US3833372A - Viscous developing liquid for use in a silver salt diffusion transfer process - Google Patents

Viscous developing liquid for use in a silver salt diffusion transfer process Download PDF

Info

Publication number
US3833372A
US3833372A US00305027A US30502772A US3833372A US 3833372 A US3833372 A US 3833372A US 00305027 A US00305027 A US 00305027A US 30502772 A US30502772 A US 30502772A US 3833372 A US3833372 A US 3833372A
Authority
US
United States
Prior art keywords
developing liquid
hydroxylamine
developing
zinc
compound
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
Application number
US00305027A
Other languages
English (en)
Inventor
K Hayashi
R Ohi
T Shishido
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Application granted granted Critical
Publication of US3833372A publication Critical patent/US3833372A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/24—Photosensitive materials characterised by the image-receiving section
    • G03C8/243—Toners for the silver image

Definitions

  • ABSTRACT A silver halide-containing viscous developing liquid to be used in a diffusion transfer process comprising an hydroxylamine type developing agent, a sulfur-free nitrogen-containing silver halide solvent, a cellulose derivative thickener, an alkali agent and a color modifying or toning agent of at least one compound represented by the following formulae (1), (II) and (III):
  • R R and R are a hydrogen atom, an alkyl or substituted alkyl group containing l-4 carbon atoms, or a phenyl group, m is an integer of 2-4, and n is O or an integer of l-4).
  • the present invention relates to the processing of a silver halide light-sensitive material and, in particular, is directed to a developing liquid composition to be used in a transfer diffusion process for a silver halide light-sensitive material.
  • the developing liquid to be used in a diffusion transfer process with such materials usually contains a developing agent, a silver halide solvent, an alkali agent, an antifogging agent, an antioxidant and a color toning agent.
  • the exposed silver halide in the negative material is first developed with a developing agent contained in a developing liquid and unexposed silver halide is reacted with a silver halide solvent contained in the developing liquid to form a soluble silver complex salt which diffuses into the positive material and deposits on the silverdeposition nuclei layer to thereby give a silver image.
  • a non-viscous liquid developer When a non-viscous liquid developer is used, processing is usually carried out by putting the exposed negative material over the positive material, and then soaking the combined material in a developing liquid.
  • a viscous developing liquid when a viscous developing liquid is used, the liquid is supplied only to the surfaces of the negative and positive materials so that the developing liquid does not permeate into the supports of the negative material and the positive material.
  • the used of a viscous developing liquid is thus much more advantageous in avoiding contamination, in enabling quick drying and in preventing leaking or spilling as is often encountered in the case when a conventional liquid developer is used, all of which are convenient for portable processing.
  • a viscous positive material often results from the residual viscous developing liquid film, which often forms upon stripping off the positive material from the negative material.
  • a second problem is that fouling or discoloration of the print during preservation may result from residual developing liquid which attaches onto the surface of the positive material and contains a developing agent, silver halide solvent, alkali agent and like contaminating materials.
  • a positive material is liable to be soiled or contaminated by the formation of oxidation products of the developing agent soaked into the layer of the positive material upon stripping the negative material from the positive material.
  • a thiosulfate, thiocyanate or thioglycolic acid is usually employed.
  • silver halide solvent which remains attached to the silver image portion reacts with the image silver to form silver sulfide which leads to discoloration.
  • a developing liquid which contains as the main developing agent a compound that forms upon oxidation a colorless or slightly yellow colored oxidation product which has a sufficient reducing ability, e.g., a hydroxylamine, and as the silver halide solvent a sulfur-free compound, e. g., amines such as diethylamine and cyclic imides such as uracil and barbituric acid.
  • a compound that forms upon oxidation e.g., a hydroxylamine
  • a sulfur-free compound e. amines such as diethylamine and cyclic imides such as uracil and barbituric acid.
  • This type of developing liquid consisting of hydroxylamine developing agent and a cyclic imide compound, however, has the drawbacks of poor physical developing activity and a slow rate of dissolving silver halide compared to conventional developing liquids comprising a hydroquinone type developing agent and a thiosulfate type solvent.
  • conventional developing liquids comprising a hydroquinone type developing agent and a thiosulfate type solvent.
  • such materials require a longer processing time than that required upon the use of a conventional developing liquid, i.e., the speed of transfer is lowered a considerable extent.
  • a developing liquid is subject to another drawback in that yellow or yellowish brown color tones are formed on the positive image silver obtained.
  • a number of toning or color modifying compounds have been used up to now, including for example, l-phenyl-S- mercaptotetrazol, 2,5 -dimercaptol ,3 ,4-thiadiazol, benzothiazol, cysteine, etc.
  • a second object of this invention is to provide a viscous developing liquid whereby positive images of high stability are obtained in a short processing period.
  • a third object of the present invention is to provide a viscous developing liquid whereby positive silver images of a blue-black tone are obtained.
  • a fourth object of this invention is to provide a viscous developing liquid whereby stable positive images free from contamination and discoloration after storage for long periods are obtained.
  • the present invention is characterized by the addition of at least one of the compounds represented by formulae (I), (II) or (III) to a viscous developing composition
  • a viscous developing composition comprising a hydroxylamine-type developing agent, a sulfur-free nitrogen-containing silver halide solvent, a cellulose wherein R R and R are each a hydrogen atom, an alkyl or substituted alkyl group containing 1-4 carbon atoms, e. g., an hydroxyalkyl group, or a phenyl group, m is an integer of 2-4.
  • R R and R in the above formulae are a hydrogen atom, a methyl, ethyl, butyl, isopropyl, isobutyl, sec. butyl, tert.
  • the amount of the compound or compounds represented by general formulae (I) to (III) is generally greater than 1 mg. per 100 g of the developing liquid, preferably from about 0.01 to about 0.1g per 100g of the developing liquid. Lesser or greater amounts can be used, of course, but if less 1 mg is used ofttimes the results achieved will not be very good, and in any case the difficulty of such exact low measurements does not make the use of smaller amounts desireable. Greater amounts do not substantially increase the results achieved, and hence are economically non-preferred.
  • the hydroxylamine type developing agent used in the present invention includes, for example, compounds such as the following: hydroxylamine, N-methyl hydroxylamine, N,N-dimethyl hydroxylamine, N,N- diethyl hydroxylamine, N-isopropyl hydroxylamine, N-methyl-N-isobutyl hydroxylamine, N,N-di-n-propyl hydroxylamine, N,N-di-(Z-methoxyethyl) hydroxylamine, N,N-di-(2-ethoxyethyl) hydroxylamine, N- methyl-N-2-dimethylaminoethyl-hydroxylamine, N-methyl-N-(N'-morpholino) methyl hydroxylamine, N,N-di-(2-methoxyethoxyethyl) hydroxylamine, N-ethyl-N-Z-ethoxyethyl hydroxylamine, N-allyl-N-2- e
  • the cellulose derivative thickener used in the present invention includes, for example, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, etc., and such compounds may be used either alone or as mixtures of two or more thereof. These and equivalent materials serve their art recognized purpose in the present invention, and other equivalent cellulose derivative thickenees may be used, e.g., modified forms of the above materials.
  • the viscous developing liquid desirably has a viscosity within the range of from about 1,000 to about 200,000 centipoise. Therefore, the amount of the thickener added is preferably determined so as to impart a viscosity in the abovedefined range.
  • the alkali agent used in this invention includes, for example, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide etc.
  • the alkali agent should be added in an amount sufficient to provide the developing liquid with a pH above about 13.5
  • the alkali metal hydroxides serve this purpose excellently, and are most preferred.
  • the developing liquid used in this invention may contain, if desired, standard ancillary additives as are used in this art, e.g., fogging inhibitors such as potassium bromide, 6-nitrobenzo-imidazol etc., antioxidants such as sodium sulfite, potassium metabisulfite, sodium benzene sulfinate, ascorbic acid, dihydroxy-benzene, phenol, etc.
  • fogging inhibitors such as potassium bromide, 6-nitrobenzo-imidazol etc.
  • antioxidants such as sodium sulfite, potassium metabisulfite, sodium benzene sulfinate, ascorbic acid, dihydroxy-benzene, phenol, etc.
  • the developing liquid may be further include zinc or a zinc compound such as zinc chloride, zinc oxide, zinc hydroxide, zinc sulfate, zinc carbonate, etc.
  • zinc or a zinc compound such as zinc chloride, zinc oxide, zinc hydroxide, zinc sulfate, zinc carbonate, etc.
  • any stripping material as is known to the art for use in diffusion transfer elements may be used, but the zinc compounds are very effective when used in an amount of from about 7 X 10 to about 0.3 moles, preferably from 7 X 10' to 0.15 moles, calculated as metallic zinc, per 100g of developing solution.
  • a greatly improved diffusion transfer processing system is provided which is not accompanied by any fouling or discoloration problems as are often encountered in conventional processes using a hydroquinonethiosulfate salt, and it is possible to achieve a greatly improved rate or speed of transfer as compared to conventional processes using hydroxylamine-cyclic imide compounds (or amine compouns).
  • the developing liquid of the present invention By using the developing liquid of the present invention, it is now unnecessary to carry out after-treatment such as neutralization of the developed positive material or stabilization of the silver halide solvent. This is because a positive material of this invention is substantially free from fouling or discoloration.
  • the characteristic features of the developing liquid of this invention can be emphasized when used in combination by with a positive material containing physical developing nuclei or a cellulose acetate base due to the inherent high physical strength of such a material which completely eliminates the necessity of the aftertreatment.
  • EXAMPLE 1 A highly sensitive momochromatic photo film comprising 3,3-diethyl-9-methylthia-carboxylamine bromide in a highly-sensitive (gold-and sulfur sensitized) gelatin-silver iodobromide emulsion (5 molar percent silver iodide) containing 8.5g of silver and 40g of gelatin per kilogram of emulsion on a triacetate cellulose film support was subjected to exposure through a light wedge.
  • a positive material to be used in combination therewith was prepared as follow:
  • a cellulose acetate film (SO/L thick) had laminated thereto a high quality paper sheet (g/m and then a polyethylene layer was coated on the back of the cellulose acetate sheet to form a layer with a thickness of 40;]..
  • the resultant sheet was immersed at 45C for 2 minutes in a solution of the following composition whereby the surface of the cellulose acetate film was hydrolyzed:
  • Viscous developing liquids having compositions A-E were prepared by mixing the ingredient shown in Table 1 under a nitrogen atmosphere. Developing liquids A, B, C and E are given for comparison purposes.
  • the emulsion layer of a negative material as described and the image-receiving layer of a positive material as described were then placed together while spreading each viscous developing liquid therebetween until a thickness of about 90p was obtained.
  • the positive layer was then stripped off after developing processing for 20 seconds and 40 seconds.
  • the quality of the print thus obtained is given in Table 2.
  • the reflection density shown in the table was measured by the use of a Type-P densitometer manufactured by Fuji Photo Film Co., Ltd.
  • compound l used in this example is not desirable as a color toning agent in a conventional diffusion-transfer system using hydroquinone-thiosulfate salt (refer to Table 2, Developing liquid E where a brown color tone was achieved, as opposed to the describable blue-black color tone).
  • Example 2 The procedure of Example 1 was followed except for using a viscous developing liquid having the composition shown in Table 3.
  • Example Compounds contained 2 3 4 Water 100 100 100 Natrosol hydroxyethyl cellulose (high viscosity") l0 l0 Carboxymethyl cellulose (low viscosity)** [5 15 N,N-di-(Z-methoxyethyl ⁇ I hydroxylamine 10 l0 l0 Uracil 30 30 Compound 2 0.1 Compound 5 0.1 Compound 7 0.01 Zinc chloride 3 3 3 Sodium hydroxide 25 25 25 *"*Manufacturcd by Hercules Co, Ltd.
  • a viscous diffusion transfer process silver halide developing liquid containing at least one hydroxylamine type developing agent, at least one sulfer-free nitrogen-containing silver halide solvent, at least one cellulose derivative thickening agent and at least one alkali agent, which developing liquid contains at least one compound represented by one of the following formulae (I), (II) and (III):
  • R R and R are each a hydrogen atom, alkyl group or a substituted alkyl group containing from 1 to 4 carbon atoms, or a phenyl group, m is an integer of from 2 to 4, and n is O or an integer of from 1-4.
  • hydroxylamine type developing agent is selected from the group hydroxylamine, N-methyl hydroxylamine, N,N- dimethyl hydroxylamine, N,N-diethyl hydroxylamine, N-isopropyl hydroxylamine, N-methyl-N-isobutyl hydroxylamine, N,N-di-n-propyl hydroxylamine, N,N-di- 2-methoxyethyl) hydroxylamine, N,N-di-(2- ethoxyethyl) hydroxylamine, N-methyl-N-2- dimethylaminoethyl hydroxylamine, N-methyl-N-(N- morpholino) methyl hydroxylamine, N-N-di-(2- methoxyethoxyethyl)-hydroxylamine, N-ethyl-N-2- ethoxyethyl hydroxylamine, N-allyl-N-2-ethoxyethylhydroxylamine
  • the sulferfree nitrogen containing silver halide solvent is selected from the group consisting of cyanuric acid, barbituric acid, uracil, 4-methyl uracil, urazol, hydantoin, succinimide, ethyl amine, triethanol amine, monoethanol amine, ethylene diamine, aminoethyl ethanolamine, and mixtures thereof.
  • the developing liquid of claim 7 where the cellu lose derivative thickener is selected from the group consisting of methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and mixtures thereof.
  • the developing liquid of claim 7 wherein the amount of the sulfur-free nitrogen containing silver halide solvent present is about 1 to about 40 percent by weight of the developing composition.
  • the viscous silver halide developing liquid comprises at least one hydroxylamine type developing agent, at least one sulferfree nitrogen-containing silver halide solvent, at least one cellulose derivative thickening agent and at least one alkali agent, which developing liquid contains at least one'compound represented by one of the following formulae (I), (II) and (III):
  • R R and R are each a hydrogen atom, an alkyl group or a substituted alkyl group containing from 1 to 4 carbon atoms, or a phenyl group, m is an 20.
  • sulfur-free nitrogen containing silver halide solvent is selected from the group consisting of cyanuric acid, barbituric acid, uracil, 4-methyl uracil, urazol, hydantoin, succinimide, ethyl amine, triethanol amine, monoethanol amine, ethylene diamine, amino-ethyl ethanolamine, and mixtures thereof.
  • said viscous silver halide developing liquid consists essentially of said at least one hydroxylamine type developing agent, said at least one sulfur-free nitrogen-containing silver halide solvent, said at least one cellulose derivative thickening agent, said at least one alkali agent and said at least one compound represented by one of the formulae (I), (II) and (III).
  • the developing liquid of claim 28 wherein the zinc compound is present in an amount of from aabout 7 X 10' to about 0.3 moles, calculated as metallic zinc, per g of developing solution.
  • Zinc compound is selected from the group consisting of zinc chloride, zinc oxide, zinc hydroxide, zinc sulfate and zinc carbonate.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00305027A 1971-11-09 1972-11-09 Viscous developing liquid for use in a silver salt diffusion transfer process Expired - Lifetime US3833372A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP8926771A JPS5436495B2 (en)) 1971-11-09 1971-11-09

Publications (1)

Publication Number Publication Date
US3833372A true US3833372A (en) 1974-09-03

Family

ID=13965962

Family Applications (1)

Application Number Title Priority Date Filing Date
US00305027A Expired - Lifetime US3833372A (en) 1971-11-09 1972-11-09 Viscous developing liquid for use in a silver salt diffusion transfer process

Country Status (4)

Country Link
US (1) US3833372A (en))
JP (1) JPS5436495B2 (en))
DE (1) DE2254873A1 (en))
GB (1) GB1378398A (en))

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4520096A (en) * 1983-06-14 1985-05-28 Fuji Photo Film Co., Ltd. Photographic elements for silver salt diffusion transfer process containing mercapto imidazole stabilizers
US4569899A (en) * 1983-12-07 1986-02-11 Fuji Photo Film Co., Ltd. Photographic element for silver salt diffusion transfer process
JPS6173951A (ja) * 1984-09-20 1986-04-16 Mitsubishi Paper Mills Ltd 銀錯塩拡散転写用処理液
JPS6173950A (ja) * 1984-09-20 1986-04-16 Mitsubishi Paper Mills Ltd 銀錯塩拡散転写用処理液
US5043245A (en) * 1989-01-31 1991-08-27 Agfa Gevaert, N.V. Process for the production of a laminated article

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2476757A1 (en) 2002-03-01 2003-09-12 Yamanouchi Pharmaceutical Co., Ltd. Nitrogen-containing heterocyclic compound

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2153619A (en) * 1937-06-19 1939-04-11 Agfa Ansco Corp Production of photographs in blueblack tones
US2514650A (en) * 1946-04-05 1950-07-11 Eastman Kodak Co Photographic developing with addition products to improve image quality
US3020155A (en) * 1956-05-23 1962-02-06 Eastman Kodak Co Photographic diffusion transfer process
US3576629A (en) * 1967-03-27 1971-04-27 Mitsubishi Paper Mills Ltd Diffusion transfer materials and process with derivatives of 4-amino-1,2,4-triazoline-5-thione as toning agents
US3577240A (en) * 1965-02-09 1971-05-04 Fuji Photo Film Co Ltd Diffusion transfer photographic materials

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE596845A (en)) * 1960-11-08
US3565619A (en) * 1968-01-18 1971-02-23 Polaroid Corp Photographic image transfer process utilizing imidazolidine-2-thione

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2153619A (en) * 1937-06-19 1939-04-11 Agfa Ansco Corp Production of photographs in blueblack tones
US2514650A (en) * 1946-04-05 1950-07-11 Eastman Kodak Co Photographic developing with addition products to improve image quality
US3020155A (en) * 1956-05-23 1962-02-06 Eastman Kodak Co Photographic diffusion transfer process
US3577240A (en) * 1965-02-09 1971-05-04 Fuji Photo Film Co Ltd Diffusion transfer photographic materials
US3576629A (en) * 1967-03-27 1971-04-27 Mitsubishi Paper Mills Ltd Diffusion transfer materials and process with derivatives of 4-amino-1,2,4-triazoline-5-thione as toning agents

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4520096A (en) * 1983-06-14 1985-05-28 Fuji Photo Film Co., Ltd. Photographic elements for silver salt diffusion transfer process containing mercapto imidazole stabilizers
US4569899A (en) * 1983-12-07 1986-02-11 Fuji Photo Film Co., Ltd. Photographic element for silver salt diffusion transfer process
JPS6173951A (ja) * 1984-09-20 1986-04-16 Mitsubishi Paper Mills Ltd 銀錯塩拡散転写用処理液
JPS6173950A (ja) * 1984-09-20 1986-04-16 Mitsubishi Paper Mills Ltd 銀錯塩拡散転写用処理液
US5043245A (en) * 1989-01-31 1991-08-27 Agfa Gevaert, N.V. Process for the production of a laminated article

Also Published As

Publication number Publication date
GB1378398A (en) 1974-12-27
JPS4854937A (en)) 1973-08-02
JPS5436495B2 (en)) 1979-11-09
DE2254873A1 (de) 1973-05-17

Similar Documents

Publication Publication Date Title
US3751255A (en) Photosensitive and thermosensitive element, composition and process
US3615440A (en) Novel photographic compositions and processes
US3833372A (en) Viscous developing liquid for use in a silver salt diffusion transfer process
US3793027A (en) Developing composition for use with photographic materials for the graphic arts
JPS5851257B2 (ja) 銀錯塩拡散転写用処理液組成物
US3232759A (en) Diffusion transfer process employing tone modifiers
US3578449A (en) Transfer image process utilizing an organic phosphine as silver halide solvent
US4022621A (en) Photographic developer composition
US3265499A (en) Photographic developing compositions
US3723117A (en) Method for developing silver halide emulsions
US3615534A (en) Photographic silver halide light-sensitive elements useful in preventing yellow fog
US3619186A (en) Photographic diffusion transfer product and process
US3343958A (en) Monobath containing cysteine-nitrogenous base combination
US3236642A (en) Process for producing direct positives by the silver salt diffusion process
JP2634646B2 (ja) 銀塩写真像の安定化方法
US3565619A (en) Photographic image transfer process utilizing imidazolidine-2-thione
US3698900A (en) Diffusion transfer process utilizing 2-mercapto imidazoles
US3563740A (en) Use of dicyanamides in and with photosensitive systems
US3640713A (en) Photographic processes and compositions therefor
JPH07107599B2 (ja) 中間調ハロゲン化銀画像のドツトエツチング法
US3620728A (en) Receiving sheet for diffusion transfer processes
EP0397926B1 (en) Processing liquid for use in silver halide photography
US3765892A (en) Viscous developer for silver halid diffusion transfer processes
US3749578A (en) Image-receiving material for use in silver salt diffusion transfer photography
US3326681A (en) Photographic products and processes