US3745013A - Method for making hardened gelatin images - Google Patents

Method for making hardened gelatin images Download PDF

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Publication number
US3745013A
US3745013A US00190258A US3745013DA US3745013A US 3745013 A US3745013 A US 3745013A US 00190258 A US00190258 A US 00190258A US 3745013D A US3745013D A US 3745013DA US 3745013 A US3745013 A US 3745013A
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US
United States
Prior art keywords
gelatin
silver halide
compound
layer
images
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
US00190258A
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English (en)
Inventor
T Shishido
R Ohi
J Hayashi
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Fujifilm Holdings Corp
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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
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • 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
    • G03C5/29—Development processes or agents therefor
    • G03C5/315—Tanning development
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/06—Silver salts
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/12—Production of screen printing forms or similar printing forms, e.g. stencils

Definitions

  • Hardened gelatin images are formed from silver halide images in the presence of (a) a silver halide solvent, (b) an alkali and (c) a compound represented by the General Formula I:
  • a and B are each non-metal atoms necessary for forming a heterocyclic ring
  • Y is a member selected from the group consisting of sulfur and selenium
  • X is an anion.
  • Another object of this invention is to provide a novel and useful method for making gelatin relief images.
  • a method for making gelatin images which comprises hardening gelatin in the non-silver image areas of a silver image-carrying gelatin-silver halide emulsion layer in the presence of (a) a silver halide solvent, (b) an alkali agent and (c) at least one compound of the Formula I:
  • a and B are each non-metal atoms necessary for forming a heterocyclic ring, Y is sulfur or selenium and X is an anion.
  • a method for making hardened gelatin images which comprises contacting a gelatin with a silver halide emulsion layer carrying a silver image in the presence of (a) a silver halide solvent, (b) an alkali agent and (c) at least one compound of the above-described General Formula I, whereby hardening gelatin in the areas of the gelatin layer corresponds to the nonsilver image areas of the emulsion layer.
  • the essential part of this invention is the simultaneous presence of (1) a gelatin layer for the hardened images to be formed thereon, (2) imagewise silver halide, (3) silver halide solvent, (4) alkali agent and (5) at least one compound of the General Formula I.
  • the method of this invention may be applied, for example, in the manner wherein a light sensitive material comprising a support having thereon a gelatin-silver halide emulsion layer is processed, after exposure and development, with an alkaline fixing solution containing the compound(s) of Formula I.
  • the compound(s) of Formula I may be incorporated in the light sensitive material prior to fixing.
  • the compound(s) may be either previously incorporated into the emulsion layer upon manufacturing the light sensitive material, or treated, prior to fixing, with an aqueous solution of the compound(s) of Formula I for introduction into the emulsion layer.
  • gelatin and silver halide are each present in separate layers, for example, the case where a light sensitive material comprising a support coated successively thereon with a gelatin layer and then silver halide emulsion layer is employed.
  • the compound(s) of Formula I may be incorporated into the gelatin layer, silver halide emulsion layer and/or processing solution.
  • the processing may be carried out by superposing the developed light sensitive material on a gelatin layer of a sheet material, also in which cases, the compound(s) of For mula I may be incorporated into the gelatin layer, emulsion layer and/or processing solution, as in the above-described cases.
  • the embodiments of any other type may be suitably adopted for the practice of the present invention.
  • the gelatin which is employed in this invention may be any of those conventionally employed in the field of photographic arts. It may advantageously constitute a layer by being coated on a suitable support. Into the gelatin layer may be incorporated the compound(s) of Formula I and optionally added various kinds of additives known in the art.
  • the silver halide emulsion may be any of these conventionally employed in photography, which comprises silver chlorine, silver bromide, silver iodide, silver chlorobromide, silver chlorobromoiodide or a mixture thereof dispersed in a high molecular weight substance, such as gelatin. It may optionally contain conventional chemical sensitizers, sensitizing dyes, stabilizers, hardeners and/or coating aids. That the present invention employs a lightsensitive substance comprising silver halide is particularly advantageous in view of sensitivity (speed) and light sensitive range.
  • the light-sensitive silver halide emulsion may be applied onto a conventional support to form the light-sensitive layer.
  • Fixing compositions conventionally employed in the processing of the usual silver halide photographic materials contain thiosulfate such as sodium thiosulfate, ammonium thiosulfate, etc.
  • the thiosulfate is one of the silver halide solvents and preferably employed in the present invention, although any other silver halide solvent may be employed as well. These silver halide solvents act as a precursor for silver ions.
  • the alkali agent is employed for the purpose of making the environment of the reaction alkaline, so that any of the alkali agents having such an efiect may be employed.
  • the gelatin hardening reaction somewhat proceeds even in an acidic environment, it is necessary to effect the reaction in an alkaline environment, in order to obtain the hardened gelatin images suitable for the purpose of this invention.
  • Synthesis 2 (Compound 3) A mixture of 16 g. of Z-methylthiobenzothiazole and g. of 1,3-dibrornopropane was heated at a temperature of 160 C. for 4 hours. After cooling, the precipitated crystals were filtered 011 and then recrystallized from ethanol to obtain 14 g. of crystals appearing as needles having a melting point of 260 C.
  • Synthesis 3 (Compound 6) A mixture of 20 g. of 2-methylthiobenzoselenazole and 20 g. of ethylene bromide was heated at a temperature of 160 C. for 4 hours. After cooling, the precipitated crystals were collected by filtration to obtain 18 g. of crystals appearing as needles having a manner as described in Chemical Abstracts, vol. 72, page 31666 (1970).
  • gelatin-silver halide emulsion layer by subjecting a conventional photographic light sensitive material having a gelatin-silver halide emulsion layer to exposure development and fixation, hardened gelatin images can be readily formed in the unexposed areas.
  • the gelatin layer having the hardened gelatin images can be used, for example, in producing duplicates by means of impregnating the layer with a water-soluble dye followed by transferring the dye to a suitable material.
  • gelatin relief images can be obtained by treating the gelatin layer with warm water, thereby removing the gelatin in the unhardened areas.
  • Such gelatin relief images can be used in various fields, as those made in known manners.
  • the surface of a support is used as the oleophilic ink depositing site and a gelatin layer as the hydrophilic site.
  • the conventional off-set printing plates such as zinc plate and RS. plate (i.e., presensitized printing plate using diazotype light sensitive materials) have narrow light sensitive ranges and poor sensitivity and therefore printing with visible light, enlargement printing and reflection printing are difficult to be applied thereto, the advantage of the off-set printing plates provided by the present invention is extremely large due to their high sensitivity resulting from the utilization of a photographic silver halide emulsion.
  • They may be used as screen printing plates by partially forming a gelatin film on an ink-permeable support, such as silk screen, thereby making the support ink-impermeable.
  • the resulting gelatin relief can be immediately visible and provided for further use, for example, as a transfer for the dye or pigment to another support using a suitable solvent for the dyes.
  • hardness of the gelatin layer or silver halide emulsion layer may be appropriately determined, depending upon specific purposes.
  • the gelatin layer should be an unhardened one and the emulsion layer should be a hardened one.
  • the upper emulsion layer is dissociated or stripped by treating with hot water after first developing, and fixing, there can be contemplated two modes of the dissociation, depending upon the bonding strength between the layers and upon the degree of progress of the hardening reaction; one mode where the unhardened areas of the lower gelatin layer are dissociated accompanying the upper layer and another mode where the hardened areas of the lower gelatin layer are dissociated accompanying the upper layer.
  • the preferable conditions in such cases can be readily determined by a preliminary test.
  • a support carrying thereon the hardened gelatin images or gelatin relief images may be of, for example, glass, metal plate, cellulose acetate film, polyethylene telephthalate film, paper, synthetic paper, water proof paper or fabrics, such as silk screen. Suitable supports may be selected depending upon the specific purpose of its utili- Zation.
  • EXAMPLE 1 To g. of a conventional fine-grain positive silver chlorobromide emulsion (50' mol percent silver chloride) was added 5 ml. of a 0.2 mol aqueous solution of Compound 1 and the mixture was applied to a glass plate followed by cooling to effect setting. After air-drying overnight at a temperature of 20 C., the sample thus formed was superposed on an original pattern and then exposed to effect contact exposure, whereafter it was developed at a temperature of 20 C. for 7 minutes and fixed for 20 minutes, using the following developing and fixing solution, respectively:
  • the sample was then dipped in warm water at 60 C. whereby the gelatin in the exposed areas where the gelatin-hardening reaction did not occur was softened and dissociated or dissolved away, while the gelatin remained on the glass plate in the unexposed areas Where the gelatinhardening occurred.
  • EXAMPLE 2 9 samples were prepared by adding several compounds of this invention, in amounts as shown in the table below, into 100 g. of a 3% aqueous gelatin solution and each sample was applied onto a triacetyl cellulose film, whereafter a composition was applied thereon, set by cooling and then dried, which composition was prepared by adding into a conventional optically sensitized high speed negative gelatin silver iodobromide emulsion (3.5 mol percent silver iodide, 3 g., per 100 g. said emulsion, of a high molecular weight hardening agent as disclosed in Example 1 of US. Pat. 3,362,827.
  • the dry thickness of the gelatin layer and silver halide emulsion layer were 1.5 and 4a, respectively.
  • Example 2 Each of these nine samples was subjected to enlargement exposure from a microfilm, whereafter it is developed and fixed with the same compositions as shown in Example 1.
  • the samples were dipped in hot water at 60 C. and the surface of such was rubbed therein, the upper silver halide emulsion layer was dissociated as a layer.
  • the hardened gelatin in the areas of the lower layer corresponding to the unexposed areas of the emulsion layer was also dissociated accompanying the upper silver halide emulsion layer.
  • the amount of the compound represented by Formula I there is no critical limitation.
  • the amount employed may vary widely depending on many factors and the preferable amount to be employed may be readily determined by those ordinarily skilled in the art of photographic procedures.
  • thiazole As to the heterocyclic ring represented by B in Formula I, there are noted thiazole, benzothiazole, naphthothiazole, thiazolone, thiazolenethione, thiadiazole, thiadiazoline, thiadiazolone, thiadiazolinethione, selenazole, benzoselenazole, naphthoselenazole, selenazoline, selenazolone, and selenazolinethione.
  • a method for making hardened gelatin images which comprises hardening gelatin in the non-silver image areas of a silver image-carrying gelatin silver halide emulsion in the presence of:
  • a and B are each non-metal atoms necessary for forming a heterocyclic ring
  • Y is a member selected from the group consisting of sulfur and selenium and X is an anion.
  • a method for making hardened gelatin images in a gelatin layer which is in contact with a silver imagecarrying silver halide emulsion layer which comprises hardening gelatin in the gelatin layer in the areas corresponding to the non-silver image areas of the emulsion layer in the presence of:
  • a method for making a hardened gelatin image which comprises treating a gelatin silver halide emulsion layer containing a silver image with a solution containing:
  • a method for making hardened gelatin image which comprises treating a gelatin silver halide emulsion layer containing a silver image with an aqueous alkaline fixing solution containing the compound of the Formula I of claim 1, thereby hardening the gelatin in the non-silver image areas.
  • a method for making a hardened gelatin image which comprises treating a gelatin silver halide emulsion layer containing a silver image and the compound of the Formula I of claim 1 with a solution containing a silver halide solvent and an alkali agent.
  • a method for forming a gelatin relief image which comprises forming a hardened gelatin image according to claim 1 and removing any remaining unhardened gelatin to form the hardened relief image.
  • a method for forming a gelatin relief image which comprises forming a hardened gelatin image according to claim 2 and removing any remaining unhardened gelatin to form the hardened relief image.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US00190258A 1970-10-19 1971-10-18 Method for making hardened gelatin images Expired - Lifetime US3745013A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45091804A JPS4839169B1 (enrdf_load_stackoverflow) 1970-10-19 1970-10-19

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US3745013A true US3745013A (en) 1973-07-10

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US (1) US3745013A (enrdf_load_stackoverflow)
JP (1) JPS4839169B1 (enrdf_load_stackoverflow)
DE (1) DE2151095C3 (enrdf_load_stackoverflow)
GB (1) GB1377193A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115118A (en) * 1974-01-31 1978-09-19 Fuji Photo Film Co., Ltd. Process for production of printing plate
US4230792A (en) * 1976-07-15 1980-10-28 Mitsubishi Paper Mills, Ltd. Lithographic printing plate from silver halide emulsion

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58158631A (ja) * 1982-03-15 1983-09-20 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
JPS58158630A (ja) * 1982-03-15 1983-09-20 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115118A (en) * 1974-01-31 1978-09-19 Fuji Photo Film Co., Ltd. Process for production of printing plate
US4230792A (en) * 1976-07-15 1980-10-28 Mitsubishi Paper Mills, Ltd. Lithographic printing plate from silver halide emulsion

Also Published As

Publication number Publication date
DE2151095C3 (de) 1975-12-18
DE2151095B2 (de) 1975-04-30
DE2151095A1 (de) 1972-05-10
GB1377193A (en) 1974-12-11
JPS4839169B1 (enrdf_load_stackoverflow) 1973-11-22

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