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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/34—Couplers containing phenols
• • 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
  • G03C1/0051—Tabular grain 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
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
  • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
• • 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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
• • 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
  • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
  • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
• • 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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03535—Core-shell grains
• • 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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03558—Iodide content
• • 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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/34—Couplers containing phenols
  • G03C7/344—Naphtholic couplers

Definitions

• This invention concerns silver halide photographic emulsions and photographic materials in which they are used, and, more precisely, it concerns silver halide emulsions which are excellent in respect of high speed, low fogging, and graininess, and high speed color photosensitive materials in which these emulsions are used.
• the basic features required of a silver halide emulsion for photographic purposes are high speed, low fogging level, fine graininess and high development activity.
• Grains which have a distinct layer structure with regions which have different halogen compositions within the grain are disclosed which improve these basic features by improving light absorption, improving quantum sensitivity by preventing the occurrence of recombination, increasing the progression of development, and improving graininess by preventing development from proceeding too far.
• JP-A-60-143331 The term "JP-A" as used herein means as "unexamined published Japanese patent application”.
• Grains which have a distinct layer structure are useful when the grain size is large or when they are isotropic grains with a low aspect ratio, and they have contributed to the development of ultra-high speed materials. However, they are inadequate in respect of high picture quality at high speeds, and conventional tubular grains which have a high iodine content and a high aspect ratio, and which have a distinct layer structure, are unsatisfactory.
• An object of the invention is to provide silver halide photographic emulsions which are excellent in respect of high speed, low fogging level, and graininess, and photosensitive materials in which these emulsions are used.
• Another object of the invention is to provide silver halide emulsions having high light absorbing efficiency and which have a high development activity, and photographic materials in which these emulsions are used.
• a silver halide photographic emulsion comprising a dispersion of silver halide grains in a binder, at least 60% by total projected area of the grains being chemically sensitized tabular grains having an aspect ratio of 3 to 10, and a total silver iodide content of at least 8 mol%; the grains having a distinct layer structure comprising at least one silver iodobromide layer in which the silver iodide content is from 15 to 45 mol%.
• a "distinct layer structure" as used herein is determined using the X-ray diffraction method.
• An example of the application of X-ray diffraction methods to silver halide grains has been described by H. Hersch on pages 129 et seq. of volume 10 of the Journal of Photographic Science (1962).
• the width of the slits (dispersion slit, light receiving slit), the time constant of the apparatus, the goniometer scanning rate, and the recording speed are selected appropriately to increase the resolution of the measuring apparatus, and it is necessary to verify the measurement accuracy using a standard sample, of silicon for example.
• the silver iodide in the high iodide layer contains 17 to 23 mol% or 30 to 45 mol%, preferably 18 to 22 mol% or 34 to 42 mol% in order to stably form the high iodide layer.
• the emulsions which have a distinct essentially double layer structure in this invention are preferably such that the diffraction intensity of the minimum value between the two peaks is not more than 90% of the diffraction intensity of the weaker of the two (or more) diffraction maxima (peaks).
• the minimum value is more desirably not more than 80%, and most desirably not more than 60%, of this value.
• the curve is a Gaussian function or a Lorentz function and to make the analysis using a curve analyzer such as that made by the DuPont Co.
• the excellent photographic performance obtained with this present invention cannot be realized with an emulsion of this type.
• the EPMA (electron probe microanalyser) method can be used as well as the X-ray diffraction method in order to ascertain whether a silver halide emulsion is an emulsion of this invention or an emulsion which contains two types of silver halide grains as described above.
• the halogen composition of at least 50 grains is checked using the EPMA method it can be ascertained whether or not the emulsion is an emulsion of this invention.
• the iodine content is preferably uniform from grain to grain in an emulsion of this invention.
• the relative standard deviation when the distribution of iodine contents between grains is measured using the EPMA method is preferably not more than 50%, and most desirably less than 35%.
• Another desirable inter-grain iodine distribution is such that there is a positive correlation between a logarithm of the grain size and the iodine content.
• the iodine content increases as the grain size increases and cases where the iodide content falls as the grain size decreases.
• Cases in which the correlation coefficients for the correlations are at least 40% are preferred.
• the silver halide other than silver iodide in the core part may be silver chlorobromide or silver bromide, but a high proportion of silver bromide is preferred.
• the silver halide composition of the outermost layer contains not more than 8 mol% silver iodide, and it preferably consists of a silver halide which contains not more than 5 mol% of silver iodide.
• the silver halide other than silver iodide in the outermost layer may be silver chloride, silver chlorobromide or silver bromide, but a high proportion of silver bromide is preferred.
• the effect of this present invention is pronounced in cases where the overall halogen composition includes at least 8 mol% of silver iodide.
• the overall silver iodide content is preferably at least 10 mol%, and most preferably at least 12 mol%.
• the size of the silver halide grains which have a distinct layer structure of this invention is preferably not more than 1.7 am, more desirably not more than 1.5 u.m, and most desirably not more than 1.3 u.m.
• the emulsions which contain tabular grains of this invention are emulsions in which tabular grains of which the ratio of the diameter of the circle corresponding to the projected area of the grain and the grain thickness (known as the aspect ratio) has a value of from 3 to 10 account for at least 60%, calculated in terms of the projected area, of the all the silver halide grains present in the emulsion.
• Emulsions in which tabular grains of aspect ratio from 3 to 10 account for at least 75%, and preferably at least 90%, of the total projected area are especially desirable.
• the mean aspect ratio of the tabular grains of aspect ratio at least 3 is preferably from 3 to 10, most desirably from 3 to 8, and most desirably from 5 to 8.
• the color sensitized speed is low when large numbers of grains which have an aspect ratio of less than 3 are present, while the rate of development is slow and practical difficulties with pressure sensitivity arise when large numbers of grains which have an aspect ratio greater than 10 are present.
• the average diameter of the tabular silver halide grains in this invention is preferably from 0.5 to 3.0 um.
• the average thickness is not more than 0.5 u.m, and preferably less than 0.35 ilm.
• the tabular silver halide grains are of a tabular form which has two parallel surfaces, and the term "thickness" as used in this invention signifies the distance between these two parallel surfaces which form the tabular silver halide grain.
• the tabular grains of this invention are preferably grains which have at least 70% of the surface area in the form of a (111) plane. Moreover, grains in which this proportion is at least 80% are most desirable.
• the area ratio of the (111) plane can be determined using the Kubelka-Munk dye adsorption method. In this method a dye which is adsorbed preferentially on either the (111) plane or the (100) plane and which has a different light spectrum when associated with the (111) plane than that observed in when it is associated with the (100) plane is selected. This dye is added to the emulsion and the area proportion of the (111) plane can be determined by investigating, in detail, the light spectrum with respect to the amount of dye which has been added.
• the emulsions used in the invention may have a wide grain size distribution, but emulsions which have a narrow grain size distribution are preferred.
• a variation coefficient of not more than 40% is preferred, while a value of less than 30% is more desirable, and most desirably the value is less than 25%.
• the shape of the tabular grains in this invention is preferably hexagonal.
• the lengths of the six sides may differ, but the lengths of the parallel sides are preferably the same.
• grains of an essentially regular hexagonal shape are the most desirable.
• the term "grains of an essentially regular hexagonal shape” signifies grains of which the variation coefficient for the lengths of the six sides is within 25%.
• the angle of a hexagon is precisely 120 * according to the rule of fixed crystal planes and angles.
• the corner parts may have a normal rounded band.
• grains which have a positive rounding are also desirable as tabular grains of this invention.
• the emulsions which have a distinct layer structure of this invention can be prepared by selecting and combining various methods which are known in the field of silver halide photographic materials.
• methods such as the acidic method, the neutral method or the ammonia method can be used to prepare the core grains, and single sided mixing methods, simultaneous mixing methods, and combinations of these methods, can be selected for the system by which the soluble halide is reacted with the soluble silver salt.
• the method in which the pAg value in the liquid phase in which the silver halide is being formed is held constant can be used as one system involving a simultaneous mixing procedure.
• the triple jet method in which a soluble halide of different composition is added independently can also be used as another system involving a simultaneous mixing procedure.
• a silver halide solvent such as ammonia, a thiocyanate, a thiourea, a thioether or an amine, can be selected and used during the preparation of the core.
• Emulsions in which the grain size distribution of the core grains is narrow are preferred.
• the mono-disperse core emulsions as mentioned earlier are especially desirable.
• Emulsions in which the halogen composition, and especially the iodide content, of the individual grains is uniform at the core stage are preferred.
• halogen compositions of the individual grains is uniform can be assessed using the techniques of X-ray diffraction and EPMA as described earlier. Emulsions in which the halogen composition of the core grains is uniform give narrower X-ray diffraction widths.
• low molecular weight gelatins or modified gelatins is especially desirable because these are not prone to setting.
• the type and concentration of the gelatin, and the temperature are preferably the same as the type of gelatin, the gelatin concentration and the temperature in the reactor so as to maintain uniform super-saturation factors in the vicinity of the addition ports so that uniform nuclei formation can be achieved.
• Uniform silver iodobromides can be obtained after forming seed crystals of silver iodobromide which have a high silver iodide concentration using methods in which the rates of addition are accelerated with the passage of time as disclosed in JP-B-48-36890 by Irie and Suzuki, or by increasing the addition concentration with the passage of time as disclosed in U.S. Patent 4,242,445 by Saito, and especially good results can be obtained using these methods (The term "JP-B" as used herein means an "examined Japanese patent publication".) In the method of Irie et al.
• sparingly soluble inorganic crystals for photographic purposes are prepared by adding at least two types of inorganic salt solutions simultaneously in more or less equal quantities in the presence of a protective colloid and carrying out a double decomposition reaction.
• the aqueous inorganic salt solutions which are reacted are added at least at a fixed rate of addition and at a rate of addition Q which is not greater than the rate of addition which is proportional to the total surface area of the sparingly soluble inorganic salt crystals during growth, which is to say at a rate ⁇ Q ⁇ t 2 + ,at + y.
• the concentrations of the aqueous inorganic salts which are reacted are increased during crystal growth in such a way that virtually no new crystal nuclei are formed during this period.
• the shell may be attached after forming the core grains without any other treatment, but the shell is preferably formed after washing the core emulsion with water for desalting purposes.
• the shell can be affixed using the various methods known in the field of silver halide photographic materials, but the simultaneous mixing methods are preferred.
• the methods of Irie and Saito described above are preferred for the preparation of emulsions which have a distinct layered structure.
• the stable mixed crystal ratio depends on the environments, such as temperature, pH pAg, concentration of gelatin solution, etc., but it is considered that it is within the range from 15 to 25 mol% or from 30 to 45 mol%.
• the conditions such as the temperature, pH, pAg and agitation conditions, should be selected appropriately.
• careful selection of the protective colloid when growing the low iodide layer, and growing the low iodide layer in the presence of compounds which are adsorbed on the surface of the silver halide, such as spectrally sensitizing dyes, anti-fogging agent, and stabilizers for example, are desirable.
• Methods in which fine grains of silver halide are added instead of adding aqueous solutions of silver salts and aqueous solutions of alkali metal halides are also effective when growing the low iodide layer.
• the dyes which can be used when growing the low iodide layer include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes holopolar-cyanine dyes, hemi-cyanine dyes, styryl dyes and hemi-oxonol dyes. Dyes from among the cyanine dyes, merocyanine dyes and complex merocyanine dyes are especially useful. Any of the nuclei normally used in cyanine dyes can be used as the basic heterocyclic nucleus in these dyes.
• nuclei Five or six membered heterocyclic nuclei, such as the pyrazolin-5-one nucleus, the thiohydantoin nucleus, the 2-thio-oxazolidin-2,4-dione nucleus, the thiazolidin-2,4-dione nucleus, the rhodanine nucleus and the thiobarbituric acid nucleus, can be used as the nucleus which has a ketomethylene structure in the merocyanine dyes and complex merocyanine dyes.
• JP-A-63-212932 are typical examples. Anti-fogging agents and stabilizers are also useful compounds when growing low iodide layers. These can be selected from among the compounds disclosed in the above Research Disclosure. However, there are compounds which are not preferred, such as the tetraazaindenes, shown in the illustrative examples. The addition of mercapto compounds is preferred in this invention, including those represented by formula (D-I).
• M 1 represents hydrogen, a cation, or a protective group for the mercapto group which is cleaved in alkaline condition
• Z represents an atomic group necessary for forming a five or six membered heterocyclic ring.
• This heterocyclic ring may have substituent groups, or it may be a condensed ring.
• M 1 represents hydrogen, a cation (for example, sodium ion, potassium ion, ammonium ion) or a protective group for the mercapto group which is cleaved in alkaline conditions (for example, -COR;, -COOH, or -CH 2 CH 2 COR', where R represents hydrogen, an alkyl group, an aralkyl group or an aryl group.
• a cation for example, sodium ion, potassium ion, ammonium ion
• a protective group for the mercapto group which is cleaved in alkaline conditions for example, -COR;, -COOH, or -CH 2 CH 2 COR', where R represents hydrogen, an alkyl group, an aralkyl group or an aryl group.
• Z represents a group of atoms which is required to form a five or six membered heterocyclic ring.
• the heterocyclic rings may contain, for example, sulfur atoms, selenium atoms, nitrogen atoms and oxygen atoms as hetero-atoms. They may be condensed rings, and there may be substituent groups on the heterocyclic rings or on the condensed rings.
• Z examples include tetrazole, triazole, imidazole, oxazole, thiadiazole, pyridine, pyrimidine, triazine, azabenzimidazole, purine, tetraazaindene, triazaindene, pentaazaindene benzotriazole, benzimidazole, benzoxazole and naphthimidazole.
• alkyl groups for example, methyl, ethyl, n-hexyl, hydroxyethyl, carboxyethyl
• alkenyl groups for example, allyl
• aralkyl groups for example, benzyl, phenethyl
• aryl groups for example, phenyl, naphthyl, p-acetamidophenyl
• p-carboxyphenyl m-hydroxyphenyl, p-sulfamoylphenyl, p-acetylphenyl, o-methoxyphenyl, 2,4-diethylaminophenyl, 2,4-dichlorophenyl
• alkylthio groups for example, methylthio, ethylthio, n-butylthio
• arylthio groups for example, phenylthio, naphthylthio
• aralkyl groups for example, methyl, eth
• the quantity of these mercapto group containing compounds used is preferably not more than 10- 3 mol per mol of silver halide.
• JP-A-63-212932 JP-A-62-89952 (corresponding to B.P. 2,176,304A) and JP-A-61-282841 (corresponding to EP-208,146A).
• the silver halide grains have a distinct layer structure as described above, there are essentially two or more regions which have different halogen compositions present within the grains, and the interior of the grain is described herein as “the core” and the surface part is described herein as the "shell".
• an intermediate layer between the core in the inner part and the outermost layer which constitutes the shell.
• Such an intermediate layer may have a silver iodide content intermediate between those of the core and the shell, or it may take the form of a layer which has a high silver chloride content.
• the third layer forms a separate region in the center on the interior core. In such a case the third layer may have a low iodide content or high iodide content (or it may consist of silver iodide) relative to that of the core, depending on the intended purpose of the layer.
• the third layer may be a separate region which is present on the outside of the shell. In this case the third layer may be a silver bromide layer which contains no iodide, a layer which has a higher silver iodide content than the shell or a layer which contains silver chloride, for example, depending on its intended purpose.
• the silver halide grains have an essentially distinct double layer structure, and even in cases where there is a high iodide content core, an intermediate part and a low iodide content shell, there are two peaks on the X-ray diffraction pattern with a single minimum between the two peaks, the diffraction intensity corresponding to the high iodide part is from 1/5 to 10/1 times, preferably from 1/3 to 5/1 times, and most desirably from 1.3 to 3/1 times, that of the low iodide part, and the minimum is not more than 90%, preferably not more than 80%, and most desirably not more than 70%, of the smaller of the two peaks.
• the silver halides of different composition may be joined with an epitaxial junction in an emulsion of this invention, or they may be joined with a compound other than silver halide, such as silver thiocyanate or lead oxide, for example.
• Grains of various crystalline forms may be used in combination with the tabular grains.
• the 5-pyrazolone and pyrazoloazole based compounds are preferred as magenta couplers, and those disclosed, for example, in U.S. Patents 4,310,619 and 4,351,897, European Patent 73,636, U.S. Patents 3,061,432 and 3,725,064, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-4365, and U.S. Patents 4,500,630 and 4,540,654 are especially desirable.
• Phenol and naphthol based couplers are used as cyan couplers, and those disclosed, for example, in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, West German Patent (OLS) 3,329,729, European Patent 121,365A, U.S. Patents 3,446,622, 4,333,999, 4,451,559 and 4,427,767, and European Patent 161,626A are preferred.
• the colored couplers for correcting the unwanted absorptions of colored dyes disclosed, for example, in Research Disclosure No. 17643 section VII-G, U.S. Patent 4,163,670, JP-B-57-39413, U.S. Patents 4,004,929 and 4,136,258, and British Patent 1,146,368, are preferred.
• couplers which release photographically useful groups on coupling are preferred in this invention.
• the DIR couplers which release development inhibitors disclosed in the patents disclosed in the aforementioned Research Disclosure No. 17643, section VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, and U.S. Patent 4,248,962 are preferred.
• couplers disclosed in British Patents 2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840 are preferred as couplers which release nucleating agents or development accelerators in the form of the image during development.
• couplers which can be used in the photosensitive materials of this invention include the competitive couplers disclosed, for example, in U.S. Patent 4,130,427, the multi-equivalent couplers disclosed, for example, in U.S. Patents 4,283,472, 4,338,393 and 4,310,618, the DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR redox compound releasing couplers or DIR coupler releasing redox compounds disclosed, for example, in JP-A-60-185950 and JP-A-62-24252, the couplers which release a dye to which color is restored after elimination as disclosed in European Patent 173,302A, the bleach accelerator releasing couplers disclosed, for example, in Research Disclosure Nos. 11449 and 242412, and JP-A-61-201247, and the ligand releasing couplers disclosed, for example, in U.S. Patent 4,553,477.
• A represents a coupler group capable of releasing (UNK) n -B by means of a coupling reaction with an oxidized primary aromatic amine developing agent
• LINK represents a groups which is bonded to the active coupling position of A and which is capable of releasing B after being released from A by the coupling reaction
• B is a group represented by formulae (Ila), (Ilb), (Ilc), (lid), (Ile), (Ilf), (llg), (Ilh), (Ili), (Ilj), (Ilk), (III), (Ilm), (IIn), (Ilo), or (Ilp) indicated below; and n is o or 1. Moreover, when n is zero, B is bonded directly to A.
• X 1 represents a substituted or unsubstituted aliphatic group which has from 1 to 4 carbon atoms (the substituent groups being selected from alkoxy groups, alkoxycarbonyl groups, hydroxyl groups, acylamino groups, carbamoyl groups, sulfonyl groups, sulfinamido groups, sulfamoyl groups, amino groups, acyloxy groups, cyano groups, ureido groups, acyl groups, halogen atoms and alkylthio groups, and the number of carbon atoms contained in these substituent groups is not more than 3) or a substituted phenyl group which has from 6 to 20 carbon atoms (the substituent groups being selected from among hydroxyl groups, alkoxycarbonyl groups, acylamino groups, carbamoyl groups, sulfonyl groups, sulfonamido groups, sulfamoyl groups, acyloxy groups,
• X 2 represents hydrogen, an aliphatic group, halogen atom, hydroxyl group, alkoxy group, alkylthio group, alkoxycarbonyl group, acylamino group, carbamoyl group, sulfonyl group, sulfonamido group, sulfamoyl group, acyloxy group, ureido group, cyano group, nitro group, amino group, alkoxycarbonylamino group, aryloxycarbonyl group or acyl group, in which these organic groups have from 1 to 20 carbon atoms.
• Xa represents hydrogen, sulfur or an imino group which has not more than 4 carbon atoms, and m is a integer of value 1 or 2. However, the total number of carbon atoms in all of the m X 2 groups is not more than 8 and, when m is 2, the two X 2 groups may be the same or different.
• Coupler residual groups which form dyes (for example, yellow, magenta and cyan dyes) on undergoing a coupling reaction with the oxidized form of a primary aromatic amine developing agent and coupler residual groups which provide coupling reaction products which have essentially no absorbance in the visible region are included among the coupler residual groups represented by A in formula (I).
• Examples of yellow image forming coupler residual groups represented by A include coupler residual groups of the pivaloylacetanilide type, the benzoylacetanilide type, the malonic acid diester type, the malonic acid diamide type, the benzoylmethane type, the benzothiazolylacetamide type, the malonic acid ester monoamide type, the benzothiazolylacetate type, the benzoxazolylacetamide type, the benzox- azolylacetate type, the benzimidazolylacetamide type and the benzimidazolylacetate type, the coupler residual groups derived from heterocyclic substituted acetamides and heterocyclic substituted acetates included in U.S.
• Patent 3,841,880 the coupler residual groups derived from acylacetamides disclosed in U.S. Patent 3,770,446, British Patent 1,459,171, West German Patent (OLS) 2,503,099, JP-A-50-139738, and Research Disclosure No. 15737, and the heterocyclic type coupler residual groups disclosed in U.S. Patent 4,046,574.
• magenta image forming coupler residual groups represented by A include the coupler residual groups which have a 5-oxo-2-pyrazoline nucleus, a pyrazolo-[1,5-a]-benzimidazole nucleus, a pyrazoloimidazole nucleus, a pyrazolotriazole nucleus or a pyrazolotetrazole nucleus, and the cyanoacetophenone type coupler residual groups.
• Preferred examples of cyan image forming coupler residual groups represented by A include coupler residual groups which have a phenol nucleus or an a-naphthol nucleus.
• Coupler residual groups of this type represented by A include those disclosed in U.S. Patents 4.052,213, 4.088,491, 3,632,345, 3,958,993 and 3,961,959. Moreover, A may be the coupler residual group of a polymerized coupler as disclosed in U.S. Patents 3,451,820, 4,080,211 and 4,367,282, and British Patent 2,102,173.
• * indicates the position which is bonded to the coupling position of A, R 3 and R 4 .
• R 3 represent hydrogen or substituent groups
• B is as defined in formula (I).
• R 3 examples include alkyl groups which have from 1 to 24 carbon atoms (for example, methyl, ethyl, benzyl, dodecyl) and aryl groups which have from 6 to 24 carbon atoms (for example, phenyl, 4-tetradecyloxyphenyl, 4-methoxyphenyl, 2,4,6-trichlorophenyl, 4-nitrophenyl, 4-chlorophenyl, 2,5-dichlorophenyl, 4-carboxyphenyl, p-tolyl), and examples of the groups represented by R 4 .
• alkyl groups which have from 1 to 24 carbon atoms for example, methyl, ethyl, undecyl, pentadecyl
• aryl groups which have from 6 to 36 carbon atoms for example, phenyl, 4-methoxyphenyl
• cyano groups alkoxy groups which have from 1 to 24 carbon atoms (for example, methoxy, ethoxy, dodecyloxy), amino groups which have from 0 to 36 carbon atoms (for example, amino, dimethylamino, piperidino, dihexylamino anilino), carbonamido groups which have from 1 to 24 carbon atoms (for example, acetamido, benzamido, tetradecanamido), sulfonamido groups which have from 1 to 24 carbon atoms, for example, methylsulfonamido, phenylsulfonamido), carboxyl groups, alkoxycarbonyl groups which have have from 1
• X may be, for example, methyl, ethyl, propyl, butyl, methoxyethyl, ethoxyethyl, iso-butyl, allyl, dimethylaminoethyl, propargyl, chloroethyl, methoxycarbonylmethyl, methylthioethyl, 4-hydroxyphenyl, 3-hydroxyphenyl, 4-sulfamoylphenyl, 3-sulfamoylphenyl, 4-carbamoylphenyl, 3-carbamoylphenyl, 4-dimethylaminophenyl, 3-acetamidophenyl, 4-propanamidophenyl, 4-methoxyphenyl, 2-hydroxyphenyl, 2,5-dihydroxypenyl, 3-methoxycarbonylaminophenyl, 3-(3-methylureido)phenyl, 3-(3-ethylureido)phenyl, 4-hydroxye
• the compounds represented by formula (I) of this invention are included in the photosensitive material in at least one of the silver halide emulsion layers, intermediate layers, filter layers (yellow filter layer, magenta filter layer), undercoating layers, antihalation layers, protective layers or other auxiliary layers, but they are preferably included in the photosensitive silver halide emulsion layers or in photosensitive layers which are adjacent thereto and, most desirably, they are included in layers which contain emulsion grains of this invention or in layers of the same color sensitivity which are adjacent thereto.
• the compounds represented by formula (I) can be included in the photosensitive material using the same methods as used for the dispersion of couplers as described below.
• the total quantity of these compounds added is from 10- 6 to 10- 3 mol/m 2 , preferably from 3x10- 6 to 5x10- 4 mol/m 2 , and most desirably from 5x10- 6 to 2x10- 4 mol/m 2 .
• R" in these formulae represents -CONR 15 R 16 , -NHCOR 15 , -NHCOOR 17 , -SO 2 NR 15 R 17 , -NHSO 2 R 17 , -NHCONR 15 R 16 or -NHSO 2 NR 15 R 16 .
• R 15 , R 16 and R 17 which may be the same or different, each represents an aliphatic group which has from 1 to 30 carbon atoms, an aromatic group which has from 6 to 30 carbon atoms, or a heterocyclic group which has from 2 to 30 carbon atoms.
• R 12 represents a halogen atom, hydroxyl group, amino group, carboxyl group, sulfonic acid group, cyano group, aromatic group, heterocyclic group, carbonamido group, sulfonamido group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, or imido group, and the number of carbon atoms contained in R 12 is from to 30. Moreover, m is 0 or an integer from 1 to 3.
• the dioxymethylene group is an example of a cyclic R 12 when m is 2.
• R 13 is represented by formula (CC-3) indicated below.
• Y represents >NH, >CO or >S0 2
• n is 0 or 1
• R 18 represents hydrogen, an aliphatic group which has from 1 to 30 carbon atoms, an aromatic group which has from 6 to 30 carbon atoms, a heterocyclic group which has from 3 to 30 carbon atoms, -OR 19 , -SR 19 , -COR 19 , -CO 2 R 21 , -SO 2 R 21 or -SO 2 OR 21 , -S0 2 R 21 or -SO 2 OR 21 .
• R 19 , R 20 and R 21 which may be the same or different, each has the same definition as R 15 .
• R 15 and R 16 in and R 19 and R 20 in in R" and R 18 may be joined together to form a nitrogen containing heterocyclic ring (for example, a morpholine ring, piperidine ring, or pyrrolidine ring).
• a nitrogen containing heterocyclic ring for example, a morpholine ring, piperidine ring, or pyrrolidine ring.
• R 14 represents an aliphatic group which has from 1 to 36 carbon atoms, an aromatic group which has from 6 to 36 carbon atoms, or a heterocyclic group which has from 2 to 36 carbon atoms, and it preferably represents an tertiary alkyl group which has from 4 to 36 carbon atoms or a group represented by formula (CC-4) below which has from 7 to 36 carbon atoms:
• R 22 and R 23 which may be the same or different, each represents hydrogen, an aliphatic group which has from 1 to 30 carbon atoms or'an aromatic group which has from 6 to 30 carbon atoms, R 24 represents a univalent group, and Z represents -O-, -S-, -SO- or -S0 2 -. Moreover, I represents 0 or an integer of 1 to 5, and where t is 2 or more the individual R 24 groups may be the same or different.
• the preferred groups for R 22 and R 23 are hydrogen and linear and branched chain alkyl groups which have from 1 to 18 carbon atoms; the preferred groups for R 24 are hydrogen; aliphatic groups, aliphatic oxy groups, carbonamido groups, sulfonamido groups which have from 1 to 30 carbon atoms; carboxyl groups which have from 1 to 30 carbon atoms; sulfo groups, cyano groups; hydroxyl groups; carbamoyl groups; sulfamoyl groups which have from 0 to 30 carbon atoms; aliphatic oxycarbonyl groups which have from 2 to 30 carbon atoms and aromatic sulfonyl groups which have from 6 to 30 carbon atoms; and Z is preferably an -O- group.
• the number of carbon atoms in R 24 is from 0 to 30, and the value of t is preferably from 1 to 3.
• Ar represents a substituted or unsubstituted aryl group, and this may have a condensed ring.
• Typical substituents for the Ar group include halogen atoms, cyano group, nitro group, trifluoromethyl group, -COOR 25 , -COR 25 , -SO 2 OR 25 , -NHCOR 25 , -OR 25 , -S0 2 R 27 , -SOR 27 , -OCOR 27 and R 25 and R 26 , which may be the same or different, each represents hydrogen, an aliphatic group, aromatic group or heterocyclic group; and R 27 represents an aliphatic group, aromatic group or heterocyclic group.
• the number of carbon atoms in Ar is from 6 to 30, and phenyl groups substituted with the aforementioned substituent groups are preferred.
• X represents hydrogen or a group which is eliminated on coupling (including the leaving atom, same below) a "coupling-off group".
• groups which are eliminated on coupling include halogen atoms, -OR28 , - SR28 , -NHCO R 2 8 , -NHSR28 , aromatic oxo groups which have from 6 to 30 carbon atoms and heterocyclic groups which have from 1 to 30 carbon atoms which are bonded to the active coupling position of the coupler via a nitrogen atom (for example, succinimido group, phthalimido group, hydantoinyl group, pyrazolyl group, 2-benzotriazolyl group).
• R 28 represents an aliphatic group which has from 1 to 30 carbon atoms, an aromatic group which has from 6 to 30 carbon atoms, or a heterocyclic group which has from 2 to 30 carbon atoms.
• the aliphatic groups in this invention can, as mentioned before, be saturated or unsaturated, substituted or unsubstituted, linear chain, branched chain or cyclic groups, and some typical examples include a methyl group, ethyl group, butyl group, cyclohexyl group, allyl group, propargyl group, methoxyethyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, trifluoromethyl group, pentafluoropropyl group, dodecyloxypropyl group, 2,4-di-tert-amylphenoxypropyl group and 2,4-di-tert-amylphenoxybutyl group.
• aromatic groups may also be substituted or unsubstituted groups, and typical examples include a phenyl group, tolyl group, 2-tetradecyloxyphenyl group, pentafluorophenyl group, 2-chloro-5-dodecyloxycarbonylphenyl group, 4-chlorophenyl group, 4-cyanophenyl group and 4-hydroxyphenyl group.
• heterocyclic groups may also be substituted or unsubstituted groups, and typical examples include a 2-pyridyl group, 4-pyridyl group, 2-furyl group, 4-thienyl group and quinolinyl group.
• Ar in general formula (CC-5) represents an aromatic group which has from 6 to 30 carbon atoms
• the preferred substituent groups include alkyl groups, alkoxy groups, halogen atoms, alkoxycarbonyl groups, carbonamido groups, sulfonamido groups, alkoxycarbonamino groups and alkylthio groups, and the most desirable substituent groups are alkoxy groups (for example, methoxy, ethoxy, propyloxy, butoxy, .
• benzyloxy methoxyethoxy, 2-ethylhexyloxy, decyloxy, dodecyloxy, tetradecyloxy, 2-hexadecyloxy, 2-dodecyloxyethoxy, 2-dodecylthiopropoxy) and halogen atoms (fluorine, chlorine, bromine, iodine).
• Couplers represented by the general formula (CC-1) can be joined at the substituent groups R11, R 12 , R 13 or X', and couplers represented by the general formulae (CC-2) and (CC-5) can be joined at the substituent groups Ar, via divalent groups or groups which have a valency of more than two to form dimers, oligomers or larger units.
• the number of carbon atoms may be outside the ranges specified for each substituent group as described earlier.
• Homopolymers or copolymers of addition polymerizable ethylenic type unsaturated compounds which have cyan dye forming coupler residual groups are typical examples in which couplers represented by the general formulae (CC-1), (CC-2) and (CC-5) form oligomers.
• the oligomer contains repeating units of general formula (CC-6), and one or more types of cyan color forming repeating unit represented by formula (CC-6) may be included in the oligomer, or the oligomer may take the form of a copolymer which contains one or more non-color forming ethylenic monomer as a copolymerization component.
• R in this formula represents an alkyl group which has from 1 to 4 carbon atoms, or a chlorine atom;
• A represents -CONH-, -COO- or a substituted or unsubstituted phenylene group;
• B represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, and
• L represents -CONH-, -NHCONH-, -NHCOO-, -NHCO-, -OCONH-, -NH-, -COO-, -OCO-, -CO-, -0-, -S-, -S0 2 -, NHSO z - or S0 2 NH-.
• Q represents a cyan coupler residual group in which a hydrogen atom other than that of the hydroxyl group in the 2-position has been eliminated from a compound represented by formula (CC-1), (CC-2) or (CC-5).
• Copolymers of the cyan color forming monomer which provides repeating units of general formula (CC-6) and the non-color forming ethylenic monomers described below are preferred as oligomers.
• a weight ratio of the comonomer is preferably from 0 to 80 wt%, the most preferably from 20 to 70 wt%.
• a molecular weight of the polymer is from 5.0 x 10 2 to 1.0 x 10 6 , preferably from 1.0 x 10 3 to 1.0 x 10 5 .
• the polymer preferably constitutes with a linear polymer.
• the acrylic acid esters, methacrylic acid esters, aromatic vinyl compounds and maleic acid esters are especially desirable.
• Two or more of the non-color forming ethylenic monomers used here can be used conjointly.
• use can be made of methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, and methyl acrylate and diacetoneacrylamide.
• couplers represented by formulae (CC-1), (CC-2), (CC-5) and (CCC-6) are indicated below, but the couplers which can be used in the invention are not to be compared as being limited to these examples.
• the group (t)C 5 H 11 is a -C(CH 3 ) 2 C 2 Hs group and the group (t)C 8 H 17 is a -C-(CH 3 ) 2 CH 2 C(CH 3 ) 3 group.
• Couplers represented by formula (CC-1) can be prepared using the methods disclosed in JP-A-60-237448, JP-A-61153640 and JP-A-61-145557.
• Couplers represented by formula (CC-2) can be prepared using the methods disclosed, for example, in U.S. Patent 3,488,193, JP-A-48-15529, JP-A-50-117422, JP-A-52-18315, JP-A-52-90932, JP-A-53-52423, JP-A-54-48237, JP-A-54-66129, JP-A-55-32071, JP-A-55-65957, JP-A-55-105226, JP-A-56-1938, JP-A-56-12643, JP-A-56-27147, JP-A-56-126832 and JP-A-58-95346.
• Couplers represented by formula (CC-5) can be prepared using the methods disclosed, for example, in U.S. Patents 4,254,212, 4,296,199 and 3,488,193, British Patent 914,507, and JP-B-54-378232.
• the total amount of the couplers represented by formulae (CC-1), (CC-2) and (CC-5) added is at least 30 mol%, preferably at least 50 mol%, more desirably at least 70 mol%, and most desirably at least 90 mol% of the total amount of cyan coupler.
• Couplers represented by the general formulae (CC-1), (CC-2) and (CC-5) are preferred and, in cases where a layer is divided into two layers of the same color sensitivity but of different speeds, the use of two-equivalent couplers in the high speed layer and four-equivalent couplers in the low speed layer is preferred. In cases where there are three or more layers of the the same color sensitivity but different speeds, two-equivalent couplers are preferably used in the highest speed layer and four-equivalent couplers are preferably used in the slowest layer, and either type may be used in the layers of intermediate speed, or both types of coupler can be used conjointly.
• the couplers used in the invention can be introduced into the photosensitive materials using various known methods of dispersion.
• Examples of high boiling point organic solvents of boiling point above 175 C at normal pressure which can be used in the oil in water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicylohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-tert-amylphenyl) phthalate, bis(2,4-di-tert-amylphenyl) isophthalate and bis(1,1-diethylpropyl)phthalate), esters of phosphoric acid or phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tri-dodecyl phosphate, tributoxyethyl phosphate, trichloroprop
• Organic solvents of boiling point above about 30 C, and preferably above 50 C. but below about 160°C can be used as auxiliary solvents, and typical examples of such solvents include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- ethoxyethyl acetate and dimethylformamide.
• the color photosensitive materials of the present invention may contain various antiseptics or antifungal agents such as benzoisothiazolone, n-butyl p-hydroxybenzoate, phenol, or 1-(4-thiazolyl) benzimidazole, which is disclosed in JP-A-63-157747, JP-A-62-272248, and Japanese Patent Application No. 62-238096.
• various antiseptics or antifungal agents such as benzoisothiazolone, n-butyl p-hydroxybenzoate, phenol, or 1-(4-thiazolyl) benzimidazole, which is disclosed in JP-A-63-157747, JP-A-62-272248, and Japanese Patent Application No. 62-238096.
• the invention can be applied to various types of color photosensitive materials. Typical examples include color negative films for general and cinematographic purposes, color reversal films for slide and television purposes, color papers, color positive films and color reversal papers.
• Suitable supports which can be used in the invention have been disclosed, for example, on page 28 of Research Disclosure No. 17643, and from the right hand column on page 647 to the left hand column on page 648 of Research Disclosure No. 18716.
• Color photograhic material s according to this invention can be developed and processed using the normal methods disclosed on pages 28-29 of Research Disclosure No. 17643 and in the left and right hand columns of page 651 of Research Disclosure No. 18716.
• the color development baths used in the development processing of photosensitive materials of this invention are preferably aqueous alkaline solutions which contain primary aromatic amine based color developing agents as the principal components.
• Aminophenol based compounds are useful as color developing agents, but the use of p-phenylenediamine based compounds is preferred.
• Typical examples of these compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ,8-hydroxyethyl aniline, 3-methyl-4-amino-N-ethyl-N-S-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-0-methoxyethylaniline, and the sulfate, hydrochloride and p-toluenesulfonate salts of these compounds. Two or more of these compounds can be used conjointly, depending on the intended purpose.
• the color development baths generaly contain pH buffers, such as alkali metal carbonates, borates or phosphates, and development inhibitors or anti-fogging agents, such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds.
• pH buffers such as alkali metal carbonates, borates or phosphates
• development inhibitors or anti-fogging agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds.
• They may also contain, as required, various preservatives, such as hydroxylamine, diethylhydroxylamine, hydrazine sulfite, phenylsemicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine(1,4-diazabicyclo[2,2,2]-octane), organic solvents, such as ethylene glycol and diethylene glycol, development accelerators, such as benzyl alcohol, poly(ethylene glycol), quaternary ammonium salts and amines, dye forming couplers, competitive couplers, fogging agents such as sodium borohydride, auxiliary developing agents such.
• various preservatives such as hydroxylamine, diethylhydroxylamine, hydrazine sulfite, phenylsemicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine(1,4-diazabicyclo[2,2,2]-octane), organic solvent
• 1-phenyl-3-pyrazolidone viscosity imparting agents
• various chelating agents as typified by the aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids, typical examples of which include ethylenediamine tetraacetic acid, nitrilo triacetic acid, diethylenetriamine pentaacetic acid, cyclohexanediamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-disphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylenediamine di-(o-hydroxyphenylacetic acid), and salts of these compounds.
• Color development is carried out after a normal black and white development in the case of reversal processing.
• the known black-and-white developing agents for example, dihydroxybenzenes suct t as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, and aminophenols such as N-methyl-p-aminophenol, can be used individually, or in combinations, in the black and white development bath.
• the pH of these color developers and black and white developers is generally within the range fro 9 to 12. Furthermore, the replenishment rate of these development baths depends on the color photograhic material which is being processed, but it is generally less than 3 liters per square meter of photosensitive material,and it is possible, by reducing the bromide ion concentration in the replenisher, to use a replenishment rate of less than 500 ml per square meter of photosensitive material.
• the prevention of loss of liquid by evaporation, and aerial oxidation, by minimizing the contact area with the air in the processing tank is desirable in cases where the replenishment rate is low.
• the replenishment rate can be reduced further by suppressing the accumulation of bromide ion in the developer.
• the color development processing time is normally set between 2 and 5 minutes, but it is possible to arrange shorter processing times by using higher temperatures, higher pH levels, and higher concentrations of the color developing agent.
• the photographic emulsion layers are normally subjected to a bleaching process after color development.
• the bleaching process may be carried out at the same time as the fixing process (in a bleach-fix process) or it may be carried out as a separate process.
• a bleach-fix process can be carried out after a bleaching process in order to speed up processing.
• processing can be carried out in two connected bleach-fix baths, a fixing process can be carried out before carrying out a bleach-fix process, or a bleaching process can be carried out after a bleach-fix process, according to the intended purpose of the processing.
• bleaching agents include ferricyanides; dichromates; organic complex salts of iron(III) or cobalt(III), for example, complex salts with aminopolycarboxylic acids, such as ethylenediamine tetraacetic acid, diethylenetriaminepentaacetic acid, cylohexanedismine tetraacetic acid, methylimino diacetic acid, 1,3-diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid, citric acid, tartaric acid, or malic acid; persulfates; bromates; permanganates and nitrobenzenes.
• aminopolycarboxylic acids such as ethylenediamine tetraacetic acid, diethylenetriaminepentaacetic acid, cylohexanedismine tetraacetic acid, methylimino diacetic acid, 1,3-diaminopropane tetraacetic acid
• aminopolycarboxylic acid iron(lll) complex salts principally ethylenediamine tetraacetic acid iron(III) complex salts, and persulfates
• amino polycarboxylic acid iron(III) complex salts are especially useful in both bleach baths and bleach-fix baths.
• the pH of the bleach or bleach-fix baths in which aminopolycarboxylic acid iron(III) complex salts are being used is normally from 5.5 to 8, but processing can be speeded up by using a lower pH.
• Bleach accelerators can be used, as required, in the bleach baths, bleach-fix baths, or bleach or bleach-fix pre-baths.
• Examples of useful bleach accelerators have been disclosed in the following publications. Thus, there are the compounds which have a mercapto group or a disulfide group disclosed, for example, in U.S.
• Patent 3,893,858 West German Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53- 104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426, and Research Disclosure No.
• these compounds those which have a mercapto group or a disulfide group are preferred in view of their large accelerating effect, and the use of the compounds disclosed in U.S.
• Patent 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 is especially desirable.
• the use of the compounds disclosed in U.S. Patent 4,552,834 is also desirable.
• These bleach accelerators may be added to the sensitive material. These bleach accelerators are especially effective when bleach-fixing camera color photosensitive materials.
• Thiosulfates, thiocyanates, thioether based compounds, thioureas, and large quantities of iodides can be used as fixing agents, but thiosulfates are generally used for for this purpose and ammonium thiosulfate, in particular, can be used in the widest range of applications. Sulfites or bisulfites, or carbonylbisulfite addition compounds, are the preferred preservatives for bleach-fix baths.
• the silver halide color photographic materials of this invention are generally subjected to a water washing and/or stabilizing process after the desilvering process.
• the amount of water used in the water washing process can be fixed within a wide range according to the nature of the photosensitive material (depending on the materials, such as couplers, which are being used), the wash water temperature, the number of washing tanks (the number of washing stages),.the replenishment system, i.e. whether a counter-flow or a'sequential-flow system is used, and various other conditions.
• the relationship between the amount of water used and the number of water washing tanks in a multi-stage counter-flow system can be obtained using the method outlined on pages 24S-253 of Journal of the Society of Motion Picture and Television Engineers, Volume 64 ( May 1955).
• the amount of wash water can be greatly reduced by using the multi-stage counter-flow system described in this article but bacteria proliferate due to the increased residence time of the water in the tanks and problems arise as a result of the sediments which are formed becoming attached to the photosensitive material.
• the method in which the calcium ion and manganese ion concentrations are reduced as disclosed in JP-A-62-288838 can be used very effectively to overcome problems of this sort in the processing of color photosensitive materials of this invention.
• the pH value of the wash water used in the processing of the photosensitive materials of invention is within the range from 4 to 9, and preferably within the range from 5 to 8.
• the wash water temperature and the washing time can be set variously according to the nature of the photosensitive material and the application, but, in general, washing conditions of from 20 seconds to 10 minutes at a temperature of from 15°C to 45 C, and preferably of from 30 seconds to 5 minutes at a temperature of from 25°C to 40 C, are selected.
• the photosensitive materials of this invention can be processed directly in a stabilizing bath instead of being subjected to a water wash as described above.
• the known methods disclosed in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can all be used for this purpose.
• stabilizing baths which contain formalin and surfactant which are used as a final bath for camera color photosensitive materials are an example of such a process.
• Various chelating agents and fungicides can be added to these stabilizing baths.
• the overflow which accompanies replenishment of the above mentioned wash water and/or stabilizer can be re-used in other processes such as the desilvering process.
• a color developing agent may also be incorporated into the silver halide color photosensitive materials of this invention in order to simplify and speed up processing.
• the incorporation of various color developing agent precursors is preferred.
• the indoaniline based compounds disclosed in U.S. Patent 3,342,597 the Schiff's base type compounds disclosed in U.S. Patent 3,342,599 and Research Disclosure Nos. 14850 and 15159
• the aldol compounds disclosed in Research Disclosure No. 13924 the metal salt complexes disclosed in U.S. Patent 3,719,492, and the urethane based compounds disclosed in JP-A-53-135628, can all be used for this purpose.
• the various processing baths in this invention are used at a temperature of from 10. C to 50 C.
• the standard temperature is normally from 33 C to 38 C, but processing is accelerated and the processing time is shortened at higher temperatures and, conversely, increased image quality and improved stability of the processing baths can be achieved at lower temperatures.
• processes using hydrogen peroxide intensification or cobalt intensification as disclosed in West German Patent 2,226,770 or U.S. Patent 3,674,499 can be carried out in order to economize on silver in the photosensitive material.
• silver halide photosensitive materials of this invention can also be used as heat developable photosensitive materials as disclosed, for example, in U.S. Patent 4,500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056, and European Patent 210,660A2.
• An aqueous solution (100 cc) which contained 5.0 grams of silver nitrate and 100 cc of an aqueous solution which contained potassium bromide and potassium iodide were mixed simultaneously over a period of 3 minutes, with stirring, in an aqueous solution obtained by dissolving 10 grams of inert gelatin and 3.0 grams of potassium bromide in 1000 ml of distilled water at a temperature of 60 C, after which an excess of potassium bromide and inert gelatin were added and the emulsion was physically ripened for 20 minutes.
• aqueous silver nitrate solution and aqueous potassium halide (a mixture of potassium bromide and potassium iodide) solution were then added using a simultaneous mixing method in accordance with the method disclosed in U.S. Patent 4,242,445, to prepare silver iodobromide core grains.
• the silver iodide content was varied to 13.3, 20, 30 and 40 mol% by adjusting the mixing ratio of the potassium bromide and the potassium iodide.
• the size of the core grains was adjusted to from 0.82 6o 1.13 ⁇ m by means of the amount of silver halide added after physical ripening. The core grains were washed with water to remove the soluble salts.
• Silver bromide shells were then grown by selecting the core grains and the amount of silver halide so as to provide the core iodide contents and core/shell ratios indicated in Table 1 and adding a 1.0 mol/liter silver nitrate solution and a 1.03 mol/liter potassium bromide solution using a simultaneous mixing method.
• the shell solution using a simultaneous mixing method.
• the shell was formed after adsorbing compound (1) of which the structural formula is indicated below when preparing emulsions 4 to 9.
• Mainly potato shaped grains of low aspect ratio were used for the core grains in the preparation of emulsion 9.
• the shell was formed after adsorbing compound (2) of which the structural formula is indicated below when preparing emulsion 10.
• the structures of emulsions 1 to 10 are summarized in Table 1. Those which are indicated as having a distinct layer structure had a layer structure in which the presence of silver iodobromide which has a silver bromide content of 15 to 45 mol% as specified in this patent could be confirmed using the X-ray diffraction used.
• the form of the grains is indicated by the value, expressed as a percentage, obtained by dividing the sum of the projected areas of grains which had an aspect ratio (the value obtained by dividing the corresponding projected area diameter by the thickness of the grain) of from 3 to 10 by the sum of the projected area of all of the grains.
• the grain size is indicated by the volume equivalent sphere diameter for the volume weight.
• Emulsions 1 to 10 were adjusted to pH 6.5, pAg 8.4, after desalting, and chemically sensitized in the presence of compound (3) of which the structural formula is indicated below using sodium thiosulfate, chloroauric acid and potassium thiocyanate. The optimum quantities of each additive were selected for each emulsion.
• the development processing used was carried out at 38°C under the condition indicated below.
• the compositions of the processing baths used in each process were as indicated below.
• Samples 101 to 106 multi-layer color photo-sensitive materials consisting of layers of which the compositions are indicated below, were prepared on undercoated cellulose triacetate film supports.
• the amounts coated are shown in units of g/m 2 of silver in the case of silver halides and colloidal silver, in units of g/m 2 in the case of couplers, and in units of mol per mol of silver halide in the same layer in the case of sensitizing dyes.
• each layer about 400 ppm in average of benzisothiazolone and about 1,000 ppm in average of n-butyl p-hydroxybenzoate based on an amount of gelatin, were added.
• the emulsions 11 to 18 shown in Table 4 were prepared using the method of grain formation described in Example 1. Each emulsion was chemically sensitized with sodium thiosulfate and chlorauric acid in the presence of spectrally sensitizing dye. The amounts of each added were selected optimally. The emulsions used in Examples 101 to 106 are shown in Table 4.
• Samples 101 to 106 all had about the same speed. It was confirmed that granularity was improved when emulsions of this invention were used. Moreover, it was confirmed that the use of emulsions of this invention was particularly desirable with combinations of more than one layer.
• Sample 301 a multi-layer color photosensitive material, was prepared by the lamination coating of the layers of which the compositions are indicated below on an undercoated cellulose triacetate film support.
• the numerical value for each component indicates the amount coated in units of g/m 2 , calculated as silver in the case of the silver halides. However, the amounts coated are indicated in units of mol per mol of silver halide in the same layer in the case of the sensitizing dyes.
• Samples 302 to 311 were prepared in the same way except that Emulsion D in the fifth layer and Emulsion E in the ninth layer of Sample 301 were replaced as shown in Table 7. Moreover, when Emulsion E was replaced by Emulsion N in the amount of ExS-5, ExS-6, and ExS-7 were increased by a factor of 1.15, when it was replaced with Emulsion 0 these amounts were increased by a factor of 1.40, and when it was replaced with Emulsions P and Q these amounts were increased by a factor of 1.60.
• Emulsions A to Q used in these samples were prepared in accordance with the method described earlier.
• the characteristics of Emulsions A to Q are summarized in Table 6.
• the samples were given an imagewise exposure, developed and processed in the way indicated below and the relative speeds of each color sensitive layer were obtained.
• the relative speeds are indicated as the logarithm of the reciprocal of the exposure required to provide a density of fog + 0.2 for each of the cyan and magenta densities, and the values are expressed as relative values taking the value for Sample 301 to be zero.
• the samples were exposed through a wedge for RMS granularity measurement purposes and the RMS values for a 48 ⁇ m diameter aperture at cyan (R) and magenta (G) densities of fog + 0.2 were measured.
• Processing was carried out as indicated below at 38 * C using an automatic processor.
• the replenishment rate for each processing bath was 1200 ml per square meter of color photosensitive material in the case of the color development bath, and 800 ml per square meter of color photosensitive material in all other baths, including the water washing baths. Furthermore, the carry over from the previous bath to the water washing process was 50 ml per square meter of color photosensitive material.
• Town water which had a calcium ion content of 32 mg/t and a magnesium ion content of 7.3 mg/l was passed through a column packed with an H-type strongly acidic cation exchange resin and an OH-type strongly basic anion exchange resin, and 20 mg per liter sodium isocyanurate dichloride was added to the treated water which had a calcium ion content of 1.2 mg/l and a magnesium ion content of 0.4 mg/l for use.
• Samples 303 to 306 which contained emulsions J to M of this invention which had a distinct layered structured and a silver iodide content of at least 8 mol% were clearly superior in respect of graininess to the samples 301 and 302 which contained Emulsions D and I which were outside the scope of the present invention.
• Samples 307 to 309 which contained Emulsions 0 to Q in which the fraction of the projected area due to emulsion grains which had an aspect ratio of from 3 to 10 was at least 60% were clearly superior in respect of high speed and graininess to the samples 301 and 306 in which Emulsion E and N which are outside the scope of this invention had been used.

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• 1989
  • 1989-03-29 JP JP7789889A patent/JPH0228637A/ja active Pending
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