EP0064861B1 - Matériau photographique d'halogénure d'argent - Google Patents

Matériau photographique d'halogénure d'argent Download PDF

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Publication number
EP0064861B1
EP0064861B1 EP19820302292 EP82302292A EP0064861B1 EP 0064861 B1 EP0064861 B1 EP 0064861B1 EP 19820302292 EP19820302292 EP 19820302292 EP 82302292 A EP82302292 A EP 82302292A EP 0064861 B1 EP0064861 B1 EP 0064861B1
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EP
European Patent Office
Prior art keywords
silver halide
photographic material
halide photographic
polymer
silver
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
Application number
EP19820302292
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German (de)
English (en)
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EP0064861A3 (en
EP0064861A2 (fr
Inventor
Masatoshi Iwata
Takeo Koitabaschi
Shuichi Kinoshita
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.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
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Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0064861A2 publication Critical patent/EP0064861A2/fr
Publication of EP0064861A3 publication Critical patent/EP0064861A3/en
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Publication of EP0064861B1 publication Critical patent/EP0064861B1/fr
Expired legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the covering power of silver in photosensitive silver halide emulsion layers of a silver halide photographic material is defined by the ratio of the optical density of the developed photographic material to the amount of silver developed per unit area. If silver covering power is improved, then higher density can be obtained from a coating with the same amount of silver or a smaller amount of silver can be used to obtain the same density. For these reasons, various proposals have been made in order to augment the covering power of silver.
  • a method is known in which certain water soluble polymers are added to a silver halide photosensitive emulsion including polysaccharides such as dextrin, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyvinyl alcohol and derivatives thereof.
  • DE-A-2 533 137 describes a silver halide colour photographic material comprising a support and a hydrophilic colloidal layer thereon containing a homopolymer or a copolymer with a number average molecular weight of about 10.000 to 500.000, preferably 20.000 to 200.000.
  • the copolymer has more than 20 mole percent vinylpyrrolidone units.
  • Acrylic acid and methacrylic acid are mentioned among a plurality of monomers which may be present in the copolymer.
  • the material is said to provide colour pictures with improved graineness without reduced sensitivity.
  • it is necessary to add a considerable amount, say several tens percent to the weight of a binder such as gelatin. Accordingly, the physical properties of the hydrophilic colloidal layer coat deteriorates because of the addition. As a result, it can be considered that the covering power is augmented because, in effect, the developed silver is more dispersed.
  • a black-and-white silver halide photographic material comprising a support with a hydrophilic colloidal layer thereon containing a polymer with a number average molecular weight of not more than 20,000 having not less than 40% by weight acrylic acid or methacrylic acid as a monomeric unit.
  • the number average molecular weight of the polymer is preferably not more than 10 000 mn.
  • the low molecular weight polymer used in this invention is a homopolymer or a copolymer having acrylic or methacrylic acid as a monomeric unit.
  • a copolymer used in this invention contains not less than 40%, and preferably not less than 50%, by weight of acrylic or methacrylic acid as units.
  • Such copolymers contain, for example, vinyl monomer units or other kinds of monomeric units capable of copolymerizing with acrylic or methacrylic acid monomer, such as acrylamide, acrylate ester, styrene or maleic acid. It is not disadvantageous to use a salt of acrylic or methacrylic acid such as an alkaline metal or ammonium salt.
  • the amount of polymer added is suitably 1-80% by weight, and preferably 3-40% by weight of the amount of binder, such as gelatin, contained in a photographic construction layer (i.e., a hydrophilic colloidal layer).
  • Suitable vinyl monomers which can be used to obtain the copolymers which can be used in this invention include styrene and the derivatives thereof, such as styrene itself, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, p-n-butyl styrene, p-tert-butyl styrene, p-n-hexyl styrene, p-n-octyl styrene, p-n-nonyl styrene, p-n-decyl styrene, p-n-dodecyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro s
  • polymerization Various polymerization methods can be used to obtain the polymers such as suspension polymerization, solution polymerization, emulsion polymerization and block polymerization; solution polymerization is preferably used.
  • Acrylic acid (30 g) was dissolved in 100 ml of dioxane and 3 g of azobisisobutylonitrile were added thereto; the solution thus obtained was poured into a pressure bottle and was then polymerized for 15 hours at a temperature of 70°C. After cooling said polymer solution, it was added dropwise with agitation into 3 of ethylether; decantation was repeated three times with agitation, and the polymer deposited was then vacuum dried up; 27 g of the desired product were thus obtained. When the product was measured for its molecular weight by the vapor pressure equilibrium method, it was found to be 4500.
  • a silver halide emulsion layer is preferred but, besides this, the other photographic constituent layers contiguous to said silver halide emulsion layer may also be used; it is also possible to incorporate said polymer in a plurality of layers at the same time.
  • polyacrylic acid and the like having high molecular weight are effective for improving covering power, similar to the case with other water-soluble polymers.
  • a conventional polyacrylic acid and the like similar to the other water-soluble polymers, causes the physical properties of a hydrophilic colloidal layer coat to deteriorate with the occurrence of pressure fogs during development when an automatic processor is used; further, the covering power improvements are less than those of the other water-soluble polymers such as polyvinyl pyrrolidone (i.e., PVP).
  • PVP polyvinyl pyrrolidone
  • using the polymers in this invention as illustrated hereafter in an example, not only is no pressure fog observed but also there is an excellent improvement in the covering power. We have been acknowledged to discover these results.
  • the effects on the covering power improvements when using other water-soluble polymers come from the developed silver spreading which results from the physical property deterioration of the hydrophilic colloidal layer coat, while it may be when using a polymer as specified for this invention, that such effects do not result from the physical property deterioration of the hydrophilic colloidal layer coat but from a smaller decrease in density during drying as a result of enervating the drying shrinkage force of a binder such as gelatin in the hydrophilic colloidal layer.
  • silver halide may be used in the silver halide emulsion layer to be used in the invention.
  • silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver iodide may be used.
  • crystal forms, crystal structures, grain diameters, grain diameter distributions and the like of the silver halide grains may be either cubic, octahedral, twin or regular crystal form and may further be either cubo-octahedral or the so-called potato-like or spherical crystal form.
  • Crystal structure may be either uniform, different between outside and inside, a layer-like structure, or joined to each different silver halide by epitaxial joining. Still further such structure may be the one forming a latent image mainly on the surface thereof or may be one forming such latent image inside.
  • the present invention brings about particularly remarkable effects on a silver halide black-and-white photographic material of which the ultimate image forming element is silver grains or filaments; it is also capable of inhibiting the optical density variations of not only a gelatin-silver halide photographic material but also an image-forming material containing both a hydrophilic binder having a shrinkage power which influences an image forming element held inside said material and an image forming element which is affected by such shrinkage power.
  • Gelatin is preferable to serve as a binder for the silver halide emulsion layer or other hydrophilic colloidal layer of the invention; in addition other hydrophilic colloids may also be used in accordance with the desired use.
  • a gelatin derivative, casein, a cellulose derivative, or a polysaccharide such as dextrin, polyvinyl alcohol, a vinyl maleic acid copolymer, poly-N-vinyl pyrrolidone or an acrylamide copolymer.
  • a silver halide emulsion to be used in the present invention may be sensitized by a usual chemical sensitization, such as a sulphur sensitization using sodium thiosulphate, allyl thiocarbamide, thiourea or allyl thiocyanate; or a noble metal sensitization in which potassium chloroplatinate, ammonium chloropalladium or ammonium chlororuthenium, rhodium, iridium or platinum can be used. It is also possible to sensitize said emulsion using a combination of such noble metal salt with a sulphur sensitizer and again in combination with ammonium thiocyanate serving as an assistant.
  • a usual chemical sensitization such as a sulphur sensitization using sodium thiosulphate, allyl thiocarbamide, thiourea or allyl thiocyanate
  • a noble metal sensitization in which potassium chloroplatinate, ammonium chloropalla
  • selenourea when using selenium sensitization processes, it is possible to sensitize said emulsion using, for example, selenourea, N,N-dimethyl selenourea or N-dimethyl selenourea; as for reduction sensitization processes, it is possible to use a tin salt, a polyamine or a quaternary ammonium salt, for example. Also, it is possible to use a sensitizing process using a polyalkylene oxide compound or a process using a thioether.
  • the desired photosensitive wavelength range can be sensitized by making use of sensitizing dye.
  • sensitizing dyes various kinds may be used and it is possible to combine two or more of them.
  • Dyes advantageously used include methine dyes such as cyanine, hemicyanine, rhodacyanine, merocyanine, oxonol, hemioxonol or styryl dyes.
  • Sensitizing dyes are effective in the invention, examples of which have been described in US Patents Nos 2 213 995, 2 503 776 and 2 945 763; DE-C-929 080 and 2 049 967; Japanese Patent Applications Nos 13821/1968, 32753/1969, 18106/1971, 8741/1972, and 37443/1972; and Japanese Patent Open to Public Inspection No 89722/1973; as for the principal dyes, reference can be made to Japanese Patent Publication Open to Public Inspection No 137134/1978.
  • the silver halide emulsion to be used in the present invention can be applied with a stabilizer and an antifoggant such as those disclosed in US Patents Nos. 2 444 607, 2 716 062, 3 512 982 and 3 342 596; DE-C-1 189 380, and 2 058 626; Japanese Patent Publication Nos 4133/1968 and 2825/1964; and Japanese Patent Publication Open to Public Inspection Nos.
  • a stabilizer and an antifoggant such as those disclosed in US Patents Nos. 2 444 607, 2 716 062, 3 512 982 and 3 342 596; DE-C-1 189 380, and 2 058 626; Japanese Patent Publication Nos 4133/1968 and 2825/1964; and Japanese Patent Publication Open to Public Inspection Nos.
  • particularly preferred compounds are 4 - hydroxy - 6 - methyl - 1,3,3a,7 - tetrazaindene, 4 - hydroxy - cyclo- pentano[f] - 1,3,3a,7 - tetrazaindene or an ester gallate (e.g., isoamyl gallate, dodecyl gallate, propyl gallate or sodium gallate); a mercaptan (e.g., 1 - phenyl - 5 - mercapto - tetrazole or 2 - mercaptobenzo - thiazole); a benzotriazole (e.g., 5-bromobenzotriazole or 4-methylbenzotriazole); a benzoimidazole (e.g., 6-nitrobenzoimidazole); or a resolsinole.
  • an ester gallate e.g., isoamyl gallate, dodecyl
  • a photographic hardening agent usually used in the coating solution of said material can be used, for example an aldehyde, an aziridine, an isoxazole, an epoxy compound, a vinyl sulfone, an acryloyl compound, a carbodimide, a maleimide, an acetylene, an ester methanesulfonate, a triazine or a macromolecular type hardening agent.
  • thickening agents those described in US Patent No 3 767 410 and Belgian Patent No 558 143 and as for gelatin plasticizing agents, a polyol or a latex may be used without difficulty.
  • matting agents which can be used those described in British Patent No 1 221 980 may be mentioned; and for gelatin derivatives which can be used, phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin or those in which a gelatin is graft-polymerized with a polymerizable monomer having an ethylene group such as styrene acrylate, an ester acrylate, methacrylic acid or an ester methacrylate may be mentioned; said hydrophilic colloids may be used either in a layer containing silver halide or in a layer not containing silver halide such as a protective layer, an interlayer, a filter layer or other constitutional layer of a photographic material.
  • gelatin derivatives which can be used, phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin or those in which a gelatin is graft-polymerized with a polymerizable monomer having an ethylene group such as styrene
  • a coating assistant such as a saponin or sulfosuccinic acid type surface-active agent and an anionic surface-active agent, can be used.
  • an ultra-violet absorbing agent a fluorescent whitening agent, an image stabilizing agent, an anti-oxidizing agent, a lubricating agent, a metallic ion blocking agent or an emulsification dispersing agent, for example, can be used.
  • the silver halide photographic materials of this invention may have the following layers, in addition to one or more silver halide emulsion layers; a protective layer, an interlayer, a filter layer, an antihalation layer, a subbing layer, an irradiation protective layer or a backing layer; suitable supports which can be used include a baryta paper, a polyethylene coated paper, a polypropylene synthetic paper, a glass plate, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, a polyester film such as polyethylene terephthalate, a polyamide film, a polycarbonate film or a styrene film. These supports are suitably selected in accordance with the usage of the silver halide photographic material.
  • the developing solutions which can be used for developing the silver halide photographic materials of this invention may be of the type ordinarily used; examples of suitable developers include hydroquinone, N-methyl-p-aminophenol, 1-phenyl-3-pyrazolidone or paraphenylenediamine, singly or in combination.
  • an alkaline agent such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or sodium metaborate or an alkanol
  • a preservative such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium pyrosulfite, formaldehyde or sodium hydrogensulfite addition products
  • a development foggant such as an azole, e.g., 5-nitrobenzoimidazole, 5-methylbenzotriazole, 8-nitrobenzotriazole or 1-phenyl-5-mercaptotetrazole
  • a hardening agent such as the well known aldehyde compounds for hardening gelatin and other macromolecular substances.
  • Preferable aldehydes include a dialdehyde such as glutaric aldehyde or maleic aldehyde or a bisulfite thereof.
  • an antioxidizing agent such as 3,6-dihydroxypyridazine; a polyamine; a polyalkyleneoxide compound; an alkylene glycol; or an alcohol such as methyl alcohol; an organic solvent such as dimethyl formamide, a cellosolve (ethylene glycol monoether) or benzyl alcohol; or ascorbic acid.
  • an antioxidizing agent such as 3,6-dihydroxypyridazine; a polyamine; a polyalkyleneoxide compound; an alkylene glycol; or an alcohol such as methyl alcohol; an organic solvent such as dimethyl formamide, a cellosolve (ethylene glycol monoether) or benzyl alcohol; or ascorbic acid.
  • a chelating agent a pH regulating agent or a buffer, for example, can be used.
  • Developing time varies according to the nature of the developing solution, the developing temperature, the nature of the photosensitive material; however, a suitable time is normally about five minutes or longer, or about five seconds but not longer than one minute; development can be made by means of a tray type or a roller conveyor type automatic processor.
  • the silver halide photographic materials of this invention can be processed by various processes depending on the nature of the photosensitive material; for example, the processing steps are as follows: Developing- Fixing-Washing-Drying.
  • a black-and-white photosensitive material for general use a photosensitive material for printing use, a photosensitive material for reproduction use, a photosensitive material for diffusion transfer use, a photosensitive material for silver dye bleaching process use or a photosensitive material for special use.
  • Cubic silver halide-gelatin emulsion (1 kg) which had been chemically sensitized using sodium thiosulfate and sodium chloroaurate (whose silver iodide content was 2 mol % and the average grain diameter was 1.2 fJ m) was added to 10 ml of a 1 % aqueous solution of 4 - hydroxy - 6 - methyl -1,3,3a,7 - tetrazaindene, 30 ml of 10% aqueous solution of saponin and 3 ml of 3% aqueous solution of formalin (this emulsion contains 80 g of gelatin per mol of silver halide).
  • the emulsion thus prepared was divided into eleven portions, and the polymers and copolymers shown in the following Table 1 were made up as aqueous solutions and added to the portions of said emulsion, the pH values adjusted with 5% aqueous solution of NaOH, and then coated onto a blue coloured polyethylene terephthalate support; thus, each of the samples (No. 1-11) was prepared.
  • the samples thus prepared were exposed to white light by means of Sensitometer KS-1 Model (mfd. by Konishiroku Photo Ind. Co., Ltd.) in conformity with the procedure provided under the JIS, and developed in a tray, fixed, washed, taken out and measured for density when they were still wet, and when dried. After they were dried, measurements were made for the fog, sensitivity and maximum density of each sample using ordinary sensitometry.
  • the density of every sample in the dry state is represented by a percentage of that of the same sample in the wet state, in order to obtain an index for the density variation of the samples.
  • the amount of the developed silver of each sample in the maximum density area was measured by fluorescence X-ray analysis and the density value was divided by the value for the amount of silver to obtain a value for the covering power.
  • the results obtained are shown in Table 1 below, wherein the sensitivity of each sample indicates the value relative to the sensitivity of Sample No. 1 of which the value is regarded as 100.
  • the developing solution used was Developer [I] which was composed as follows, and the processing conditions were: temperature-20°C and time ⁇ 4 min. 30- sec.
  • the polymers used in this invention reduce the density reduction and also improve the covering power, relative to sodium polyacrylate having a high molecular weight.
  • Example 1 An emulsion prepared in the same manner as in Example 1 was divided into six parts and the compounds shown in the following Table 2 were respectively added to each of the parts; each of the mixtures and a protective layer material were coated over a support made of polyethylene terephthalate film; thus the samples (No. 12-17) were prepared in the same manner as in Example 1.
  • Each of the samples was developed by Developing Solution [I] in the same manner as in Example 1 and then the density variations and the covering powers in the dry state were measured. The development of each sample was made using a roller type automatic processor performing a series of processing steps; Developing-Fixing-Washing-Drying; the degree of pressure fog produced was examined. The following is the formula of Developing Solution [II] that was used in the processing with said automatic processor:
  • the results obtained therefrom are shown in the following Table 2.
  • the degree of pressure fogs caused by the automatic processor are represented by the mark 0 which indicated no fog caused, the mark A which indicate only a little fog caused and the mark x that indicates considerable fog caused.
  • the polymers used in this invention give excellent results as regards covering power, density variation in the dry state and the degree of pressure fog.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (7)

1. Matériau photographique noir-et-blanc à halogénure d'argent, comprenant un support et une couche colloïdale hydrophile déposée sur celui-ci et contenant un polymère ayant une masse moléculaire moyenne en nombre ne dépassant pas 20.000 et ne contenant pas moins de 40% en poids de motifs d'acide acrylique et/ou d'acide méthacrylique, ou d'un sel de celui-ci.
2. Matériau photographique à halogénure d'argent selon la revendication 1, dans lequel la couche colloïdale hydrophile est une couche d'émulsion d'halogénure d'argent photosensible.
3. Matériau photographique à halogénure d'argent selon la revendication 1, dans lequel la couche colloïdale hydrophile est une couche adjacente à une couche d'émulsion d'halogénure d'argent photosensible.
4. Matériau photographique à halogénure d'argent selon l'une quelconque des revendications 1 à 3, dans lequel le polymère a une masse moléculaire moyenne en nombre ne dépassant pas 10.000.
5. Matériau photographique à halogénure d'argent selon l'une quelconque des revendications 1 à 4, dans lequel le polymère est un homopolymère ayant des motifs d'acide acrylique ou d'acide méthacrylique.
6. Matériau photographique à halogénure d'argent selon l'une quelconque des revendications 1 à 4, dans lequel le polymère est un copolymère ayant des motifs d'acide acrylique ou d'acide méthacrylique.
7. Matériau photographique à halogénure d'argent selon la revendication 6, dans lequel le copolymère comprend des motifs d'un monomère vinylique.
EP19820302292 1981-05-07 1982-05-05 Matériau photographique d'halogénure d'argent Expired EP0064861B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP67588/81 1981-05-07
JP6758881A JPS57182732A (en) 1981-05-07 1981-05-07 Silver halide photographic material

Publications (3)

Publication Number Publication Date
EP0064861A2 EP0064861A2 (fr) 1982-11-17
EP0064861A3 EP0064861A3 (en) 1983-06-15
EP0064861B1 true EP0064861B1 (fr) 1987-01-07

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EP (1) EP0064861B1 (fr)
JP (1) JPS57182732A (fr)
DE (1) DE3275024D1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69419949T2 (de) * 1993-02-22 2000-01-20 Mitsubishi Paper Mills Ltd Photographisches lichtempfindliches Silberhalogenidmaterial
US5709983A (en) * 1995-08-31 1998-01-20 Eastman Kodak Company Nonaqueous solid particle dye dispersions

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3713833A (en) * 1970-10-28 1973-01-30 Eastman Kodak Co Preparation of silver salts in an organic liquid medium
US3925083A (en) * 1973-01-02 1975-12-09 Polaroid Corp Synthetic silver halide emulsion binder
JPS49106821A (fr) * 1973-02-12 1974-10-09
JPS5114022A (ja) * 1974-07-24 1976-02-04 Fuji Photo Film Co Ltd Gazokeiseihoho
JPS537231A (en) * 1976-07-08 1978-01-23 Fuji Photo Film Co Ltd Image formation
JPS541621A (en) * 1977-06-06 1979-01-08 Konishiroku Photo Ind Co Ltd Silver halide color photographic material
DD133476B1 (de) * 1977-09-14 1980-02-13 Wolfen Filmfab Veb Verfahren zum einbringen von organischen zusaetzen in hydrophile kolloidschichten
DE2800466C3 (de) * 1978-01-05 1981-12-03 Agfa-Gevaert Ag, 5090 Leverkusen Photographisches Material

Also Published As

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DE3275024D1 (en) 1987-02-12
EP0064861A3 (en) 1983-06-15
EP0064861A2 (fr) 1982-11-17
JPS57182732A (en) 1982-11-10

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