US2893865A - Single powder photographic developers - Google Patents
Single powder photographic developers Download PDFInfo
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- US2893865A US2893865A US630436A US63043656A US2893865A US 2893865 A US2893865 A US 2893865A US 630436 A US630436 A US 630436A US 63043656 A US63043656 A US 63043656A US 2893865 A US2893865 A US 2893865A
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- Prior art keywords
- anhydrous
- lithium hydroxide
- developer
- alkali
- single powder
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- 239000000843 powder Substances 0.000 title claims description 23
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 93
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- -1 SILVER HALIDE Chemical class 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 239000003755 preservative agent Substances 0.000 claims description 5
- 230000002335 preservative effect Effects 0.000 claims description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 26
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 25
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 22
- 239000003381 stabilizer Substances 0.000 description 19
- 239000003513 alkali Substances 0.000 description 16
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 12
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 12
- 235000010265 sodium sulphite Nutrition 0.000 description 12
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 11
- 229940043349 potassium metabisulfite Drugs 0.000 description 11
- 235000010263 potassium metabisulphite Nutrition 0.000 description 11
- 230000000087 stabilizing effect Effects 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910021538 borax Inorganic materials 0.000 description 6
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 6
- 239000004328 sodium tetraborate Substances 0.000 description 6
- 235000010339 sodium tetraborate Nutrition 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 4
- 229940081974 saccharin Drugs 0.000 description 4
- 235000019204 saccharin Nutrition 0.000 description 4
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 229960004889 salicylic acid Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 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
- 230000000694 effects Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- BYACHAOCSIPLCM-UHFFFAOYSA-N 2-[2-[bis(2-hydroxyethyl)amino]ethyl-(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)CCN(CCO)CCO BYACHAOCSIPLCM-UHFFFAOYSA-N 0.000 description 1
- SUBDBMMJDZJVOS-UHFFFAOYSA-N 5-methoxy-2-{[(4-methoxy-3,5-dimethylpyridin-2-yl)methyl]sulfinyl}-1H-benzimidazole Chemical compound N=1C2=CC(OC)=CC=C2NC=1S(=O)CC1=NC=C(C)C(OC)=C1C SUBDBMMJDZJVOS-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XXPUHUHGYZFFIO-UHFFFAOYSA-N Croton linearis Alkaloid E Natural products C1=2C3=C(O)C(OC)=CC=2CCN(C)C1CC13CCC(O)C=C1 XXPUHUHGYZFFIO-UHFFFAOYSA-N 0.000 description 1
- XHBMDODHHPEVOL-UHFFFAOYSA-N Discolorin Natural products COc1c(O)cc2CCN(C)C3CC4(CCC(O)C=C4)c1c23 XHBMDODHHPEVOL-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WRUZLCLJULHLEY-UHFFFAOYSA-N N-(p-hydroxyphenyl)glycine Chemical compound OC(=O)CNC1=CC=C(O)C=C1 WRUZLCLJULHLEY-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
- G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/167—X-ray
Definitions
- the present invention relates to single powder photographic developers in which all of the essential ingredients of the developer are intimately admixed in dry powder form and more particularly, to an improved alkaline stabilizer for such developers.
- Photographic developers contain as their essential ingredients one or more organic developing agents such as hydroquinone, l-phenyl-B-pyrazolidone (phenidone), para-aminophenol hydrochloride, p-methylaminophenol sulfate (metol), pyrogallol, p-phenylene diamine and its N,N-dialkyl substituted derivatives, an alkali such as sodium carbonate, borax, sodium metaborate or the like, a preservative such as an alkali metal sulfite and an anti-foggant such as potassium bromide or sodium bromide.
- organic developing agents such as hydroquinone, l-phenyl-B-pyrazolidone (phenidone), para-aminophenol hydrochloride, p-methylaminophenol sulfate (metol), pyrogallol, p-phenylene diamine and its N,N-dialkyl substituted derivatives, an alkali such as sodium carbonate
- lithium hydroxide has been used in photographic developers as an alkali, particularly for the preparation of highly concentrated liquid developers.
- the lithium hydroxide is employed in combination with other alkali hydroxides to insure that crystallization of developer ingredients does not take place at low temperatures.
- anhydrous lithium hydroxide is an effective stabilizer for single powder photographic developers either alone or in combination with said acid stabilizers.
- Single powder developers containing anhydrous lithium hydroxide alone or in combination with the usual acidic stabilizers constitute the purposes and objects of the present invention.
- the photographic developing agent may be any ,of
- the preservative is an alkali metal sulfite preferably sodium sulfite usually in its anhydrous condition, the antifoggins a n s s iumxorp tassium omid oz of the organic ntio in :a entsrsu has. 6.- n enzimidazole, S-nitrobenzimidazole, Z-mercaptqbe imidazole, S-chlorobenzimidazole, 6 ehlorobenzimidazole, tetrazole or benzotriazole.
- the alkali may be any of h e used n.
- comrcuudinsrhctcsranhi deve op such a od um garb .p tassiu wa b a e v on ium. tetraher sodium metahor te. d odium p a e. rthe arger f Sodium sulfit yap @lQQLLhk-Hfifi rforiqaddi tional alkalir n. which es;.theed msulfiteractsboth as n lkal anilap eserva ite. '1'
- anhydrous lithium hydroxide offers many advantages andrepresents a marked improvement over the previously usedstabilizers.
- the fact thatlithium-hydroxide is a strong ,alkali makes itpos sible to substitute all or part of the alkali normally used in a developer with a weaker alkali.
- borax instead of sodium metaborate,bicarbonate instead of carbonate, and to use sodium sulfite without sodium carbonate.
- lithium hydroxide discolorin a -period of a few months.
- the acidic stabilizers and-the anhydrous lithium hydroxide are present together in asingle powder developer, thestabilityof the developer is greatly magnifiedand no discolorationappears.even, after storing the developer for more than 12 months.
- anhydrous lithium hydroxide may be combinedwith sodium bisulfite 'or potassium metabisulfite to provide a truly superior stabilizing action. This is surprising in view of the fact that sodium bisulfite or potassium metabisulfite exert only a mild stabilizing action which is practically non-existent under humid conditions. Yet, it reinforces very markedly the much better stabilizing action of lithium hydroxide. Somewhat similar results are obtained by combining lithium hydroxide with such acidic stabilizers as phthalic acid and saccharin.
- Example I Gm. p-Methylaminophenol sulfate 0.75 Sodium sulfite (anhydrous) 11 Hydroquinone 3 Sodium carbonate (monohydrate) 16 Potassium bromide 0.5 Lithium hydroxide (anhydrous) 1.2
- This paper developer which is free from acidic stabilizers kept for 6 months without discoloration or decomposition.
- This borax containing fine-grain developer remained stable without discoloration for more than a year.
- Example III Gm. Metol 1.5 Sodium sulfite (anhydrous) 80 Hydroquinone 3 Borax 3 Potassium bromide 0.5 Lithium hydroxide (anhydrous) 0.3 Potassium metabisulfite 1.6
- This fine-grain developer which contained only lithium hydroxide as a stabilizer remained stable for more than 6 months.
- This paper developer did not decolorize or show any other signs of decomposition when stored for more than a year.
- Example Vl Gm Metol 1.3 Hydroquinone 3.7 Sodium sulfite (anhydrous) 12.8 Sodium carbonate (monohydrate) 24 Potassium bromide 0.5 Lithium hydroxide (anhydrous) 0.8 Potassium metabisulfite 4 This energetic single-powder negative developer kept without decomposition or discoloration for more than a year.
- Example VII This X-ray type single powder developer could be stored without decomposition for more than a year.
- This single powder developer which serves as a first developer for color film of the reversal type could be stored for more than a year without decomposition or discoloration.
- an alkali thiocyanate on the order of (2-3 grams) sodium thiocyanate per liter may be added as a silver halide solvent.
- composition as defined in claim 1, wherein said stabilizing amount is on the order of from 0.2 to 8 grams based on the amount of developer powder required to make up one liter of developer solution.
- a stable single pwoder photographic developer cona n g a mixture of an organic silver halide developing agent, anhydrous lithium hydroxide, an alkali metal salt of sulfurous acid and an anti-fogging agent.
- a stable single powder photographic developer containing in addition to an organic silver halide developing agent, an alkali, an alkali metal salt of sulfurous acid, an acidic stabilizing agent selected from the group consisting of boric anhydride, metaboric acid, phthalic anhydride, phthalic acid, salicylic acid, phthalimide, saccharin, maleic anhydride and anhydrous oxalic acid and an anti-foggant; a stabilizing amount of anhydrous lithium hydroxide.
- a stable single powder developer having the following composition:
- a stable single powder developer having the following composition:
Description
tat.
SINGLE POWDER PHOTOGRAPHIC DEVELQPERS No Drawing. Application December 26, 1956 Serial No. 630,436
11 Claims. (Cl. 96-66) The present invention relates to single powder photographic developers in which all of the essential ingredients of the developer are intimately admixed in dry powder form and more particularly, to an improved alkaline stabilizer for such developers.
Photographic developers contain as their essential ingredients one or more organic developing agents such as hydroquinone, l-phenyl-B-pyrazolidone (phenidone), para-aminophenol hydrochloride, p-methylaminophenol sulfate (metol), pyrogallol, p-phenylene diamine and its N,N-dialkyl substituted derivatives, an alkali such as sodium carbonate, borax, sodium metaborate or the like, a preservative such as an alkali metal sulfite and an anti-foggant such as potassium bromide or sodium bromide. Under ordinary conditions of mixing and storage, such dry developers undergo a decomposition reaction which manifests itself by a color change to a deep brown and adversely affects the photographic activity of the developers. It has always been presumed that this decomposition was caused by the aerial decomposition of the developing agent in the presence of alkali.
The art has been aware ofthis phenomenon and etforts have been made to abate such decomposition by adding to single powder developer mixtures an acidic stabilizer such as phthalic acid, boric anhydride, metaboric acid, potassium metabisulfite and the like. While these various acid stabilizers serve to promote the keeping qualities of such developers, they do not lead to optimurn results, and developers containing these acidic stabilizers generally discolor within a period of two to three months. Moreover, all of these acidic substances have inherent disadvantages; they are sparingly soluble in water or dissolve very slowly; they react with such components as sulfites and carbonates to form gas which may build up objectionable pressures in sealed cans; their use requires additional alkali in the formula to maintain developer activity; their stabilizing action is seriously impaired when the individual chemicals contain absorbed moisture and/or when the admixture is subjected to humid conditions, and, they provide no noticeable stabilizing action in developers containing alkali metaborates.
It is known that lithium hydroxide has been used in photographic developers as an alkali, particularly for the preparation of highly concentrated liquid developers. When used for this purpose, the lithium hydroxide is employed in combination with other alkali hydroxides to insure that crystallization of developer ingredients does not take place at low temperatures.
We have now discovered that anhydrous lithium hydroxide is an effective stabilizer for single powder photographic developers either alone or in combination with said acid stabilizers. Single powder developers containing anhydrous lithium hydroxide alone or in combination with the usual acidic stabilizers constitute the purposes and objects of the present invention.
The developers which are contemplated herein conice sulting dry powder is to be used to make ajliter of de veloping solution:
Parts Lithium hydroxide (anhydrous) 0.2 to; 8 Organic developing agent -a 3 to 15 Alkali 1 5 to Preservative v p -30 to Anti-fogging agent a 0.3 to 2 Acid stabilizer (optional) 0.5 to 12 The photographic developing agent may be any ,of
those previously'lmentioned or any ofuthe commonly used developing agents such.,as-pyrocatechol, chlorohydroquinone (adurol), p -hydroxyphenylamino acetic acid (glycin), 2,4-diaminophenol*(amidoly These developing agents may be used alone or in admixture with each other. Typically, we may use a mixture-of metol and hydroquinone, metoland 1-phenyl-3 -pyrazolidone (phenidone), phenidone and hydroquinone -or phenidone, metoland hydroquinone.
The preservative is an alkali metal sulfite preferably sodium sulfite usually in its anhydrous condition, the antifoggins a n s s iumxorp tassium omid oz of the organic ntio in :a entsrsu has. 6.- n enzimidazole, S-nitrobenzimidazole, Z-mercaptqbe imidazole, S-chlorobenzimidazole, 6 ehlorobenzimidazole, tetrazole or benzotriazole. The alkali may be any of h e used n. comrcuudinsrhctcsranhi deve op such a od um garb .p tassiu wa b a e v on ium. tetraher sodium metahor te. d odium p a e. rthe arger f Sodium sulfit yap @lQQLLhk-Hfifi rforiqaddi tional alkalir n. which es;.theed msulfiteractsboth as n lkal anilap eserva ite. '1'
Among the si i tab ize whishleenhe ard not y those e mera ed eyeibutalso maleic anhydride, phthalic anhydride, benzoic anhydride, salicylic acid, phthalimide, saccharin, rand';anhydrous oxalic acid. In compounding the aforesaid developer mixtures, one may proceedbyfirst. mixing the ..acidic stabilizer or stabilizers, addingandadmixing the alkali, then'the developingagent. and finallythe other ingredients, adding the anhydrous lithium hydroxide .last. .However if'itbe preferred, all the ingredients maybe admixed simultaneously. The use, of. anhydrous lithium hydroxide offers many advantages andrepresents a marked improvement over the previously usedstabilizers. The fact thatlithium-hydroxide is a strong ,alkalimakes itpos sible to substitute all or part of the alkali normally used in a developer with a weaker alkali. For example, it is possible to use borax instead of sodium metaborate,bicarbonate instead of carbonate, and to use sodium sulfite without sodium carbonate. Moreover, single powder developers containing the usual acidic stabilizers absent the anhydrous,
lithium hydroxide discolorin a -period of a few months. When, however, the acidic stabilizers and-the anhydrous lithium hydroxide are present together in asingle powder developer, thestabilityof the developer is greatly magnifiedand no discolorationappears.even, after storing the developer for more than 12 months.
One of the most important advantages of anhydrous lithium hydroxide lies in the fact that its stabilizing action Patented-July 7, .1959- is not impaired to the extent of other known stabilizers when the chemicals are subjected to humid conditions such as during storage and blending. In this connection, it is noteworthy that anhydrous lithium hydroxide may be combinedwith sodium bisulfite 'or potassium metabisulfite to provide a truly superior stabilizing action. This is surprising in view of the fact that sodium bisulfite or potassium metabisulfite exert only a mild stabilizing action which is practically non-existent under humid conditions. Yet, it reinforces very markedly the much better stabilizing action of lithium hydroxide. Somewhat similar results are obtained by combining lithium hydroxide with such acidic stabilizers as phthalic acid and saccharin.
It is manifest, the facts being as stated, that the results must be attributable to some peculiar coaction between the anhydrous lithium hydroxide and the acidic stabilizer which serves to greatly intensify the stabilizing action of the acidic component, particularly of the alkali bisulfites and metabisulfites.
. The following examples will serve to illustrate our invention but are not restricted thereto. The quantity of the single powder developers represented by the following formulae is to be dissolved in suflicient water to give one liter of developer solution and the components are blended as previously indicated.
, Example I Gm. p-Methylaminophenol sulfate 0.75 Sodium sulfite (anhydrous) 11 Hydroquinone 3 Sodium carbonate (monohydrate) 16 Potassium bromide 0.5 Lithium hydroxide (anhydrous) 1.2
This paper developer which is free from acidic stabilizers kept for 6 months without discoloration or decomposition.
This borax containing fine-grain developer remained stable without discoloration for more than a year.
Example III Gm. Metol 1.5 Sodium sulfite (anhydrous) 80 Hydroquinone 3 Borax 3 Potassium bromide 0.5 Lithium hydroxide (anhydrous) 0.3 Potassium metabisulfite 1.6
This developer which contained lesser amounts of lithium hydroxide and potassium metabisulfite than the developer of Example H, did not show any discoloration after 6 months storage.
Example IV Gm. Metol 1.5 Sodium sulfite (anhydrous) 80 Hydroquinone 3 Boric acid I 1.9 Potassium bromide 0.5 Lithium hydroxide 0.35
This fine-grain developer which contained only lithium hydroxide as a stabilizer remained stable for more than 6 months.
'4 l Example V p-Methylaminophenol sulfate 4 Hydroquinone 10 Sodium sulfite (anhydrous) 45 Sodium carbonate (monohydrate) 64 Potassium bromide 0.9 Lithium hydroxide (anhydrous) 0.9 Phthalic acid 0.6 Potassium metabisulfite 1.5
This paper developer did not decolorize or show any other signs of decomposition when stored for more than a year.
Example Vl Gm. Metol 1.3 Hydroquinone 3.7 Sodium sulfite (anhydrous) 12.8 Sodium carbonate (monohydrate) 24 Potassium bromide 0.5 Lithium hydroxide (anhydrous) 0.8 Potassium metabisulfite 4 This energetic single-powder negative developer kept without decomposition or discoloration for more than a year.
Example VII This X-ray type single powder developer could be stored without decomposition for more than a year.
Example VIII Gm. Ethylenediamine tetracetic acid 0.8 Potassium metabisulfite 2 Phthalic acid 0.5 Phenidone 0.5 Hydroquinonc 9 Sodium sulfite (anhydrous) a- 67.5 Sodium carbonate (monohydrate) 45 Potassium bromide 2 Lithium hydroxide (anhydrous) 1.5 Potassium iodide 20 This single powder developer which serves as a first developer for color film of the reversal type could be stored for more than a year without decomposition or discoloration. If desired, an alkali thiocyanate on the order of (2-3 grams) sodium thiocyanate per liter may be added as a silver halide solvent.
Modifications of the invention will occur to persons skilled in the art. We, therefore, do not intend to be limited in the patent granted except as necessitated by the appended claims.
We claim:
1. A stable single powder photographic developer con taining, an organic silver halide developing agent, an alkali, a preservative, an anti-fogging agent and a stabilizing amount of anhydrous lithium hydroxide.
2. The composition as defined in claim 1, wherein said stabilizing amount is on the order of from 0.2 to 8 grams based on the amount of developer powder required to make up one liter of developer solution.
3. A stable single pwoder photographic developer cona n g a mixture of an organic silver halide developing agent, anhydrous lithium hydroxide, an alkali metal salt of sulfurous acid and an anti-fogging agent.
4. A stable single powder photographic developer containing in addition to an organic silver halide developing agent, an alkali, an alkali metal salt of sulfurous acid, an acidic stabilizing agent selected from the group consisting of boric anhydride, metaboric acid, phthalic anhydride, phthalic acid, salicylic acid, phthalimide, saccharin, maleic anhydride and anhydrous oxalic acid and an anti-foggant; a stabilizing amount of anhydrous lithium hydroxide.
5. A stable single powder photographic developer containing as its essential components for the preparation of a liter of developing solution:
Grams Lithium hydroxide (anhydrous) 0.2 to 8 Organic silver halide developing agent 3 to Alkali 5 to 100 Alkali metal sulfite 30.0 to 120 Anti-fogging agent 0.3 to 12 And an acid stabilizer selected from the group consisting of alkali bisulfites, alkali metal bisulfites, boric anhydride, mctaboric acid, phthalic anhydride, phthalic acid, salicylic acid, phthalimide, saccharin, maleic anhydride and anhydrous oxalic acid 0.5 to 12 Grams p-Methylaminophenol sulfate 1.5 Sodium sulfite (anhydrous) 80 Hydroquinone 3 Borax 3 Potassium bromide 0.5 Lithium hydroxide (anhydrous) 1.2 Potassium metabisulfite 6.4
8. A stable single powder developer having the following composition:
Grams p-Methylaminophenol sulfate 1.5 Sodium sulfite (anhydrous) Hydroquinone 3 Borax 3 Potassium bromide 0.5 Lithium hydroxide (anhydrous) 0.3 Potassium metabisulfite 1.6
9. A stable single powder developer having the following composition:
Grams p-Methylaminophenol sulfate 1.5 Sodium sulfite (anhydrous) 80 Hydroquinone 3 Boric acid 1.9 Potassium bromide 0.5 Lithium hydroxide (anhydrous) 0.35
10. A stable single powder developer having the fol- 11. A stable single powder developer having the following composition:
Grams p-Methylaminophenol sulfate 1.3 Hydroquinone 3.7 Sodium sulfite (anhydrous) 12.8 Sodium carbonate (monohydrate) 24 Potassium bromide 0.5 Lithium hydroxide (anhydrous) 0.8 Potassium metabisulfite 4 References Cited in the file of this patent UNITED STATES PATENTS Rasch et al. Mar. 27, 1956 OTHER REFERENCES Handbook of Chemistry and Physics, 38th ed. (1956- 57), page 540.
Claims (1)
1. A STABLE SINGLE POWDER PHOTOGRAPHIC DEVELOPER CONTAINING, AN ORGANIC SILVER HALIDE DEVALOPING AGENT, AN ALKALI, A PRESERVATIVE, AN ANTI-FOGGING AGENT AND A STABILIZAMOUNT OF ANHYDROUS LITHIUM HYDROXIDE.
Priority Applications (1)
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US630436A US2893865A (en) | 1956-12-26 | 1956-12-26 | Single powder photographic developers |
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Application Number | Priority Date | Filing Date | Title |
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US630436A US2893865A (en) | 1956-12-26 | 1956-12-26 | Single powder photographic developers |
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US2893865A true US2893865A (en) | 1959-07-07 |
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US630436A Expired - Lifetime US2893865A (en) | 1956-12-26 | 1956-12-26 | Single powder photographic developers |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3221023A (en) * | 1961-05-01 | 1965-11-30 | Eastman Kodak Co | (2-hydroxymethyl-3-pyrazolidones) |
US4055422A (en) * | 1975-07-28 | 1977-10-25 | Minnesota Mining And Manufacturing Company | Additive for inhibitor removing bath |
US4131467A (en) * | 1977-11-23 | 1978-12-26 | E. I. Du Pont De Nemours And Company | 4,7-Dihydroxybenzimidazole hydrobromide as antifogger |
US4753869A (en) * | 1984-11-30 | 1988-06-28 | Ciba-Geigy Ag | Photographic developing agents containing stable, soluble, pyrazolidinones |
US4917992A (en) * | 1985-03-15 | 1990-04-17 | Ciba-Geigy Ag | Developing agents |
US4987060A (en) * | 1989-04-03 | 1991-01-22 | Minnesota Mining And Manufacturing Company | Concentrated photographic developer composition and method of making it |
WO1993015437A1 (en) * | 1992-01-31 | 1993-08-05 | Fuji Hunt Photographic Chemicals, Inc. | Making flowable alkali or ammonium thiosulfate or sulfite and its product-by-process |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2739894A (en) * | 1954-04-01 | 1956-03-27 | Eastman Kodak Co | Single powder photographic developers containing lithium hydroxide |
-
1956
- 1956-12-26 US US630436A patent/US2893865A/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2739894A (en) * | 1954-04-01 | 1956-03-27 | Eastman Kodak Co | Single powder photographic developers containing lithium hydroxide |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3221023A (en) * | 1961-05-01 | 1965-11-30 | Eastman Kodak Co | (2-hydroxymethyl-3-pyrazolidones) |
US4055422A (en) * | 1975-07-28 | 1977-10-25 | Minnesota Mining And Manufacturing Company | Additive for inhibitor removing bath |
US4131467A (en) * | 1977-11-23 | 1978-12-26 | E. I. Du Pont De Nemours And Company | 4,7-Dihydroxybenzimidazole hydrobromide as antifogger |
US4753869A (en) * | 1984-11-30 | 1988-06-28 | Ciba-Geigy Ag | Photographic developing agents containing stable, soluble, pyrazolidinones |
US4917992A (en) * | 1985-03-15 | 1990-04-17 | Ciba-Geigy Ag | Developing agents |
US4987060A (en) * | 1989-04-03 | 1991-01-22 | Minnesota Mining And Manufacturing Company | Concentrated photographic developer composition and method of making it |
WO1993015437A1 (en) * | 1992-01-31 | 1993-08-05 | Fuji Hunt Photographic Chemicals, Inc. | Making flowable alkali or ammonium thiosulfate or sulfite and its product-by-process |
US5270154A (en) * | 1992-01-31 | 1993-12-14 | Fuji Hunt Photographic Chemicals Inc. | Method of making flowable alkaline thiosulfate/alkaline sulfite and the product thereof |
US5328814A (en) * | 1992-01-31 | 1994-07-12 | Fuji Hunt Photographic Chemicals, Inc. | Method of making flowable alkaline thiosulfate/alkaline sulfite and the product thereof |
USRE35795E (en) * | 1992-01-31 | 1998-05-12 | Fuji Hunt Photographic Chemicals, Inc. | Method of making flowable alkaline thiosulfate/alkaline sulfite and the product thereof |
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