EP0551994B1 - Matériau photographique à l'halogénure d'argent sensible à la lumière - Google Patents

Matériau photographique à l'halogénure d'argent sensible à la lumière Download PDF

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Publication number
EP0551994B1
EP0551994B1 EP93300103A EP93300103A EP0551994B1 EP 0551994 B1 EP0551994 B1 EP 0551994B1 EP 93300103 A EP93300103 A EP 93300103A EP 93300103 A EP93300103 A EP 93300103A EP 0551994 B1 EP0551994 B1 EP 0551994B1
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EP
European Patent Office
Prior art keywords
gelatin
sensitive material
light
layer
silver halide
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EP93300103A
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German (de)
English (en)
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EP0551994A1 (fr
Inventor
Hirokazu Konica Corporation Sato
Takashi Konica Corporation Kadowaki
Hidetoshi Konica Corporation Ito
Kazuhiko Konica Corporation Saito
Koichi Konica Corporation Yoneyama
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Konica Minolta Inc
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Konica Minolta Inc
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    • 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
    • G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins
    • 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
    • G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins
    • G03C2001/0471—Isoelectric point of gelatine

Definitions

  • the present invention relates to a silver halide light-sensitive material (hereinafter occasionally referred to as a light-sensitive material), particularly to a silver halide light-sensitive material containing an alkali-processed cattle-bone gelatin having an isoelectric point of not less than 5.2 as a binder.
  • a silver halide light-sensitive material hereinafter occasionally referred to as a light-sensitive material
  • a silver halide light-sensitive material particularly to a silver halide light-sensitive material containing an alkali-processed cattle-bone gelatin having an isoelectric point of not less than 5.2 as a binder.
  • Gelatin is widely known as binder of a photographic light-sensitive material. And, in recent years, an alkali-processed or lime-processed cattle-bone gelatin having an isoelectric point of 4.5 to 5.0 is generally used for the reason that it exerts little adverse influence upon photographic properties.
  • Japanese Pat. Exam. Pub. Nos. 43777/1976, 23142/1981 and 28900/1984 disclose the use of acid-processed gelatins as binder for a surface protective layer of a light-sensitive material.
  • Japanese Pat. O.P.I. Pub. Nos. 117534/1986 and 233737/1986 disclose the use of a pigskin lime-processed gelatin.
  • EP-A-0285994 discloses a photographic material having a protecting layer containing an alkali processed gelatin from bone or skin.
  • JP-A-2188753 provides a silver halide photosensitive material having a lime-treated gelatin of pI 4.5 to 5.2 in one of the silver halide emulsion layers, and in the outermost layer, a gelatin having pI 5.2 to 6.0.
  • an alkali-processed gelatin having a pI of 4.5 to 5.3.
  • Light-sensitive materials are generally stored in a refrigerator and taken out for use in serial order.
  • a light-sensitive material is touched with fingers and thereby subjected to pressure immediately after it has been taken out of a refrigerator, desensitization marks are formed in the shape of finger prints, hereinafter referred to as finger printing.
  • finger printing When a light-sensitive material having a high silver chloride content becomes liable to cause such finger prints and thereby requires much severe control in handling, when it contains an acid-processed gelatin or a pigskin gelatin as binder.
  • a first object of the invention is to provide a silver halide photographic light-sensitive material capable of forming images with high surface gloss.
  • a second object of the invention is to provide a silver halide photographic light-sensitive material excellent in coatability in the manufacture and less in causing unevenness in density and failure spots attributable to uneven coating and coating failures.
  • a third object of the invention is to provide a silver halide photographic light-sensitive material less in finger printing.
  • a silver halide photographic light-sensitive material comprising a support having thereon one or more photographic component layers including a silver halide emulsion layer, wherein the silver halide emulsion layer comprises silver halide grains having a silver chloride content of not less than 95 mol%, and at least one of said photographic component layers contains a alkali-processed cattle-bone gelatin without chemical modification, which has an isoelectric point not lower than 5.2, and the sum of the amount of the hydrophilic colloid including gelatin coated on the support is not more than 8g/m 2 .
  • the effects of the invention are advantageously brought out when at least the outermost photographic component layer formed at the farthest position from the support contains a alkali-processed cattle-bone gelatin having an isoelectric point not lower than 5.2.
  • Gelatins used in the photographic industry are usually extracted from cattle-bones, cattle skins or pigskins and classified into two types according to the manufacturing process from collagen: an alkali-processed gelatin which is treated with lime or the like and an acid-processed gelatin which is treated with hydrochloric acid or the like.
  • At least one of the photographic component layers constituting the light-sensitive material of the invention contains a alkali-processed cattle-bone gelatin having an isoelectric point not lower than 5.2, hereinafter referred to as the gelatin used according to the invention.
  • the isoelectric point of the gelatin used according to the invention is preferably 5.2 to 6.0, especially 5.2 to 5.5.
  • isoelectric point used here is expressed as a hydrogen ion concentration at which the algebraic sum of electric charges in an aqueous solution of an amphoteric electrolyte becomes zero, and it is determined according to the PAGI Method issued by The Joint Coucil for the Method of Testing Photographic Gelatin, 6th edition, Oct., 1987. To be concrete, it is determined by passing a 1% aqueous solution of gelatin through a mixed bed column of cationic and anionic ion exchange resins and then measuring the pH.
  • the isoelectric point of the gelatin used according to the invention is for a gelatin before it is subjected to hardening; that is, it is determined by the isoelectric point of a gelatin to be added to a coating solution to form a photographic component layer.
  • the gelatin used according to the invention is used in an amount of desirably not less than 50 wt% and more desirably not less than 80 wt% of the total amount of gelatin contained in the photographic component layer to which it is added and, in the most desirable embodiment of the invention, the addition amount is substantially 100 wt% of the total amount of gelatin.
  • the isoelectric point after blending is preferably not less than 5.2.
  • the difference between the pH of a coating solution to form a photographic component layer containing the gelatin used according to the invention and the isoelectric point of the gelatin used according to the invention be not less than 0.3.
  • the jelly strength according to the PAGI Method of the gelatin used according to the invention is preferably not less than 250 g, especially not less than 270 g.
  • the calcium content according to the PAGI Method of the gelatin used according to the invention is preferably not more than 1000 ppm, especially not more than 500 ppm.
  • treatment with an ion exchange resin column is preferred.
  • gelatin used according to the invention may be subjected to oxidizing treatment by use of hydrogen peroxide or the like to minimize its photographic activity.
  • the molecular weight of the gelatin used according to the invention is not limitative, but it is preferably 10,000 to 200,000 in terms of average molecular weight.
  • the gelatin used according to the invention which is an alkali-processed cattle-bone gelatin, is obtained by the steps of removing calcium phosphate contained in cattle-bones with hydrochloric acid and the liming the resulting ossein under controlled conditions.
  • the gelatin used according to the invention which is made from cattle-bone by alkali-processing method and has an ioselectric point not less than 5.2, is available from the market.
  • an alkali-treated gelatin having an isoelectric point not less than 5.2 can be obtained by subjecting the usual cattle-bone alkali-processed gelatin having an isoelectric point not more than 5.0 to chemical modification such as amidation or esterification so as to decrease its carboxyl group content and, thereby, raising its isoelectric point, such a chemically treated gelatin cannot exhibit the effects of the invention sufficiently.
  • the light-sensitive material of the invention may be either one having a single photographic component layer or one having a plurality of photographic component layers. When it is composed of a plurality of photographic component layers, the effect of the invention can be advantageously brought out by incorporating the gelatin used according to the invention in the surface protective layer formed at the farthest position from the support.
  • the light-sensitive material of the invention may use, as binder or protective colloid, other hydrophilic colloids such as gelatin derivatives, graft polymers obtained by grafting a polymer on gelatin, proteins, sugar derivatives, cellulose derivatives and synthetic hydrophilic homo- or copolymers.
  • hydrophilic colloids such as gelatin derivatives, graft polymers obtained by grafting a polymer on gelatin, proteins, sugar derivatives, cellulose derivatives and synthetic hydrophilic homo- or copolymers.
  • the sum of the amounts of hydrophilic colloids including gelatin coated on the support of the light-sensitive material of the invention is not more than 8.0 g/m 2 .
  • the gelatin contained in the light-sensitive material of the invention is hardened by a hardener.
  • Usable hardeners are not particulaly limited, and there can be used conventional photographic hardeners such carboxyl-activating type and polymer type hardeners including aldehyde type, active vinyl type, active halogen type, epoxy type, ethleneimine type, methanesulfonate type, carbodiimide type, isooxazole type and carbamoyl pyridinium salts.
  • vinylsulfone type hardeners for example, compounds H-1 to H-24 described on pages 13-14 of Japanese Pat. O.P.I. Pub. No. 188753/1990, chlorotriazine type hardeners (for example, compounds II-1 to II-13 and III-1 to III-10 described on pages 20-21 of Japanese Pat. O.P.I. Pub. No. 216340/1989) and carboxyl-activating type hardeners including those described in Japanese Pat. O.P.I. Pub. Nos. 82237/1990, 129245/1989.
  • the swelling rate of the light-sensitive material of the invention is preferably 1.5 to 4.0 and especially 2.0 to 3.0.
  • the swelling rate is defined as the ratio of thickness of a hydrophilic colloidal layer in a processing solution/thickness of a dry hydrophilic colloidal layer.
  • the light-sensitive material of the invention When the light-sensitive material of the invention is a color photographic light-sensitive material, it takes a multilayer coating structure comprising a plurality of silver halide emulsion layers each having a different light-sensitive wavelength region and a plurality of nonlight-sensitive hydrophilic colloidal layers.
  • the slide hopper method and the curtain coating method each of which can coat plural layers simultaneously.
  • the slide hopper method is particularly preferred for its capability of providing stable coating; techniques to practice this method can be seen, for example, in Japanese Pat. O.P.I. Pub. Nos. 115214/1977, 1350/1979, 108566/1981, 126648/1985, 83066/1990 and 216139/1990.
  • the coating speed for the light-sensitive material of the invention is 100 m/min or more, preferably 150 m/min or more.
  • Silver halide used in the silver halide emulsion layer of the invention may be any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide and silver chloroiodide.
  • Silver halide grains used in the invention are those having a silver chloride content not less than 95 mol%; desirably, the silver bromide content is not more than 5 mol%, and the silver iodide content is not more than 0.5 mol%. More desirable are silver chlorobromide grains of which silver bromide content is 0.1 to 2 mol%. These silver halide grains may be used singly or in combination with other types of grains different in composition; these may also be used together with silver halide grains having a silver chloride content not more than 95 mol%.
  • the ratio of silver halide grains having a silver chloride content not less than 95 mol% to the total silver halide grains contained therein is not less than 60 wt%, preferably not less than 80 wt%.
  • the composition of such silver halide grains may be uniform from the inner portion to the outer portion of the grains, or may be different from the inner portion to the outer portion. In the latter case, the composition may change continuously or discontinuously.
  • the size of the silver halide grains are not particularly limited, but it is preferably 0.2 to 1.6 ⁇ m, especially 0.25 to 1.2 ⁇ m in view of rapid processability, sinsitivity and other photographic properties.
  • the size distribution of the silver halide grains may be polydispersed or monodispersed, but monodipersed grains having a coefficient of variation not more than 0.22, especially not more than 0.15, are preferred.
  • the silver halide grains used in the invention may be prepared by any of the acid method, the neutral method and the ammoniacal method. These grains may be grown in one step, or in two steps of forming seed grains and growing the resulting seed grains.
  • the method for making seed grains and that for growing seed grains may be the same or different.
  • the reaction between a soluble silver salt and a soluble halide may be carried out by any of the single-jet method, the reverse-jet method, the double-jet method and combinations thereof, but the double-jet method is preferred. Further, there may also be used the pAg-controlled double-jet method disclosed in Japanese Pat. O.P.I. Pub. No. 48521/1979 as a modification of the double-jet method.
  • silver halide solvents such as thioether and imidazole may be used.
  • mercapto-group-containing compounds, nitrogen-containing heterocyclic compounds and compounds such as sensitizing dyes may be added in the process of silver halide grain formation or after the formation of silver halide grains.
  • the form of the silver halide grains is not limitative.
  • One preferred example is a cube having ⁇ 100 ⁇ faces as crystal face.
  • Other useful examples include those octahedrons, tetradecahedrons and dodecahedrons which can be synthesized according to the methods described, for example, in U.S. Pat. Nos. 4,183,756, 4,225,666, Japanese Pat. O.P.I. Pub. No. 26589/1980, Japanese Pat. Exam. Pub. No. 42737/1980 and J. Photgr. Sci., Vol. 21, p. 39 (1973).
  • the silver halide grains used in the invention may comprise those having a single form, or those in which grains of different forms are mixed.
  • metal ions may be incorporated in the inner portion or outer portion of silver halide grains while these grains are being formed and/or being grown, by use of cadmium salts, zinc salts, lead salts, thallium salts, iridium salts and complex salts thereof, rhodium salts and complex salts thereof, iron salts and complex salt thereof. Further, there may be provided reduced sensity specks in the inner portion or outer portion of grains by placing these grains in a reducing environment.
  • Emulsions containing silver halide grains may be subjected to desalting after completion of grain formation to remove useless soluble salts, or these soluble salts may be left unremoved.
  • silver halide grains used in the emulsion may be those in which latent images are formed mainly on the surface, or those in which latent images are formed mainly in the inner portion; but, preferred are those in which latent images are formed mainly on the surface.
  • the emulsion is chemically sensitized by the usual method.
  • sulfur sensitization which uses sulfur-containing compounds reactive to silver ions, or active gelatin
  • selenium sensitization which uses selenium compounds
  • reducing sensitization which uses reducing substances
  • noble metal sensitization which uses noble metals such as gold and other noble metals.
  • the emulsion may be spectrally sensitized to a desired wavelength region by use of sensitizing dyes.
  • sensitizing dyes are cyanine dyes, merocyanine dyes, conjugated cyanine dyes, conjugated merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes. Typical examples thereof include the compounds exemplified on pages 76-82 of Japanese Pat. Appl. No. 76278/1990 by denotations of BS-1 to BS-9, GS-1 to GS-5, RS-1 to RS-8, and IRS-1 to IRS-10. And examples of the supersensitizer usable in conjunction with these sensitizing dyes include exemplified compounds SS-1 to SS-9 on pages 84-85 of Japanese Pat. Appl. No. 76278/1990.
  • Dye forming couplers used in the light-sensitive material of the invention are usually selected so as to form, in an emulsion layer, a dye capable of absorbing the light to which the emulsion layer is spectrally sensitive. Therefore, yellow dye forming couplers are used in a blue-sensitive emulsion layer, magenta dye forming couplers in a green-sensitive emulsion layer, and cyan dye forming couplers in a red-sensitive emulsion layer. However, other combinations may be used in the manufacture of the light-sensitive material when a specific requirement arises.
  • acyl acetanilide type couplers are used as yellow dye forming couplers. Amoung them, benzoyl acetanilide type and pivaloyl acetanilide type couplers are advantageous.
  • Other usable yellow couplers include exemplified compounds Y-1 to Y-146 on pages 7-16 of Japanese Pat. O.P.I. Pub. No. 85631/1988, exemplified compounds Y-1 to Y-98 on pages 6-10 of Japanese Pat. O.P.I. Pub. No. 97951/1988, exemplified compounds Y-1 to Y-24 on pages 18-20 of Japanese Pat. O.P.I. Pub. No. 156748/1989, exemplified compounds I-1 to I-50 on pages 4-7 of Japanese Pat. O.P.I. Pub. No. 298943/1990, and exemplified compounds Y-1 to Y-48 on pages 114-120 of Japanese Pat. O.P.I. Pub. No. 215272/1987.
  • conventional couplers of 5-pyrazolone type, pyrazoloazole type and pyrazolobenzimidazole type can be used as magenta dye forming couplers.
  • magenta couplers The following are preferred examples of the magenta couplers:
  • Usable magenta couplers other than the above include exemplified compounds 1 to 223 on pages 18-32 of Japanese Pat. O.P.I. Pub. No. 166339/1987, exemplified compounds M-1 to M-29 on pages 5-6 of Japanese Pat. O.P.I. Pub. No. 100048/1990, exemplified compounds M-1 to M-30 on pages 9-12 of Japanese Pat. O.P.I. Pub. No. 214155/1991, and exemplified compounds M-1 to M-47 on pages 104-114 of Japanese Pat. O.P.I. Pub. No. 215272/1987.
  • naphthol type and phenol type couplers are preferably used as cyan dye forming couplers.
  • the light-sensitive material of the invention is for direct appreciation such as color paper
  • those 2,5-diacylaminophenol type cyan couplers which are disclosed in U.S. Pat. No. 2,895,826, Japanese Pat. O.P.I. Pub. Nos. 112038/1975, 109630/1978, 163537/1980, 96656/1988, and those phenol type cyan couplers having an alkyl group of two or more carbon atoms at the 5-position which are disclosed in U.S. Pat. Nos. 3,772,002 and 4,443,536.
  • useful cyan couplers for having a high color reproducibility, image preservability and recoloring property, include the imidazole type cyan couplers disclosed in Japanese Pat. O.P.I. Pub. Nos. 156748/1989, 174153/1991, 196039/1991; the pyrazoloazole type and pyrozoloazine type cyan couplers disclosed in Japanese Pat. O.P.I. Pub. Nos. 136854/1990, 196039/1991; the hydroxypyridine type and hydroxyazine type cyan couplers disclosed in Japanese Pat. O.P.I. Pub. Nos. 103848/1991, 103849/1991; and the aminopyridine type cyan couplers disclosed in Japanese Pat. O.P.I. Pub. No. 206450.
  • hydrophobic compounds such as the dye forming couplers are incorporated into a desired hydrophilic colloidal layer generally by steps of dissolving them in a high boiling solvent or water-insoluble high-molecular compound each having a boiling point about 150°C and more or, if necessary, jointly using a low boiling solvent and/or a water-soluble organic solvent, and then dispersing the resulting solution in a hydrophlic binder, such as gelatin, with the aid of a surfactant using a dispersing means such as a stirrer, homogenizer, colloid mill, flow jet mixer or supersonic dispersing device.
  • a dispersing means such as a stirrer, homogenizer, colloid mill, flow jet mixer or supersonic dispersing device.
  • the high boiling solvent used in the invention includes esters such as phthalates and phosphates, organic acid amides, ketones and hydrocarbon compounds. Examples thereof include exemplified compounds A-1 to A-120 on pages 4-7, exemplified compounds II-1 to II-29 on pages 8-9 and exemplified compounds H-1 to H-22 on pages 14-15 of Japanese Pat. O.P.I. Pub. No. 196048/1989; exemplified compounds S-1 to S-69 on pages 3-7 of Japanese Pat. O.P.I. Pub. No. 209446/1989; and exemplified compounds I-1 to I-95 on pages 10-12 of Japanese Pat. O.P.I. Pub. No. 253943/1988.
  • the water-insoluble high-molecular compound used for dispersing couplers includes (1) vinylpolymers and copolymers (2) condensation polymers between a polyvalent alcohol and a polybasic acid, (3) polyesters obtained by ring-opening polymerization, (4) other polymers including polycarbonates, polyurethanes and polyamides.
  • the number average molecular weight of these polymers is not particularly limited, but it is preferably not more than 200,000, especially 5,000 to 100,000.
  • suitable polymers include exemplified compounds P-1 to P-200 on pages 10-15 of Japanese Pat. O.P.I. Pub. No. 537/1989.
  • the light-sensitive material of the invention may optionally use antifoggants, image stabilizers, hardeners, plasticizers, anti-irradiation dyes, polymer latices, UV absorbents, formaline scavengers, development accelerators, development retarders, optical whitening agents, matting agents, lubricants, antistatic agents and surfactants. These compounds are described, for example, in Japanese Pat. O.P.I. Pub. Nos. 215272/1987, 46436/1988.
  • the light-sensitive material of the invention forms images when subjected to color development according to the usual method.
  • a multilayer color light-sensitive material, sample 101 was prepared by forming the component layers shown in Tables 1 and 2 simultaneously, using a slide hopper, on the titanium-oxide-bearing side of a paper support laminated with polyethylene on one side and with titanium-oxide-containing polyethylene on the other side. Coating solutions used were prepared as follows:
  • the dispersion was mixed with a bule-sensitive silver halide emulsion containing 10 g of silver prepared under the following conditions, followed by addition of anti-irradiation dye (AI-3) to give a coating solution for the 1st layer.
  • AI-3 anti-irradiation dye
  • hardener (HH-1) was added to the 2nd and 4th layers, and hardener (HH-2) in the 7th layer.
  • surfactants (SU-1) and (SU-3) were used to adjust the surface tension.
  • the pH of each coating solution was adjusted to 5.9 with a dilute sulfuric acid or a dilute aqueous potassium hydroxide.
  • a silver chlorobromide emulsion comprising grains having an average size of 0.7 ⁇ m and a silver bromide content of 90 mol% was chemically sensitized at 57°C with sodium thiosulfate and, then, sensitizing dye (D-1) and stabilizer (Z-1) were added.
  • a silver chlorobromide emulsion comprising grains having an average size of 0.5 ⁇ m and a silver bromide content of 70 mol% was chemically sensitized at 59°C with sodium thiosulfate and, then, sensitizing dye (D-2) and stabilizer (Z-1) were added.
  • a silver chlorobromide emulsion comprising grains having an average size of 0.4 ⁇ m and a silver bromide content of 60 mol% was sensitized at 60°C with sodium thiosulfate, sensitizing dye (D-3) and a phenol resin and, then, stabilizer (Z-1) was added.
  • Stabilizer (Z-1) 4-Hydroxy-6-methyl-1,3,3a,7-tetrazaindene
  • Samples 102 to 114 were prepared in the same manner as sample 101, except that the gelatin used in sample 101 was changed as follows: Sample No. 1st layer 2nd layer 3rd layer 4th layer 5th layer 6th layer 7th layer 101 A A A A A A A A 102 A A A A A A B 103 A A A A A A A C 104 A A A A A A A D 105 A A A A A A E 106 A A A A A A A A F 107 A A A A A A A A A A A A G 108 A A A A A A A A A A H 109 A A A A A A A A A A A A I 110 A A A A A A A A A A A A G G 112 A G A G A G G 113 G G G G G G G G 114 E E E E E E E E E E E
  • gelatins used were as follows: isoelectric points are given in parentheses
  • Gelatins A to E and F to H were subjected to cation and anion exchange treatment, and calcium contents of gelatins A to E and F to J were not more than 100 ppm, respectively.
  • Samples 113 and 114 gelatin used for emulsion preparation were also replaced by gelatin G and E, respectively.
  • each sample was once cooled to set the gelatin contained therein and then dried at 50°C.
  • Each sample was further subjected to hardening for 5 days at 35°C and 60% RH.
  • each unexposed sample was taken out and immediately transferred into a dark place of 23°C and 80% RH, allowed to stand for 60 seconds and then touched with the finger on the coated side. After being exposed to white light and processed under the following conditions, the sample was visually examined upon the desensitization appearing in the shape of finger prints.
  • compositions of the processing solutions were as follows: Color Developer Benzylalcohol 15 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 0.7 g Sodium chloride 0.2 g Potassium carbonate 30.0 g Hydroxylamine sulfate 3.0 g Polyphosphoric acid (TPPS) 2.5 g 3-Methyl-4-amino-N-ethyl-N-( ⁇ -methanesulfonamidoethyl)aniline sulfate 5.5 g Optical whitening agent (4,4'-diaminostilbene -disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Water is added to make 1 liter, and the pH is adjusted to 10.20.
  • samples 106 to 113 using the gelatin of the invention are high in gloss, less in unevenness in density, and excellent in finger printing resistance.
  • samples 106, 107 and 111 to 113 which use gelatin F or G of the invention having an isoelectric point within the desirable limits of 5.2 to 5.5, clearly demonstrate the effect of the invention. It can also be found that use of the gelatin of the invention in the surface protective layer is useful in bringing out the effect of the invention sufficiently.
  • a multilayer color light-sensitive material, sample 201, was prepared, as in Example 1 by forming the component layers shown in Tables 4 and 5 on the support used in Example 1.
  • the coating solutions used were prepared in the following procedure.
  • a coating solution for the 1st layer was prepared by steps of dissolving 26.7 g of yellow coupler (YC-8), 10.0 g of dye image stabilizer (ST-1), 6.67 g of dye image stabilizer (ST-2), 0.67 g of antistain agent (HQ-1) and 6.67 g of high boiling organic solvent (DNP) in 60 ml of ethyl acetate, dispersing the resulting solution in 220 ml of 10% aqueous gelatin solution containing 7 ml of 20% surfactant (SU-2) with a supersonic homogenizer, mixing the yellow coupler dispersion so prepared with the blue-sensitive silver halide emulsion containing 8.67 g of silver described later, and adding anti-irradiation dye (AI-3) thereto.
  • YC-8 yellow coupler
  • ST-1 dye image stabilizer
  • ST-2 dye image stabilizer
  • DNP high boiling organic solvent
  • Coating solutions for the 2nd to 7th layers were also prepared in similar manners.
  • hardener (HH-1) was added in the 2nd and 4th layers, and hardener (HH-2) in the 7th layer.
  • surfactants (SU-1) and (SU-3) were used to adjust the surface tension.
  • the pH of each coating solution was adjusted to 5.9 with a diluted sulfuric acid or a diluted aqueous potassium hydroxide.
  • the following solutions A and B were simultaneously added over a period of 30 minutes to 1000 ml of 2% aqueous gelatin solution kept at 40°C, while controlling the pAg at 7.3 and the pH at 5.5. Then, the following solutions C and D were simultaneously added over a period of 180 minutes, with the reaction liquor controlled at pAg 7.3 and pH 5.5.
  • the control of the pAg was carried out according to the method disclosed in Japanese Pat. O.P.I. Pub. No. 45437/1984, and that of the pH was made using a diluted sulfuric acid or an aqueous solution of potassium hydroxide.
  • Solution A Sodium chloride 3.42 g Potassium bromide 0.03 g Water is added to make 200 ml Solution B Silver nitrate 10 g Water is added to make 200 ml Solution C Sodium chloride 102.7 g Potassium bromide 1.0 g Water is added to make 600 ml Solution D Silver nitrate 300 g Water is added to make 600 ml
  • Emulsion EMP-1 prepared as above comprised monodispersed cubic grains having an average size of 0.85 ⁇ m, a coefficient of variation of 0.07 and a silver chloride content of 99.5 mol%.
  • Blue-sensitive silver halide emulsion Em-B was obtained by subjecting emulsion EMP-1 to chemical ripening at 50°C for 90 minutes using the following compounds.
  • Sodium thiosulfate 0.8 mg/mol AgX Chloroauric acid 0.5 mg/mol AgX Stabilizer (STAB-1) 6 ⁇ 10 -4 mol/mol AgX Sensitizing dye (D-1) 4 ⁇ 10 -4 mol/mol AgX Sensitizing dye (D-4) 1 ⁇ 10 -4 mol/mol AgX
  • Emulsion EMP-2 comprising monodispersed cubic grains having an average size of 0.43 ⁇ m, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was prepared in the same manner as emulsion EMP-1, except that the addition time of solutions A and B as well as that of solutions C and D were changed.
  • Green-sensitive silver halide emulsion Em-G was obtained by subjecting emulsion EMP-2 to chemical ripening at 55°C for 120 minutes using the following compounds.
  • Sodium thiosulfate 1.5 mg/mol AgX
  • Chloroauric acid 1.0 mg/mol AgX Stabilizer (STAB-1) 6 ⁇ 10 -4 mol/mol AgX Sensitizing dye (D-2) 4 ⁇ 10 -4 mol/mol AgX
  • Emulsion EMP-3 comprising monodispersed cubic grains having an average size of 0.50 ⁇ m, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was prepared in the same manner as emulsion EMP-1, except that the addition time of solutions A and B as well as that of solutions C and D were changed.
  • Green-sensitive silver halide emulsion Em-R was prepared by subjecting emulsion EMP-3 to chemical ripening at 60°C for 90 minutes using the following compounds.
  • Sodium thiosulfate 1.8 mg/mol AgX Chloroauric acid 2.0 mg/mol AgX Stabilizer (STAB-1) 6 ⁇ 10 -4 mol/mol AgX Sensitizing dye (D-3) 1 ⁇ 10 -4 mol/mol AgX
  • Samples 202 to 214 were prepared in the same manner as sample 201, except that the same gelatins as those used in samples 102 to 114 were employed in place of the gelatin used in sample 201.
  • each sample was once cooled to set gelatin contained therein, dried at 50°C and then subjected to hardening for 5 days at 35°C and 60% RH.
  • Process Processing Temp Processing Time Color developing 35.0 ⁇ 0.3°C 45 sec Bleach-fixing 35.0 ⁇ 0.5°C 45 sec Stabilizing 30 to 34°C 90 sec Drying 60 to 80°C 60 sec
  • the replenishing rate of a processing solution was 80 ml per square meter of light-sensitive material.
  • composition of each processing solution was as follows: Color Developer Tank Sol. Replenisher Water 800 ml 800 ml Triethanolamine 10 g 18 g N,N-Diethylhydroxylamine 5 g 9 g Potassium chloride 2.4 g 1-Hydroxyethylidene-1,1-diphsphoinic acid 1.0 g 1.8 g 3-Methyl-4-amino-N-Ethyl-N-( ⁇ -methanesulfonamidoethyl) aniline sulfate 5.4 g 8.2 g Optical whitening agent (4,4'-diamino-stilbenesulfonic acid derivative) 1.0 g 1.8 g Potassium carbonate 27 g 27 g Water is added to make 1 liter, and the pH of the tank solution is adjusted to 10.10 and that of the replenisher to 10.60.
  • Bleach-fixer (thank solution and replenisher are the same) Ammonium ferric ethylenediaminetetracetate dihydrate 60 g Ethylediaminetetracetic acid 3 g Ammonium thiosulfate (70% solution) 100 ml Ammonium sulfite (40% solution) 27.5 ml Water is added to make 1 liter, and the pH is adjusted to 5.7 with potassium carbonate or glacial acetic acid.
  • Stabilizer (tank solution and replenisher are the same)
  • F-1 1.0 g Ethylene glycol 1.0 g 1-Hydroxyethylidene-1,1-diphsphonic acid 2.0 g Ethylenediaminetetracetic acid 1.0 g Aqueous ammonia (20%) 3.0 g
  • Optical whitening agent (4,4'-diaminostilbene-sulfonic acid derivative) 1.5 g Water is added to make 1 liter, and the pH is adjusted to 7.0 with sulfuric acid or potassiun hydroxide.

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  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Claims (7)

  1. Matériau photographique photosensible à base d'halogénure d'argent, comprenant un support portant une ou plusieurs couches d'un composant photographique comprenant une couche d'émulsion à base d'halogénure d'argent, dans lequel la couche d'émulsion à base d'halogénure d'argent comprend des grains d'halogénure d'argent ayant une teneur en chlorure d'argent qui n'est pas inférieure à 95 % en moles, et dans lequel au moins l'une des couches de composant photographique contient une gélatine d'os bovin obtenue par traitement alcalin, sans modification chimique, ayant un point isoélectrique qui n'est pas inférieur à 5,2, et le total de la quantité de colloïde hydrophile, y compris la gélatine appliquée sur le support, n'est pas supérieur à 8 g/m2.
  2. Matériau photosensible selon la revendication 1, dans lequel la couche de composant photographique contenant la gélatine d'os bovin obtenue par traitement alcalin, ayant un point isoélectrique qui n'est pas inférieur à 5,2, est une couche dont la position est la plus éloignée du support parmi les couches de composant photographique.
  3. Matériau photosensible selon la revendication 1 ou 2, dans lequel la gélatine d'os bovin obtenue par traitement alcalin présente un point isoélectrique de 5,2 à 6,0.
  4. Matériau photosensible selon la revendication 3, dans lequel la gélatine d'os bovin obtenue par traitement alcalin présente un point isoélectrique de 5,2 à 5,5.
  5. Matériau photosensible selon l'une quelconque des revendications précédentes, dans lequel la gélatine ayant un point isoélectrique qui n'est pas inférieur à 5,2 est contenue dans la couche de composant photographique dans un rapport qui n'est pas inférieur à 50 % en poids de la gélatine totale contenue dans la couche de composant photographique.
  6. Matériau photosensible selon l'une quelconque des revendications précédentes, dans lequel le point isoélectrique d'un mélange de gélatine dans la couche de composant photographique n'est pas inférieur à 5,2.
  7. Matériau photosensible selon l'une quelconque des revendications précédentes, dans lequel la différence entre le pH d'une solution de revêtement destinée à former la couche de composant photographique contenant la gélatine, ayant un point isoélectrique qui n'est pas inférieur à 5,2, et le point isoélectrique de la gélatine, n'est pas inférieure à 0,3.
EP93300103A 1992-01-14 1993-01-07 Matériau photographique à l'halogénure d'argent sensible à la lumière Expired - Lifetime EP0551994B1 (fr)

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JP4004945A JP2952535B2 (ja) 1992-01-14 1992-01-14 ハロゲン化銀写真感光材料
JP4945/92 1992-01-14

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Publication number Priority date Publication date Assignee Title
US5378598A (en) * 1992-12-21 1995-01-03 Eastman Kodak Company Use of acid processed ossein gelatin and chain-extened acid processed ossein gelatin as peptizers in the preparation of photographic emulsions
ITSV20010044A1 (it) * 2001-11-20 2003-05-20 Ferrania Spa Foglio di registrazione a getto di inchiostro con gelatina modificata

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JPS5623140B2 (fr) * 1974-04-17 1981-05-29
DE3712074A1 (de) * 1987-04-09 1988-10-20 Agfa Gevaert Ag Fotografisches material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Ullman's Encyclopedia of Industrial chemistry", Fifth completely revised edition, Volume A12, pages 307-317 (1989) *

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DE69317582D1 (de) 1998-04-30
EP0551994A1 (fr) 1993-07-21
JPH05188513A (ja) 1993-07-30

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