EP0327274A2 - Light-sensitive silver halide photographic material - Google Patents
Light-sensitive silver halide photographic material Download PDFInfo
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- EP0327274A2 EP0327274A2 EP89300813A EP89300813A EP0327274A2 EP 0327274 A2 EP0327274 A2 EP 0327274A2 EP 89300813 A EP89300813 A EP 89300813A EP 89300813 A EP89300813 A EP 89300813A EP 0327274 A2 EP0327274 A2 EP 0327274A2
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- European Patent Office
- Prior art keywords
- light
- silver halide
- sensitive silver
- group
- sensitive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- 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
- G03C7/392—Additives
- G03C7/39208—Organic compounds
- G03C7/39212—Carbocyclic
- G03C7/39216—Carbocyclic with OH groups
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- 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
Definitions
- This invention relates to a light-sensitive silver halide photographic material, more particularly to a light-sensitive silver halide color photographic material having little color turbidity and excellent color reproducibility.
- a light-sensitive silver halide color photographic material has three kinds of silver halide emulsion layers for photography spectrally sensitized selectively so as to have light sensitivity to blue light, green light and red light provided by coating on a support.
- a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer are generally provided by coating, and further an intermediate layer or a protective layer, including UV-ray absorbing layer, etc. are provided.
- the reaction rate between the diffusion-resistant coupler contained in each light-sensitive silver halide emulsion layer with a color developing agent oxidized product is generally different between the respective emulsion layers. For this reason, the excessive oxidized product of the color developing agent generated in an emulsion layer containing a diffusion-resistant coupler with small reaction rate with the oxidized product of the color developing agent will be diffused to other silver halide emulsion layers than the layer of itself, whereby there are the drawbacks that color turbidity is liable to occur and that color reproducibility will be readily lowered.
- the light-sensitive silver halide color photographic material is subjected to running by an automatic developing machine provided in each laboratory, and as a part of improvement of service for users, it has been demanded to perform development processing and return the processed product to users within the very day when the development is ordered. Recently, it has been even demanded to return the product within several hours from the order, and thus development of a light-sensitive silver halide color photographic material capable of rapid processing has been increasingly hastened.
- the present invention has been accomplished in view of the state of the art as described above and an object of the present invention is to provide a light-sensitive silver halide color photographic material having little color turbidity and excellent color reproducibility.
- a light-sensitive silver halide photographic material comprising at least two light-sensitive silver halide emulsion layers containing diffusion-resistant couplers and at least one non-light-sensitive intermediate layer sandwiched between said light-sensitive silver halide emulsion layers provided on a support, wherein said non-light-sensitive intermediate layer contains a compound which deactivates the oxidized product of a color developing agent, the relative color formation speed ratio k1/k2 (lower color formation speed is defined as k1, and higher color formation speed as k2; when the color formation speeds are equal, either one may be applicable) between the diffusion-resistant couplers contained in the respective two light-sensitive silver halide emulsion layers adjacent to said non-light-sensitive intermediate layer is 0.25 ⁇ k1/k2 ⁇ 1, and the relationship of said k1/k2 to the ability Sc is represented by Formula (I): Sc ⁇ k1/k2 ⁇ 0.2 Formula (I
- the relative color formation speed ratio k1/k2 between the diffusion-resistant couplers in the present invention is determined as described below on the basis of the principle which is basically similar to the above method.
- a coupler is dispersed by use of 0.5 g of dioctyl phthalate per 1 mmol of the coupler, and in the dispersion were mixed a coupler solution A (coupler concentration 2 x 10 ⁇ 2 mol, silver chloride concentration 4 x 10 ⁇ 3 mol) added with a silver chloride emulsion (AgCl 100 %, average particle size 0.14 ⁇ m) and a color developer B (N-ethyl-N- ⁇ -methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 2 x 10 ⁇ 2 mol, anhydrous potassium carbonate 40 g/liter, sodium sulfite 1 g/liter, pH 10.0) at 25 °C at a volume ratio of 1 : 1 (coupler solution A : color developer B).
- coupler solution A coupler concentration 2 x 10 ⁇ 2 mol, silver chloride concentration 4 x 10 ⁇ 3 mol
- a color developer B N-e
- the ratio of the absorbances obtained is determined as k1/k2. In this case, the smaller absorbance is made k1 and the larger one k2. When absorbances are equal, either one may be made k1 or k2.
- the ability Sc of the compound to deactivate the oxidized product of the color developing agent in the non-light-sensitive intermediate layer in the present invention is determined based on the method described above and according to the method as described below.
- a dispersion is prepared by use of 0.5 g of dioctyl phthalate per 1 mmol of the compound which deactivates the oxidized product of the color developing agent, and the same measurement is performed under the same conditions as in determination of (ABS) R except for adding the dispersion into the above coupler solution A (concentration of the compound which deactivates the oxidized product of the color developing agent : 2 x 10 ⁇ 3 mol), and the absorbance obtained is made (ABS) S . Sc is given by the following formula (II).
- Cs represents moles (mmol units) of the compound which deactivates the oxidized product of the color developing agent contained per 1 m2 of the non-light-sensitive intermediate layer.
- the present invention is defined by the above k1/k2 and Sc, and is not limited only by the chemical structures of the coupler and the compound which deactivates the oxidized product of the color developing agent employed.
- the above k1/k2 is required to be 0.25 or more and 1 or less, preferably 0.30 or more and 1 or less.
- the product of Sc represented by the above formula (I) and k1/k2 is required to be 0.2 or more, preferably 0.3 or more.
- a light-sensitive silver halide color photographic material of the present invention which contains a hydroquinone type compound as the compound which deactivates the oxidized product of the color developing agent in the non-light-sensitive intermediate layer, and a yellow coupler in one of the two light-sensitive silver halide emulsion layers adjacent to said non-light-sensitive intermediate layer and a magenta coupler in the other of the emulsion layers.
- the non-light-sensitive intermediate layer of the present invention is required to have the ability Sc to deactivate the oxidized product of the color developing agent which satisfies the relationship of the above formula (I). Sc can be controlled as desired according to the kind and the amount added of the compound which deactivates the oxidized product of the color developing agent.
- hydroquinone derivatives aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. as mentioned above, preferably hydroquinone derivatives.
- hydroquinone type compounds which deactivate the oxidized product of the color developing agent preferably used in the present invention are represented by the formula (HQ) shown below.
- R1 represents a substituted or unsubstituted alkyl group
- n represents an integer of 1 to 3.
- the total sum of carbon numbers of R1 is 8 or more, and when n is 2 or more, the plural number of R1 may be either the same or different.
- R2 represents a halogen atom, hydroxyl group, sulfo group, carboxyl group.
- m represents an integer of 0 to 3, and when m is 2 or more, the plural number of R2 may be either the same or different.
- the sum of n + m is 4 or less.
- the alkyl group represented by R1 may be preferably a straight and branched alkyl group having 1 to 20 carbon atoms, including, for example, methyl, ethyl, propyl, t-butyl, octyl, t-dodecyl groups and the like.
- the substituent possessed by R1 may include sulfo group, carboxyl group, cyano group, hydroxyl group, halogen atoms (e.g. fluorine, chlorine, bromine atoms, etc.), -COOR4, -COR5, -OR6, -SO2R7, -NHSO2R8, etc.
- R4, R5, R6, R7 and R8 represent alkyl group, alkenyl group, cycloalkyl group, aryl group.
- alkyl group represented by R4 through R8 may be the same as the alkyl represented by the above R1, examples of cycloalkyl group may be cyclopentyl, cyclohexyl groups, etc., and as the alkenyl group one having 2 to 18 carbon atoms is preferred, such as allyl, octenyl, octadecenyl groups, etc., and the aryl groups may be phenyl, naphthyl groups, etc. Also, R4, R5, R6, R7 and R8 may further have substituents.
- R2 in the formula (HQ) represents a halogen atom (e.g. fluorine, chlorine, bromine atoms, etc.), hydroxyl group, sulfo group, carboxyl group, preferably sulfo group and carboxyl group.
- halogen atom e.g. fluorine, chlorine, bromine atoms, etc.
- n may be preferably 1 or 2, and m preferably 0 or 1.
- the compounds which deactivate the oxidized product of the color developing agent to be used in the present invention may include in addition to the above compounds, for example, those as described in U.S. Patents 2,360,290, 2,336,327, 2,418,613, 2,673,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735,765, Japanese Unexamined Patent Publications. Nos. 92988/1975, 92989/1975, 93928/1975, 110337/1975, 146235/1977, Japanese Patent Publication No. 23813/1975, Japanese Unexamined Patent Publications Nos. 24141/1983, 5247/1984, 81639/1987, etc. and further Japanese Unexamined Patent Publication No. 39851/1987, page 5 right lower col. to page 7 right low col, and Japanese Unexamined Patent Application No. 93538/1986, page 19 to page 29, and they can be synthesized easily according to the methods as described in the above patents.
- the compound which deactivates the oxidized product of the color developing agent to be used in the present invention can be used either singly or in combination of two or more kinds. Sc in this case is determined as the sum of Sc's for the respective compounds.
- the hydroquinone type compound it is also possible to add a quinone type compound which is the oxidized product of said hydroquinone type compound in combination.
- the compound which deactivates the oxidized product of the color developing agent according to the present invention may be contained in the non-light-sensitive intermediate layer of the present invention preferably in an amount of 2 x 10 ⁇ 4 to 1 x 10 ⁇ 2 mol per 1 m2, more preferably 3 x 10 ⁇ 4 to 5 x 10 ⁇ 3 mol.
- the compound which deactivates the oxidized product of the color developing agent to be used in the present invention in a photographic constituting layer, it can be also added in the state as such in the coating solution for forming the layer or in a solution dissolved at an appropriate concentration in a solvent which does not deleteriously affect the light-sensitive material such as water, alcohol, etc., but there can be also preferably employed a method in which it is dissolved in a high boiling organic solvent and/or a low boiling organic solvent, followed by emulsification into an aqueous solution before addition.
- the yellow coupler preferably used in the present invention is represented by the following formula (Y).
- R Y1 represents a halogen atom.
- R Y2 represents a hydrogen atom or a group substitutable on the benzene ring, and B represents a ballast group.
- Z represents a hydrogen atom, a halogen atom or a group eliminable through the reaction with the oxidized product of the color developing agent.
- the halogen atom represented by R Y1 may be preferably chlorine atom, and R Y2 may be preferably a hydrogen atom.
- ballast group represented by B may include acylamino, alkoxycarbonyl, aryloxycarbonyl, alkylsulfamoyl, arylsulfamoyl, alkylsulfonamide, arylsulfonamide, alkylureido, arylureido, succinimido, alkoxy, aryloxy, alkoxycarbonylamino, alkylcarbamoyl, arylcarbamoyl, alkylsulfamoylamino, arylsulfamoylamino, alkyl, alkenyl, acyloxy, etc., particularly preferably a group having total carbon atoms of 8 to 30.
- Z may be preferably a halogen atom or an eliminable group through the reaction with the oxidized product of the color developing agent.
- the halogen atom chlorine atom is preferable
- the eliminable group through the reaction with the oxidized product of the color developing agent may be preferably a group represented by (wherein R Z1 represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed with said R Z1 may have also substituents) or -OR Z2 (wherein R Z2 represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group).
- a yellow coupler containing at least one functional group A shown below in at least one of the groups represented by B and Z in the above formula (Y) is most preferably used.
- R1 - R4, R6, R7 and R10 each represent an alkyl group or an aryl group
- R5, R8, R9 and R11 each represent hydrogen atom, an alkyl group or an aryl group.
- the alkyl group represented by R1 to R11 may be preferably a straight or branched alkyl group having 1 to 20 carbon atoms
- the aryl group represented by R1 to R11 may be preferably phenyl group
- the alkyl group and the aryl group represented by R1 to R11 include those having substituents.
- the functional group A is contained in at least one of the groups represented by B and Z, but particularly preferably in the group represented by B.
- the yellow coupler to be used in the present invention also include, in addition to the above compounds, the yellow couplers as described in Japanese Unexamined Patent Publications Nos. 155538/1982, 6652/1986, 70841/1980, 24321/1972, 66834/1973, Japanese Patent Publication No. 19031/1971, Japanese Unexamined Patent Publications Nos. 87650/1975, 123342/1975, U.S. Patent 3,408,194, etc. and further Japanese Unexamined Patent Publication No. 72239/1986, page 5 left lower col. to page 8 left upper col., Japanese Patent Applications Nos. 231525/1986, page 22 to page 40, 243865/1986, page 20 to page 38, and also synthesized according to the methods described in these.
- magenta coupler known 5-pyrazolone type couplers, pyrazoloazole type couplers, etc. can be preferably used. More preferably, they are couplers represented by the following formulae (M-I) to (M-III).
- Ar represents an aryl group
- R P1 hydrogen atom or a substituent
- R P2 represents a substituent
- Y represents hydrogen atom or a group eliminable through the reaction with the oxidized product of the color developing agent
- W represents -NH-, -NHCO- (N atom is bonded to the carbon atom of the pyrazolone nucleus) or -NHCONH-
- m is an integer of 1 or 2.
- X M represents hydrogen atom or a group eliminable through the reaction with the oxidized product of the color developing agent
- each of R M1 , R M2 and R M3 represents hydrogen atom or a substituent.
- the aryl group represented by Ar may be preferably phenyl group, more preferably a phenyl group having at least one halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, acylamino group or cyano group as the substituent.
- the substituent represented by R P1 may be preferably a halogen atom or an alkoxy group, more preferably chlorine atom.
- the substituent represented by R P2 is not particularly limited, but at least one of R P2 is a ballast group. As the ballast group represented by R P2 , known ballast groups in this field of art may be included. W may be preferably -NH-.
- the group eliminable through the reaction with the oxidized product of the color developing agent represented by Y may include preferably aryloxy, alkoxy, heterocyclicoxy, silyloxy, phosphoneoxy, alkylthio, arylthio, heterocyclicthio, acylthio, thiocyano, aminothiocarbonylthio, acylamino, sulfonamide, alkoxycarbonylamino, aryloxycarbonylamino or nitrogen-containing heterocyclic group bonded through nitrogen atom at the active site of the pyrazolone ring, etc.
- R M1 , R M2 and R M3 are not particularly limited, but representative of them may be alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, etc., and otherwise there may be also included halogen atoms and cycloalkenyl, alkynyl, heterocyclic ring, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclicoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonyla
- R M1 on the above heterocyclic ring is one represented by the formula (M-IV) shown below. wherein R M4 , R M5 and R M6 have the same meanings of the above R M1 , R M2 and R M3 .
- R M4 two of the above R M4 , R M5 and R M6 , for example, R M4 are R M5 may be bonded to form a saturated or unsaturated ring (e.g. cycloalkane, cycloalkene, heterocyclic ring), and further R M6 may be bonded to said ring to constitute a bridged hydrocarbon compound residue.
- R M4 saturated or unsaturated ring
- R M6 may be bonded to said ring to constitute a bridged hydrocarbon compound residue.
- R M4 to R M6 are alkyl groups and the case (ii) wherein one of R M4 to R M6 , for example, R M6 is hydrogen atom, and the other two R M4 and R M5 are bonded together to form a cycloalkyl together with the root carbon atom.
- (i) is the case wherein two of R M4 - R M6 are alkyl groups, and the other one is hydrogen atom or an alkyl group, and most preferred is the case wherein all of R M4 - R M6 are alkyl groups.
- Examples of the group eliminable through the reaction with the oxidized product of the color developing agent represented by X M in the formulae (M-II) and (M-III) may include halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclicoxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclicthio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded through N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl groups, etc., preferably halogen atoms, particularly chlorine atom.
- magenta coupler may also form a polymer dimer or higher through Y, Ar, R P1 or R P2 in the above formula (M-I), and through X M , R M1 , R M2 or R M3 in the above formulae (M-II) and (M-III).
- magenta coupler to be used in the present invention is not limited.
- the magenta couplers to be used in the present invention may include, in addition to the above compounds, those as disclosed in U.S. Patent 3,684,514, U.K. Patent 1,183,515, Japanese Patent Publications Nos. 6031/1965, 6035/1965, 15754/1969, 40757/1970, 19032/1971, Japanese Unexamined Patent Publications Nos. 13041/1975, 129035/1978, 37646/1976, 62454/1980, U.S. Patent 3,725,067, U.K. Patents 1,252,418, 1,334,515, Japanese Unexamined Patent Publications Nos. 171956/1984, 162548/1984, 43659/1985, 33552/1985, 39852/1987, Research Disclosure No.
- the light-sensitive silver halide photographic material can be applied to, for example, color nega- and posi-film, as well as for color printing paper, etc., but above all the effect of the present invention can be exhibited when applied to a color printing paper to be provided for direct viewing.
- the light-sensitive silver halide photographic material including the color printing paper is a light-sensitive silver halide photographic material for multi-color use, and for effecting color reproduction by the color subtractive method, has generally a structure comprising silver halide emulsion layers containing the respective couplers of magenta, yellow and cyan as the couplers for photography laminated in a suitable number of layers and order of layers on a support, and said layer number and layer order may be suitably changed depending on the important performance, and purpose of use.
- couplers of the above formula (Y) are preferred, and as the magenta coupler, couplers represented by the above formulae (M-I) to (M-III) are preferably used.
- cyan coupler phenol type compounds, naphthol type compounds, etc. can be used.
- hydrophobic compounds such as couplers, compounds which deactivate the oxidized product of the color developing agent, etc.
- hydrophobic compounds such as couplers, compounds which deactivate the oxidized product of the color developing agent, etc.
- various methods such as the solid dispersion method, the latex dispersion method, the oil-in-water type emulsification and dispersion method, etc.
- the oil-in-water type emulsification and dispersion method may be carried out by dissolving a hydrophobic compound such as couplers, etc.
- a hydrophilic binder such as an aqueous gelatin solution by use of a surfactant, and then adding the emulsion into the desired hydrophilic colloid layer.
- silver halide to be used in the present invention there may be included any desired silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide, etc.
- silver halide grains containing 90 mol% or more of silver chloride are preferred, and the silver bromide content may be preferably 10 mol% or less and the silver iodide content preferably 0.5 mol% or less. More preferably, silver chlorobromide having a silver bromide content of 0.1 - 2 mol% may be employed.
- the silver halide grains may be used either alone or as the mixture with other silver halide grains having a different composition. Also, they can be used as the mixture with silver halide grains having a silver chloride content of 10 mol% or less.
- the ratio of the silver halide grains having a silver chloride content of 90 mol% in the total silver halide grains contained in said emulsion layer may be 60 % by weight or more, preferably 80 % by weight or more.
- the composition of the silver halide grain may be uniform from the inner portion to the outer portion of the grain, but may be also different in the inner portion and the outer portion of the grain. When the compositions in the inner portion and the outer portion of the grain are different, the composition may be varied continuously or incontinuously.
- the grain size of the silver halide grain is not particularly limited, but preferably within the range of 0.2 to 1.6 ⁇ m, more preferably 0.25 to 1.2 ⁇ m when other photographic performances such as rapid processability and sensitivity, etc. are taken into consideration.
- the above grain size can be measured according to various methods generally employed in the related field of art. Representative methods are described in Rabland "Grain Size Analytical Method" (A.S.T.M. Symposium on Light Microscopy, 1955, pp. 94 - 122) or "Theory of Photographic Process” (Mieth and James, co-authors, third edition, McMillan Co., 1966, Chapter 2).
- the grain size can be measured by use of the projected area or an approximate value of diameter of grain.
- the grain size distribution can be represented considerably accurately as diameter or projected area.
- the distribution of the grain sizes of silver halide grains may be either poly-dispersed or mono-dispersed.
- mono-dispersed silver halide grains having its fluctuation coefficient of 0.22 or less, more preferably 0.15 or less in the grain size distribution of silver halide grains may be employed.
- the fluctuation coefficient is a coefficient indicating the breadth of the grain size distribution, which is defined by the following formula.
- ri represents grain size of individual grain
- ni represents its number.
- the grain size as mentioned here refers to its diameter in the case of a spherical silver halide grain, while it represents the diameter when the projected image is calculated to a circular image of the same area in the case of grain of cubic body or a shape other than sphere.
- the silver halide grains to be used in the emulsion may be obtained according to any of the acidic method, the neutral method and the ammonia method. Said grains may be grown either at one time or may be grown after preparation of seed grains. The method for making seed grains and the method for growing the grains may be either the same or different.
- the mode for reacting a soluble silver salt with a soluble halogen salt there may be employed either of the normal mixing method, the reverse mixing method, the simultaneous mixing method or combinations thereof, but preferably one obtained by the simultaneous mixing method is preferred. Further, as one mode of the simultaneous mixing method, it is also possible to use the PAg-controled double jet method as described in Japanese Unexamined Patent Publication No. 48521/1979.
- a silver halide solvent such as thioether, etc. may be also employed.
- compounds such as mercapto-containing compounds, nitrogen-containing heterocyclic compounds or sensitizing dyes may be also added during formation of silver halide grains or after completion of grain formation.
- the shape of silver halide grains may be any desired one. A preferable example is cubic body having ⁇ 100 ⁇ plane as the crystal surface.
- grains having octahedral, tetradecahedral, dodecahedral bodies, etc. may be made according to the methods as described in U.S. Patents 4,183,756, 4,225,666, Japanese Unexamined Patent Publication No. 26589/1980, Japanese Patent Publication No. 42737/1980, The Journal of Photographic Science (J. Photgr. Sci.), 21 , 39 (1973), etc. and these can be also used. Further, grains having twin crystal surface may be also used.
- silver halide grains either grains comprising a single shape or a mixture of grains with various shapes may be employed.
- the silver halide grains to be used in the emulsion can contain metal ions by use of cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex thereof, rhodium salt or complex thereof, iron salt or complex thereof internally of the grains and/or on the surface of the grains by adding them in the process of forming the grains and/or in the process of growing them, and also by placing them in an appropriate reducing atmosphere, reducing sensitizing nuclei can be imparted internally of the grains and/or the surface of the grains.
- the emulsion containing the silver halide grains may have unnecessary soluble salts removed therefrom after completion of the growth of the silver halide grains, or may also contain them as such. When said salts are to be removed, it can be practiced on the basis of the method described in Research Disclosure No. 17643.
- the silver halide grains to be used in the emulsion may be either the grains in which latent images are formed primarily on the surfaces or alternatively the grains in which latent images are formed primarily internally of the grains. Preferably, grains in which latent images are formed primarily on the surfaces may be employed.
- the emulsion to be used in the present invention is chemically sensitized according to conventional methods. That is, there may be employed the sulfur sensitization method by use of a compound containing sulfur which can react with silver ions or active gelatin, the selenium sensitizing method by use of a selenium compound, the reducing sensitizing method by use of a reducing substance, the noble metal sensitizing method by use of gold or other noble metal compounds either singly or as a combination.
- the silver halide emulsion can be optically sensitized to a desired wavelength region by use of a dye known as sensitizing dye in the field of photography.
- the light-sensitive silver halide photographic material of the present invention there can be used as desired color antifoggant, film hardener, plasticizer, polymer latex, UV-ray absorber, formalin scavenger, mordant, developing accelerator, developing retarder, fluorescent brighener, matting agent, lubricant, antistatic agent, surfactant, etc.
- the light-sensitive silver halide photographic material can form an image by performing various color developing processes.
- the light-sensitive silver halide color photographic material of the present invention by making the above k1/k2 0.25 or more and 1 or less and also satisfying the relationship of the above formula [I] between said k1/k2 and said Sc, can improve remarkably the effect of preventing color turbidity, and improve color reproducibility to great extent.
- the layers 1 - 7 shown below were successively provided by coating (simultaneous coating) on a paper support coated on the both surfaces with polyethylene to prepare light-sensitive silver halide color photographic materials 1 - 33 (in the following examples, the amount added is shown in an amount per 1 m2 of the light-sensitive material).
- the blue light absorption density D'B at the unexposed portion, the blue light absorption density DB at the exposed portion, the green light absorption density D'G at the unexposed portion and the green light absorption density DG at the exposed portion were determined by a densitometer (Sakura Densitometer PDA-60, produced by Konishiroku Photo Industry).
- the ratio (Q) of the blue light absorption density to the green light absorption density excluding the fog density was determined.
- the samples No. 11 to N. 33 of the present invention having k1/k2 and Sc k1/k2 within the ranges specified in the present invention have remarkably small Q1 and Q2 as compared with comparative samples, whereby it can be appreciated that color turbidity is effectively prevented and color reproducibility is improved.
- Light-sensitive silver halide color photographic material samples No. 34 to 66 were prepared in entirely the same manner as in Example 1 except for replacing the blue-sensitive silver halide emulsion in Layer 1 of the light-sensitive silver halide color photographic material prepared in Example 1 with Em-4 shown in Table 1, the green-sensitive silver halide emulsion in Layer 3 with Em-5 in Table 1, and the red-sensitive silver halide emulsion in Layer 5 with Em-6 in Table 1, respectively and using the yellow coupler, magenta coupler and the compound which deactivates the oxidized product of the color developing agent in Layer 1, Layer 3 and Layer 2, respectively.
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Abstract
Sc·k₁/k₂ ≧ 0.2 Formula (I)
wherein Sc represents an abilty of the compound to deactivate the oxidized product of the color developing agent in the non-light-sensitive intermediate layer.
Description
- This invention relates to a light-sensitive silver halide photographic material, more particularly to a light-sensitive silver halide color photographic material having little color turbidity and excellent color reproducibility.
- In general, a light-sensitive silver halide color photographic material has three kinds of silver halide emulsion layers for photography spectrally sensitized selectively so as to have light sensitivity to blue light, green light and red light provided by coating on a support. For example, in a light-sensitive silver halide photographic material for color printing paper, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer are generally provided by coating, and further an intermediate layer or a protective layer, including UV-ray absorbing layer, etc. are provided.
- In a multiple layer light-sensitive color photographic material having such plural layers, the reaction rate between the diffusion-resistant coupler contained in each light-sensitive silver halide emulsion layer with a color developing agent oxidized product is generally different between the respective emulsion layers. For this reason, the excessive oxidized product of the color developing agent generated in an emulsion layer containing a diffusion-resistant coupler with small reaction rate with the oxidized product of the color developing agent will be diffused to other silver halide emulsion layers than the layer of itself, whereby there are the drawbacks that color turbidity is liable to occur and that color reproducibility will be readily lowered.
- As the means for preventing such color turbidity, there have been known the techniques in which compounds which deactivate the oxidized product of color developing agent such as hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. are contained in the intermediate layer as disclosed in U.S. Patents 2,360,290, 2,336,327, 2,403,721, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735,765, Japanese Unexamined Patent Publications Nos. 92988/1975, 92989/1975, 93928/1975, 110337/1975, 146235/1977, Japanese Patent Publication No. 23813/1975, etc. However, although improvement of color turbidity can be effected by these techniques, improvement is not yet satisfactory, and particularly concerning color turbidity to another layer in the region with higher color formed density in its own layer, further improvement has been desired.
- On the other hand, in recent years, in this field of art, it has been desired to have a light-sensitive silver halide color photographic material which can be rapidly processed.
- That is, it has been practiced that the light-sensitive silver halide color photographic material is subjected to running by an automatic developing machine provided in each laboratory, and as a part of improvement of service for users, it has been demanded to perform development processing and return the processed product to users within the very day when the development is ordered. Recently, it has been even demanded to return the product within several hours from the order, and thus development of a light-sensitive silver halide color photographic material capable of rapid processing has been increasingly hastened.
- As one of the techniques responding to the demands concerning such rapid processing, there has been known the technique of making the silver halide low silver bromide contents as described in Japanese Unexamined Patent Publication No. 184142/1983, Japanese Patent Publication No. 18939/1981. Further, it has been known that a high chloride silver halide emulsion (which means silver halide containing 80 mol% or more of silver chloride) is capable of rapid processing to great extent.
- Whereas, there is involved the problem that the tendency of increasing color turbidity is marked when a light-sensitive silver halide color photographic material having such high chloride silver halide emulsion layer is subjected to color developing processing ultra-rapidly with a color developer containing no bromide ion, and improvement of this problem has been strongly demanded.
- The present invention has been accomplished in view of the state of the art as described above and an object of the present invention is to provide a light-sensitive silver halide color photographic material having little color turbidity and excellent color reproducibility.
- The present inventors have studied intensively, and consequently the above object of the present invention has been accomplished by a light-sensitive silver halide photographic material comprising at least two light-sensitive silver halide emulsion layers containing diffusion-resistant couplers and at least one non-light-sensitive intermediate layer sandwiched between said light-sensitive silver halide emulsion layers provided on a support, wherein said non-light-sensitive intermediate layer contains a compound which deactivates the oxidized product of a color developing agent, the relative color formation speed ratio k₁/k₂ (lower color formation speed is defined as k₁, and higher color formation speed as k₂; when the color formation speeds are equal, either one may be applicable) between the diffusion-resistant couplers contained in the respective two light-sensitive silver halide emulsion layers adjacent to said non-light-sensitive intermediate layer is 0.25 ≦ k₁/k₂ ≦ 1, and the relationship of said k₁/k₂ to the ability Sc is represented by Formula (I):
Sc·k₁/k₂ ≧ 0.2 Formula (I)
wherein Sc represents an abilty of said compound to deactivate the oxidized product of the color developing agent in the non-light-sensitive intermediate layer. - In the following, the construction of the present invention is described in more detail.
- Concerning relative color formation speed of coupler, for example, as described in Japanese Unexamined Patent Publication No. 60437/1984, it can be determined by adding a mixture of two kinds of different dyes which can be distinctly separated from each other into an emulsion and measuring the amounts of the respective dyes obtained by color developing of the emulsion.
- However, according to this method, which employs a magenta coupler as the standard for cyan coupler, and a cyan coupler as the standard for magenta coupler and yellow coupler, it is difficult to determine a united standard.
- The relative color formation speed ratio k₁/k₂ between the diffusion-resistant couplers in the present invention is determined as described below on the basis of the principle which is basically similar to the above method.
- A coupler is dispersed by use of 0.5 g of dioctyl phthalate per 1 mmol of the coupler, and in the dispersion were mixed a coupler solution A (coupler concentration 2 x 10⁻² mol, silver chloride concentration 4 x 10⁻³ mol) added with a silver chloride emulsion (AgCl 100 %, average particle size 0.14 µm) and a color developer B (N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 2 x 10⁻² mol, anhydrous potassium carbonate 40 g/liter, sodium sulfite 1 g/liter, pH 10.0) at 25 °C at a volume ratio of 1 : 1 (coupler solution A : color developer B). After the color forming reaction, 1/2-fold volume of methanol and 1-fold volume of ethyl acetate based on the volume of the mixture were added to extract the color formed dyes into the organic solvent phase, and absorbance of the extract at the maximum absorption wavelength in the visible region is measured.
- The same measurement is performed for the two couplers to be compared, and the ratio of the absorbances obtained is determined as k₁/k₂. In this case, the smaller absorbance is made k₁ and the larger one k₂. When absorbances are equal, either one may be made k₁ or k₂.
- The ability Sc of the compound to deactivate the oxidized product of the color developing agent in the non-light-sensitive intermediate layer in the present invention is determined based on the method described above and according to the method as described below.
- In the above measurement to determine k₁/k₂, the following C-1 is used as the coupler and the absorbance obtained is made (ABS)R.
- Next, a dispersion is prepared by use of 0.5 g of dioctyl phthalate per 1 mmol of the compound which deactivates the oxidized product of the color developing agent, and the same measurement is performed under the same conditions as in determination of (ABS)R except for adding the dispersion into the above coupler solution A (concentration of the compound which deactivates the oxidized product of the color developing agent : 2 x 10⁻³ mol), and the absorbance obtained is made (ABS)S. Sc is given by the following formula (II).
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- The present invention is defined by the above k₁/k₂ and Sc, and is not limited only by the chemical structures of the coupler and the compound which deactivates the oxidized product of the color developing agent employed.
- In the present invention, the above k₁/k₂ is required to be 0.25 or more and 1 or less, preferably 0.30 or more and 1 or less. On the other hand, the product of Sc represented by the above formula (I) and k₁/k₂ is required to be 0.2 or more, preferably 0.3 or more.
- As the preferable embodiment of the present invention, the following embodiment may be included.
- A light-sensitive silver halide color photographic material of the present invention, which contains a hydroquinone type compound as the compound which deactivates the oxidized product of the color developing agent in the non-light-sensitive intermediate layer, and a yellow coupler in one of the two light-sensitive silver halide emulsion layers adjacent to said non-light-sensitive intermediate layer and a magenta coupler in the other of the emulsion layers.
- The non-light-sensitive intermediate layer of the present invention is required to have the ability Sc to deactivate the oxidized product of the color developing agent which satisfies the relationship of the above formula (I). Sc can be controlled as desired according to the kind and the amount added of the compound which deactivates the oxidized product of the color developing agent.
- As the compound which deactivates the oxidized product of the color developing agent to be used in the present invention, there may be included hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. as mentioned above, preferably hydroquinone derivatives.
-
- In the formula, R₁ represents a substituted or unsubstituted alkyl group, and n represents an integer of 1 to 3. However, the total sum of carbon numbers of R₁ is 8 or more, and when n is 2 or more, the plural number of R₁ may be either the same or different. R₂ represents a halogen atom, hydroxyl group, sulfo group, carboxyl group. m represents an integer of 0 to 3, and when m is 2 or more, the plural number of R₂ may be either the same or different. The sum of n + m is 4 or less.
- In the above formula (HQ), the alkyl group represented by R₁ may be preferably a straight and branched alkyl group having 1 to 20 carbon atoms, including, for example, methyl, ethyl, propyl, t-butyl, octyl, t-dodecyl groups and the like. The substituent possessed by R₁ may include sulfo group, carboxyl group, cyano group, hydroxyl group, halogen atoms (e.g. fluorine, chlorine, bromine atoms, etc.), -COOR₄, -COR₅, -OR₆, -SO₂R₇, -NHSO₂R₈, etc. Here, R₄, R₅, R₆, R₇ and R₈ represent alkyl group, alkenyl group, cycloalkyl group, aryl group.
- Further, the alkyl group represented by R₄ through R₈ may be the same as the alkyl represented by the above R₁, examples of cycloalkyl group may be cyclopentyl, cyclohexyl groups, etc., and as the alkenyl group one having 2 to 18 carbon atoms is preferred, such as allyl, octenyl, octadecenyl groups, etc., and the aryl groups may be phenyl, naphthyl groups, etc. Also, R₄, R₅, R₆, R₇ and R₈ may further have substituents.
- R₂ in the formula (HQ) represents a halogen atom (e.g. fluorine, chlorine, bromine atoms, etc.), hydroxyl group, sulfo group, carboxyl group, preferably sulfo group and carboxyl group.
- n may be preferably 1 or 2, and m preferably 0 or 1.
-
- The compounds which deactivate the oxidized product of the color developing agent to be used in the present invention may include in addition to the above compounds, for example, those as described in U.S. Patents 2,360,290, 2,336,327, 2,418,613, 2,673,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735,765, Japanese Unexamined Patent Publications. Nos. 92988/1975, 92989/1975, 93928/1975, 110337/1975, 146235/1977, Japanese Patent Publication No. 23813/1975, Japanese Unexamined Patent Publications Nos. 24141/1983, 5247/1984, 81639/1987, etc. and further Japanese Unexamined Patent Publication No. 39851/1987, page 5 right lower col. to page 7 right low col, and Japanese Unexamined Patent Application No. 93538/1986, page 19 to page 29, and they can be synthesized easily according to the methods as described in the above patents.
- The compound which deactivates the oxidized product of the color developing agent to be used in the present invention can be used either singly or in combination of two or more kinds. Sc in this case is determined as the sum of Sc's for the respective compounds. In the case of the hydroquinone type compound, it is also possible to add a quinone type compound which is the oxidized product of said hydroquinone type compound in combination.
- The compound which deactivates the oxidized product of the color developing agent according to the present invention may be contained in the non-light-sensitive intermediate layer of the present invention preferably in an amount of 2 x 10⁻⁴ to 1 x 10⁻² mol per 1 m², more preferably 3 x 10⁻⁴ to 5 x 10⁻³ mol.
- For adding the compound which deactivates the oxidized product of the color developing agent to be used in the present invention in a photographic constituting layer, it can be also added in the state as such in the coating solution for forming the layer or in a solution dissolved at an appropriate concentration in a solvent which does not deleteriously affect the light-sensitive material such as water, alcohol, etc., but there can be also preferably employed a method in which it is dissolved in a high boiling organic solvent and/or a low boiling organic solvent, followed by emulsification into an aqueous solution before addition.
-
- In the formula, RY1 represents a halogen atom. RY2 represents a hydrogen atom or a group substitutable on the benzene ring, and B represents a ballast group. Z represents a hydrogen atom, a halogen atom or a group eliminable through the reaction with the oxidized product of the color developing agent.
- In the above formula (Y), the halogen atom represented by RY1 may be preferably chlorine atom, and RY2 may be preferably a hydrogen atom.
- In the above formula (Y), examples of the ballast group represented by B may include acylamino, alkoxycarbonyl, aryloxycarbonyl, alkylsulfamoyl, arylsulfamoyl, alkylsulfonamide, arylsulfonamide, alkylureido, arylureido, succinimido, alkoxy, aryloxy, alkoxycarbonylamino, alkylcarbamoyl, arylcarbamoyl, alkylsulfamoylamino, arylsulfamoylamino, alkyl, alkenyl, acyloxy, etc., particularly preferably a group having total carbon atoms of 8 to 30.
- In the above formula (Y), Z may be preferably a halogen atom or an eliminable group through the reaction with the oxidized product of the color developing agent. As the halogen atom, chlorine atom is preferable, and the eliminable group through the reaction with the oxidized product of the color developing agent may be preferably a group represented by
- In the present invention, a yellow coupler containing at least one functional group A shown below in at least one of the groups represented by B and Z in the above formula (Y) is most preferably used.
-
- In the group represented by the functional group A, the alkyl group represented by R¹ to R¹¹ may be preferably a straight or branched alkyl group having 1 to 20 carbon atoms, the aryl group represented by R¹ to R¹¹ may be preferably phenyl group, and the alkyl group and the aryl group represented by R¹ to R¹¹ include those having substituents. The functional group A is contained in at least one of the groups represented by B and Z, but particularly preferably in the group represented by B.
-
- The yellow coupler to be used in the present invention also include, in addition to the above compounds, the yellow couplers as described in Japanese Unexamined Patent Publications Nos. 155538/1982, 6652/1986, 70841/1980, 24321/1972, 66834/1973, Japanese Patent Publication No. 19031/1971, Japanese Unexamined Patent Publications Nos. 87650/1975, 123342/1975, U.S. Patent 3,408,194, etc. and further Japanese Unexamined Patent Publication No. 72239/1986, page 5 left lower col. to page 8 left upper col., Japanese Patent Applications Nos. 231525/1986, page 22 to page 40, 243865/1986, page 20 to page 38, and also synthesized according to the methods described in these.
-
- In the formula, Ar represents an aryl group, RP1 hydrogen atom or a substituent and RP2 represents a substituent. Y represents hydrogen atom or a group eliminable through the reaction with the oxidized product of the color developing agent, W represents -NH-, -NHCO- (N atom is bonded to the carbon atom of the pyrazolone nucleus) or -NHCONH-, m is an integer of 1 or 2.
- In the formulae, XM represents hydrogen atom or a group eliminable through the reaction with the oxidized product of the color developing agent, each of RM1, RM2 and RM3 represents hydrogen atom or a substituent.
- In the above formula (M-I), the aryl group represented by Ar may be preferably phenyl group, more preferably a phenyl group having at least one halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, acylamino group or cyano group as the substituent.
- The substituent represented by RP1 may be preferably a halogen atom or an alkoxy group, more preferably chlorine atom. The substituent represented by RP2 is not particularly limited, but at least one of RP2 is a ballast group. As the ballast group represented by RP2, known ballast groups in this field of art may be included. W may be preferably -NH-.
- In the above formula (M-I), the group eliminable through the reaction with the oxidized product of the color developing agent represented by Y may include preferably aryloxy, alkoxy, heterocyclicoxy, silyloxy, phosphoneoxy, alkylthio, arylthio, heterocyclicthio, acylthio, thiocyano, aminothiocarbonylthio, acylamino, sulfonamide, alkoxycarbonylamino, aryloxycarbonylamino or nitrogen-containing heterocyclic group bonded through nitrogen atom at the active site of the pyrazolone ring, etc.
- In the above formulae (M-II) and (M-III), the substituents represented by RM1, RM2 and RM3 are not particularly limited, but representative of them may be alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, etc., and otherwise there may be also included halogen atoms and cycloalkenyl, alkynyl, heterocyclic ring, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclicoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclicthio groups, and also spiro compound residues, bridged hydrocarbon compound residues, etc.
-
- Also, two of the above RM4, RM5 and RM6, for example, RM4 are RM5 may be bonded to form a saturated or unsaturated ring (e.g. cycloalkane, cycloalkene, heterocyclic ring), and further RM6 may be bonded to said ring to constitute a bridged hydrocarbon compound residue.
- Of the compounds of the formula (M-IV) are preferred the case (i) wherein at least two of RM4 to RM6 are alkyl groups and the case (ii) wherein one of RM4 to RM6, for example, RM6 is hydrogen atom, and the other two RM4 and RM5 are bonded together to form a cycloalkyl together with the root carbon atom.
- Further, preferable of (i) is the case wherein two of RM4 - RM6 are alkyl groups, and the other one is hydrogen atom or an alkyl group, and most preferred is the case wherein all of RM4 - RM6 are alkyl groups.
- Examples of the group eliminable through the reaction with the oxidized product of the color developing agent represented by XM in the formulae (M-II) and (M-III) may include halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclicoxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclicthio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded through N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl groups, etc., preferably halogen atoms, particularly chlorine atom.
- Also, the above magenta coupler may also form a polymer dimer or higher through Y, Ar, RP1 or RP2 in the above formula (M-I), and through XM, RM1, RM2 or RM3 in the above formulae (M-II) and (M-III).
-
- The magenta couplers to be used in the present invention may include, in addition to the above compounds, those as disclosed in U.S. Patent 3,684,514, U.K. Patent 1,183,515, Japanese Patent Publications Nos. 6031/1965, 6035/1965, 15754/1969, 40757/1970, 19032/1971, Japanese Unexamined Patent Publications Nos. 13041/1975, 129035/1978, 37646/1976, 62454/1980, U.S. Patent 3,725,067, U.K. Patents 1,252,418, 1,334,515, Japanese Unexamined Patent Publications Nos. 171956/1984, 162548/1984, 43659/1985, 33552/1985, 39852/1987, Research Disclosure No. 24626 (1984), Japanese Unexamined Patent Publications Nos. 120147/1986, 120148/1986, 120149/1986, 120152/1986, 230146/1986, 230147/1986, Japanese Patent Application No. 9791/1986, etc., and can be synthesized according to the methods described in these.
- The light-sensitive silver halide photographic material can be applied to, for example, color nega- and posi-film, as well as for color printing paper, etc., but above all the effect of the present invention can be exhibited when applied to a color printing paper to be provided for direct viewing.
- The light-sensitive silver halide photographic material, including the color printing paper is a light-sensitive silver halide photographic material for multi-color use, and for effecting color reproduction by the color subtractive method, has generally a structure comprising silver halide emulsion layers containing the respective couplers of magenta, yellow and cyan as the couplers for photography laminated in a suitable number of layers and order of layers on a support, and said layer number and layer order may be suitably changed depending on the important performance, and purpose of use.
- As the yellow coupler, couplers of the above formula (Y) are preferred, and as the magenta coupler, couplers represented by the above formulae (M-I) to (M-III) are preferably used.
- As the cyan coupler, phenol type compounds, naphthol type compounds, etc. can be used.
- In the present invention, hydrophobic compounds such as couplers, compounds which deactivate the oxidized product of the color developing agent, etc. can be added into the light-sensitive silver halide photographic material by use of various methods such as the solid dispersion method, the latex dispersion method, the oil-in-water type emulsification and dispersion method, etc. For example, the oil-in-water type emulsification and dispersion method may be carried out by dissolving a hydrophobic compound such as couplers, etc. generally in a high boiling organic solvent with a boiling point of about 150 °C or higher, optionally by use of a low boiling and/or water-soluble organic solvent in combination, emulsifying the solution in a hydrophilic binder such as an aqueous gelatin solution by use of a surfactant, and then adding the emulsion into the desired hydrophilic colloid layer.
- As the silver halide to be used in the present invention, there may be included any desired silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide, etc.
- However, in the light-sensitive silver halide photographic material for which particularly rapid developability is demanded such as color printing paper, etc., silver halide grains containing 90 mol% or more of silver chloride are preferred, and the silver bromide content may be preferably 10 mol% or less and the silver iodide content preferably 0.5 mol% or less. More preferably, silver chlorobromide having a silver bromide content of 0.1 - 2 mol% may be employed.
- The silver halide grains may be used either alone or as the mixture with other silver halide grains having a different composition. Also, they can be used as the mixture with silver halide grains having a silver chloride content of 10 mol% or less.
- In the silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more, the ratio of the silver halide grains having a silver chloride content of 90 mol% in the total silver halide grains contained in said emulsion layer may be 60 % by weight or more, preferably 80 % by weight or more.
- The composition of the silver halide grain may be uniform from the inner portion to the outer portion of the grain, but may be also different in the inner portion and the outer portion of the grain. When the compositions in the inner portion and the outer portion of the grain are different, the composition may be varied continuously or incontinuously.
- The grain size of the silver halide grain is not particularly limited, but preferably within the range of 0.2 to 1.6 µm, more preferably 0.25 to 1.2 µm when other photographic performances such as rapid processability and sensitivity, etc. are taken into consideration. The above grain size can be measured according to various methods generally employed in the related field of art. Representative methods are described in Rabland "Grain Size Analytical Method" (A.S.T.M. Symposium on Light Microscopy, 1955, pp. 94 - 122) or "Theory of Photographic Process" (Mieth and James, co-authors, third edition, McMillan Co., 1966, Chapter 2).
- The grain size can be measured by use of the projected area or an approximate value of diameter of grain. When the grain is substantially uniform in shape, the grain size distribution can be represented considerably accurately as diameter or projected area.
- The distribution of the grain sizes of silver halide grains may be either poly-dispersed or mono-dispersed. Preferably, mono-dispersed silver halide grains having its fluctuation coefficient of 0.22 or less, more preferably 0.15 or less in the grain size distribution of silver halide grains may be employed. Here, the fluctuation coefficient is a coefficient indicating the breadth of the grain size distribution, which is defined by the following formula.
- Here, ri represents grain size of individual grain, ni represents its number. The grain size as mentioned here refers to its diameter in the case of a spherical silver halide grain, while it represents the diameter when the projected image is calculated to a circular image of the same area in the case of grain of cubic body or a shape other than sphere.
- The silver halide grains to be used in the emulsion may be obtained according to any of the acidic method, the neutral method and the ammonia method. Said grains may be grown either at one time or may be grown after preparation of seed grains. The method for making seed grains and the method for growing the grains may be either the same or different.
- As the mode for reacting a soluble silver salt with a soluble halogen salt, there may be employed either of the normal mixing method, the reverse mixing method, the simultaneous mixing method or combinations thereof, but preferably one obtained by the simultaneous mixing method is preferred. Further, as one mode of the simultaneous mixing method, it is also possible to use the PAg-controled double jet method as described in Japanese Unexamined Patent Publication No. 48521/1979.
- Further, if necessary, a silver halide solvent such as thioether, etc. may be also employed. Also, compounds such as mercapto-containing compounds, nitrogen-containing heterocyclic compounds or sensitizing dyes may be also added during formation of silver halide grains or after completion of grain formation. The shape of silver halide grains may be any desired one. A preferable example is cubic body having {100} plane as the crystal surface. Also, grains having octahedral, tetradecahedral, dodecahedral bodies, etc. may be made according to the methods as described in U.S. Patents 4,183,756, 4,225,666, Japanese Unexamined Patent Publication No. 26589/1980, Japanese Patent Publication No. 42737/1980, The Journal of Photographic Science (J. Photgr. Sci.), 21, 39 (1973), etc. and these can be also used. Further, grains having twin crystal surface may be also used.
- As the silver halide grains, either grains comprising a single shape or a mixture of grains with various shapes may be employed.
- The silver halide grains to be used in the emulsion can contain metal ions by use of cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex thereof, rhodium salt or complex thereof, iron salt or complex thereof internally of the grains and/or on the surface of the grains by adding them in the process of forming the grains and/or in the process of growing them, and also by placing them in an appropriate reducing atmosphere, reducing sensitizing nuclei can be imparted internally of the grains and/or the surface of the grains.
- The emulsion containing the silver halide grains may have unnecessary soluble salts removed therefrom after completion of the growth of the silver halide grains, or may also contain them as such. When said salts are to be removed, it can be practiced on the basis of the method described in Research Disclosure No. 17643.
- The silver halide grains to be used in the emulsion may be either the grains in which latent images are formed primarily on the surfaces or alternatively the grains in which latent images are formed primarily internally of the grains. Preferably, grains in which latent images are formed primarily on the surfaces may be employed.
- The emulsion to be used in the present invention is chemically sensitized according to conventional methods. That is, there may be employed the sulfur sensitization method by use of a compound containing sulfur which can react with silver ions or active gelatin, the selenium sensitizing method by use of a selenium compound, the reducing sensitizing method by use of a reducing substance, the noble metal sensitizing method by use of gold or other noble metal compounds either singly or as a combination.
- The silver halide emulsion can be optically sensitized to a desired wavelength region by use of a dye known as sensitizing dye in the field of photography.
- In the light-sensitive silver halide photographic material of the present invention, there can be used as desired color antifoggant, film hardener, plasticizer, polymer latex, UV-ray absorber, formalin scavenger, mordant, developing accelerator, developing retarder, fluorescent brighener, matting agent, lubricant, antistatic agent, surfactant, etc.
- The light-sensitive silver halide photographic material can form an image by performing various color developing processes.
- The light-sensitive silver halide color photographic material of the present invention, by making the above k₁/k₂ 0.25 or more and 1 or less and also satisfying the relationship of the above formula [I] between said k₁/k₂ and said Sc, can improve remarkably the effect of preventing color turbidity, and improve color reproducibility to great extent.
- The present invention is described in detail by referring to Examples, but the embodiments of the present invention are not limited to these.
-
- Six kinds of silver halide emulsions shown in Table 1 were prepared according to the neutral method and the simultaneous mixing method.
- Next, the layers 1 - 7 shown below were successively provided by coating (simultaneous coating) on a paper support coated on the both surfaces with polyethylene to prepare light-sensitive silver halide color photographic materials 1 - 33 (in the following examples, the amount added is shown in an amount per 1 m² of the light-sensitive material).
- Layer 1 A layer containing gelatin (1.2 g), 0.29 g (calculated on silver, hereinafter the same) of a blue-sensitive silver halide emulsion (Em-1) and 0.3 g of dinonyl phthalate (DNP) containing 1.0 mmol of yellow coupler shown in Table 2, 0.3 g of photostabilizer ST-1 and 0.015 g of 2,5-dioctylhydroquinone (HQ-1) dissolved therein.
- Layer 2 A layer containing gelatin (0.9 g) and 0.2 g of diocryl phthalate (DOP) containing the compound which deactivates the oxidized product of the color developing agent shown in Table 2 dissolved therein.
- Layer 3 A layer containing gelatin (1.4 g), 0.2 g of green-sensitive silver halide emulsion (Em-2), 0.3 g of DOP containing 1.0 mmol of magenta coupler shown in Table 2, 0.25 g of the photostabilizer ST-2 and 0.01 g HQ-1 dissolved therein and 6 mg of a filter dye AI-1 shown below.
- Layer 4 A layer containing gelatin (1.2 g) and 0.3 g of DNP containing 0.6 g of UV-absorber UV-1 shown below and 0.05 g of HQ-1 dissolved therein.
- Layer 5 A layer containing gelatin (1.4 g), 0.20 g of red-sensitive silver halide emulsion (Em-3) and 0.3 g of DOP containing 0.18 g of cyan coupler (C-1), 0.36 g of cyan coupler (C-2), 0.3 g of ST-1 and 0.01 g of HQ-1 dissolved therein.
- Layer 6 A layer containing gelatin (1.1 g), 0.2 g of DOP containing 0.2 g of UV-1 dissolved therein and 5 mg of a filter dye AI-2 shown below.
- Layer 7 A layer containing gelatin (1.0 g) and 0.05 mg of 2,4-dichloro-6-hydroxy-s-triazine sodium.
- After each of the above light-sensitive material samples No. 1 - 33 was exposed to blue light through an optical wedge (by use of an interference filter with a center wavelength of 460 nm), processing was performed following the development processing steps shown below.
- After the developing processing, the blue light absorption density D'B at the unexposed portion, the blue light absorption density DB at the exposed portion, the green light absorption density D'G at the unexposed portion and the green light absorption density DG at the exposed portion were determined by a densitometer (Sakura Densitometer PDA-60, produced by Konishiroku Photo Industry).
-
- The Q value under the condition where the optical density (D) is DB = 1.0 is made Q₁, and the Q value under the condition of DB = 2.0 is made Q₂. The results are shown in Table 2.
[Processing steps] Color developing 3 min 30 sec temperature 33 °C Bleach-fixing 1 min 30 sec temperature 33 °C Water washing 3 min temperature 33 °C Color developing solution recipe N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.9 g Hydroxylamine sulfate 2.0 g Potassium carbonate 25.0 g Sodium bromide 0.6 g Anhydrous sodium sulfite 2.0 g Benzyl alcohol 13 ml Polyethylene glycol (average polymerization degree 400) 3.0 ml (made up to 1 liter with addition of water, and adjusted to pH 10.0 with sodium hydroxide) Bleach-fixing solution recipe Iron sodium ethylenediaminetetraacetate 6.0 g Ammonium thiosulfate 100 g Sodium bisulfite 10 g Sodium metabisulfite 3 g (made up to 1 liter with addition of water, and adjusted to pH 7.0 with ammonia water) - As is apparent from Table 2, the samples No. 11 to N. 33 of the present invention having k₁/k₂ and Sc k₁/k₂ within the ranges specified in the present invention have remarkably small Q₁ and Q₂ as compared with comparative samples, whereby it can be appreciated that color turbidity is effectively prevented and color reproducibility is improved.
- Light-sensitive silver halide color photographic material samples No. 34 to 66 were prepared in entirely the same manner as in Example 1 except for replacing the blue-sensitive silver halide emulsion in Layer 1 of the light-sensitive silver halide color photographic material prepared in Example 1 with Em-4 shown in Table 1, the green-sensitive silver halide emulsion in Layer 3 with Em-5 in Table 1, and the red-sensitive silver halide emulsion in Layer 5 with Em-6 in Table 1, respectively and using the yellow coupler, magenta coupler and the compound which deactivates the oxidized product of the color developing agent in Layer 1, Layer 3 and Layer 2, respectively.
- Samples obtained were subjected to exposure with blue light similarly as described in Example 1, processed according to the developing processing steps as shown below, followed by the same measurement as described in Example 1. The results are shown in Table 3.
[Processing steps] Temperature Time Color developing 34.7 ± 0.3 °C 45 sec Bleach-fixing 34.7 ± 0.5 °C 50 sec Stabilizing 30 - 34 °C 90 sec Drying 60 - 80 °C 60 sec [Color developing solution] Pure water 800 ml Triethanolamine 8 g N,N-diethylhydroxyamine 5 g Potassium chloride 2 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5 g Sodium tetrapolyphosphate 2 g Potassium carbonate 30 g Potassium sulfite 0.2 g Fluorescent brightener (4,4-diaminostylbenedisulfonic acid derivative) 1 g (made up to the total amount of 1 liter with addition of pure water, and adjusted to pH 10.2) [Bleach-fixing solution] Ferric ammonium ethylenediaminetetraacetate dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% solution) 100 ml Ammonium sulfite (40% solution) 27.5 ml (made up to the total amount of 1 liter with addition of water, and adjusted to pH 5.7 with potassium carbonate or glacial acetic acid) [Stabilizing solution] 5-Chloro-2-methyl-4-isothiazolin-3-on 1 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2 g (made up to the total amount of 1 liter with addition of water, and adjusted to pH 7.0 with sulfuric acid or potassium hydroxide) - As is apparent from Table 3, also in the present Examples by use of silver halide emulsions with higher silver chloride content, the effect of the present invention could be obtained. Further, when compared with Example 1, it can be appreciated that the effect of the present invention can be exhibited more remarkably when a silver halide emulsion with higher silver chloride content as in these Examples.
Claims (12)
Sc·k₁/k₂ ≧ 0.2 Formula (I)
wherein Sc represents an abilty of said compound to deactivate the oxidized product of the color developing agent in the non-light-sensitive intermediate layer.
Sc·k₁/k₂ ≧ 0.3 Formula (I′)
wherein Sc represents an abilty of said compound to deactivate the oxidized product of the color developing agent in the non-light-sensitive intermediate layer.
and R₂ represents a halogen atom, hydroxyl group, sulfo group, carboxyl group, m represents an integer of 0 to 3, and when m is 2 or more, the plural number of R₂ may be either the same or different;
and the sum of n + m is 4 or less.
-COOH,-OH,-SO₂R¹,-SOR², -COOR³, -OCOR⁴,
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63020357A JP2767422B2 (en) | 1988-01-30 | 1988-01-30 | Silver halide photographic material |
JP20357/88 | 1988-01-30 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0327274A2 true EP0327274A2 (en) | 1989-08-09 |
EP0327274A3 EP0327274A3 (en) | 1990-03-21 |
EP0327274B1 EP0327274B1 (en) | 1995-11-15 |
Family
ID=12024853
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19890300813 Expired - Lifetime EP0327274B1 (en) | 1988-01-30 | 1989-01-27 | Light-sensitive silver halide photographic material |
Country Status (3)
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---|---|
EP (1) | EP0327274B1 (en) |
JP (1) | JP2767422B2 (en) |
DE (1) | DE68924790T2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992003762A1 (en) * | 1990-08-16 | 1992-03-05 | Eastman Kodak Company | Photographic material |
EP0371325B1 (en) * | 1988-11-16 | 1997-02-12 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive materials |
US6666592B1 (en) | 2002-09-20 | 2003-12-23 | Eastman Kodak Company | Photographic processing system |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100247818B1 (en) * | 1995-09-26 | 2000-03-15 | 손욱 | Lcd device |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0080905A1 (en) * | 1981-12-02 | 1983-06-08 | Konica Corporation | Silver halide color photographic material |
EP0107112A2 (en) * | 1982-09-30 | 1984-05-02 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive materials |
EP0233641A2 (en) * | 1986-02-20 | 1987-08-26 | Konica Corporation | Silver halide photographic lightsensitive materials |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6286363A (en) * | 1985-10-11 | 1987-04-20 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
JPS6279451A (en) * | 1985-10-03 | 1987-04-11 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
JPS62145244A (en) * | 1985-12-20 | 1987-06-29 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
JPH0682202B2 (en) * | 1986-04-18 | 1994-10-19 | 富士写真フイルム株式会社 | Image forming method of silver halide color photographic light-sensitive material |
JPH07119964B2 (en) * | 1986-12-02 | 1995-12-20 | 富士写真フイルム株式会社 | Silver halide color photographic light-sensitive material and color photographic print |
-
1988
- 1988-01-30 JP JP63020357A patent/JP2767422B2/en not_active Expired - Fee Related
-
1989
- 1989-01-27 EP EP19890300813 patent/EP0327274B1/en not_active Expired - Lifetime
- 1989-01-27 DE DE1989624790 patent/DE68924790T2/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0080905A1 (en) * | 1981-12-02 | 1983-06-08 | Konica Corporation | Silver halide color photographic material |
EP0107112A2 (en) * | 1982-09-30 | 1984-05-02 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive materials |
EP0233641A2 (en) * | 1986-02-20 | 1987-08-26 | Konica Corporation | Silver halide photographic lightsensitive materials |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0371325B1 (en) * | 1988-11-16 | 1997-02-12 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive materials |
WO1992003762A1 (en) * | 1990-08-16 | 1992-03-05 | Eastman Kodak Company | Photographic material |
US6666592B1 (en) | 2002-09-20 | 2003-12-23 | Eastman Kodak Company | Photographic processing system |
Also Published As
Publication number | Publication date |
---|---|
JP2767422B2 (en) | 1998-06-18 |
EP0327274A3 (en) | 1990-03-21 |
JPH01196042A (en) | 1989-08-07 |
EP0327274B1 (en) | 1995-11-15 |
DE68924790T2 (en) | 1996-06-13 |
DE68924790D1 (en) | 1995-12-21 |
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