EP0327274A2

EP0327274A2 - Light-sensitive silver halide photographic material

Info

Publication number: EP0327274A2
Application number: EP89300813A
Authority: EP
Inventors: Hirokazu Sato; Akiyoshi Tai
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1988-01-30
Filing date: 1989-01-27
Publication date: 1989-08-09
Anticipated expiration: 2009-01-27
Also published as: EP0327274B1; EP0327274A3; DE68924790T2; JPH01196042A; DE68924790D1; JP2767422B2

Abstract

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 the light-sensitive silver halide emulsion layers provided on a support, wherein the 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 the non-light-sensitive intermediate layer is 0.25 ≦ k₁/k₂ ≦ 1, and the relationship of the k₁/k₂ to the ability Sc is represented by Formula (I):
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.

According to the light-sensitive silver halide color photographic material of the present invention, the effect of preventing color turbidity and color reproducibility can be remarkably improved.

Description

BACKGROUND OF THE INVENTION

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.

SUMMARY OF THE INVENTION

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.

DETAILED DESCRIPTION OF THE INVENTION

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).
In the formula, 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.
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.
The 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.
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.
In the following, representative specific examples of the compounds which deactivates the oxidized product of the color developing agent to be used in the present invention are enumerated, by which the present invention is not limited.
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.
The yellow coupler preferably used in the present invention is represented by the following formula (Y).
In the formula, 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.
In the above formula (Y), the halogen atom represented by R_Y1 may be preferably chlorine atom, and R_Y2 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
(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).
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.

Functional group A:

-COOH,-OH,-SO₂R¹,-SOR²,-COOR³, -OCOR⁴,
Here, 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.
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.
In the following, representative specific examples of the yellow coupler to be used in the present invention are enumerated, but the present invention is not limited by these.
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 present invention, as the 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).
In the formula, Ar represents an aryl group, R_P1 hydrogen atom or a substituent and 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.
In the formulae, 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.
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 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-.
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 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, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclicthio groups, and also spiro compound residues, bridged hydrocarbon compound residues, etc.
Most preferred as the substituent 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.
Also, 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.
Of the compounds of the formula (M-IV) are preferred the case (i) wherein at least two of 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.
Further, preferable of (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.
Also, the above 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).
In the following, representative specific examples of the magenta coupler to be used in the present invention are enumerated, by which 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. 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.

Example 1

(Preparation of silver halide emulsions)

Six kinds of silver halide emulsions shown in Table 1 were prepared according to the neutral method and the simultaneous mixing method.
Into the respective silver halide emulsions was added after completion of chemical sensitization 1 x 10⁻⁴ mol of STB-1 shown below as the emulsion stabilizer per 1 mol of silver halide.

(Preparation of light-sensitive halide color photographic material sample)

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).
Next, according to the following formula, the ratio (Q) of the blue light absorption density to the green light absorption density excluding the fog density was determined.

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.

Example 2

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

1. 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.

2. The light-sensitive silver halide photographic material according to Claim 1, wherein said relative color formation speed ratio k₁/k₂ 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 0.30 ≦ k₁/k₂ ≦ 1.

3. The light-sensitive silver halide photographic material according to Claim 1, wherein the relationship of said k₁/k₂ to the ability Sc is represented by Formula (I′):
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.

4. The light-sensitive silver halide photographic material according to Claim 1, wherein said compound which deactivates the oxidized product of a color developing agent is selected from the group consisting of hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives and ascorbic acid derivatives.

5. The light-sensitive silver halide photographic material according to Claim 4, wherein said compound which deactivates the oxidized product of a color developing agent is hydroquinone derivatives represented by the formula (HQ):

wherein R₁ represents a substituted or unsubstituted alkyl group, n represents an integer of 1 to 3 with the proviso that 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;
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.

6. The light-sensitive silver halide photographic material according to Claim 5, wherein the alkyl group represented by R₁ is methyl, ethyl, propyl, t-butyl, octyl or t-dodecyl groups; the substituent possessed by R₁ is sulfo group, carboxyl group, cyano group, hydroxyl group, halogen atoms, -COOR₄, -COR₅, -OR₆, -SO₂R₇ or -NHSO₂R₈; and R₄, R₅, R₆, R₇ and R₈ represent alkyl group, alkenyl group, cycloalkyl group or aryl group.

7. The light-sensitive silver halide photographic material according to Claim 1, wherein said compound which deactivates the oxidized product of the color developing agent is contained in the non-light-sensistive intermediate layer in an amount of 2 x 10⁻⁴ to 1 x 10⁻² mol per 1m².

8. The light-sensitive silver halide photographic material according to Claim 7, wherein said compound which deactivates the oxidized product of the color developing agent is contained in the non-light-sensistive intermediate layer in an amount of 3 x 10⁻⁴ to 5 x 10⁻³ mol per 1m².

9. The light-sensitive silver halide photographic material according to Claim 1, wherein said diffusion-resistant coupler is a yellow coupler represented by Formula (Y):

wherein R_Y1 represents a halogen atom, R_Y2 represents a hydrogen atom or a group substitutable on the benzene ring, B represents a ballast group and Z represents a hydrogen atom, a halogen atom or a group eliminable through the reaction with the oxidized product of the color developing agent.

10. The light-sensitive silver halide photographic material according to Claim 9, wherein at least one of said B and Z in Formula (Y) contains at least one functional group selected from the group consisting of:
-COOH,-OH,-SO₂R¹,-SOR², -COOR³, -OCOR⁴,

wherein 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.

11. The light-sensitive silver halide photographic material according to Claim 1, wherein said diffusion-resistant coupler is a yellow coupler or a magenta coupler and the yellow coupler is contained in one of the two light-sensitive silver halide emulsion layers adjacent to said non-light-sensitive intermediate layer and the magenta coupler is contained in the other of the emulsion layers.

12. The light-sensitive silver halide photographic material according to Claim 1, wherein the silver halide grains in said light-sensitive silver halide photographic material contain 90 mol% or more of silver chloride.