carbon atoms as constituent components, as for example,
etc; and suitable combinations thereof.
The anthrapyridone dye developers may be represented by the formula:
wherein:
Each of R R R R R R", R and R may be 1-Z, hydrogen, aryl, alkyl and preferably lower alkyl,
halogen, amino, cyano, acyl, nitro, carboallzoxy, carboxy sulfo, alkoxy, hydroxyl, carboxamido, or aralkyl;
R may be Y-Z, hydrogen, alkyl and preferabl lower alkyl, aryl or aralkyl;
-Y-Z has the same significance as previously noted At least one developing group YZ is present; And wherein more than one developing group YZ is present, each such group Y Z may be the same or different.
intended to include and B-hydroxyethyl, etc.
of anthrapyridone dye developers the formula:
of lower alkylene, sulfonamido, sulfamyl, carboxamido, carbamyl, phenylene,
O H @lower alkylene, lower alkylene-C- developing least one of As examples of useful anthrapyridone dye developers within the scope of the last-mentioned formula, mention may be made of the following compounds:
O L/K CHPC I T-om-onh anthrapyridone.
It has been found that anthrapyridone dye developers within'the preferred group, which have a 6-alkylamino or 6-arylarnino substituent, are magenta dye developers 40 having exceptionally good spectral,characteristics, since they absorponly a minimal amount of light which ideally should be transmitted. Thus, these dye developers are particularly useful in multicolor products and processes such are described in the aforementioned US. Patent No. 2,983,686. Moreover, those analogues having a 6-ary1- amino substituent have been found to possess unusually good stability. It will be appreciated that the alkylarnino 3 or arylamino substituent may in turn be substituted, as l illustrated in the above-named compounds, and may, for N example, contain a developing function.
- As examples of other anthrapyridone dye developers,
mention may be made of the following compounds. (8) 6H 3- 2' EZ-Gihydroxy henyD-a-methyl]-ethyl-6-[4'-B-(2" 5 55.1
[5 diliydroxyphenl)=ethy1]-anilino-anthrapyridone 0'. 14542';5'-dihydroxyphenyI)=u methy1]-ethy1%3rmethylanthrapyridone,
OH O I H n I H o ILTH-QCHz-CH The anthrapyridone dye developers of this invention may be prepared by methods similar to those used to prepare anthrapyridone dyes. Thus, the anthrapyridone dye developers may be synthesized by cyclization of 1-acetarnidoanthraquinones, the acetyl group of which may be unsubstituted or substituted, for example, preferably substituted with a halogen group such as chlorine, by ester condensations with anthraquinones having a primary or secondary amino group alpha to a carbonyl group, e.g., l-arninoanthraquinone, or by cyclization of suitably substituted benzoic acids, e.g., m-carboxyanilides or phenylpropiolic acid, phenylpropionic acid or phenylpropargylio acid. The desired developer group or groups X may be introduced before or after formation of the anthrapyridone nucleus, as illustrated in Examples 1 and 2, respectively. It will be apparent that various groups may be substituted before or after formation of the anthrapyridone nucleus for the purpose of modifying the color, solubility, or other properties.
One preferred method of preparing the aforementioned anthrapyridone dye developers wherein the desired developer group or groups is introduced prior to formation of the anthrapyridone nucleus comprises condensing an anthraquinone dye having at least one group of the formula:
H -l\ r-Y-z wherein Y and Z have the same significance as previously set forth; substituted on the anthraquinone nucleus in u-position to a carbonyl group with an ester selected from the group consisting of acetoacetic, malonic and cyanoacetio esters.
The aforementioned ester condensations are preferably effected in the presence of a suitable catalyst, as for ex ample, a mixture of sodium acetate and cuprous chloride.
Another preferred method of preparing anthrapyridone dye developers wherein the desired developer group or groups is introduced prior to formation of the anthrapyridone nucleus comprises acetylating an anthraquinone dye developer having a secondary amino group, such as the aforementioned substituent wherein Z is an ortho or dihydroxyphenyl radical, substituted on the anthraquinone nucleus in a position a, to a carbonyl group and then internally condensing the acetylated compound to effect cyclization thereof to form the anthrapyridone. The acetylation may be accomplished, for example, by refluxing the anthraquinone dye developer with acetyl chloride. It should be noted that this treatment concurrently acetylates the developing group. The cyclization may be carried out, for example, by refluxing with an alkaline solution in an inert atmosphere, such as under a blanket of nitrogen. The acetylated developer group is hydrolyzed to the free developer during this cyclization.
A preferred method of preparing the aforementioned anthrapyridone dye developers wherein the desired develg oper group or groups is introduced subsequent to formation of the anthrapyridone nucleus comprises reacting an anthrapyridone dye having a nitro or halogen group substitutcd in position 6 with a compound of the formula:
wherein Y has the same significance as previously noted, X represents a primary or secondary amino group, and Z represents a protected developer group, e.g., 2',5-diacyloxyphenyl, etc.
Another method of preparing the aforementioned anthrapyridone dye developers comprises effecting a condensation reaction between an anthrapyridone dye having substituted thereon one or more sulfonyl chloride and/ or acid chloride groups and a compound within the lastmentioned formula.
As an example of the last-mentioned anthrapyridone dye intermediates, mention may be made of the sulfonyl chloride derivative of N-CH;
As examples of compounds within the aforementioned formula X-Y-Z, mention may be made of the follow- Amino-ethyl-hydroquinone, the preparation of which is disclosed in the copending U.S. application of Milton Green, Serial No. 514,095, filed June 8, 1955;
Amino-phenethyl-hydroquinone, the preparation of which is disclosed in the copending U.S. application of Elkan R. Blout, Milton Green, Howard G. Rogers, Myron S. Simon and Robert B. Woodward, Serial No. 612,051, filed September 25, 1956; and in a continuationin-part thereof, Serial No. 98,287, filed March 27, 1961, now U.S. Patent No. 3,019,107;
Amino-phenethyl-thio-hydroquinone, the preparation of which is disclosed in the copending U.S. application of Milton Green and Howard G. Rogers, Serial No. 663,876, filed June 6, 1957, now U.S. Patent No. 3,009,958;
Amino-phenoxy-hydroquinone, the preparation of which is disclosed in the copending U.S. application of Milton Green and Warren E. Solodar, Serial No. 680,406, filed August 26, 1957;
Amino-propyl-amino-hydroquinone, the preparation of which is disclosed in the copending U.S. application of Milton Green and Myron S. Simon, Serial No. 711,812, filed January 29, 1958, now U.S. Patent No. 3,002,997; and
Amino-hydroquinone, amino-phenyl-hydroquinone, and amino-phenyl-sulfonyl-hydroquinone, etc., which may be prepared by known chemical reactions.
In addition, the aforementioned anthrapyridone dye developers may be prepared by effecting a condensation reaction between an anthrapyridone dye having substituted thereon one or more primary and/or secondary amino groups and a compound of the formula:
wherein Y and Z have the same significance as previously noted and W represents an acid chloride or sulfonyl chloride group.
The enumeration and preparation of compounds within the last-mentioned formula are set forth in the following copending U.S. applications:
Serial No. 471,542, filed November 26, 1954, in the names of Elkan R. Blout, Saul G. Cohen, Milton Green, Howard G. Rogers, Myron S. Simon, and Robert B.
9 r Woodward, and now abandoned, and. in Serial No. 1,442 and 1,443, both filed lanuary 11, 1960, and each a continuation-impart thereof; and
Serial No. 771,718, filed November 4, 1958, in the names of Elkan R. Blout and Richard S. Corley and now abandoned.
It may be desirable to protect the hydroxyl and/r amino groups of the developing function, during the above-mentioned reactions, to avoid undesirable side reactions, that is to employ a protected derivative of Z. The protected derivatives of. Z- set forth in formula X--Y-Z may be prepared by the selective acylation of Z according to the procedure disclosed" in the copending US. application of Milton Green and Helen P. Husek, Serial'No. 612,063, filed September 25, 1956, and which was abandoned in favor of Serial No. 805,673, filed April 13, 1959, now US. Patent No. 3,0l9j,254. The protected derivatives of Z set forth in formula W--Y--Z may be prepared by conventional acylation of Z according to procedures Well known to the art. After reaction and prior to use as a photographic dye developer, the acyloxy groups may be removed by deesterification as, for example, by hydrolysis in the presence. of alkali.
The following examples show by Way of illustration and not by way or limitation the preparation of novel dye developers within the scope of this invention.
Example 1,
en -o I Nr-CHrCHr on NHGHz-CH2- on whose spectral absorption curve in ethanol exhibits absorption maxirna at 514 Inn and 545 mp.
Example 2 24.2 g. (.10 mole) of leucoquinizarin, 60.0 g. (.225 mole) of amino-phenethyl-hydroquinone hydrochloride, 12.4 g. (.2 mole) of boric acid, 21.0 g. (.25 mole) of sodium bicarbonate, and 250 ml. of methyl Cellosolvewere mixed together and refluxed under a blanket of nitrogen for about 20 hours with stirring. 24.6 g. (.1 mole) of, practical grade chloranil was then added and refluxing was continued until oxidation was complete. The mixture was then cooled, filtered, and the filtrate poured into excess dilute hydrochloric acid to yield a precipitate. This precipitate was filtered off, rinsed with cold water and dried to yield 56.1 g. of a cyan dye developer, 1,4-bis-[4'-B-(2",5"-dihydroxyphenyl)-ethyl] anillno-anthraquinone, havinga melting-point of 205 C., exhibiting a spectral absorption curve in ethanol having a. X of 652 mp and 607m e,=.1'7,00,0 andhaving the following, structural formula:
33.2 g. (.05 mole) of the above compound and 600 ml. of benzene were, refluxed through a water trap until dry. The trap was removed and 01.5 ml. of pyridine and the 55 ml. (.77 mole) of acetylchloride were slowly added 'over a 15 minute period and refluxingwas continued while using a, CaCl tube to exclude moisture. After refluxing for an hour, an additional 50 ml. of acetyl chloride was added and refluxing was continued for another 15 hours. The mixture was then cooled, decanted from the sludge and evaporated dry. The residue was redissolved in about 250-350 ml. of benzene, the solution filtered, and the filtrate poured into 3 l. of hexane, the resulting pink precipitate was filtered oil and dried to yield 22.5 g. ofthe acetyl derivative, a pink solid meltingat110-l 15 C., 22.5 g. (.0246 mole) of the acetyl derivative was dissolved in 250 ml. of methyl Cellosolve at room temperature and the mixture was brought to reflux under a blanket of nitrogen. A deaerated solution of 10 g. (.179' mole) of potassium hydroxide in 20 ml. of water was added dropwise to the refluxing solution under nitrogen over a period of 3' to 5 minutes and the reflux was then, continued for an additional 10 to 15 minutes. The solution was then allowed to cool, poured quickly into excess dilute hydrochloric acid to form a precipitate which was filtered off, rinsed and dried. The precipitate was then crystallized from methyl Cellosolve to yield 4.6 g. of a dark purple solid, 3-[4'--(2",5"-dihydroxyphenyl)-ethyl]-phenyl-6-[4'-p (2",5",dihydroxyphenyl)-ethyl]-anilino-anthrapyridone, which melted at 256-258 C., was soluble in pyridine, dimethyl formamide and dilute alkali, and has the following structural formula:
NED-@CHFCHPQ of nitrogen in 50 ml. of methyl Cellosolve. A nitrogendeaerated solution of 5.6 g. (.1 mole) of potassium hydroxide in 20 ml. of methyl Cellosolve and ml. of water was added under nitrogen over a period of 3 minutes. Reflux was then continued for an additional 7 minutes, after which the solution was cooled for minutes and 10 ml. of acetic acid was added. The solution was then poured into 1 1. of dilute acetic acid to precipitate out a magenta solid, which was filtered off and dried to yield .1 g. of crude product. Purification by chromatography yielded 1.55 g. of 3-[fi-(2',5-dihydroxyphenyl)art-methyl]- ethyl-6- [,B- (2,5'-dihydroxyphenyl -u-methyl] -ethylamino- 'anthrapyridone, having the following structural formula:
and a spectral absorption curve in methyl Cellosolve exhibiting absorption maxima at 542 and 510 m e=l2,200.
Example 4 A mixture of 24.0 g. (.10 mole) of quinizarin, 60.0 g. (.226 mole) of amino-phenethyl-hydroquinone hydrochloride, 12.4 g. (.20 mole) of sodium bicarbonate and 21.0 g. of boric acid in 250 ml. of pyridine was refluxed under nitrogen for about 48 hours until no further change in the visible spectrum was observed. The mixture was then cooled under an atmosphere of nitrogen and filtered. The filtrate was poured into a large volume of an excess of cold dilute hydrochloric acid with vigorous stirring. The precipitate was filtered oh and dried to yield 43 g. or" 4 [4 p-(2",5"-dihydroxyphenyl)ethyl]-anilino-1-hydroxy-anthraquinone, having the following structural formula:
A mixture of 20.0 g. (.0443 mole) of the above compound, 14.84 g. (.060 mole) of fi-(2,5-dihydroxyphenyl)- m-methyl-ethylamine hydrobromide, 5.13 g. (.061 mole) of sodium bicarbonate, and 200 ml. of methyl Cellosolve was refluxed under a blanket of nitrogen, thereby evolving carbon dioxide gas. When the evolution of gas ceased, 10 ml. of acetic acid was added and refluxing was continued for 24-48 hours until no further change in the visible spectrum was observed. The mixture was then cooled under nitrogen, filtered, and the filtrate poured into a large volume of cold dilute hydrochloric acid with vigorous stirring. The resulting precipitate was filtered 12 off and vacuum dried to yield a crude product, 1-[fl-(2',5'- dihydroxyphenyl) a-methyl]-ethylarnino-4-[4-;3-(2",S"- dihydroxyphenyl)ethyl]-anilino-anthraquinone of the foliowing structural formula:
OH OH;
I O NH 011- C H2- I I OH The last-mentioned product was purified by precipitation into hexane from ethyl acetate solution followed by repeated extractions in acetone and evaporations until dry, until 8 g. of purified product was recovered. 6.5 g. of the purified product (.0108 mole), 23 ml. (.324 mole) of acetyl chloride and 270 ml. of dry benzene were refluxed together on a steam bath for about 24 hours until the )t of the solution was about 500 me. This solution was then cooled and filtered and the residue was rinsed with benzene. The rinsings were also filtered and the filtrates were then combined and precipitated into about 3 l. of hexane. The precipitate was filtered oil and vacuum dried to yield 6.7 g. of acetylated anthraquinone product. 4 g. of this product was refluxed in 40 ml. of methyl Cellosolve under a blanket of nitrogen. A deaerated solution of 3.92 g. (.07 mole) of potassium hydroxide in 4 ml. of water was then added under nitrogen during a one minute period. The reflux was continued for another 4 minutes, then the mixture was cooled, acidified with acetic acid and precipitated into cold dilute hydrochloric acid with vigorous stirring. The precipitate was then filtered and dried to yield 3.2 g. of crude product. Purification by chromatography gave two separate fractions: (1) 3 [B-(2',5-dihydroxyphenyl)-ot-methyl]-ethyl-6-[4- B (2",5" dihydroxyphenyl) ethyl]-anilino-anthrapyridone, having the following structural formula:
. 13 V 6.- [3- (2,,5 -dihydroxyphenyllmethyll-ethylaminm anthrapyridone, having the, following structural formula:
only, proportions being by weight unless otherwise indicated, are:
Example A photosensitive element is prepared by coating a gelatin coated, film base with a solution comprising:
Acetone 50 Tetrahydrofuran 50 Cellulose acetate hydrogen phthalate 4 1 acetyl 3-p-(2f,5'-dihydroxyphenyl)ethyl-Sp-(2',
5'-dihydroxypheuyl)-ethylamino-anthrapyridone 3.8
' After this coating has dried, a silver iodobromide emulsion is applied. The photosensitive element is exposed and an aqueous liquid processing composition comprising:
. Percent Sodium carboxymethyl cellulose 4.5 l-phenyl-3-pyrazolidone 0.2 Sodium hydroxide u 2.0 Potassium bromide 0.2
is spread between the exposed photosensitive element and an image-receiving element as said elements are brought into superposed relationship. The image-receiving element comprises a cellulose acetate-coated baryta paper which has. been coated with a 6% aqueous polyvinyl alcoholsolutionl After an imbibition period of approximately one minute, the image-receiving element is separated and is found to contain a reddishpinlc, positive image of the photographed subject matter.
Example 6 Percent Sodium carboxymethyl cellulose 4.5 Potassium bromide 0.2 Sodium hydroxide V 1.5 l-phenyl-S-pyrazolidone 0.2
gives a magenta, positive image on a superposed imagereceiving element prepared as described in Example 2.
14 Example 7 A photosensitive element was prepared by coating a gelatin subcoated cellulose; acetate film base with a solution comprising 0.25 g. of 3-[fi-(2,5-dihydroxyphenyl)-amethyl} ethyl 6 [4f ,8 (2",5" dihydroxyphenyD- ethyll-anilino-anthrapyridone, dissolved in 10 cc. of a solution of 4% cellulose acetate hydrogen phthalate in a 50:50mixture, by volume, of methanol and tetrahydrofuran. After this coating dried, a green-sensitive silver iodobromide. emulsion was applied and allowed to dry. This. photosensitiveelement was exposed and brought into superposed relationship with an image-receiving element as an aqueous composition comprising:
Water cc NaOH V g-.. 5.17 Hydroxy cellulose (high viscosity) [commercially available from Hercules Power Co., under the trade name Natrosol 2 5O] g 4.03 Sodium thiosulfate u g 1.15 Benzotriazole g 2.3 N-benzyl-a-picolinium bromide r g 2.3
was spread between said elements. The image-receiving element comprised a 2:1 mixture by weight of polyvinyl alcohol and pol -4-vinylpyridine on a baryta paper support. After an imbibition period of approximately one minute, the image-receiving element was separated and contained a magenta positive image.
Example 8 Water cc 100 NaOH g 3.0
Hydroxyethyl cellulose (high viscosity) [commercially available from Hercules Powder 00., under the trade name Natrosol 250] g 3.5 Sodium thiosulfate g 1.2 Benzotriazole -g 1.5 N-benzyl-e-picolinium bromide g 2.3
was spread between said elements. The. image-receiving element comprised a 2:1 mixture by weight of polyvinyl alcohol and poly-4-vinylpyridine on a baryta paper support. After an imbibition period of approximately one minute, the image-receiving elementwas separated and contained a magentapositive image.
It will be appreciated that the dye developers may, for example, be dispersed in a layer of gelatin in lieu of the procedures described in the aforementioned photographic examples. This dispersion may be made by procedures known in, the art. For example, the dispersion may be made by dissolving the dye developer in a suitable organic solvent or mixtureof solvents and agitating this solution in a Waring Blender with an aqueous gelatin solution and. a suitable dispersing agent. The resulting dispersion may be. diluted, if desired, and coated onto a gelatin subcoated. film base in the manner heretofore described.
The dye developers of this invention are also useful in integral multilayer photosensitive. elements for use in multicolor diffusion transfer processes. As an example of such photosensitive elements, mention may be made of the photosensitive elements disclosed and claimed in the copending- US. application of Edwin H. Land and Howard G. Rogers, Serial No. 565,135, filed February 13,
aoveeos 1956, wherein at least two selectively sensitized photoensitive strata are superposed on a single support and are processed, simultaneously and without separation, with a single common image-receiving element. A suitable arran ement of this type comprises a support carrying a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having as sociated therewith, respectively, a cyan dye developer, at magenta dye developer and a yellow dye developer. In one of the preferred embodiments of photosensitive elements of this type, the dye developers are disposed in separate alkali-permeable layers behind the photosensitive silver halide emulsion stratum with which they are associated.
The photosensitive elements within the scope of this invention may be used in roll film units which contain a plurality of photosensitive frames. The photosensitive elements or this invention are especially useful in composite roll film intended for use in a Polaroid Land Camera, sold by Polaroid Corporation, Cambridge 39, Massachusetts, or a similar camera structure such, for example, as the camera forming the subject matter of U.S. Patent No. 2,435,717, issued to Edwin H. Land on February 10, 1948. in general, such composite roll films comprise a photosensitive roll, a roll of image-receiving material and a plurality of pods containing an aqueous alkaline processing solution. The rolls and pods are so associated with each other that, upon processing, the photosensitive element my be superposed on the image-receiving element and the pods may be ruptured to spread the aqueous alkaline processing solution between the superposed elements. The nature and construction of the pods used in such units are well known to the art. See, for example, US. Patents Nos. 2,543,181 and 2,634,886, issued to Edwin E. Land.
it will be noted that the liquid processing composition may contain one or more auxiliary or accelerating silver halide developing agents, such as p-methylaminophenol (Metol); 2,4-diaminophenol (Amidol); benzylarninophenol', hydroquinone; a substituted hydroquinone such as toluhydroquinone, phenylhydroquinone, or 4'-methylphenylhydroquinone; or a 3-pyrazolidone such as l-phenyl-3-pyrazolidone. These silver halide developing agents are substantially colorless, at least in their unoxidized form. It is possible that some of the dye developer oxidized in exposed areas may be oxidized by an energy transfer reaction with oxidized auxiliary developing agent.
In addition, development may be eifected in the presence of an onium compound, particularly a quaternary ammonium compound, in accordance with the processes disclosed and claimed in the copending application of Milton Green and Howard G. Rogers, Serial No. 50,851, filed August 22, 1960.
The dye developers of this invention may be used also in conventional photographic processes, such as tray or tank development of conventional photosensitive films, plates or papers to obtain black-and-white, monochromatic or toned prints or negatives. By way of example, a developer composition suitable for such use may comprise an aqueous solution of approximately 1-2% of the dye developer, 1% sodium hydroxide, 2% sodium sulfite and 0.05% potassium bromide. After development is completed, any unreacted dye developer is Washed out of the photosensitive element, preferably with an alkaline washing medium or other medium in which the unreacted dye developer is soluble. The expression toned is used to designate photographic images wherein the silver is retained with the precipitated dye whereas monochromatic is intended to designate dye images free of silver.
It should be noted that the dye developers of this medium are seli-sufiicient to provide the desired color image and do not depend upon coupling reactions to produce the desired color. They thus provide a complete departure from conventional photographic color processes in which id the color is produced bya coupling reaction between a color former or coupler and the oxidized developing agent, as well as so-called auto-coupling processes in which color is obtained by a reaction or the oxidized developing agent with unoxidized developing agent.
It will be apparent that, by appropriate selection of the image-receiving element from among suitable known opaque and transparent materials, it is possible to obtain either a colored positive reflection print or a colored positive transparency. Likewise, the inventive concepts herein set forth are adaptable for multicolor work by the use of special photographic materials, for example, film materials of the type containing two or more photosensitized elements associated with an appropriate number of imagerecciving elements and adapted to be treated with one or more liquid processing compositions, appropriate dye developers suitable to impart the desired subtractive colors being incorporated in the photosensitized elements or in the liquid processing compositions. Examples of such photographic materials are disclosed in U.S. Patent No. 2,647,049 to Edwin H. Land.
As examples of useful image-receiving materials, mention may be made of nylon, e.g., N-methoxymethyl-polyhexamethyiene adipamide, polyvinyl alcohol, and gelatin, particularly polyvinyl alcohol or gelatin containing a dye mordant such as polyl-vinylpyridine. The image-receiving element also may contain a development restrainer, e.g., l-phenyl-5-mercaptotetrazole, as disclosed in the copending application of Howard G. Rogers and Harriet W. Lutes, Serial No. 50,849, filed August 22, 1960.
The dye developers here-in set forth are also useful in the formation of colored images in accordance with the photographic products and processes described and claimed in U.S. Patent No. 2,968,554, issued to Edwin H. Land on January 17, 1961.
The novel compounds herein disclosed are also suitable for use as dyes for textile fibres, such as nylon.
In the preceding portions of the specification, the expression color has been frequently used. This expression is intended to include the use of a plurality of colors to obtain black.
This application is in. part a continuation of our copending application, Serial No. 799,425, filed March 16, 1959, and now abandoned, which in turn is in part a continuation of application Serial No. 522,843, filed July 18, 1955, and now abandoned.
Our copending U.S. application, Serial No. 150,657, filed November 11, 1961, claims the photographic utilization of the novel compounds of the present invention.
Since certain changes may be made in the above products, compositions and processes without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.
What is claimed is:
1. A dye developer of the formula:
wherein R is selected from the group consisting of hydrogen and acetyl; R is selected from the group consisting of benzene and naphthalene snuclei substituted by two groups the group consisting of hydrogen and --Y--Z; Y is a divalent organic linking group selected from the group con sisting of lower alkylene, phenylene, and
lower alkylene Z is an aryl nucleus selected from the group consisting of benzene and naphthaleen nuclei substituted by two groups selected from the group consisting of hydroxyl and amino groups, one of said groups being substituted in one of the ortho and para positions with respect to the other of said groups so as to be capable of developing an exposed silver halide emulsion and at least one of said R and R is -Y--Z.
2. "1-acety1-3fi-(2',5' dihydroxyphenyl) ethyl-6 942, S'-dihydroxyphenyl)-ethylarnino-anthrapyridone.
3. 3-[,B-(Z,5 dihydroxyphenyl)-u-methyl]-ethyl-6-]fl- (2',5-dihydroxyphenyl)-a-methyl] ethylamino anthrapyridone.
4. 3-[,8-(2',5'-dihydroxyphenyl) a methyH-ethyl-G- [4'-;3-(2",5-dihydroxyphenyl) ethyl] aniline-anthrapyridone.
5. 3-[4' B (2,5"-dihydroxyphenyl)-ethyl]-phenyl- 6-[B (2,S'-dihydroxyphenyl)-a-methy1] ethylamino-anthrapyridone.
6. 3-[4'-p-(2",5" dihydroxyphenyl) ethyl]-phenyl- 6-[4'-;9-(2-5"-dihydroxyphenyl)-ethyl] anilino-anthrapyridone.
7. The process of preparing 3-[fl-(2',S'-dihydroxyphenyl)-a-methyl]-ethyl 6 [l8 (2',5 dihydroxyphenyl)-umethyl]-ethylamino-anthrapyridone which comprises acetylating 1,4-bis-[B-(2,5'-dihydroxyphenyl)a-methyH-ethylamino-anthraquinone by refluxing with acetyl chloride, and internally condensing said last-named compound to effect cyclization thereof, thereby forming said pyrimidone.
8. The process of forming a compound selected from the group consisting of 3-(fl-(2,5-dihydroxyphenyl)-amethyl] ethy1-6- [4-B-(2",5" dihydroxyphenyl)-ethyl]- anilin-o-anthrapyridone and 3-[4 B (2",5"-dihydroxyphenyl)-ethyl]-phenyl 6 [B-(2,5'-dihydroxyphenyl)-amethyl]-ethylamino-anthrapyridone which comprises refluxing quinizarin with amino-phenethyl-hydroquinone hydrochloride in an inert atmosphere; refluxing the resulting product with fl-(2,5-dihydroxyphenyl) a methyl-ethylamine hydrobromide in an inert atmosphere to form a 1,4- bis-substituted anthraquinone dye developer, acetylating said dye developer by refluxing with acetyl chloride; and condensing the acetylated reaction product to efiect cyclization thereof, thereby forming an isomeric mixture comprising 3-[ 8-(2',5'-dihydroxyphenyl) a methylJ-ethyl-G [fl-(2',5'-dihydroxyphenyl) a methyl] -ethy-larnino anthrapyridone and 3-[,B-(2',5-dihydroxyphenyl)-u-methyl]-ethyl 6 [4' 8-(2,5-dihydroxyphenyl)-ethyl]-anilino-anthrapyridone.
9. The process which comprises acetylating 1,4-bis-[4'- fi-(2",5" dihydroxyphenyl) ethyl]-anilinoanthraquinone to form 1,4-bis-(2',5-diacetoxy)-phenethyl-acetanilido-anthraquinone and condensing said last-named compound, thereby efiecting cyclization thereof, to form 3- [4-/3-(2",5"-dihydroxyphenyl)-ethyl] phenyl 6[4-B- (2",5 "-dihydroxyphenyl) -et-hyl] -anilino-anthrapyridone.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3,076,808 February 5, 1963 Elkan R Blout et al.
It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 6, line 41, for "absorp" read absorb column 8, line 41, after "September 25, 1956" insert now U. So Patent No. 3,019,107 lines 42 and 43, strike out -n-ow U0 So Patent Non 3,019,107 column 10, line 66, for "542" read 532 column 14, line 17, for "Hydroxy" read Hydroxyetbyl column 16, line 74, for "benzene and naphthalene snuclei subsgituted by two groups" read hydrogen, lower alkyl and -Y-'Z; R is selected from column 17, line 10, for "naphthaleen" read naphthalene column 18, line 4, for "ii-(E read 3[B Signed and sealed this 26th day of November 19630 (SEAL) Anew I EDWIN La REYNOLDS ERNEST W. SWIDER Attesting Officer A ti g Commissioner of Patents
Claims (1)
1. A DYE DEVELOPER OF THE FORMULA:
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
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US3209016A (en) * | 1963-10-25 | 1965-09-28 | Polaroid Corp | Anthraquinone derivatives containing an ortho- or para-dihydroxyphenylalkylamino substituent |
US3236893A (en) * | 1956-02-13 | 1966-02-22 | Polaroid Corp | 2-aminoarylalkylene-dihydroxy-benzenes |
US3239339A (en) * | 1961-05-05 | 1966-03-08 | Polaroid Corp | Novel photographic products, compositions and processes |
US3255206A (en) * | 1962-10-23 | 1966-06-07 | Polaroid Corp | 2, 3-anthraquinone-dicarboximide dye developers |
US4124393A (en) * | 1974-10-08 | 1978-11-07 | Fuji Photo Film Co., Ltd. | Shifted anthraquinone dye developing agents |
EP0288400A1 (en) * | 1987-04-23 | 1988-10-26 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Substituted isoquinolines |
US5183892A (en) * | 1988-07-29 | 1993-02-02 | Sumitomo Chemical Company, Limited | Anthrapyridone compounds |
US20040082801A1 (en) * | 2002-09-27 | 2004-04-29 | Xerox Corporation. | Methods for making colorant compounds |
US20060025616A1 (en) * | 2004-07-29 | 2006-02-02 | Xerox Corporation | Colorant compounds |
EP1626071A1 (en) | 2004-08-13 | 2006-02-15 | Xerox Corporation | Anthrapyridone colorant compounds |
WO2013051724A1 (en) * | 2011-10-04 | 2013-04-11 | Canon Kabushiki Kaisha | Water-insoluble coloring matter compound, ink using the water-insoluble coloring matter compound, thermal transfer recording sheet and resist composition for color filter |
US20130108952A1 (en) * | 2011-11-02 | 2013-05-02 | Canon Kabushiki Kaisha | Colored resin powder and toner using the colored resin powder |
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Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3236893A (en) * | 1956-02-13 | 1966-02-22 | Polaroid Corp | 2-aminoarylalkylene-dihydroxy-benzenes |
US3239339A (en) * | 1961-05-05 | 1966-03-08 | Polaroid Corp | Novel photographic products, compositions and processes |
US3255206A (en) * | 1962-10-23 | 1966-06-07 | Polaroid Corp | 2, 3-anthraquinone-dicarboximide dye developers |
US3209016A (en) * | 1963-10-25 | 1965-09-28 | Polaroid Corp | Anthraquinone derivatives containing an ortho- or para-dihydroxyphenylalkylamino substituent |
US4124393A (en) * | 1974-10-08 | 1978-11-07 | Fuji Photo Film Co., Ltd. | Shifted anthraquinone dye developing agents |
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