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
  • G03C1/015—Apparatus or processes for the preparation of emulsions
• • 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
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes

Definitions

• the present invention relates to silver halide photographic materials, and more particularly to silver halide photographic materials excellent in rapid processability, low in fogging, and high in sensitivity and contrast.
• photographic materials Currently commercially-available silver halide photographic materials (hereinafter referred to as photographic materials), and methods of forming images using them are various, and examples of their use can be found in a variety of fields.
• the composition of the silver halide emulsions used in these photographic materials consists of silver bromoiodide, silver bromochloride, or silver chlorobromide, these being mainly composed of silver bromide to provide high contrast.
• Japanese Patent Application (OPI) Nos. 95736/1983 and 108533/1983 disclose techniques directed to high-silver-chloride emulsions that have a layered-type structure.
• Japanese Patent Application (OPI) No. 95736/1983 although an emulsion that can be subjected to rapid processing and is high in sensitivity, can be obtained by allowing a layer mainly composed of silver bromide to be present inside the grains, it was found that in actual practice when pressure is applied to the emulsion grains, the desensitization becomes too great for the emulsion to be of practical use. Further, according to Japanese Patent Application (OPI) No.
• photographic materials having such a photographic emulsion layer change highly in sensitivity due to a change in humidity when exposed, and in many cases the color reproduction of a color image is remarkably deteriorated.
• an object of the present invention is to provide a silver halide photographic material that is excellent in rapid processability, low in fogging, and high in sensitivity and contrast.
• Another object of the present invention is to ' provide a silver halide photographic material excellent in sharpness and low in sensitivity due to a change in humidity when exposed.
• a further object of the present invention is to provide a silver halide photographic material especially suitable for a color photographic paper that is excellent in rapid processability and sharpness, low in fogging, and low in the change in sensitivity due to a change in humidity when exposed, and high in sensitivity and contrast.
• a silver halide photographic material having on a base at least one photosensitive emulsion layer containing a silver halide photographic emulsion, characterized in that the said silver halide photographic emulsion comprises silver chlorobromide or silver chloride substantially free from silver iodide, and the step of the preparation of the silver halide photographic emulsion comprising forming silver halide grains in the presence of a hydrophilic colloid, physical ripening, desalting, and chemical ripening, and in which a photographic spectral-sensitizing dye is added after the addition of at least 85 wt.% of a soluble silver salt solution, required for formation of silver halide grains, but before the desalting step.
• the above-mentioned silver halide photographic material further characterized in that the photographic material contains a layer on the base at least one of compounds represented by the formula (I), (II), or (III):
• Z' and Z 2 which may be the same or different, each represent a group of nonmetal atoms required to form a heterocyclic ring
• L represents a methine group, in which L and L may connect each other to form a ring
• n is 0, 1, or 2.
• the heterocyclic rings formed by a group of nonmetal atoms represented by Z 1 and Z 2 are preferably 5-or 6-membered rings, which may be single rings or condensed rings, and examples of the heterocyclic rings include a 5-pyrazolone ring, barbituric acid, isooxazolone, thiobarbituric acid, rhodanine, imidazopyridine, pyrazolopyridine. and pyrrolidone. which may have a substituent.
• the heterocyclic ring formed by Z' or Z 2 is barbituric acid or a 5-pyrazolone ring that has at least one sulfonic acid group or carboxylic acid group.
• Oxonol dyes having a pyrazolone nucleus or a barbituric acid nucleus are described, for example, in British Patent Nos. 506.385, 1.177.429, 1,311,884, 1,338,799, 1,385,371, 1,467,214, 1,433,102, and 1,553,516, Japanese Patent Application (OPI) Nos. 85130/1973. 114420/1984, 161233/1980, and 111640/1984, and U.S. Patent Nos. 3,247,127, 3,469.985, and 4,078,933.
• the methine group represented by L may have a substituent (e.g., an alkyl group preferably having 1 to 4 carbon atoms such as methyl or ethyl, an aryl group preferably having 6 to 10 carbon atoms such as phenyl, and a halogen atom such as chlorine), and the Ls may join together to form a ring (e.g. 4,4-dimethyl-1-cyclohexene).
• a substituent e.g., an alkyl group preferably having 1 to 4 carbon atoms such as methyl or ethyl, an aryl group preferably having 6 to 10 carbon atoms such as phenyl, and a halogen atom such as chlorine
• spectral sensitizing dyes are added to an emulsion that has been chemically sensitized before the emulsion is applied.
• the effect of the present invention cannot be obtained that way.
• U.S. Patent No. 4,425,426 a method is disclosed wherein a spectral sensitizing dye is added immediately before the start of chemical sensitization or during chemical sensitization.
• U.S. Patent Nos. 2,735,766, 3,628,960. 4,183.756, and 4,225,666 disclose methods wherein spectral sensitizing dyes are added to emulsions before the completion of formation of silver halide grains.
• the effect of the present invention that by adding a spectral sensitizing dye to an emulsion after the addition of at least 85 wt.% of a soluble silver salt solution but before the desalting step, a silver chlorobromide emulsion having a high silver chloride content can be provided with high sensitivity and that fogging can be remarkably decreased, was a new finding that could not be entirely expected from prior known publications.
• a spectral sensitizing dye in the preparation of silver halide emulsion grains, it is required to add a spectral sensitizing dye after the addition of at least 85 wt.% of a soluble silver salt solution, but before the desalting step. If the spectral sensitizing dye is added earlier than that, it causes problems such as, for example, that the shape of the silver halide grains becomes irregular and the grain size distribution becomes wide. Further, if the spectral sensitizing dye is added after the desalting step, it is not adequate because the effect of the present invention for providing high sensitivity cannot be exhibited.
• the spectral sensitizing dye be added within 30 min. after the addition of the soluble silver salt solution, but before the desalting step.
• Spectral sensitizing dyes used in the present invention include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, halopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Of these, particularly preferable are cyanine dyes, merocyanine dyes, and composite cyanine dyes.
• Examples of the preferred cyanine dyes include those represented by the above-mentioned (A) and (B) in formula (III).
• As the preferred merocyanine dyes may be mentioned dyes represented by the following formula (C):
• sensitizing dyes employed in the present invention include the dyes represented by formula (IV), (V), (VI), (VII), (VIII), or (IX).
• Formula (IV) is as follows: wherein Z 11 represents an atomic group necessary to form a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a dihydronaphthothiazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a dihydronaphthoselenazole nucleus; Z 1 represents an atomic group necessary to form a benzothiazole nucleus, a naphthothiazole nucleus.
• a dihydronaphthothiazole nucleus a benzoselenazole nucleus, a naphthoselenazole nucleus or a dihydronaphthoselenazole nucleus: with the proviso that the nitrogen-containing heterocyclic nuclei represented by Z 11 and Z 12 may optionally have one or more substituents.
• Preferred examples of the substituents on Z 1 and Zt 2 include a lower alkyl group (more preferably an alkyl group having 6 or less carbon atoms), a lower alkoxy group (more preferably an alkoxy group having 6 or less carbon atoms), a chlorine atom, a lower alkoxycarbonyl group (more preferably an alkoxycarbonyl group having 5 or less carbon atoms), an optionally substituted phenyl group (e.g., a phenyl group, a tolyl group, an anisyl group, a chlorophenyl group, etc.) or a hydroxyl group.
• a phenyl group e.g., a phenyl group, a tolyl group, an anisyl group, a chlorophenyl group, etc.
• Typical examples of the nitrogen-containing heterocyclic groups represented by Z 11 and Z 12 are, for example, a 5-hydroxybenzoxazole group, a 5-methoxybenzoxazole group, a ethoxybenzoxazole group, a 5-phenylbenzoxazole group, a 5,6-dimethylbenzoxazole group, a 5-methyl-6-methoxybenzoxazole group, a 6- ethoxy-5-hydrobenzoxazole group, a naphtho[1,2-d] oxazole group, a naphtho[2.3-d]oxazole group, a naphtho[2,1-d]oxazole group, a 5-methyl benzothiazole group, a 5-methoxybenzothiazole group, a 5-ethylbenzothiazole group, a 5-p-tolylbenzothiazole group, a 6-methyl benzothiazole group, a 6-ethylben- zothi
• R 11 and R 12 in formula (IV) may be the same or different, and each represents an alkyl group or alkenyl group which has 10 or less carbon atoms and which can optionally be substituted.
• Suitable substituents on the alkyl or alkenyl group include, for example, a sulfo group and an alkoxy group having 6 or less carbon atoms, a halogen atom, a hydroxyl group, an optionally substituted aryl group having 8 or less carbon atoms (e.g., a phenyl group, a furyl group, a thienyl group, a tolyl group, a p-butylphenyl group, a xylyl group, an anisyl group, a sulfophenyl group, a hydroxyphenyl group, a carboxyphenyl group, a chlorophenyl group, etc.), a phenoxy group which has 8 or less carbon atoms and which may optionally
• R 13 and R 15 in formula (IV) each represents a hydrogen atom.
• R 13 may be linked with R 15 to form a 5-or 6-membered ring.
• R represents a hydrogen atom.
• R 14 represents an alkyl group having 4 or less carbon atoms or a phenylalkyl group having 10 or less carbon atoms.
• R 14 represents a hydrogen atom
• R 13 is linked with R 15 to form a 5-or 6-membered ring; or R 13 and R 15 both are hydrogen atoms, and R 14 represents an alkyl group having 4 or less carbon atoms or a benzyl group.
• R 16 represents a hydrogen atom or may be linked with R 12 to form a 5-or 6-membered carbon ring.
• heterocyclic nuclei are napthoxazoles, benzothiazoles having at least one electron-donating group with a negative Hammett's op value, dihydronaphthothiazoles, naphthothiazoles and benzoselenazoles.
• X 11 ⁇ in formula (IV) represents an acid anion residue; and m 11 represents 0 or 1, and when the compound of formula (IV) is an internal salt, m 1 is 0.
• the most preferred of the nitrogen-containing heterocyclic nuclei which contain Z 21 are a naphtho[1,2-d] thiazole nucleus, a naphtho[2,1-d]thiazole nucleus, a naphtho[1,2-d]selsnazole nucleus, a naphtho[2.1-d]-selenazole nucleus or benzoselenazole nuclei having at least one electron-donating group with a negative Hammett's ap vaiue.
• X 21 e represents an acid anion residue
• m 21 represents 0 or 1 with the proviso that when the compound of formula (V) forms an internal salt, m 21 is 0.
• Formula (VI) is as follows: wherein Z 31 has the same definition as Z 1 in formula (IV) or Z 31 represents an atomic group capable of forming a naphthoxaiole nucleus, and may optionally have one or more substituents selected from substituents referred to above for the nitrogen-containing heterocyclic nuclei represented by Z 11 or Z 12 in formula(IV);
• Z 32 represents a sulfur atom, a selenium atom or
• the present invention thus provides a silver halide color photographic material which contains a high silver chloride emulsion and which has been spectrally sensitized by a spectral sensitizing dye represented by the above-mentioned general formula(IV), (V) or (VI) , wherein the photographic material is able to be subjected to color-development with a color developer which substantially excludes benzyl alcohol and which contains bromide ion in an amount of about 0.002 mol/liter or less for a short period of time of about 2 minutes and 30 seconds or less and then is successively processed with a blix solution having pH of about 6.5 or less, more preferably a pH of 6.0 or less, for a period of time of about 75 seconds or less, even possibly for a shorter period of time of 60 seconds or less, resulting in the formation of color images.
• a blix solution having pH of about 6.5 or less, more preferably a pH of 6.0 or less, for a period of time of about 75 seconds or less, even
• Z 1 represents an oxygen atom, a sulfur atom or a selenium atom.
• V 11 and V 13 each represents a hydrogen atom
• V 12 represents a phenyl group or a phenyl group substituted by an alkyl group or an alkoxy group containing up to 3 carbon atoms or a chlorine atom (particularly preferably a phenyl group), or V, , and V 12 , or V 12 and V 13 , may be linked to each other to form a fused benzene ring.
• V 11 and V 13 each represents a hydrogen atom
• V 12 represents a phenyl group.
• V 11 represents a sulfur atom or a selenium atom.
• V 11 represents an alkyl group or an alkoxy group containing up to 4 carbon atoms or a hydrogen atom
• V 12 represents an alkyl group containing up to 5 carbon atoms, an alkoxy group containing up to 4 carbon atoms, a chlorine atom, a hydrogen atom, an optionally substituted phenyl group (e.g., a tolyl group, an anisyl group, a phenyl group, etc.) or a hydroxy group
• V 13 represents a hydrogen atom, or V 11 and V 12 , or V 12 and V 13 , may be linked to each other to form a fused benzene ring.
• V 11 and V 13 each represents a hydrogen atom and V, 2 represents an alkoxy group containing up to 4 carbon atoms, a phenyl group or a chlorine atom; V " represents an alkoxy group or an alkyl group containing up to 4 carbon atoms and V 12 represents a hydroxy group or an alkyl group containing up to 4 carbon atoms; or V 12 and V 13 are linked to each other to form a fused ring.
• V 14 , V 15 , and V 16 are respectively. the same as defined for V 11 , V 12 , and V 13 in connection with the case where Z 11 represents a selenium atom.
• V 14 represents a hydrogen atom, an alkoxy group containing up to 4 carbon atoms or an alkyl group containing up to 5 carbon atoms
• V 15 represents an alkoxy group containing up to 4 carbon atoms, an optionally substituted phenyl group (preferably a phenyl group; exemplified by a tolyl group and an anisyl group), an alkyl group containing up to 4 carbon atoms, a chlorine atom or a hydroxy group
• V 16 represents a hydrogen atom, or V 14 and V 15 , or V 15 and V 16 , may be linked to each other to form a fused benzene ring.
• V 14 and V 16 each represents a hydrogen atom
• V 15 represents an alkoxy group containing up to 4 carbon atoms, a chlorine atom or a phenyl group; or V 15 and V, 16 are linked to each other to form a fused benzene fing.
• Z 11 and Z 12 both represent a sulfur atom
• V 14 and V 16 each represents a hydrogen atom and V 15 represents an optionally substituted phenyl group (e.g., a phenyl group or a tolyl group), or V 14 represents a hydrogen atom and V 15 and V 16 are linked to each other to form a fused benzene ring.
• V 14 and V 16 each represents a hydrogen atom
• V 15 represents a chlorine atom, an optionally substituted phenyl group or an alkoxy group containing up to 4 carbon atoms, or V, 5 and V 16 may be linked to each other to form a fused benzene ring; more preferably, V 14 and V 16 each represents a hydrogen atom and V 15 represents a phenyl group, or V 15 and V 16 are linked to each other to form a fused benzene ring.
• X 11 represents a counter ion which is required to neutralize a charge on a cyanine dye of formula (VII) or (VIII).
• these ions are a halogen ion such as CI- , Br - , I - , etc.; ; Rhodan ion, etc., as an anion; and an alkali metal ion such as Li + Na + , K + , etc.; an alkali earth metal ion such as Ca 2+ , etc, as a cation.
• n 0 or 1 and, in the case of forming inner salt, m 11 represents 1.
• Z 21 represents an oxygen atom, a sulfur atom, a selenium atom. or and Z 22 represents an oxygen atom or
• Z 31 represents atoms forming a heterocyclic nucleus of thiazoline, thiazole, benzothiazole, naphthothiazole, selenazoline, selenazole, benzoselenazole, naphthoselenazole, benzimidazole, naphthoimidazole, oxazole. benzoxazole, naphthoxazole, or pyridine, with the heterocyclic nucleus being optionally substituted.
• Z 31 represents atoms forming a benzimid azole nucleus or a naphthoimidazole nucleus.
• substituents for.the nitrogen atom at the 1-position other than R 31 include those illustrated for R 26 or R 27 of general formula (VI) described above.
• Substituents in the fused benzene ring of benzimidazole include, for example, a chlorine atom, a cyano group, an alkoxycarbonyl group containing up to 5 carbon atoms, an alkylsulfonyl group containing up to 4 carbon atoms or a trifluoromethyl group.
• the benzimidazole nucleus is substituted by a chlorine atom at the 5-position and by a cyano group, a chlorine atom or a trifluoromethyl group at the 6-position.
• Substituents for heterocyclic nuclei other than the benzimidazole nucleus, selenazoline nucleus, and thiazoline nucleus include an optionally substituted alkyl group containing a total of up to 8 carbon atoms (examples of the substituents being a hydroxy group, a chlorine atom, a fluorine atom, an alkoxy group, a carboxy group, an alkoxycarbonyl group, a phenyl group or a substituted phenyl group), a hydroxy group, an alkoxycarbonyl group containing up to 5 carbon atoms, a halogen atom, a carboxy group, a furyl group, a thienyl group, a pyridyi group, a phenyl group or a substituted phenyl group (e.g., a tolyl group, an anisyl group, a chlorophenyl group, etc.).
• substituents being
• Substituents for the selenazoline nucleus or thiazoline nucleus include an alkyl group containing up to 6 carbon atoms, a hydroxyalkyl or alkoxycarbonylalkyl group containing up to 5 carbon atoms, etc.
• the amount of these spectral sensitizing dyes to be added may vary within a wide range depending on the particular case, preferably the amount is in the range of 1.0 x 10 -6 to 1.0 ⁇ 10 -2 per mol of a silver halide, more preferably in the range of 1.0 ⁇ 10 -5 to 1.0 x 1 0- 3 .
• the dye used is dissolved in a suitable organic solvent (e.g., methanol, ethanol, and ethyl acetate) to form a solution having a suitable concentration, and the solution may be added to the emulsion.
• a suitable organic solvent e.g., methanol, ethanol, and ethyl acetate
• the dye used can be added as an aqueous dispersion formed by, for example. dispersing the dye into an aqueous solution using, for example, a surface-active agent, or by dispersing the dye into an aqueous gelatin solution having a suitable concentration.
• spectral sensitizing dyes that can be used in the present invention are shown below, but the invention is not limited to them:
• known spectral sensitizing dyes can be used, and these compounds can be easily synthesized by referring to methods described by F.M. Hamer in "Heterocyclic Compounds-Cyanine Dyes and Related Compounds", Chapter 5, pages 116 to 147 (John Wiley and Sons, 1964), by D.M. Sturmer in "Heterocyclic Compounds - Special Topics in Heterocyclic Chemistry", Chapter 8. Section 5. pages 482 to 515 (John Wiley and Sons, 1977), in Japanese Patent Publication Nos. 13823/1968, 16589/1969. 9966/1973, and 4936/1968, and in Japanese Patent Application (OPI) No. 82416/1977.
• the silver halide emulsion that can be applied to the present invention comprises silver chloride or silver chlorobromide substantially free from silver iodide.
• substantially free from silver iodide means that the content of silver iodide is 3 mol% or less, preferably 1 mol% or less, more preferably nil.
• Preferable halogen compositions are those having a silver chloride content of 30 mol% or over, more preferably 80 mol% or over, and most preferably 95 mol% or over.
• the silver halide grains contained in the emulsion may have the so-called layered-type structure that is made up of layers whose inner halogen composition is different from the surface halogen composition, or a multi-layer structure wherein portions whose halogen compositions are different are joined, or they may be ones wherein the halogen composition is present uniformly throughout the grains. These silver halide grains may be present as a mixture.
• the average size of the silver halide grains for use in the present invention is preferably 2.0 am or less and larger than 0.1 am, more preferably 1.0 am or less and larger than 0.15 u.m.
• the distribution of grain size is not restricted, a silver halide emulsion of excellent monodispersability is preferable. That is, the value obtained by dividing the standard deviation of statistics calculated from the curve of the size distribution by the average grain size (the deviation coefficient) is preferably 0.22 or less, more preferably 0.15 or less.
• two or more monodisperse silver halide emulsions may be mixed in a single layer, or they may be coated as different layers having essentially the same color sensitivity.
• the silver halide photographic emulsion for use in this invention may be a mixed emulsion each having the grain size distribution of 0.15 or less in terms of the deviation coefficient.
• silver halide grains for use in this invention may have any shape, grains which have a regular crystal structure, such as cubic, hexahedral, rohmbic dodecahedral, or tetradecahedral, are preferable. Silver grains may be used which form a latent image primary on the grain surface, or which form a latent image primary in the interior of the grains.
• the photographic emulsion for use in this invention can be prepared by processes described in P. Glafkides, "Chimie et Physique Photographique” (Paul Montel, 1967), G.F. Duffin. "Photographic Emulsion Chemistry” (The Focal Press, 1966), V.L. Zelikman et al., “Making and Coating Photographic Emulsions” (The Focal Press, 1964), etc. Any one of an acidic process, a neutral process, and an ammoniacal process can be used. As a means of reacting a soluble silver salt with a soluble halide salt, any of the single jet method, double jet method, or a combination thereof may be employed.
• a process of forming grains in the presence of excess silver ion can be employed as well.
• the "controlled double jet” process can be employed, wherein the pAg in the liquid phase of the silver halide formation is kept constant. This process provides a silver halide emulsion containing regular silver halide grains having an approximately monodisperse particle size.
• cadmium salts zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc., may also be present.
• Precipitation, physical ripening, and chemical ripening can be carried out in the presence of conventional silver halide solvents (e.g., ammonia, potassium thiocyanate, thioether, and thiones described in U.S. Patent No. 3,271,157, Japanese Patent Application (OPI) Nos. 12360/1976, 82408/1978, 144319/1978. 100717/1979, and 155828/1979). Removing of the soluble salts from the emulsions after physical ripening can be achieved by noodle washing, flocculation precipitation, ultrafiltration, etc.
• conventional silver halide solvents e.g., ammonia, potassium thiocyanate, thioether, and thiones described in U.S. Patent No. 3,271,157, Japanese Patent Application (OPI) Nos. 12360/1976, 82408/1978, 144319/1978. 100717/1979, and 155828/1979.
• sulfur sensitization using active gelatin or sulfur-containing compounds capable of reacting with silver e.g., thiosulfates. thioureas. mercapto compounds, rhodanines, etc.
• reduction sensitization using a reductive substance e.g., stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, etc.
• noble metal sensitization using noble metal compounds e.g., complex salts of the Group VIII metals such as Pt. Ir, Pd, Rh, Fe, etc., as well as gold complex salts
• noble metal compounds e.g., complex salts of the Group VIII metals such as Pt. Ir, Pd, Rh, Fe, etc., as well as gold complex salts
• the photographic materials comprise a substrate having thereon at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer, and at least one blue-sensitive emulsion layer.
• the order of these layers may be optionally selected as the case demands.
• the preferable order of layres from the substrate side is red-sensitive, green-sensitive, and blue-sensitive, or green-sensitive, red-sensitive, and blue-sensitive.
• Each of the above-mentioned emulsion layers may consist of two or more layers which have different sensitivity, and a non-photosensitive layer may exist between two or more emulsion layers that have the same sensitivity.
• the red-sensitive layer contains a non-diffusible cyan-forming coupler
• the green-sensitive layer contains a non-diffusible magenta-forming coupler
• the blue-sensitive layer contains a non-diffusible yellow-forming coupler, but another combination may be employed if needed.
• Concerning the cyan, magenta, and yellow couplers to be used preferably in the present invention compounds can be mentioned, for example, as are described on page 44 line 8 to page 81, especially the cyan couplers (C-1) to (C-46), the magenta couplers (M-1) to (M-20), and the yellow couplers (Y-1) to (Y-8) on pages 57 to 81. of Japanese Patent Application No. 39825/1987. More specifically, the following compounds can be mentioned.
• monopolymers or copolymers described in the above-mentioned Japanese Patent Application No. 39825/1987 which consist of at least one type of repeating units having no acid group on the main chain or the side chain and which are insoluble in water and soluble in organic solvents, can also be used, and/or high-boiling organic solvents can be used independently.
• high-boiling solvents are described in the above-mentioned Japanese Patent Application No. 39825/1987, pages 82 to 96.
• the photographic material according to the present invention may have auxiliary layers, such as protective layers, intermediate layers, filter layers, antihalation layers, backing layers, etc., if necessary, in addition to the silver halide emulsion layers.
• a binder or protective colloid to be used in the present invention it is beneficial to use gelatin, but a hydrophilic colloid other than gelatin can be used.
• a transparent base may be used, but the preferable substrate is a reflective base, such as, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, or a transparent base having a reflective layer or combined with a reflective material, such as, for example, glass plate, vinyl chloride resin, cellulose acetate, cellulose nitrate, film of polyesters such as polyethylene terephthalate, polyamide film, polycarbonate film, and polystyrene film.
• a reflective base such as, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, or a transparent base having a reflective layer or combined with a reflective material, such as, for example, glass plate, vinyl chloride resin, cellulose acetate, cellulose nitrate, film of polyesters such as polyethylene terephthalate, polyamide film, polycarbonate film, and polystyrene film.
• a reflective base such as, for example, baryta paper, polyethylene-coated
• a conventional black and white developing solution such as described in "Shashinkagaku” by Shinichi Kikuchi, Chapter 7 to Chapter 11 of Kyoritsu-shisho
• a developing solution for use in a color-forming method, diffusion transfer method and silver-dye bleaching method (Chapter 11 to Chapter 16 of "The Theory of Photographic Process” by T.H. James, 4th Edition) can be used.
• the color-developing solution used in the present invention contains an ordinary aromatic primary amine color-developing agent.
• aromatic primary amine color-developing agents are p-phenylenediamine derivatives. Representative examples are given below, but they are not meant to limit the present invention:
• p-phenylenediamine derivatives may be in the form of salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates.
• the amount of aromatic primary amine developing agent to be used is about 0.1 g to about 20 g, preferably about 0.5 g to about 10 g, per liter of developer.
• the pH of the developing solution of the present invention is 9.0 to 12.5, preferably 9.0 to 12.0, and more preferably 9.8 to 11.5.
• additives such as preservative, buffer, chelating agent, development accelerater, anti-fogging agent and brightening agent and the amount of them to be added to the color developing solution are described in Japanese Patent Application (OPI) No. 63526/1987.
• the colbr-developing solution of the present invention is substantially free from benzyl alcohol.
• the processing temperature using the color-developing solution is between 20 to 50°C, preferably 30 to 40°C.
• the processing time is between 20 sec. to 5 min., preferably 30 sec. to 2 min. It is preferable to use a smaller amount of replenisher, generally 20 to 600 ml, preferably 50 to 300 ml, and more preferably 100 to 200 ml, per m 2 of the photographic material.
• the photographic emulsion layer after color development, is subjected to bleaching processing.
• Bleaching processing may be effected together with fixing processing as a one-bath bleach-fixing, or it may be effected separately from the fixing processing.
• bleach-fixing processing may be effected after bleaching processing or fixing processing.
• the bleaching solution or the bleach-fixing solution of the present invention may use, as a bleaching agent, an aminopolycarboxylic acid iron complex salt.
• additives to be used in the bleaching solution or the bleach- fix solution use can be made of various compounds described in Japanese Patent Application (OPI) No. 215272/1987 (from the right lower column of page 6 to the right lower column of page 8).
• washing and/or stabilizing is effected.
• the washing water or stabilizing solution use can be made of water that has been softened.
• softening water can be mentioned a method that uses a reverse osmosis apparatus or ion exchange resins described in Japanese Patent Application (OPI) No. 28838/1987.
• OPI reverse osmosis apparatus or ion exchange resins described in Japanese Patent Application (OPI) No. 28838/1987.
• OPI Japanese Patent Application
• the smaller the amount of the replenishing solution the more preferable.
• the amount of the replenishing solution is 0.1 to 50 times, more preferably 3 to 30 times, the amount of the carried-over from the previous bath per unit area of the photographic material.
• the photographic materials of the present invention are not only useful for photographic paper, particularly color photographic paper, but they also can be used for all types of other silver halide photographic materials.
• the photographic material of the present invention can be used for black and white and color photographic materials for photographing, photographic materials for a color diffusion transfer process.
• photographic materials for a silver salt diffusion transfer process heat development type photographic materials, color reversal paper, color reversal film for photographing, and black and white and color direct positive photographic materials.
• the preferable coating amount of the compounds represented by formula (I), (II), and (III) for use in the present invention is in the range of 1 x 10 -6 to 2 x 10 -4 mol/m 2 , although it is not restricted to the above range.
• These compounds represented by the formula (I), (II), and (III) may be added to an arbitrary hydrophilic layer on the substrate, for example, a silver halide emulsion layer, an intermediate layer, or a protective layer.
• the photographic materials of the present invention are suitable for rapid processing, low in fogging, and high in sensitivity. and gradation.
• the silver halide photographic materials of the present invention are not only high in sensitivity and gradation but also excellent in sharpness, and exhibit such an excellent effect that the change in sensitivity due to change of humidity when exposed is less.
• the silver halide photographic materials of the present invention can be subjected to rapid processing and are excellent-in color reproduction of color images.
• Silver halide emulsion (1) used in this example according to the invention was prepared as follows.
• the first solution was heated to 60°C, and the second and third solutions were added thereto. Thereafter, the fourth and fifth solutions were simultaneously added thereto over 8 minutes. After a further 8 minutes had passed, the sixth and seventh solutions were simultaneously added thereto over 10 minutes. Five minutes later the temperature was lowered and desalting was effected. Then water and dispersed gelatin were added and the pH was adjusted to 6.2, thereby giving a monodisperse cube pure silver chloride emulsion having an average grain size of 0.45 ⁇ m and a deviation coefficient (a value obtained by dividing the standard deviation by the average grain size: s/d) of 0.08.
• Emulsion (2) In the preparation of Emulsion (1), 5.minutes before completion of the addition of the sixth and seventh solutions, a green-sensitive sensitizing dye, (a) shown below, was added in an amount of 4.0 x 10 -4 mol per mol of the silver halide, to prepare Emulsion (2).
• Emulsion (3) was prepared.
• Emulsion (4) In the preparation of Emulsion (1 immediately after completion of the addition of the sixth and seventh solutions, the green-sensitizing dye (a) was added, and then desalting was effected to prepare Emulsion (4).
• Emulsions (1) to (4) were optimally sensitized chemically by adding sodium thiosulfate.
• green-sensitizing dye (a) was added, thereby preparing Emulsion (5).
• Emulsion (5) was also optimally sensitized chemically by adding sodium thiosulfate.
• Table 1 The grain sizes and the deviation coefficient of the thus-obtained Emulsions (1) to (5) are shown in Table 1.
• the green-sensitizing dye (a) shown above was added to the previously-prepared Emulsion (1) in an amount of 4.0 x 10 -4 mol per mol of the silver halide thereby preparing a green-sensitive emulsion, and the green-sensitive emulsion and Emulsions (2) to (5) were combined with the emulsified dispersion obtained above to prepare coating liquids, and the coating liquids were applied together with a protective layer of gelatin onto a two-side polyethylene-laminated paper base, thereby preparing Samples 1 to 5.
• the construction of the samples are shown in Table 2.
• Samples 1 to 5 were subjected to gradation exposure for 0.5 sec for sensitometry through a green filter using a sensitometer (FWH model, manufactured by Fuji Photo Film Co., Ltd.; color temperature of the light source: 3200 K).
• FWH model manufactured by Fuji Photo Film Co., Ltd.; color temperature of the light source: 3200 K.
• UVD-33S manufactured by Toshiba.
• the processing included color development, bleach-fixing, and rinsing; the color development was effected at 35°C for 45 sec. the bleach-fixing was effected at 35°C for 45 sec, and the rinsing was effected at 35°C for 90 sec.
• Emulsion (1) the amount of sodium thiosulfate added was increased further, followed by chemical sensitization, thereby preparing Emulsion (5').
• dye (a) was added to Emulsion (5') in an amount of 4.0 x 10 -4 mol per mol of the silver halide, and it was combined with the above magenta coupler-emulsified dispersion to prepare Sample 5' in the same manner as Samples 1 to 5.
• samples that used the emulsions of the present invention showed high contrast, low fogging, and very high sensitivity.
• Sample 2 which used an emulsion wherein the addition of the spectral-sensitizing dye was effected in the earlier stage showed high sensitivity, it was not suitable for practical use because of soft gradation.
• Sample 5 which used an emulsion wherein after the desalting step and before chemical ripening a spectral sensitizing dye was added, did not give enough sensitivity.
• Example 1 was repeated to prepare emulsions, except that in the first, fourth, and sixth solutions, the amounts of NaC were reduced and KBr was added in suitable amounts. In addition to make the grain size uniform, the temperature, the period over which the addition was effected, and the amount of the silver halide solvent in the third solution were adjusted. Sodium thiosulfate was added to these emulsions in such amounts that fogging of the emulsions did not increase excessively; thereby the emulsions were optimally sensitized chemically. The obtained emulsions were monodisperse cube silver chlorobromide grains numbered (6) to (10), as shown in Table 5.
• Monodisperse cube silver chlorobromide Monodisperse cube silver chlorobromide. emulsions were also prepared that had the same halogen composition as above by adding dye (a) in an amount 4 X 10- 4 mol per mol of the silver halide 1 minute after completion of the grains, and then by desalting. These emulsions were also optimally sensitized chemically to such a degree that fogging was not excessive, and they were numbered (11) to (15).
• the green-sensitive sensitizing dye (a) mentioned above was added in an amount of 4.0 x 10 -4 mol per mol of the silver halide to Emulsions (6) to (10) to prepare green sensitive emulsions, and the green-sensitive emulsions and Emulsions (11) to (15) were combined with the emulsified dispersion shown in Example 1 to prepare coating liquids, thereby forming Samples 6 to 15 the same way as in Example 1.
• the constitution of the layers and the compositions of the Samples were as shown in Example 1.
• Emulsion (1) in Example 1 was repeated, with the temperature and the amount of the silver halide solvent in the third solution controlled, thereby obtaining Emulsions (16) to (18), with the grain size altered as shown in Table 8.
• Emulsions (16) to (18) 1 minute after the completion of the addition of the silver nitrate solution and the sodium chloride solution, dyes (e) to (g), shown below, were added to obtain Emulsions (19) to (21) respectively.
• Emulsions (16) to (21) were optimally sensitized chemically by adding sodium thiosulfate to such an extent that fogging did not become excessive.
• the profiles of Emulsions (16) to (21) are shown in Table 8. and
• a multi-layer color photographic paper having a layer constitution as shown in Table 9 was prepared on a two-sided polyethylene-laminated paper base.
• the coating liquids were prepared as follows.
• This emulsion and the above-emulsified dispersion were mixed and dissolved to prepare a first-layer coating liquid of the composition shown in Table 9.
• Coating liquids for the second to the seventh layers were prepared in the same manner as for the first-layer coating liquid, except that to prepare the green-sensitive emulsion of the third layer, the green-sensitizing dye (f) mentioned above was added to Emulsion (17), and to prepare the red-sensitive emulsion of the fifth layer, the red sensitive sensitizing dye (g) mentioned above was added to Emulsion (18), respectively in the previously-shown amounts.
• gelatin hardener for the layers use was made of 1-oxy-3.5-dichloro-s-triazine sodium salt.
• the following compound was added in an amount of 2.6 ⁇ 10 -3 mol per mol of the silver halide.
• 1-(5-methylureidephenyl)-5-mercaptotetrazole was added respectively in amounts of 8.5 ⁇ 10 -5 mol, 7.7 ⁇ 10 -4 mol, and 7.5 x 10 -4 mol per mol of the silver halide.
• the following dye was added to the emulsion layers.
• Sample A The thus-obtained coated sample was designated Sample A.
• Sample B was prepared in the same way as Sample A, except that instead of Emulsion (16), to which the blue-sensitive sensitizing dye had been added, Emulsion (19), to which the blue-sensitive sensitizing dye had been added before the desalting, was used, and instead of Emulsion (17), to which the green-sensitive sensitizing dye had been added.
• Emulsion (20), shown in Table 8 was used, and instead of Emulsion (18), to which the red-sensitive sensitizing dye had been added, Emulsion (21), shown in Table 8, was used.
• Example 3 was repeated, except that the green-sensitive emulsion layer (the third layer) in each of Samples A and B were changed as shown below, thereby preparing Samples C and D.
• Color-image stabilizer (x) 0.05 g/m 2
• Emulsions (1) to (5) were prepared using the same procedure as in Example 1.
• red-sensitizing dye (g) in the amount of 0.9 ⁇ 10 -4 mol per mol of the silver halide was added, instead of green-sensitizing dye (a), thereby preparing Emulsion (6).
• Emulsion (7) which consists of pure silver chloride cubic grains (average grain size of 1.04 um), was prepared by adjusting the temperature and the volume of the solvent for the silver halide in the third solution as in the preparation of Emulsion (1).
• Emulsion (8) was prepared by adding blue-sensitizing dye (e) in the amount of 5.0 mol per mol of the silver halide immediately after completion of the addition of the sixth and seventh solutions in the preparation of Emulsion (7).
• a multi-layer color photographic paper consisting of layers as shown in Table 9 (Example 3) was prepared on a two-side polyethylene-laminated paper base.
• the coating liquids were prepared as shown below.
• a yellow coupler (h) and 4.4 g of a color-image stabilizer (i) were added 27.2 m t of ethyl acetate and 7.7 mt of a solvent (j), and they were mixed until dissolved.
• the resulting solution was dispersed and emulsified in 185 ml of a 10% aqueous gelatin solution containing 8 m of 10% sodium dodecylbenzenesulfate.
• the above-shown blue-sensitizing dye (e) was added to the silver chloride emulsion (7)(containing 70g of Ag per kg) in an amount of 5.0 ⁇ 10 -4 mol per mol of silver. to obtain an emulsion.
• This emulsion and the above emulsified-dispersion were mixed and dissolved to prepare the first-layer coating liquid, of the composition shown in Table 9 of Example 3.
• Coating liquids for the second to the seventh layers were prepared by the same procedure as the first-layer coating liquid, except that to prepare the green-sensitive emulsion of the third layer, the above-mentioned green-sensitizing dye (a) was added to Emulsion (1) in an amount of 4.0 ⁇ 10 -4 mol per mol of the silver halide.
• the above-mentioned red-sensitizing dye (g) was added to Emulsion (1) in an amount of 0.9 ⁇ 10 -4 mol per mol of the silver halide.
• the following compound was added in an amount of 2.6 ⁇ 10 -3 mol per mol of the silver halide.
• Sample B was prepared using the same procedure as for Sample A, except for the addition of the following dye 1 into the green-sensitive emulsion layer and the following dye 2 into the red-sensitive layer.
• Samples C to H were prepared by changing the emulsion of each layer in Sample B to those shown in Table 13. However, for emulsions such as (2), (3), (4), (5), (6) and (8), to which had been added a sensitizing dye at the formation of grains and before chemical ripening, the corresponding sensitizing dye was not added in the preparation of the coating liquid.
• the samples shown in Table 13 were subjected to gradation exposure for 10 sec (corresponding to 250 CMS of exposure) using the same sensitometer as in Example 1 through a blue filter, a green filter, and a red filter..
• relative sensitivity means the relative value of the sensitivity designated by a reciprocal of the amount of light exposure at the lowest density +5 on the characteristic curve of the color image expossed to light at 25°C and 55% rh, with Sample A assumed as 100.
• the gradation y is given by the density difference between the above sensitivity point and the point increased by 0.5 in terms of the logarithm (log E)'of the exposure quantity.
• desensitivity means the difference of relative sensitivities when the photographic material is exposed to light under conditions of 25°C/55% rh. and 25°C/85% rh.
• the sharpness is a quantity indicating the clearness of the outline of an image and the ability to depict fine images, and herein the value called CTF was used.
• CTF is given in terms of % by the damping factor of the amplitude against the spatial frequency as a square waveform. In Table 3, sharpness in 15 spatial frequencies/mm is shown. The greater the value, the higher the sharpness.
• samples D and E consisting of green-sensitive emulsion layers of the present invention
• sample H consisting of blue-, green-, and red-sensitive emulsion layers of the present invention

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• 1988
  • 1988-04-14 EP EP19880105987 patent/EP0287100B1/de not_active Expired - Lifetime
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