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
  • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material
• • 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
  • G03C1/485—Direct positive emulsions
  • G03C1/48538—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure

Definitions

• the present invention relates to a photographic image forming method, and particularly to a direct positive image forming method providing a high quality image.
• the invention relates a direct positive image forming method advantageously used for preparation of a color proof, which is used for quickly checking the final color or tone of a color print in the printing industry.
• the internal latent image type silver halide emulsion means a photographic silver halide emulsion which has sensitivity specks substantially inside of silver halide grains. Therefore, a latent image is formed inside of the grains by exposure.
• the direct positive image formation is described below.
• an internal latent image is formed inside of silver halide.
• the latent image causes the so-called surface desensitizing action. Accordingly, fog specks are formed selectively on the surface of unexposed silver halide grains.
• a photographic image directly positive image is formed within the unexposed area by the normal (so-called surface) development process.
• the known methods for forming the fog specks selectively are classified into the so-called “light fogging method", in which all area of the photosensitive layer is exposed to light (cf. U.K. Patent No. 1,151,363), and the so-called “chemical fogging method”, in which a nucleating agent is used.
• the latter method is disclosed in Research Disclosure vol.151, No. 15162 (published in Nov., 1976) pp. 76-78.
• a direct positive color image is obtained by the above-mentioned fogging process, a surface color development of the internal latent image type silver halide photosensitive material and bleaching and fixing (or bleach-fix) treatments. After the bleaching and fixing treatments, washing and/or stabilizing treatment are generally carried out.
• a color print is prepared by a transparent black and white halftone image formed by color separation of a color original.
• a color proof Prior to preparation of a printing plate from the transparent black and white halftone image, a color proof is usually prepared.
• the color proof is used for quickly checking the final color print.
• the preparation of color proof has an advantage of quick operation and low cost, compared with a test printing.
• Various silver halide photographic materials can be used for preparation of color proof.
• a positive photographic material is preferred, since the transparent black and white halftone image usually is positive type.
• the direct positive color photographic material described above is most advantageous to preparation of a color proof because the process for the direct positive material is very simple.
• the developing speed is relatively slow. In other words, its processing time is long compared with the conventional negative image forming method. Therefore, the developing solution has been used at a high pH value or a high temperature to shorten the processing time.
• the pH value causes a problem that the minimum image density in the obtained direct positive image is generally increased.
• the developing agent is easy to be deteriorated by air oxidation at the high pH value, and the pH value tends to be reduced by carbon dioxide in the air. As a result, the developing activity is remarkably decreased.
• Additives which have a function of accelerating the developing speed in the direct positive image forming method are known.
• the additives include hydroquinone derivatives disclosed in U.S. Patent No. 3,227,552 and mercapto compounds having a carboxyl group or a sulfo group disclosed in Japanese Patent Provisional Publication No. 60(1985)-170843.
• the effect of these additives is not powerful.
• An effective technique to enhance the maximum density of direct positive image has not yet been proposed. Particularly, it has been desired to obtain a high maximum image density without increasing the minimum image density.
• Japanese Patent Provisional Publication No. 1 (1989)-197742 reports that when a mercapto compound is added to a core/shell internal latent image type silver halide emulsion at the stage of after-ripening of the core, the maximum density is increased and the minimum density is decreased. However, the white ground and the tone of the image is not sufficiently improved (particularly in a copying process).
• the direct positive image forming method itself has some problems, though the method has an advantage of simple operation.
• the color reproducibility of the direct positive image is insufficient, since a masking technique in the conventional negative-positive process using two negative photosensitive materials can not be applied to the direct positive image formation. Further, the color reproducibility of the direct positive image for the color proof should be similar to the color of the printing ink.
• a difference between the obtained color image and the printed image is sometimes observed with respect to a color tone and a color density in a monochromatic area. This problem is often caused by a difference in the hue between the coloring matter in the color photographic material and the printing ink. The difference in the magenta color has particularly been reported.
• An object of the present invention is to provide a direct positive color image forming method which forms an image having a high maximum image without increasing the minimum image density.
• Another object of the invention is to provide a direct positive color image forming method which exhibits an excellent color reproducibility.
• a further object of the invention is to provide a direct positive color image forming method for a color proof which has an excellent color reproducibility, particularly the reproducibility of the red color which is similar to the printing ink.
• a furthermore object of the invention is to provide a direct positive color image forming method for a color proof, which has a high contrast and an excellent effect of cutting off the toe of an image.
• a direct positive color image forming method which comprises:
• the fogging process is preferably carried out in the presence of a nucleating agent having the formula (N-I) or (N-II): in which Z is a non-metallic atom group which forms a 5- or 6-membered heterocyclic ring; R" is an aliphatic group; R 12 is a hydrogen atom, an aliphatic group or an aromatic group; R 12 may be combined with the heterocyclic ring of Z to form another ring; at least one of R 11 , R 12 and Z contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R 11 and R 12 form a dihydropyridinium ring; Y is a counter ion for charge balance; and n is 0 or 1, in which R 21 is an aliphatic group, an aromatic group or a heterocyclic group; R 22 is hydrogen, an alkyl group, an aralkyl group, an aryl group, alkoxy group, an ary
• the layer containing the compound having the formula (I) of the photographic photosensitive materia preferably further contains a yellow coupler which is a compound having the formula (Y): in which R 31 is a tertiary alkyl group or an aryl group; R 32 is hydrogen, a halogen atom, an alkoxy group, an aryloxy group, an alkyl group or a dialkylamino group; R 33 is a substituent group of the benzene ring; X' is hydrogen or a group which can be eliminated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent; 1 is an integer of 0 to 4; and when I is 2 or more, the groups of R 33 may be different from each other.
• a yellow coupler which is a compound having the formula (Y): in which R 31 is a tertiary alkyl group or an aryl group; R 32 is hydrogen, a halogen atom, an alkoxy group, an aryloxy group, an
• the pyrazoloazole coupler having the formula (I) has been known as a magenta coupler in a conventional negative photographic material. But, this coupler has an absorption band at short wave length, compared with the other magenta couplers used in the negative photographic method. Therefore, this coupler has scarcely been used in the negative photographic method.
• the above-mentioned problems of the pyrazoloazole coupler having the formula (I) in the negative image forming method is not present in the direct positive image forming method, particularly in the preparation of a color proof.
• the hue of this coupler having an absorpotion band at short wave length is very similar to the hue of a printing ink. Therefore, the color reproducibility of the direct positive image forming method is greatly improved by the coupler having the formula (I). This effect of the present invention cannot be expected from the disclosure of the negative image forming method.
• a preferable short wavelength type pyrazoloazole magenta coupler having the formula (I) is a compound having the formula (II), (III), (IV), (V), (VI) or (VII). in which each of R 1 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 is hydrogen or a substituent group; X is hydrogen or a group which can be eliminated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent.
• Hammett's substituent value ⁇ p (hereinafter simply referred to as " ⁇ p ") of R 1 , R 6 or R 7 is not less than -2.00 and not more than -0.41, or the sum of their ⁇ p values is not less than -2.00 and not more than -0.41.
• ⁇ p of R 1 , R 8 or R 9 is not less than -2.00 and not more than -0.41, or the sum of their ⁇ p values is not less than -2.00 and not more than -0.41.
• ⁇ p of R 1 or R 10 is not less than -2.00 and not more than -0.41, or the sum of their ⁇ p values is not less than -2.00 and not more than -0.41.
• ⁇ p of R 1 or R 11 is not less than -2.00 and not more than -0.41, or the sum of their ⁇ p values is not less than -2.00 and not more than -0.41.
• ⁇ p of R 1 is not less than -2.00 and not more than -0.41.
• the ⁇ p value of R 12 is not particularly restricted, but preferably is a small value.
• a morepreferable short wavelength type pyrazoloazole magenta coupler of the invention is a compound having the formulae (IV), (V) or (VI).
• a compound having the formula (IV) is most preferred.
• R 1 and R 6- R 12 in formulae (II)-(VII) include hydrogen, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, an acylamino group, an anilino group, an ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclicoxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imido group, a heterocyclicthio group, a sulfin
• X is hydrogen, a halogen atom, a carboxyl group or a group which is eliminated by a coupling reaction.
• An oxygen atom, a nitrogen atom, a carbon atom or a sulfur atom of the elimination group connects to a carbon atom at the coupling position.
• Each of R 1 , R 6- R 12 and X may be a divalent linking group to form a dimer.
• Each of the compounds may be a polymer in which Ri, R 6 -R 12 or X is a divalent linking group connecting to a main chain of the polymer.
• R 1 and R 6- R 12 include hydrogen, a halogen atom (e.g., chlorine atom or bromine atom), an alkyl group (an alkyl group of straight branched chain having 1-32 carbon atoms), an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group and a cycloalkenyl group. These groups may be substituted with a substituent group containing a connective atom or group (such as oxygen, nitrogen, sulfur, a carbonyl group), hydroxyl, amino, nitro, carboxyl, cyano or a halogen atom.
• a halogen atom e.g., chlorine atom or bromine atom
• an alkyl group an alkyl group of straight branched chain having 1-32 carbon atoms
• an aralkyl group an alkenyl group, an alkynyl group, a cycloalkyl group and a cycloalkeny
• alkyl group examples include methyl, propyl, t-butyl, trifluoromethyl, tridecyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl, 3- ⁇ 4- ⁇ 2-[4-(4-hydroxyphenylsulfonyl)phenoxy]-dodecaneamido ⁇ phenyl ⁇ propyl, 2-ethoxytridecyl, trifluoromethyl and cyclopentyl and 3-(2,4-di-t-amyl- phenoxy)propyl.
• aryl group examples include phenyl, 4-t-butylphenyl, 2,4-di-t-aminophenyl and 4-tetradecaneamidophenyl.
• heterocyclic group examples include 2-furyl, 2-thienyl, 2-pyrimidinyl and 2-benzothiazolyl
• alkoxy group examples include methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy and 2- methanesulfonylethoxy.
• aryloxy group examples include phenoxy, 2-methylphenoxy and 4-t-butylphenoxy.
• acylamino group examples include acetamido, benzamido, tetradecaneamido, a-(2,4-di-t-amyl- phenoxy) butylamido, -y-(3-t-butyl-4-hydoxyphenoxy)butylamido and a-(4-(4-hydroxyphenylsulfonyl)-phenoxyldecanamido.
• anilino group examples include phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneamidoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino and 2-chloro-5- ⁇ -(3-t-butyl-4-hydroxyphenoxy)-dodecanamido)anilino.
• ureido group examples include phenyleneureido, methylureido and N,N-dibutylureido.
• Examples of the sulfamoylamino group include N,N-dipropylsulfamoylamino and N-methyl-N-decyl- sufamoylamino.
• alkylthio group examples include methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio and 3-(4-t-butylphenoxy)propylthio.
• arylthio group examples include phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio and 4-tetradecaneamidephenylthio.
• alkoxycabonylamino group examples include methoxycarbonylamino and tetradecyloxycar- bonylamino.
• sulfonamido group examples include methanesufonamido, hexadecanesulfonamido, benzenesulfonamido, p-toluenesulfonamido, octadecanesulfonamido and 2-methyloxy-5-t-butylbenzenesulfonamido
• Examples of the carbamoyl group include N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecylox- yethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl and N- ⁇ 3-(2,4-di-tert-amylphenoxy)propyl ⁇ carbamoyl.
• Examples of the sulfamoyl group include N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecylox- yethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N,N-diethylsulfamoyl and N,N-diethylsulfamoyl group.
• sulfonyl group examples include methanesulfonyl, octanesulfonyl, benzenesulfonyl and toluenesulfonyl.
• alkoxycarbonyl group examples include methoxycarbonyl, butyloxycarbonyl, dodecylcarbonyl and octadecylcarbonyl.
• heterocyclicoxy group examples include 1-phenyltetrazole-5-oxy and 2-tetrahydropyranyloxyl.
• acyloxy group is acetoxy.
• Examples of the carbamoyloxy group include acetylaminoxy and benzoylaminoxy.
• silyloxy group examples include trimethylsilyloxy and dibutylmethylsilyloxy.
• aryloxycarbonylamino group is phenoxycarbonylamino.
• imido group examples include N-succinimido, N-phenylimido and 3-octadecenylsuccinimido.
• heterocyclicthio group examples include 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio and 2-pyridylthio.
• sulfinyl group examples include dodecanesulfinyl, 3-pentadecylphenylsulfinyl and 3-phenox- ypropylthio.
• Examples of the phosphonyl group include phenoxyphosphonyl, octyloxyphosphonyl and phenyl- phosphonyl.
• aryloxycarbonyl group is phenoxycarbonyl.
• acyl group examples include acetyl, 3-phenylpropanoyl, benzoyl and 4-dodecyloxybenzoyl.
• ⁇ p value of R 1 , R 6 or R 7 in the formula (II) is not less than -2.00 and not more than -0.41
• ⁇ p value of R 1 , R 8 or R 9 in the formula (III) is not less than -2.00 and not more than -0.41
• ⁇ p value of R 1 or R 10 in the formula (IV) is not less than -2.00 and not more than -0.41
• ⁇ p value of R 1 or R 11 in the formula (V) is not less than -2.00 and not more than -0.41
• substituent group examples of the substituent group are described below.
• X is hydrogen atom, a halogen atom, a carboxyl group, a group containing oxygen as a connective atom, a group containing nitrogen as a connective atom, a group containing sulfur as a connective atom or a group containing carbon as a connective atom.
• halogen atom examples include chlorine, bromine and iodine.
• Examples of the group containing oxygen as a connective atom include acetoxy, propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenoxy, 4-methanesulfonamidephenoxy, 4-methanesulfonylphenoxy, a-naphthoxy, 3-pentadecyl- phenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, 2-phenethyloxy, 2-phenoxyethoxy, 5-phenyltetrazolyloxy and 2-benzothiazolyloxy.
• Examples of the group containing nitrogen as a connective atom include benzenesulfonamido, N-ethyltoluenesulfonamido, heptafluorobutanamido, 2,3,4,5,6-pentafluorobenzamido, octanesulfonamido, p-cyanophenylureido, N,N-diethylsulfamoylamino, 1-piperidyl, 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl, 1-benzyl- ethoxy-3-hydantoinyl, 2H-1,1 -dioxo-3(2H)-oxo-1,2-benzoisothiazolyl, 2-oxo-1,2-dihydro-1-pyridinyl, imidazolyl, pyrazolyl, 3,5-diethyl-1,2,4-triazole-1-yl, 5-
• Examples of the group containing sulfur as a connective atom include group include phenylthio, 2-carboxyphenylthio, 2-methoxy-5-t-octylphenylthio, 4-methanesulfonylphenylthio, 4-octanesulfonamidephenyl- thio, benzylthio, 2-cyanoethylthio, 1-ethoxycarbonyltridecylthio, 5-phenyl-2,3,4,5-tetrazolylthio, 2-benzothiazolyl, thiocyano, N,N-diethylthiocarbonylthio and dodecyloxythiocarbonylthio.
• Examples of the group containing carbon as a connective atom include a triphenylmethyl, a hydroxymethyl, a N-morpholinomethyl group and a group having the following formula. in which each of R 21 and R 22 is hydrogen, an alkyl group, an aryl group or a heterocyclic group; and each of R 1 , Z a , Z b and Z c has the same meanings as is described above.
• R 1 , R 6 , R 7 , R 8 , R 9 , R1°, R 11 , R 12 or X is an alkyl group or a group containing an alkyl group (e.g., an alkoxy group, an alkylthio group, an alkoxycarbamoyl group and alkoxycarbonyl group), the alkyl group usually contains 1-50, preferably 1-40, more preferably 1-30 carbon atoms. In the case that the group is an acyl group, the number of carbon atoms is the same as defined above.
• R 1 , R 6- R 12 or X may be a divalent linking group. In this case, a dimer is formed.
• Examples of the divalent linking group of R 1 , R 6- R 12 or X include a substituted or non-substituted alkylene group (e.g., methylene, ethylene, 1,10-decylene and -CH 2 CH 2 -0-CH 2 CH 2 -), a substituted or non-substituted phenylene group
• L 1 is a substituted or non-substituted alkylene group or a substituted or non-substituted phenylene group (e.g., and and -S-L 2- S- group in which L 2 is a substituted or non-substituted alkylene group (e.g., or
• X functions as the linking group of the dimer.
• the short wavelength type pyrazoloazole magenta coupler having the formula (II)-(VII) may be a polymer in which R 1 , R 6 -R 11 or R 12 is a divalent linking group connected to a main chain of the polymer.
• linking group examples include an alkylene group (a substituted or non-substituted alkylene group; e.g., methylene, ethylene, 1,10-decylene and -CH 2 CH 2 -O-CH 2 CH 2 -), a phenylene group (a substituted or non-substituted phenylene group; e.g., 1,4-phenylene, 1,3-phenylene, and A group formed by combination of the above groups is also available.
• alkylene group a substituted or non-substituted alkylene group
• a substituted or non-substituted alkylene group e.g., methylene, ethylene, 1,10-decylene and -CH 2 CH 2 -O-CH 2 CH 2 -
• a phenylene group a substituted or non-substituted phenylene group
• 1,4-phenylene 1,3-phenylene
• linking groups are shown below.
• the short wavelength type pyrazoloazole magenta coupler having the formulae (II)-(VII) is a polymer (i.e., a polymer coupler)
• the examples of the polymer are described in U.S. Patent No. 4,540,654.
• monomers having the formulae (II)-(VII) may be polymerised with each other to form a polymer. Further, they may be polymerised to form a copolymer with a non-color developing ethylenic monomer which does not be coupled with an oxidant of an aromatic primary amine developing agent.
• non-color developing ethylenic monomer which does not be coupled with an oxidant of an aromatic primary amine developing agent
• examples of the non-color developing ethylenic monomer which does not be coupled with an oxidant of an aromatic primary amine developing agent include acrylic acid, a-chloroacrylic acid, a-alkylacrylic acid (e.g., methacrylic acid), esters and amides derived from these acrylic acids (e.g., acrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methacrylamide, methylacrylate, ethylacrylate, n-propylacrylate.
• Two or more non-color developing ethylenic monomers described above can be used in combination.
• Examples of the combination of the monomers include the combination of n-butylacrylate and methylacrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, and methylacrylate and diacetoneacrylamide.
• the non-color developing ethylenic monomer with which solid water-insoluble monomer coupler is polymerized to form a copolymer can be selected in consideration of physical and/or chemical properties of the formed copolymer (e.g., solubility), compatibility with the binder of photographic colloidal composition (e.g., gelatin), flexibility and heat stability.
• Polymer coupler used the invention may be either water soluble or water insoluble.
• a polymer coupler latex is particularly preferred.
• the short wavelength type pyrazoloazole magenta coupler of the invention having the formula (I) can be synthesized in accordance with an appropriate method selected from methods of synthesizing pyrazoloazoles described in U.S. Patents No. 3,061,432, No. 3,725,067, No. 4,500,630 and No. 4,540,654, British Patent No. 1,334,515, and Japanese Patent Provisional Publications No. 60(1985)-33552, No. 60-(1985)-43659, No. 61(1986)-93098 and No. 1(1989)-40831.
• the compound having the formula (I) is used in an amount of 0.001 mole to 1 mole, preferably 0.03 mole to 0.3 mole per 1 mole of silver halide.
• a compound having the following formula (M) is particularly preferred.
• R 51 is an alkyl group or an aryl group
• Z is a non-metallic atom group which forms a 5-membered azole ring containing two, three or four nitrogen atoms; the azole ring may have a substituent group (including a condensed ring)
• X is hydrogen or a group which can be eliminated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent; and X is not a halogen atom when R 51 is an alkyl group.
• the alkyl group and the aryl group is preferably substituted with an alkoxy group or an aryloxy group.
• magenta coupler having the formula (M) is described below.
• the ring of the coupler having the formula (M) preferably is 1 H-imidazo[1,2-b]pyrazole, 1 H-pyrazolo[1,5-b][1,2,4]triazole, 1H-pyrazolo[5,1-c][1,2,4]triazole or 1-H-pyrazole[1,5-b]tetrazole.
• Each of them has the following formulae (M-I), (M-II), (M-III) or (M-IV).
• R 61 is an alkyl group (normal or straight, branched or cyclic chain having 1-32 carbon atoms) or an aryl group (such as phenyl, naphthyl).
• the alkyl group and the aryl group may be substituted with a group containing carbon, oxygen, nitrogen or sulfur as a connective atom or a halogen atom.
• alkyl group examples include methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 2-phenoxyethyl, 2-ethoxyethyl, 2-acetylaminoethyl, 2-(2,4-di-t-amylphenoxy)ethyl, ethoxycarbonylmethyl, 2,2,2-trifluoroethyl, 2-(phthalimidoyl)ethyl and 2-hydroxyethyl.
• Preferred are methyl, ethyl, 2-phenoxyethyl and 2-ethoxyethyl.
• the aryl group preferably has an electron donating group.
• Examples of the aryl group include 2-methoxyphenyl, 2,4-dimethoxyphenyl, 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2,6-dimethoxy-4-methylphenyl, 2,4-di(N,N-dimethylamino)phenyl and 2-methyl-4-(N,N-dimethylamino)phenyl.
• Preferred are 2-methoxyphenyl, 2,4-dimethoxyphenyl and 2,6-dimethoxyphenyl.
• R 62 is hydrogen, an alkyl group or an aryl group.
• the alkyl group and the aryl group may be substituted with a group containing carbon, oxygen, nitrogen or sulfur as a connective atom or a halogen atom.
• alkyl group examples include methyl, ethyl, isopropyl, t-butyl, tridecyl, 3-(4-acylaminophenyl)-propyl, 3-(4-alkylsulfonamidophenyl)propyl, 3-(4-arylsulfonamidophenyl)propyl, 2-acylaminoethyl, 2-alkylsulfonamidoethyl, 2-arylsulfonamidoethyl, 2-acylamino-1-methylethyl, 2-alkylsulfonamido-1-methylethyl, 2- arylsulfonamido-1-methylethyl, acylaminomethyl, alkylsulfonamidomethyl, arylsulfonamidomethyl, 1-acylaminoethyl, 1-alkylsulfonamidoethyl and 1-arylsulfonamido
• aryl group examples include phenyl, 3 or 4-acylaminophenyl, 3 or 4-alkylsulfonamidophenyl, 3 or 4-arylsulfonamidophenyl, 3-acylamino-2,4,6-trimethylphenyl, 3-alkylsulfonamido-2,4,6-trimethylphenyl and 3- arylsulfonamido-2,4,6-trimethylphenyl.
• Preferred are 3-acylaminophenyl, 3-arylsulfonamidophenyl, 3- acylamino-2,4,6-trimethylphenyl and 3-arylsulfonamido-2,4,6-trimethylphenyl.
• R 63 is hydrogen, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group and an acyl group.
• the alkyl group preferably is a normal or straight or branched chain having 1-32 carbon atoms.
• Examples of the alkyl group, the aralkyl group, the alkenyl group, the alkynyl group, the cycloalkyl group and the cycloalkenyl group include methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, trifluoromethyl, heptafluoropropyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl, 3- ⁇ 4- ⁇ 2-[4-(4-hydroxyphenylsul- fonyl)phenoxy]dodecanamidolphenyllpropyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl and 3-(2,4-di-t-amylphenoxy)propyl.
• aryl group examples include phenyl, pentafluorophenyl, pentachlorophenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl and 4-tetradecanamidophenyl.
• heterocyclic group examples include 2-furyl, 2-thienyl, 2-pyrimidinyl and 2-benzothiazolyl.
• alkoxycarbonyl group examples include methoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl and octadecyloxycarbonyl.
• carbamoyl group examples include N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecylox- yethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl and N-[3-(2,4-di-t-amylphenoxy)propyl)carbamoyl.
• Examples of the sulfamoyl group include N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecylox- yethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl and N,N-diethylsulfamoyl.
• sulfonyl group examples include methanesulfonyl, octanesulfonyl, benzenesulfonyl and toluenesulfonyl.
• R 63 preferably is an alkoxycarbonyl group or a carbamoyl group.
• R 61 is an aryl group
• X is hydrogen or a group which can be eliminated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent.
• Examples of the elimination group include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, an acylamino group, an alkylsulfonamido group, an arylsulfonamido group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkylthio group, an arylthio group, a heterocyclicthio group, a carbamoylamino group, a 5 or 6-membered nitrogen-containing heterocyclic group, an imido group and an arylazo group. These groups may have a substituent group.
• halogen atom examples include fluorine, chlorine and bromine.
• alkoxy group examples include ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carbox- ypropyloxy, methylsulfonylethoxy and ethoxycarbonylmethoxy.
• aryloxy group examples include 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy and 2-carboxyphenoxy.
• acyloxy group examples include acetoxy, tetradecanoyloxy and benzoyloxy.
• alkyl or arylsulfonyloxy group examples include methanesulfonyloxy and toluenesulfonyloxy.
• acylamino group examples include dichloroacetylamino and heptafluorobutylylamino.
• alkyl or arylsulfonamido group examples include methanesulfonamido, trifluoromethanesul- fonamido and p-toluenesulfonylamido.
• alkoxycarbonyloxy group examples include ethoxycarbonyloxy and benzyloxycarbonyloxy.
• aryloxycarbonyloxy group is phenoxycarbonyloxy.
• alkyl, aryl or heterocyclicthio group examples include dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio and tetrazolylthio.
• Examples of the carbamoylamino group include N-methylcarbamoylamino and N-phenylcar- bamoylamino.
• Examples of the 5 or 6-membered nitrogen-containing heterocyclic group include imidazolyl, pyrazolyl, triazolyl, tetrazolyl and 1,2-dihydro-2-oxo-1-pyridyl.
• imido group examples include succinimido and hydantoinyl.
• arylazo group examples include phenylazo and 4-methoxyphenylazo.
• X may be an elimination group which has a carbon atom of an aldehyde or a ketone as the connective atom. In this case, the elimination group forms a tetramer of the coupler. Further, X may contain a photographic functional group such as a development inhibiting group or a development accelerating group.
• R 61 is an aryl group
• X preferably is a halogen atom, an aryloxy group, an alkylthio group, an arylthio group or a 5 or 6-membered nitrogen-containing heterocyclic group which can be attached to a coupling position at the nitrogen atom.
• a halogen atom, an alkylthio group and an arylthio group are particularly preferred.
• R 61 is an alkyl group
• X is not a halogen atom.
• X preferably is an alkylthio group, an arylthio group or a 5 or 6-membered nitrogen-containing heterocyclic group which can be attached to a coupling position at the nitrogen atom.
• An arylthio group is particularly preferred.
• the prazoloazole rings having the formula (M-II) or (M-lll) is preferred.
• the formula (M-II) is most preferred.
• magenta coupler having the formula (M) examples are described below.
• magenta coupler having the formula (M) can be synthesized in accordance with an appropriate method selected from methods described in Japanese Patent Provisional Publications No. 62(1987)-209457, No. 63(1988)-250386, No. 63(1988)-307453 and No. 2(1990)-115183.
• nucleating agent having the formula (N-I) or (N-II) is described in detail.
• heterocyclic ring comprising Z in the formula (N-I) examples include a quinolinium ring, a benzothiazolium ring, a benzimidazolium ring, a pyridinium ring, a thiazolinium ring, a thiazolium ring, a naphthothiazolinium ring, a selenazolium ring, a benzoselenazolium ring, a imidazolium ring, a tetrazolium ring, a indolenium ring, a pyrrolinium ring, a acridinium ring, a phenanthridinium ring, an isoquinolinium ring, an oxazolium ring, a naphthoxazolium ring and a benzoxazolium ring.
• substituent group of Z examples include an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkynyl group, hydroxyl, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylthio group, an arylthio group, an acyloxy group, an acylamino group, a sulfonyl group, a sulfonyloxy group, a sulfonylamino group, a carboxyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an ureido group, an urethane group, a carboxylic ester group, a hydrazine group, a hydrazone group and an imino group. At least one group selected from the these groups can be used as the substituent group of
• the substituent group of Z may be a heterocyclic quaternary ammonium group comprising Z and an appropriate linking group "L".
• the compound is the so-called dimer.
• Preferred examples of the heterocyclic ring comprising z include a quinolinium ring, a benzothiazolium ring, a benzimidazolium ring, a pyridinium ring, an acridinium ring, a phenanthridinium ring and an isoquinolinium ring. More preferred examples include a quinolinium ring and a benzothiazolium ring, and the most preferred example is quinolinium ring.
• the aliphatic group of R 11 and R 12 is a non-substituted alkyl group having 1-18 carbon atoms or a substituted alkyl group in which the alkyl part has 1-18 carbon atoms.
• Examples of the substituent group are the same as those of Z described above.
• the aromatic group of R 12 is a group having 6-20 carbon atoms, such as phenyl and naphtyl. Examples of the substituent group are the same as those of Z described above.
• a preferred group of R 12 is an aliphatic group and the most preferred examples include methyl, a substituted methyl group and a group connecting to the heterocyclic ring comprising Z to form another ring.
• R 12 and Z has an alkynyl group, an acyl group, a hydrazine group or a hydrazone group; or R 11 and R 12 form a 6-membered dihydropyridinium ring. These groups may be substituted with the substituent groups, which are the same as those of Z described above.
• At least one of R", R 12 , Z and a substituent group of the ring preferably is an alkynyl group or an acyl group.
• R" and R 12 preferably form a 6-membered dihydropyridinium ring.
• At least one of R", R 12 , Z and a substituent group of the ring more preferably is an alkynyl group, and most preferably is propargyl.
• An adsorption promoting group contained in the substituent group of R 11 , R 12 and Z preferably is a group having the formula, X 1 -(L 1 ) m - in which X 1 is a group promoting adsorption on silver halide, L' is a connecting group, and m is 0 or 1.
• Examples of the group promoting adsorption on silver halide represented by X 1 include a thioamido group, a mercapto group and a 5 or 6-membered nitrogen-containing heterocyclic group.
• thioamido group is a non-cyclic thioamido group (e.g., a thiourethane group or a thioureido group).
• a particularly preferred mercapto group of X 1 is a heterocyclic mercapto group (e.g., 5-mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mercapto-1,3,4-thiadiazole and 2-mercapto-1,3,4-oxadiazole).
• a heterocyclic mercapto group e.g., 5-mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mercapto-1,3,4-thiadiazole and 2-mercapto-1,3,4-oxadiazole.
• a 5- or 6-membered nitrogen-containing heterocyclic group of X comprises nitrogen, oxygen, sulfur or carbon.
• the heterocyclic group preferably is a group forming an iminosilver, for example, benztriazole or aminothiatriazole.
• a divalent linking group of L 1 is an atom or an atomic group containing carbon (C), nitrogen (N), sulfur (S) or oxygen (O).
• Examples of a counter ion, Y for charge balance include bromide ion, chloride ion, iodide ion, p-toluenesulfonate ion, ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion, thiocyanate ion, tetrafluoroborate ion and hexafluorophosphate ion.
• R 21 preferably is an aromatic group, an aromatic heterocyclic group or a methyl group substituted with an aryl group, and more preferably is an aryl group (e.g., phenyl and naphtyl). R 21 may have a substituent group.
• substituent groups include an alkyl group, an aralkyl group, an alkoxy group, an alkyl or aryl substituted amino group, an acylamino group, a sulfonylamino group, an ureido group, an urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an aryl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, a hydroxyl group, a halogen atom, a cyano group, a sulfo group, a carboxyl group and a phosphoric amido group.
• An ureido group and a sulfonylamino group are particularly preferred. These groups may further have a substituent group.
• Two or more of these groups may form a ring.
• R 22 preferably is hydrogen, an alkyl group (e.g., methyl), an aralkyl group (e.g., 2-hydroxybenzyl) or an aryl group (e.g., 2-hydroxymethylphenyl). Hydrogen and an aryl group are particularly preferred.
• substituent group of R 22 are not only those of R 21 , but also such groups as an acyl group, an acyloxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkenyl group, an alkynyl group and a nitro group. These groups may further have a substituent group. Two or more of these groups may form a ring.
• R 21 or R 22 may have a nondiffusion group, which is contained in a nondiffusion coupler; and also may have a group expressed by X 2- (L 2 ) m2 - which promotes adsorption on the surface of silver halide grains, where the group connects preferably through ureido group or sulfonylamino group.
• X 2 represents the same meaning as X 1 in the formula (N-I), and preferably is a thioamido group, mercapto group or a 5 or 6-membered nitrogen-containing heterocyclic group.
• L 2 is a divalent linking group and represents the same meaning as L l in the formula (N-I), and m2 is 0 or 1.
• Preferred examples of X 2 include a non-cyclic thioamido group (e.g., a thioureido group and a thiourethane group), a cyclic thioamido group (i.e., a nitrogen-containing heterocyclic ring substituted with mercapto group, such as 2-mercaptothiadiazolyl, 3-mercapto-1,2,4-triazolyl, 5-mercaptotetrazolyl, 2-mercapto-1,3,4-oxadiazolyl and 2-mercaptobenzoxazolyl) and a nitrogen-containing heterocyclic group (e.g., a benzotriazolyl, benzimidazolyl and indazolyl).
• a non-cyclic thioamido group e.g., a thioureido group and a thiourethane group
• a cyclic thioamido group i.e., a nitrogen-containing
• X 2 preferably is a nitrogen-containing heterocyclic ring substituted with a mercapto group or a nitrogen-containing heterocyclic ring which forms an iminosilver.
• Each of R 23 and R 24 preferably is hydrogen.
• G most preferably is a carbonyl group.
• the compound having the formula (N-II) preferably has a group promoting adsorption to silver halide, an ureido group or a sulfonylamino group.
• the compound (N-II) of hydrazine-type nucleating agent having a group promoting adsorption onto silver halide can be synthesized in accordance with the process described in U.S. Patents No. 4,030,925, No. 4,080,207, No. 4,031,127, No. 3,718,470, No. 4,269,927, No. 4,276,364, No. 4,278,748, No. 4,385,108, No. 4,459,347. No. 4,478,922, No. 4,560,632, U.K. Patent No. 2,011,391 B, Japanese Patent Provisional Publications No. 54(1979)-74729, No. 55(1980)-163533, No. 55(1980)-74536 and No. 60(1985)-179734.
• hydrazine-type nucleating agents are described in Japanese Patent Provisional Publication No. 57(1982)-86829, and U.S. Patents No. 4,560,638, No. 4,478,928, No. 2,563,785 and No. 2,588,982.
• the photographic photosensitive material containing the compound having the formula (N-I) or (N-II) can be prepared by adding a solution in which the compound is dissolved in an organic solvent mixable with water, such as an alcohol (e.g., methanol and ethanol), an ester (e.g., ethylacetate) and a ketone (e.g., acetone); or an aqueous solution (in the case that the compound is water-soluble) into a hydrophilic colloidal solution.
• an organic solvent mixable with water such as an alcohol (e.g., methanol and ethanol), an ester (e.g., ethylacetate) and a ketone (e.g., acetone); or an aqueous solution (in the case that the compound is water-soluble) into a hydrophilic colloidal solution.
• the addition can be carried out at any time within the period from the beginning of chemical ripening until the beginning of coating, but preferably it is performed after chemical ripening.
• the nucleating agent having the formula (N-I) or (N-II) may be contained in a hydrophilic colloidal layer which is adjacent to a silver halide emulsion layer.
• the nucleating agent is preferably contained in a silver halide emulsion layer.
• the amount of the agent added to the layer varies in a wide range, because the amount practically depends on the character of the silver halide, the chemical structure of the agent and the developing conditions.
• a practically used amount is within a range of 1 x 10- 8 to 1 x 10- 2 mole per 1 mole of silver in the silver halide, and preferably is within a range of 1 x 10- 7 to 1 x 10- 3 mole per 1 mole of silver.
• a preferred nucleating agent used in the invention is the compound having the formula (N-I), and further the compound having the formula (N-I) in which R 12 connects to the heterocyclic ring comprising Z to form another ring is more preferred.
• R 33 examples include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, a nitro group, a heterocyclic group, a cyano group, an acyl group, an acyloxy group, an alkylsulfonyloxy group and an arylsulfonyloxy group.
• Examples of the elimination group include a heterocyclic group of which nitrogen connects to a coupling position, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, a heterocyclicoxy group and a halogen atom.
• R 31 in the formula (Y) include t-butyl, phenyl, a halogen atom and a phenyl group substituted with an alkyl group or an alkoxy group.
• R 32 preferably is a halogen atom, an alkoxy group or phenoxy.
• R 33 preferably is a halogen atom, an alkoxy group, an alkoxycarbonyl group, a carbonamido group, a sulfonamido group, a carbamoyl group or a sulfamoyl group.
• X 1 preferably is an aryloxy group or a 5 or 7-membered heterocyclic group in which nitrogen connects to coupling position.
• the heterocyclic ring may further contains N, S, O or P.
• I preferably is 0, 1 or 2.
• the coupler having the formula (Y) may form a dimer, an oligomer, a homopolymer or a copolymer having non-color developing unit, which connects at the substituent group R 31 , X or to a divalent or more multivalent group.
• the compound having the formula (Y) is used in an amount of 0.001 mole to 1 mole per 1 mole of silver halide, and preferably in an amount of 0.01 mole to 0.5 mole.
• Any silver halide selected from silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride can be used for the photographic emulsion layer of the photographic photosensitive material used in the present invention.
• the shape of the silver halide grain in the photographic emulsion may be either in the form of a regular crystal such as cube, octahedron and tetradecahedron (these are the so-called regular grains), or in the form of an irregular crystal such as globular shapes, or in the form of a crystal having crystal defect such as twinning plane. Further, the shape of the grain may be complex of these crystals. A mixture of grains of various crystals is also available.
• the silver halide grains may be either fine grains whose size is not more than approx. 0.1 ⁇ rn or large grains whose projected area is approx. 10 ⁇ m in diameter. There is no specific limitation on the grain size distribution of silver halide grains. Silver halide grains having an almost uniform grain size distribution are preferably employed in view of gradation adjustment and image quality control.
• a photographic emulsion of silver halide available for the invention can be prepared in accordance with a known method, for example, described in "Emulsion Preparation and Types", Research disclosure, vol. 176, No. 17643 (December, 1978), pp. 22-23; or ibid., vol. 187, No. 18716 (November, 1979), pp. 648.
• a photographic emulsion available for the invention can be prepared in accordance with a method described in "Chimie et Physique Photographique” by P. Glafkides, Paul Montel, 1967; “Photographic Emulsion Chemistry” by G.F. Duffin, Focal Press, 1966; or “Making and Coating Photographic Emulsion” by V.L. Zelikman et al., Focal Press, 1964). Namely, any of acid process, neutral process and ammonia process can be used.
• a soluble silver salt can be reacted with a soluble halogen salt in accordance with any of one side mixing process, simultaneous mixing method and a combination of them.
• a process in which grains are formed in the presence of excess silver ion is also available.
• a so-called “controlled double jet method”, which is a kind of simultaneous mixing method, can also be used. In this method, pAg value of the liquid phase in which silver halide is formed is kept at a constant value.
• a silver halide emulsion in which silver halide grain has a regular crystal and the grain size is almost uniform can be prepared.
• a known silver halide solvent e.g., ammonia, potassium rhodanide, a thioethers and a thionic compound described in U.S. Patent No. 3,271,157, Japanese Patent Provisional Publications No. 51(1976)-12360, No. 53(1978)-82408, No. 53-(1978)-144319, No. 54(1979)-100717 and No. 54(1979)-155828.
• a silver halide emulsion in which silver halide grain has a regular crystal and in which the grain size is almost uniform can also be prepared.
• the above-mentioned silver halide emulsion comprising regular grains can be obtained by controlling pAg value and pH value in the process of forming silver halide grains.
• Photographic Science and Engineering vol. 6 (1962), pp 159-165; Journal of Photographic Science, vol. 12-(1964), pp. 242-251; U.S. Patent No. 3,655,394 and U.K. Patent No. 1,413,748.
• a typical silver halide emulsion preferably used in the invention has such a characteristic that the silver halide grains have a mean grain size of not less than approx. 0.05 L m and the sizes of 95 wt.% of the grains are within a range of ⁇ 40 % of the mean grain size.
• the silver halide emulsion used in the present invention may have such as characteristic that the mean grain size is in a range of 0.15 to 2 lim and the sizes of 95 % by weight or by number of grains are within a range of ⁇ 20 % of the mean grain size.
• the syntheses of such emulsion are described in U.S. Patents No. 3,574,628, No. 3,655,394 and U.K. Patent No. 1,413,748.
• a tabular silver halide grain having an aspect ratio of not less than 5 can also be employed in the invention.
• a tabular silver halide grain can be easily prepared in accordance with methods described in "Photographic Science and Engineering" by Gutoff, vol. 14 (1970), pp. 248-257; U.S. Patents No. 4,434,226, No. 4,414,310, No. 4,433,048, No. 4,439,520 and U.K. Patent No. 2,112,157.
• the tabular silver halide grain enhances the covering power and the efficiency of color sensitization by sensitizing dyes.
• the shape of the grains can be controlled with a sensitizing dye or an additive.
• the crystal structure may be either homogeneous or heterogeneous. In the heterogeneous structure, the halogen compositions inside and outside are different each other.
• the crystalline may be a layered structure.
• These emulsions and grains are disclosed in U.K. Patent No. 1,027,146, U.S. Patents No. 3,505,068, No. 4,444,877 and Japanese Patent Provisional Publication No. 60(1985)-143331.
• Some silver halides in which halogens are different each other may connect by epitaxial bond to form the crystal, or a salt other than silver halide such as silver rhodanite and lead oxide also may connect to the silver halide crystal by epitaxial bond.
• These emulsion grains are disclosed in U.S. Patents No.
• the silver halide emulsion may contain grains of so-called internal latent type which are prepared by the process comprising chemically ripening the surface of the crystal to form sensitivity specks (e.g., Ag 2 S, Agn or Au) and further forming silver halide on the surface.
• sensitivity specks e.g., Ag 2 S, Agn or Au
• the process of forming silver halide grains or physical ripening may be carried out in the presence of a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or its complex salt, a rhodium salt or its complex salt, an iron salt or an iron complex salt.
• the non-pre-fogged internal latent image type silver halide emulsion used in the invention contains silver halide grains in which the surface has not been pre-fogged and a latent image is formed mainly in the inside of the grains.
• the ratio of the maximum density formed by using the following developing solution A (internal type developing solution) to that formed by using the following developing solution B (surface type developing solution) preferably is not less than 5 to 1, and more preferably is not less than 10 to 1.
• the maximum density of the solution A is determined by a normal photographic density measurement of the sample prepared by the process comprising: coating a certain amount of the emulsion on a transparent support; exposing to light the emulsion for a certain period within 0.01 to 10 seconds; and developing the emulsion in the developing solution A at 20 ° C for 6 minutes.
• the maximum density of the solution B is determined in the same manner, except that development is carried out in the developing solution B at 18 ° C for 5 minutes.
• Examples of the internal latent image type emulsion include conversion type silver halide emulsions described in U.K. Patent 1,011,062, U.S. Patents No. 2,592,250 and No. 2,456,943; and core/shell type silver halide emulsions described in Japanese Patent Provisional Publications No. 47(1972)-32813, No. 47-(1942)-32814, No. 52(1977)-134721, No. 52(1977)-156614, No. 53(1978)-60222, No. 53(1978)-66218, No. 53(1978)-66727, No. 55(1980)-127549, No. 57(1982)-136641, No. 58(1983)-70221, No.
• Soluble silver salt can be removed from the emulsion before or after physical ripening in accordance with a noodle washing method, a flocculation sedimentation method or an ultrafiltration method.
• the emulsion used in the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in these process are described in Research Disclosure No. 17643 (December, 1978) and ibid., No. 18716 (November, 1979). The pages in which the additives are described are set forth below.
• the color coupler is a compound which forms or releases a substantially non-diffusion color by a coupling reaction with an oxidation product of an aromatic primary amine color developing agent.
• the coupler itself preferably is a substantially nondiffusion compound.
• Typical examples of the color coupler used in the invention include naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds, and non-cyclic or heterocyclic ketomethylene compounds. Concrete examples of cyan, magenta and yellow couplers used in the invention are described in Research Disclosure No. 17643 (December, 1978), P25Vll-D term; ibid., No. 18717 (November, 1979), Japanese Patent Provisional Publication No. 62(1987)-215272, and the patents cited in these documents.
• a yellow divalent coupler of oxygen eliminating type or nitrogen eliminating type is a typical example of the coupler which can be used in addition to the compound (I) of the invention.
• a developed color dye given by an a-pivaloylacetoanilide coupler has an excellent stability, particularly for light.
• An a-ben- zoylacetoanilide coupler shows a high color developing density. Therefore, these couplers are preferably used.
• a referred example of a 5-pyrazolones magenta coupler used in addition to the compounds (I) of the invention is a coupler of 5-pyrazolones in which 3-position is substituted with an arylamino group or an acylamino group (particularly, a divalent coupler of sulfur eliminating type is preferred).
• Pyrazoloazole couplers are further preferred.
• Pyrazolo[5,1-c][1,2,4]triazoles described in U.S. Patent No. 3,725,067 are furthermore preferred.
• Imidazo[1,2-b]pyrazoles described in U.S. Patent No. 4,500,630 is particularly, since it has a small incidental absorption in yellow wavelength range and it is stable to light.
• Pyrazolo[5,1-b][1,2,4]triazole described in U.S. Patent No. 4,540,654 is more particularly preferred.
• Examples of a cyan coupler preferably used in the invention include a naphthol or phenol coupler described in U.S. Patents No. 2,474,293 and No. 4,052,212; and a cyan coupler of phenols having an alkyl group (which is not smaller than ethyl) at meta-position of phenol nucleus described in U.S. Patent No. 3,772,002. Further, 2,5-diacylamino substituted phenol coupler is also available, since it forms a excellent stable color image.
• a colored coupler to compensate an incidental absorption of a formed dye in short wavelength range
• a coupler which gives a color developing dye exhibiting proper diffusion
• a non-colored coupler a DIR coupler releasing a developing inhibitor by a coupling reaction
• a polymerized coupler a colored coupler to compensate an incidental absorption of a formed dye in short wavelength range
• a color coupler is normally used in an amount of 0.001 mole to 1 mole per 1 mole of photosensitive silver halide.
• a yellow coupler is used in an amount of 0.01 mole to 0.5 mole
• a magenta coupler is used in an amount of 0.03 mole to 0.3 mole
• a cyan coupler is used in an amount of 0.002 mole to 0.3 mole.
• a color enhancing agent can be used for the invention. Typical examples are described in Japanese Patent Provisional Publication No. 62(1987)-215272, pp. 374-391.
• the coupler of the invention is dissolved in an organic solvent having a high boiling point and/or a solvent having a low boiling point, and the resulting solution is emulsified or dispersed in gelatin or other hydrophilic colloidal aqueous solution by means of a high speed stirring device such as a homogenizer, a pulverizing machine such as a colloid mill and/or a machine using supersonic wave.
• a high speed stirring device such as a homogenizer, a pulverizing machine such as a colloid mill and/or a machine using supersonic wave.
• the obtained emulsion is then added to the silver halide emulsion layer.
• the photosensitive material of the invention preferably contains at least one compound which reacts with formaldehyde gas to fix it.
• the compound which reacts with formaldehyde gas to fix it (hereinafter referred to as "formalin scavenger") used in the invention has the following formula (S-I) or (SII).
• the below-defined reduced molecular weight of the compound per 1 unit of active hydrogen is not more than 300.
• each of R 1 and R 2 is hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group or an amino group; R 1 and R 2 may form a ring; at least one of R 1 and R 2 is an acyl group, an alkoxycarbonyl group, a carbamoyl group or an amino group; X is R 3 is hydrogen, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group; R 3 may connect to the phenyl group to form a condensed ring; and n is an integer not less than 2.
• a combination of two or more formalin scavengers can be used for the invention.
• the formalin scavenger is contained in at least one layer of silver halide color photographic photosensitive material, such as silver halide emulsion layer, undercoating layer, protective layer, intermediate layer, filter layer, antihalation layer and other auxiliary layers.
• the scavenger may be contained either in a silver halide emulsion layer including magenta polymer coupler of which photographic properties are deteriorated by contact with formaldehyde gas, or in a layer provided closer to the support than the emulsion layer, or in a layer provided farther from the support than the layer.
• the formalin scavenger is added to the coating solution for forming the above layers in the form of the compound itself or its solution in a proper concentration.
• the solvent of the solution e.g., water or alcohols
• the formalin scavenger may be added in the form of an emulsion obtained by the process comprising dissolving in an organic solvent of a high boiling point and/or a solvent of a low boiling point, and emulsifying and dispersing in water.
• the scavenger may be added in any time of the process. However, it is generally preferred to add the scavenger to a coating solution just before coating.
• the amount of the formalin scavenger to be added is generally within a range of 0.01 g to 10 g per 1 m 2 of silver halide photographic color photosensitive material, and preferably within a range of 0.05 g to 5 g.
• the photosensitive material of the invention is a color photosensitive material
• various antidiscoloration agents can be used.
• organic antidiscoloration agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols such as bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ethers or ester derivatives obtained by alkylizing or silylizing the phenol hydroxyl groups of these compounds.
• metal complexes such as (bissalicylaldoximato) nickel complex and (bis-N,N-di-alkyldithiocar- bamato) nickel can be also used.
• a compound having both partial structure of hindered amine and that of hindered phenol, described in U.S. Patent No. 4,268,593, is effective for preventing yellow color image from deteriorating by heat, humidity and light.
• Compounds of spiroindanes described in Japanese Patent Provisional Publication No. 56(1981 )-159644, hydroquinone diethers described in Japanese Patent Provisional Publication No. 55-(1980)-09835, and chromans substituted with monoethers are effective for preventing magenta color image from deteriorating particularly by light.
• Each of these compounds is co-emulsified with the corresponding color coupler in an amount of, generally, 5-100 wt.% of the coupler, so that it may be contained the photosensitive layer.
• an ultraviolet absorbent is introduced in both layers provided in contact with the top and bottom surface of the cyan color developing layer.
• An ultraviolet absorbent may be contained in a hydrophilic colloidal layer such as a protective layer.
• Agents such as a dye for preventing irradiation or halation, an antistatic agent and an agent for improving slipperiness are also available for the invention.
• a multilayered multicolor photographic material generally has at least one red sensitive emulsion layer, at least one green sensitive emulsion layer and at least one blue sensitive emulsion layer on a support.
• the order of these layers can be optionally determined. Examples of preferable order of the layers include: support, red, green and blue; support, blue, green and red; support, blue, red and green; and support, green, red and blue.
• Each of these emulsion layers may consist of two or more emulsion layers having different sensitivities, and there may be a non- photosensitive layer between a plural number of emulsion layers having the same sensitivities.
• a red sensitive emulsion layer contains a cyan forming coupler
• a green sensitive emulsion layer contains a magenta forming coupler
• a blue sensitive emulsion layer contains a yellow forming coupler.
• the photosensitive material of the invention is optionally provided with auxiliary layers other than silver halide emulsion layer (e.g., protective layer, intermediate layer, filter layer, antihalation layer and white reflection layer).
• auxiliary layers other than silver halide emulsion layer (e.g., protective layer, intermediate layer, filter layer, antihalation layer and white reflection layer).
• a direct positive color image can be obtained by the process comprising developing, bleaching and fixing with a surface type developer containing p-phenylenediamine color developing agent after and/or during a fogging treatment with a nucleating agent, following an imagewise exposure.
• the above photosensitive material of the invention is advantageous.
• nucleating promoter which promotes the effect of nucleating agent
• examples of available nucleating promoter include tetrazaindenes, triazaindenes and pentazaindenes (these azaindenes have at least one mercapto group which may be optionally substituted with alkaline metal atoms or ammonium groups), and the compounds described in Japanese Patent Provisional Publication No. 63(1988)-106656, pp. 5-16.
• a nucleating promoter may be contained either in the photosensitive material or in a processing solution. Preferably, it is contained in the internal latent image type silver halide emulsion layer or other hydrophilic colloidal layers, such as intermediate layer or protective layer, of the photosensitive material. It is particularly preferable that a nucleating promoter is contained in the silver halide emulsion layer or the layers being in contact with the emulsion layer.
• the amount of the nucleating promoter to be added is within a range of 10- 6 mole to 10- 2 mole per 1 mole of silver halide, and preferably within a range of 10- 5 mole to 10- 2 mole.
• the amount of the promoter to be added is preferably within a range of 10- 8 mole to 10- 3 mole per 1 I of the liquid, and more preferably within a range of 10- 7 mole to 10-4. mole.
• a combination of two or more nucleating promoters can be used for the invention.
• the photographic emulsion layer and other layers of the photosensitive material of the invention are provided by coating on a flexible support such as plastic film, paper and cloth, or on a rigid support consisting of glass, ceramics and metal (these supports are generally used for known photosensitive materials).
• a flexible support in-included film of synthetic or semi-synthetic polymer such as cellulose nitrate, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate; and paper coated or laminated with baryta layer or an olefin polymer (e.g., polyethylene, polypropylene or ethylene/butene copolymer).
• a support may be colored with dye or pigment.
• Coating of the silver halide photographic emulsion layer and other hydrophilic colloidal layers can be carried out in accordance with various known methods such as dip coating method, roller coating method, curtain coating method, extruding coating method, and optionally, mutilayer simultaneous coating method described in U.S. Patents No. 2,681,294, No. 2,761,791, No. 3,526,528 and No. 3,508,947.
• a dye developer can be used as a coloring agent, but it is more advantageous to use a coloring agent which is nondiffusion (nontransferring) in alkaline condition (in a developer) in itself but which releases a diffusing dye (or its precursor) by developing.
• a diffusing dye releasing-type color agent DRR compound
• couplers or redox compounds which release diffusing dyes. These compounds are usable for not only color diffusion transfer process (wet type) but also heat development process (dry type) described in Japanese Patent Provisional Publication No. 58(1983)-58543.
• the photographic emulsion may be coated either on the same support on which the image receiving layer is coated, or on another support.
• Silver halide photographic emulsion layer (photosensitive element) and image receiving layer (image receiving element) may be either combined to provide in the form of a film unit, or severally provided as independent photographic materials.
• the film unit may be either used in a body through the whole process of exposure, development and viewing the transfer image, or cloven after developing. The latter is effective for the invention.
• the present invention can be applied for various photographic photosensitive materials.
• Typical examples of such materials include color reversal film for slide or TV, color reversal paper and instant color film.
• the invention can be also applied for full color copy machine and color hard copy to store CRT image.
• the invention can be further applied for a monochrome photosensitive material using a mixture of three color couplers described in Research Disclosure No. 17123 (July, 1978).
• the color developer employed for development of the photosensitive material of the invention is preferably an alkaline aqueous solution in which main component is a color developing agent of aromatic primary amines. Though aminophenol compounds are usable for the color developing agent, p-phenylenediamine compounds are preferably used.
• Typical examples of the compounds include 3-methyl-4-am ino-N, N-diethylan i line, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-,B-methanesulfoneamidethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline, and sulfates, chlorides or p-toluenesulfonates of these compounds. These compounds can be used in a combination of two or more compounds, according to desired purpose.
• a color developer generally contains pH buffer such as carbonates, borates and phosphates of alkaline metal, and a development restrainer or an antifoggant such as bromide, iodide, benzimidazoles, ben- zothiazoles and mercapto compounds.
• pH buffer such as carbonates, borates and phosphates of alkaline metal
• an antifoggant such as bromide, iodide, benzimidazoles, ben- zothiazoles and mercapto compounds.
• a color developer may contain various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, phenylsemicarbazidos, triethanolamine, catechol sulfonates and triethylenediamine (1,4-di-azabicyclo[2,2,2]octane)s; organic solvents such as ethylene glycol and diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines; dye-forming couplers; competing couplers; fogging agents such as sodium boron hydride; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscous agents; various chelating agents such as aminopolycarboxlic acids, aminopolyphospholic acids, alkylphospholic acids and phosphonocaboxylic acids (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriamine
• the pH value of the color developer is generally within a range of 9-12, preferably 9.5-11.5.
• the amount of the replenisher depends upon the color photographic photosensitive material to be treated, but generally it is not more than 1 I per 1 m 2 of the photosensitive materials.
• the amount of the replenisher can be reduced to 300 ml or below by reducing a concentration of bromide ion. In the case that the amount is reduced, it is preferable to make the area where the liquid is in contact with air as small as possible in order to prevent the liquid from evaporation or air oxidation.
• the amount of the replenisher can be also reduced by inhibiting accumulation of bromide ion in the developer.
• a photographic emulsion layer is generally subjected to a bleaching treatment after development.
• Bleaching treatment and fixing treatment may be carried out either at the same time (bleach-fix treatment) or independently. Further, bleach-fix treatment may be carried out after bleaching treatment in order to shorten the time for the process. Furthermore, any of bleaching treatment using two successive bleach-fix baths, bleaching treatment before bleach-fix treatment and bleaching treatment after bleach-fix treatment can be optionally carried out.
• Bleaching agents are, for example, compounds of multivalent metal such as iron (III), cobalt (III), chromium (VI) and copper (II); peracids; quinones or nitro compounds.
• bleaching agent examples include: ferricyanides; dichromates; organic complex salts of iron (III) or cobalt (III) such as aminopolycaboxylates (e.g., ethylenediaminetetraacetate, diethylenetriaminepentaacetate, cyclohex- anediaminetetraacetate, methyliminodiacetate, 1,3-diaminopropanetetraacetate or glycolether- diaminetetraacetate), citrate, tartrate and malate; persulfates; bromate; permanganate and nitrobenzenes.
• aminopolycaboxylates e.g., ethylenediaminetetraacetate, diethylenetriaminepentaacetate, cyclohex- anediaminetetraacetate, methyliminodiacetate, 1,3-diaminopropanetetraacetate or glycolether- diaminetetraacetate
• a bleaching accelerator can be optionally added to bleaching bath, bleach-fix bath or their prebaths.
• the silver halide color photographic photosensitive material is generally subject to washing and/or stabilizing process after desilvering treatment.
• the amount of water in washing process is determined according to various conditions such as properties of the photosensitive material (which depend upon employed elements such as coupler), usage, temperature, number of washing tank (plate), replenishing method (e.g., counter current system or not) and so on.
• properties of the photosensitive material which depend upon employed elements such as coupler
• usage temperature
• number of washing tank (plate) replenishing method (e.g., counter current system or not) and so on.
• a relation between an amount of water and number of washing tank in multiplate counter current system can be obtained in accordance with the method described in Journal of the Society of Motion Picture and Television Engineers, vil. 64 (May, 1955), pp. 248-253.
• the pH value of the washing water in the process of the photosensitive material of the invention is generally within a range of 4-9, preferably 5-8. Temperature and period in washing are determined according to the conditions such as properties of the photosensitive material, usage and so on. Generally, washing is carried out for 20 seconds to 10 minutes at 15 to 45 C, and preferably for 30 seconds to 5 minutes at 25 to 40 C.
• the photosensitive material of the invention may be treated directly with a stabilizer. For such stabilizing process, every known methods described in Japanese Patent Provisional Publications No. 57(1982)-8543, No. 58(1983)-14834 and No. 60(1985)-220345 are available.
• Various chelating agents and antifungal agents can be added to the stabilizing bath. Liquid over-flowed by replenishing of above-mentioned washing water and/or stabilizer can be used again in other process such as desilvering.
• Various processing liquids in the invention are used at the temperature of 10 to 50 C.
• the temperature is usually within a range of 33 to 38 C, but it may be adjusted either to a higher degree in order to accelerate the process to shorten the processing time, or to a lower degree, on the contrary, in order to improve the image quality or the stability of processing liquids.
• the ratio of the amount of replenisher to that of carried liquid of the prebath based on unit area of the photosensitive material is preferably within a range of 0.1 to 50, more preferably within a range of 3 to 30.
• the photosensitive material containing the internal latent image type emulsion of the invention presents a direct positive image through developing with a surface type developer.
• Developing process employing a surface type developer is substantially induced by a latent image or fog specks on the surface of silver halide grain.
• the developer preferably contains no silver halide solvent, but as far as the internal latent image does not substantially contribute until the development by developing specks on the surface of silver halide is accomplished, the developer may contain silver halide solvent (e.g., sulfites).
• the developer may contain an alkaline agent or a buffer agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium tertiary phosphate and sodium metaborate.
• a buffer agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium tertiary phosphate and sodium metaborate.
• the amounts of these agents added are determined so that the pH value of the developer may be within a range of 9 to 13, preferably within a range of 10 to 11.2.
• the developer contains benzimidazoles (e.g., 5-nitrobenzimidazole), benzotriazoles (e.g., benzotriazole), 5-methyl-benzotriazoles and compounds usually used as an antifoggant.
• benzimidazoles e.g., 5-nitrobenzimidazole
• benzotriazoles e.g., benzotriazole
• 5-methyl-benzotriazoles e.g., 5-methyl-benzotriazoles and compounds usually used as an antifoggant.
• a viscous developing solution is a liquid composition containing components necessary to development of silver halide emulsion (and formation of diffusion transfer color image).
• the solvent of it is mainly water, and occasionally includes hydrophilic solvent such as methanol and methyl cellosolve.
• the composition preferably contains hydrophilic polymer such as polyvinyl alcohol having high molecular weight, hydroxyethyl cellulose and sodium carboxymethyl cellulose. These polymers are added to the processing composition so that viscosity of the composition may be 1 poise or more, preferably within a range of 500-1000 poise.
• composition is charged in pressure breakable capsule described in U.S. Patents No. 2,543,181, No. 2,643,886, No. 2,653,732, No. 2,723,051, No. 3,056,491, No. 3,056,492 and No. 3,152,515.
• a paper was laminated with polyethylene on both sides to prepare a paper support (thickness: 100 w m). On the top surface of the paper support, the following first to fourteenth layers are provided, and then the fifteenth to sixteenth layers are provided on the bottom surface to prepare a color photographic photosensitive material.
• Polyethylene laminated on the top surface included titanium oxide (4 g/m 2 ) as a white pigment and small amount (0.003 g/m 2 ) of ultramarine as a blue dye. (Chromaticities of the surface of the support were determined to be 88.0, -0.20, - 0.75 in L * , a * , b * system, respectively.)
• composition and its amount (g/m 2 ) of each of the layers is set forth below.
• the values for the silver halide emulsions mean the coating amount of silver.
• Emulsions employed for each of the layers were prepared in the same manner as to the preparation of the emulsion EM-1, except that the emulsion of the fourteenth layer was a Lippmann emulsion which had not been subjected to surface chemical sensitization.
• the third layer Low red sensitive layer
• the forth layer (High red sensitive layer)
• the sixth layer (Low green sensitive layer)
• the seventh layer (High green sensitive layer)
• the eighth layer (Intermediate layer)
• the eleventh layer (Low blue sensitive layer)
• the twelfth layer (High blue sensitive layer)
• the fourteenth layer (Protective layer)
• the fifteenth layer (Reverse layer)
• the sixteenth layer (Reverse protective layer)
• the obtained grains were further grown under the same condition as for the first precipitate to prepare octahedral core/shell silver bromide emulsion of uniform grain size distribution in which mean grain size was 0.7 ⁇ m and coefficient of variation was approximately 10 %.
• the resulting emulsion was subjected to chemical sensitization by heating at 60 °C for 60 minutes to obtain an internal latent image type silver halide emulsion.
• Nucleating agents of ExZK-1 and ExZK-2, and nucleating promoter of Cpd-22 were added to each of the photosensitive layers in amounts of 10- 3 , 10- 2 and 10- 2 wt., respectively, based on the amount of silver halide.
• Alkanol tradename of Du Pont
• sodium alkylbenzene sulfonate were added to each of the layers as a dispersing agent.
• a succinic acid ester and Magefac F120 (trade name of Dainippon ink Co. Ltd.) were also added to each of the layers as an coating agent.
• Stabilizers of Cpd-23, 24 and 25 were added to each of the layers containing silver halide or colloidal silver. The prepared sample was numbered as No. 101.
• Each of the prepared photosensitive materials was imagewise exposed to light through blue and red filters, and then subjected to successive process by means of an automatic developing machine under the conditions described below.
• the process was terminated.
• the washing water was replenished in accordance with so-called counter current replenishing system in which the replenisher was introduced to the washing bath (2) and the over flowed liquid of the washing bath (2) was introduced to the washing bath (1).
• the amount of the liquid carried by the photosensitive material from the bleach-fix bath into the washing bath (1) was 35 ml/m 2 , and the ratio of the amount of the replenishing water to that of the carried liquid was 9.1.
• Water was deionized through a mixed-bed system column charged with strongly acidic cation exchange resin of H type (Amberlite IR-120B available from Rohm & Haas Co.) and anion exchange resin of OH type (Amberlite IR-400 available from Rohm & Haas Co.) to contain calcium and magnesium ions in an amount of not more than 3 mg/I.
• H type Amberlite IR-120B available from Rohm & Haas Co.
• anion exchange resin of OH type Amberlite IR-400 available from Rohm & Haas Co.
• the samples of No. 102 - 108, in which the recording layers contain the couplers (I) and/or (Y) of the invention form a clear image having not only a low minimum image density but also a high maximum image density, compared with the comparison sample (No. 101) . Further, the images given by the samples of the invention are more reddish than the image of No. 101. Therefore, the materials of the invention are advantageously used as a color proof.
• Example 1 preparation of No. 101 was repeated except that magenta couplers (ExM-1, -2 and -3) in the sixth layer (low green sensitive layer) and the seventh layer (high green sensitive layer) were replaced with the same amount (by mole) of the compounds in Table 2, and the nucleating agents (ExZK-1 and -2) in each layer were also replaced with the compounds in Table 2 in amounts shown in Table 2, to prepare the samples of No. 202 - 208.
• magenta couplers ExM-1, -2 and -3
• the seventh layer high green sensitive layer
• the image of the obtained samples were obtained in the same manner as described in Example 1.
• the maximum image density (D max ) and the minimum image density (D min ) of the image was measured at ⁇ max .
• the developed color was also observed.
• the results are set forth in Table 2.
• the samples No. 202 - 208 in which the green sensitive layers contain the coupler (I) of the invention and each of the photosensitive layers contains the nucleating agent of the invention, form a clear image having not only a low minimum image density but also a high maximum image density compared with the comparison samples (No. 101 - 203). Further, the images given by the samples of the invention are more reddish than the image of the comparison samples. Therefore, the materials of the invention are advantageously used as a color proof.
• Example 1 and Example 2 were subjected to color development in which the procedure of Example 1 was repeated except that N-ethyl-N-( ⁇ -methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate in the developer was replaced with the same amount (by mole) of N-ethyl-N-( ⁇ -methanesulfonamidoethyl)-4-aminoaniline sulfate or N-ethyl-N-( ⁇ -hydroxyethyl)-4-aminoaniline sulfate.
• the measurements were also carried out in the same manner described in Example 1. Excellent results were obtained by the samples of the invention.
• a paper was laminated with polyethylene on both sides to prepare a paper support (thickness: 100 u m). On the top surface of the paper support, the following first to eleventh layers are provided, and then the twelfth to thirteenth layers are provided on the bottom surface to prepare a color photographic photosensitive material.
• Polyethylene laminated on the top surface included titanium oxide (4 g/m 2 ) as a white pigment and small amount (0.003 g/m 2 ) of ultramarine as a blue dye. (Chromaticities of the surface of the support were determined to be 88.0, -0.20, - 0.75 in L * , a * , b * system, respectively.)
• composition and its amount (g/m 2 ) of each of the layers is set forth below.
• the values for sensitizing dyes mean the amount (by mole) based on 1 mole of silver.
• the values for the silver halide emulsions mean the coating amount of silver.
• Emulsions employed for each of the layers were prepared in the same manner as the preparation of the emulsion EM-1, except that the grain size was changed by arranging the temperature.
• the emulsion of the eleventh layer was a Lippmann emulsion which had not been subjected to surface chemical sensitization.
• the third layer (Red sensitive layer)
• the fourth layer (Intermediate layer)
• the fifth layer (Green sensitive layer)
• the sixth layer (Intermediate layer)
• the seventh layer (Yellow filter layer)
• the eighth layer (Intermediate layer) The same as the fourth layer
• the ninth layer (Blue sensitive layer)
• the eleventh layer (Protective layer)
• the thirteenth layer (Reverse protective layer)
• the obtained grains were further grown under the same condition as the first precipitation to prepare octahedral core/shell silver bromide emulsion of uniform grain size distribution in which the mean grain size was 0.7 ⁇ m and coefficient of variation was approximately 10 %.
• the resulting emulsion was subjected to chemical sensitization by heating at 60 ° C for 60 minutes to obtain an internal latent image type silver halide emulsion.
• Nucleating agents of ExZK-1 and ExZK-2 (in amounts of 10- 3 and 10- 2 wt.% respectively based on the amount of silver halide) and nucleating promoters of Cpd-22, 28 and 28 (in amounts of 10- 2 , 10- 2 and 10- 2 wt.% respectively based on the amount of silver halide) were added to each of the photosensitive layers.
• Alkanol (tradename of Du Pont) and sodium alkylbenzene sulfonate were added to each of the layers as a dispersing agent.
• a succinic acid ester and Magefac F120 (trade name of Dainippon ink Co. Ltd.) were also added to each of the layers as an coating agent.
• Stabilizers of Cpd-23, 24 and 25 (in the ratio of 1:1:1) were added to each of the layers containing silver halide or colloidal silver.
• the prepared sample was numbered as No. 401.
• each of the prepared samples was exposed to white light through a red filter (SC-60, tradename of Fuji Photo Film Co., Ltd.). Then, each of the samples was exposed to white light through a green filter (BPB-53, tradename of Fuji Photo Film Co., Ltd.), and finally exposed to white light through a blue filter (BPB-45, tradename of Fuji Photo Film Co., Ltd.).
• the light source was a color rendering fluorescent lamp (produced by Tokyo Shibaura Electric Co., Ltd.)
• the washing water was replenished in accordance with so-called counter current replenishing system in which the replenisher was introduced to the washing bath (2) and the over flowed liquid of the washing bath (2) was introduced to the washing bath (1).
• the amount of the liquid carried by the photosensitive material from the bleach-fix bath into the washing bath (1) was 35 ml/m 2 , and the ratio of the amount of the replenishing water to that of the carried liquid was 9.1.
• Water was deionized through a mixed-bed system column charged with strongly acidic cation exchange resin of H type (Amberlite IR-120B available from Rohm & Haas Co.) and anion exchange resin of OH type (Amberlite IR-400 available from Rohm & Haas Co.) to contain calcium and magnesium ions in an amount of not more than 3 mg/I.
• H type Amberlite IR-120B available from Rohm & Haas Co.
• anion exchange resin of OH type Amberlite IR-400 available from Rohm & Haas Co.
• the image density was measured using a self-recording densitometer (TCD, produced by Fuji Photo Film Co., Ltd.). Further, the chromaticity at magenta density of 1.5 was measured using a spectrophotometer (produced by Yunisoku Ltd.). For reference, with respect to ten printed matters, the chromaticity at magenta density of 1.5 was also measured, and the average was calculated.
• TCD self-recording densitometer
• chromaticity at magenta density of 1.5 was measured using a spectrophotometer (produced by Yunisoku Ltd.). For reference, with respect to ten printed matters, the chromaticity at magenta density of 1.5 was also measured, and the average was calculated.
• the samples 402 to 410 of the present invention form an improved clear image having a high maximum density (Dmax) and a high contrast. Further, the toe of the image is cut off, and the hue of the image is similar to the printed matter (cf., values of L * , a * and b'). Therefore, the image formed by the present invention can be advantageously used as a color proof.
• Samples No. 501 to 510 were prepared in the same manner as in preparation of the sample No. 401 to 410 respectively in Example 4, except that the nucleating agents (ExZK-1) and (ExZK-2) were not used.
• Each of the prepared samples was exposed to white light through a green filter (BPB-53, tradename of Fuji Photo Film Co., Ltd.). Then, each of the samples was exposed to white light through a red filter (SC-60, tradename of Fuji Photo Film Co., Ltd.), and finally exposed to white light through a blue filter (BPB-45, tradename of Fuji Photo Film Co., Ltd.).
• the light source was a color rendering fluorescent lamp (produced by Tokyo Shibaura Electric Co., Ltd.)
• the direct positive color image forming method of the invention an image having a high maximum image density can be obtained without increasing the minimum image density. Further, since the method can enhance reddish color of the green sensitive layer, the obtained image has an excellent color reproducibility. Therefore, the direct positive color image forming method of the invention is very advantageously used in preparation of a color proof.

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