JPS62177548A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having improved color reproducibility and storage stability under a high humidity by incorporating a compd. capable of releasing a diffusive developing restrainer or its precursor by reacting with an oxidant of the developing agent together with >=2 kinds of colorless couplers having a specific relationship in at least one layer of an emulsion layers. CONSTITUTION:The titled material contains the compd. (diffusive DIR compd. D) capable of releasing the diffusive developing restrainer or its precursor by reacting with the oxidant of the developing agent together with >=2 kinds of colorless couplers satisfying the following condition in at least one layer of the emulsion layers. Namely, the prescribed condition lies in satisfying the following relationship DBeff/DAeff<0.70, wherein DAeff is the development restraining effect of the diffusive DIR compd. D in the coupler A system, DBeff is the development controlling effect of the diffusible DIR compd. D in the coupler B system. The relationship can be applicable for each of the red sensitive emulsion layer, the green sensitive emulsion layer and the blue sensitive emulsion, and preferably, for the green sensitive emulsion, and more preferably, its emulsion having the high sensitivity. Thus, the titled material having an emphasized effect of between the layers and the improved color reproducibility and storage stability of the photosensitive material under the high humidity, is obtd.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, the interimage effect (interlayer effect, hereinafter referred to as 1-1-E) is enhanced to improve color reproduction. The present invention relates to a silver halide color photographic material that has excellent properties and improved storage stability. [Background of the Invention] In general, silver halide color photographic light-sensitive materials consist of three types of photographic silver halide emulsions on a support that are selectively spectrally sensitized to have sensitivity to blue light, green light, and red light. The layers are coated. For example, silver halide 1 for color negatives
f In true light-sensitive materials, the blue-sensitive silver halide emulsion layer is generally formed from the side to be exposed. A green-sensitive silver halide emulsion layer and a red-sensitivity silver halide emulsion layer are coated in this order. Usually, a blue-sensitive silver halide emulsion layer is coated between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer. Does it absorb the three colors of light that pass through the silver oxide layer? A single layer of yellow filter capable of bleaching is provided in b. Generally speaking, each emulsion layer is provided with an intermediate layer and a protective layer as the outermost layer for various special purposes. It is also known that each of these photosensitive silver halide emulsion layers is provided in a different arrangement from the above, and each silver halide emulsion layer is sensitive to substantially the same wavelength range for each color light. It is also known to use a photosensitive silver halide emulsion layer consisting of two or more layers having different properties and sensitivities. In these silver halide color photographic materials,
The exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and a dye is formed by the reaction between the oxidation product of the color developing agent and the dye-forming coupler. An image is formed. In this method, phenolic or naphthol cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, 1 indacylones or cyanocouplers are usually used to form cyan, magenta and yellow dye images, respectively. An acetyl magenta coupler and an acylacetamide yellow coupler are used. These dye-forming couplers are contained in the light-sensitive silver halide emulsion layer or in the formulation solution. The present invention is suitable as a silver halide color photographic light-sensitive material in which the coupler is previously non-diffused and contained in the silver halide emulsion layer. [Prior art and its problems] In general, in silver halide color photographic light-sensitive materials, the shading of the pixel groups forming the image must be smooth and not rough, that is, the graininess must be good, or the outline of the image must be clear. Moreover, delicate images are depicted without blurring,
That is, photographic properties such as good sharpness are required. In recent years, with the increasing sensitivity of color g-light materials and the miniaturization of cameras, such demands have become increasingly strong. As a technique for improving graininess, it is known to provide an intermediate layer between a high-speed emulsion layer and a low-speed emulsion layer. In Japanese Patent Publication No. 4B-15495, a gelatin layer or a medium-sensitivity silver halide emulsion layer with low coloring density is provided as an intermediate layer, and in Japanese Patent Application Publication No. 53-723, an oxidized color developing agent is provided as an intermediate layer. JP-A-57-155539 discloses the provision of a medium-sensitivity silver halide layer containing a DIR compound that reacts with the compound to release a development inhibiting substance.
A technique is described in which a non-photosensitive intermediate layer is provided as an intermediate layer, which develops the same hue as the high-speed emulsion layer and contains a coupler having a coupling rate lower than that of the high-speed emulsion layer. However, these techniques for providing an intermediate layer have many drawbacks, such as not only insufficient improvement in graininess but also the provision of an intermediate layer increases the thickness of the film j7 and deteriorates sharpness. . It is also known that sharpness can be improved by utilizing the contiguous effect of various diffusive substances released during development. This effect is due to changes in the diffusivity-inhibiting substances released during development, and specifically, diluting the developer with water, vigorously stirring during development, and reacting with the oxide of the developing agent. A method is known in which a light-sensitive material contains a compound that releases a diffusive development inhibitor. Among these, compounds that react with oxides of developing agents to release diffusible development inhibitors include, for example, color developing agents such as those described in U.S. Pat. No. 3,148.062 and U.S. Pat. Compounds that couple with oxidants to form dyes and release development inhibitors, or U.S. Pat. No. 3.632
Compounds are known which release development inhibitors upon coupling with oxidized forms of color developing agents and do not form dyes, such as those described in No. 1, No. 345, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. Further, JP-A-54-145135 discloses a DIR substance which indirectly releases an inhibitor through a secondary reaction induced by the reaction with an oxidized product of a color developing agent. The adjacency effect of these diffusible development inhibitor substances released during development has been disclosed in patent publications and other publications in addition to the above-mentioned technical disclosures.On the other hand, color reproducibility is still at a sufficiently satisfactory level. In particular, there are many deficiencies in reproducing color saturation (chroma).This is due to the spectral characteristics of the coloring dye obtained from the coupler used (sufficient absorption in a specific wavelength range). (or there is unnecessary absorption in other wavelength ranges such as phenolic cyan couplers having a ureido group at the 2-position), color mixture due to movement of spectral sensitizing dyes, and color mixture due to oxidized color developer. One of the properties required for color photographic materials is that when one color-sensitive layer forms a dye image, the oxidized product of the color developing agent generated therein causes the formation of other color-sensitive layers. It means that the color is not cloudy when it develops, that is, it has high color purity. Conventionally, an isolation layer (also called an intermediate layer) was used between different color-sensitive layers.
A scavenger for the oxidized color developing agent or a colorless coupler is added to the isolation layer (IL), or a diffusion inhibitor such as an aggravating dye is added to the isolation layer (IL), such as fine particle halogenation. It is known to add silver particles, cationic hydrophilic synthetic polymers, polymer latex, etc. However, even these methods have not yet achieved the ability to exhibit sufficiently satisfactory color reproducibility. Another known method for improving color mixture is automatic masking technology using colored couplers, which is commonly used in negative silver halide color photographic materials, but the level of color reproducibility is still not satisfactory. do not have. There is a technique to improve color reproducibility by emphasizing l-1-E using a DIR coupler, but these
Various IR compounds are used. For example, a so-called DIR coupler reacts with an oxidized form of a color developing agent to form a coloring dye and releases a development inhibitor during development; So-called DIR that does not form coloring pigments
Substances that directly release a development inhibitor by reacting with an oxidized form of a color developing agent and those that release a development inhibitor indirectly. For example, JP-A No. 54-145135, No. 5
No. 7-154234, No. 5B-162949, No. 58
-205150, 59-195643, 59-
No. 206834, No. 59-206863, No. 59-2
Examples include those described in No. 10440 and No. 60-7429 (hereinafter referred to as timing DIR compounds). In this specification, what represents the above DIR effect is D
Collectively called IR compounds. When these DIR compounds are used in a silver halide color light-sensitive material, a development inhibitor is released from the DIR compound during development, resulting in the effect of inhibiting the development of other silver halide emulsion layers, that is, ■I-E. In particular, DIR compounds that can release so-called diffusible inhibitory groups or diffusible development inhibitor precursors are effective and have been used in recent silver halide color films with good results. Japanese Patent Publication No. 55-47379 and Japanese Unexamined Patent Publication No. 57-198 disclose a technique that uses a so-called diffusible DIR compound and emphasizes ■/I-E in a different color-sensitive layer from one color-sensitive layer to another. -93344, 57-56837, 5
No. 9-131937 and the like. On the other hand, as well as the demand for higher image quality of photosensitive materials as mentioned above, in recent years, the storage stability of the photosensitive materials themselves has become increasingly important, especially as the uses of photosensitive materials for amateurs have diversified and the areas in which they are used have expanded. There are also increasing demands that are more stringent than ever before. That is, it is becoming more common for products to be stored for long periods at high temperatures and high humidity, which were previously considered special conditions. Various techniques have been studied to improve storage stability under high temperature and high humidity conditions. For example, silver halide stabilizer 1 Spectral sensitizing dye type and usage method. Regarding the structure of color couplers, there are many technical disclosures from the perspective of storage stability, but none of these are fully satisfactory (they do not provide a level of storage stability. Furthermore, the above-mentioned high image quality On the other hand, the technology for improving the color reproducibility or the technology for increasing the sensitivity often destroys the storage stability of the photosensitive material. Therefore, it has been found that the storage stability of photosensitive materials with increased IrE using so-called diffusible DIR compounds deteriorates more than before.In particular, the storage stability of photosensitive materials under high humidity conditions deteriorates. [Objective of the present invention] Therefore, the object of the present invention is to emphasize the IIE effect, improve color reproducibility, and improve storage stability, especially when stored at high temperatures. [Structure of the Invention] The above object of the present invention is to prepare a red-sensitive silver halide emulsion Iz containing a cyan coupler and a green-sensitive halide emulsion containing a magenta cazoler on a support. In a light-sensitive material comprising a silver emulsion layer and a blue-sensitive silver halide emulsion layer containing a yellow coupler, at least one of the emulsion layers is
A compound that reacts with the oxidized form of a developing agent to release a diffusible development inhibitor or a development inhibitor precursor (diffusible D
This is achieved by a silver halide color light-sensitive material characterized by containing an IR compound D) and two or more colorless couplers that satisfy the following relationship. [Conditions] The development inhibitory effect DA, ff of the "1-° diffusive DIR compound D in the coupler AJ system" is "the development inhibitory effect D of the diffusible DIR compound in the coupler BJ system". is D B6f, /D Adtl < Q, 7Q
There is a relationship between Research results by the present inventor Two points: When a diffusive DIR compound is used to emphasize IIE for the purpose of improving color reproducibility, IIE increases, but this diffusive DIR compound
It has been found that when a photosensitive material containing an IR compound is stored under high humidity, it shows significant deterioration. This phenomenon causes deterioration of both the red-sensitive emulsion layer, the green-sensitive emulsion layer, and the blue-sensitive emulsion layer, but the desensitization and density reduction of the green-sensitive emulsion layer are especially large, and the layer is practically unusable. The inventor is
In order to solve this problem, as a result of extensive research, it was discovered that the structure of the present invention as described above can emphasize [IE] and improve storage stability under high humidity. That is, by containing two or more types of colorless couplers having different development inhibiting effects on the diffusible DIR compound in the layer containing the diffusible DIR compound, the storage stability under high humidity can be improved while 11B is emphasized. 'Q'

[<This is the desired result. The present invention can be applied to any of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer, but is preferably applied to a green-sensitive emulsion layer, and more preferably to a high-speed green-sensitive emulsion layer. [Specific structure of the invention]

A compound that reacts with an oxidized form of a developing agent to release a diffusible development inhibitor or a development inhibitor precursor,
The diffusivity of the development inhibitor or the development inhibitor precursor (hereinafter referred to as the development inhibitor including this precursor) can be evaluated by the following method. Photosensitive materials samples (1) and (II) consisting of layers having the following compositions were prepared on a (transparent) support. Sample (I): A sample having a green-sensitive silver halide emulsion layer Spectrally sensitized to green-sensitivity silver iodobromide (silver iodide 6 mol%, average grain size 0.48 μm) and exemplary coupler (M-1). A gelatin coating solution containing 0.07 mol per 1 mol of i was coated so that the amount of coated silver was 1.1 g/m and the amount of gelatin applied was 3.0 g/m, and a protective layer; A gelatin coating solution containing silver iodobromide (silver iodide 2 mol %, average grain size 0.08 μm) that has not been subjected to sensitization or spectral sensitization has a coating amount of 0.1 g/rr! , gelatin amount is 0.8g/rrf
It was applied so that Sample (■) 2 The silver iodobromide is removed from the ai-retaining layer of the above sample (H. Each layer contains a gelatin hardening agent and a surfactant in addition to the above. Sample (1), (n ) was exposed to white light using a wedge, and then processed according to the processing method described in Example 1 below, except that the development time was 2 minutes and 40 seconds. , -ΔlogE=0.22)
One was added with various development inhibitors in an amount that suppressed the above, and the other was added without any development inhibitor. The sensitivity of sample (1) without the addition of a development inhibitor is S. and the sensitivity of sample (II) is S. ', and the sensitivity of sample (1) when a development inhibitor is added is S. If the sensitivity of sample (n) is S, then *Sensitivity of sample (II) Δs, = s, ' -sV Desensitization of sample (1) Δ5 = So Sw Diffusivity = ΔS/ΔS0 . However, all sensitivities were set as the logarithm (-1ogE) of the reciprocal of the exposure amount at the density point of fog density +0.3. The value obtained by this method was used as a measure of diffusivity. Diffusivity of several types of development inhibitors are exemplified in Table 1. As is clear from Example I below in the margin, those with relatively low diffusivity (A-5: 0.34 or less)! -I
-E is also small, so it is preferable that the diffusivity exceeds 0.34. In the present invention, it is more preferable that the diffusivity is 0.4 or more. In the silver halide color light-sensitive material of the present invention, each (or at least one layer) of the same light-sensitive emulsion layer has three layers.
Although it can be divided into more than two layers, it is preferable not to exceed three layers due to the diffusibility of the inhibitor or inhibitor precursor produced from the DIR compound of the present invention in the layers. The following margin (゛Next, the diffusible DIR compound preferably used in the present invention will be described. The preferred diffusible DIR compound is generally expressed by the following formula % Diffusible DIR compound general formula (1) A+Y)lI where A is a coupler component , m represents 1 or 2, and Y is a group that binds to the coupling position of the coupler component and leaves by reaction with the oxidized product of the color developing agent, and is a group that binds to the coupling position of the coupler component and is released by reaction with the oxidized product of the color developing agent. Represents a group that can be released. A only needs to have the properties of a coupler, and it is not necessarily necessary to create a dye by coupling. In the present invention, the group Y in the above general formula (1) is D represented by the following formulas (2A) to (2E), (3) to (5).
IR compounds can be preferably used. More preferably, the leaving group Y has the formula (2A) (2B) (2F, )(
4), particularly preferably a compound represented by the formula (2)
B) (2E) (4). General formula of Y (2A) General formula of Y (2B) General formula of Y (2C) I-1 submersion formula (2D) General formula of Y (4) General formula of Y (5 general formulas (2A) above) ~(2D) and (3), R
, is an alkyl group, an alkoxy group, an acylamino group, a halogen atom, the general formula (2E) of alkoxycarbonyl Y, and X is O, S or Se. , acyloxy group, carbamoyl group, N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group,
Nitro group, amino group, N-arylcarbamoyloxy group, sulfamoyl group, N-alkylcarbamoyloxy group, hydroxy group, alkoxycarbonylamino group,
It represents an alkylthio group, an arylthio group, an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group or an aryloxycarbonylamino group. n represents 1 or 2, and when n is 2, R1 may be the same or different,
The total number of carbon atoms contained in n R1s is preferably 0 to 10. R2 in the above general formula (2E) is R1 in (2A) to (2D)
X represents an oxygen atom or a sulfur atom, and in general formula (4), R2 represents an alkyl group, an aryl group, or a heterocyclic group. In the general formula (5), R3 represents a hydrogen atom, an alkyl group, an aryol group, or a \terocyclic group, and R4 represents a hydrogen atom, an alkyl group, an aryol group, a halogen atom, an acylamino group, or an alkoxycarbonyl group. Represents an amino group, an alkanesulfonamide group, a cyano group, a -terocyclic group, an alkylthio group, or an amino group. When R+, Rz, R3 or R4 represents an alkyl group, it may be substituted or unsubstituted, straight or branched, or cyclic alkyl. Substituents are halogen atoms, nitro groups, cyano groups,
Oryl group, alkoxy group, oryloxy group, alkoxycarbonyl group, oryloxycarbonyl group, sulfamoyl group, carbamoyl group, hydroxy group, alkanesulfonyl group, arylsulfonyl group, alkylthio group, or arylthio group, etc. It is. When RIt Rz, R3 or R4 represents an aryl group, the aryl group may be substituted. As a substituent, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, a nitro group, an amino group, a sulfamoyl group, a hydroxy group, a carbamoyl group, a carbonylamino group, an alkoxycarbonylamino group, an acylamino group. group, cyano group, or ureido group. RIt Rz+ When R3 or R4 represents a heterocyclic group, it represents a 5- or 6-membered monocyclic ring or fused ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, such as a pyridyl group, a quinolyl group, or a furyl group. , benzothiazolyl group, oxacylyl group, imidazolyl group, thiazolyl group, triazolyl group, benzotriazolyl group, imide group,
It is selected from oxazine groups and the like, and these may be further substituted with substituent 5 listed for the aryl group. - In (2E) and (4), the number of carbon atoms contained in R2 is preferably 1 to 15. In the above general formula (5), the total number of carbon atoms contained in R1 and R4 is preferably 1 to 15. In the above general formula (1), Y can take the structure of the following general formula (6). General formula (6) of Y: % formula % In the formula, T1 layer E5 is bonded to the coupling position of the coupler,
It is a group that can be cleaved by reaction with a color developing agent, and is a group that can release one-layer HIBITS in an appropriately controlled manner after being cleaved from a coupler. A one-layer HIBIT group is a group that provides a development inhibitor or a compound capable of releasing a development inhibitor. In general formula (6) -T IME-r NHI B■
The 'r group can be represented by the following general formulas (7) to (13). General formula of Y (7) General formula of Y (8) General formula of Y (9) (R,). General formula of Y (10) % Formula % General formula of Y (li) General formula of Y (12) General formula of Y (13) In general formulas (7) to (13), R3 is a hydrogen atom, a halogen atom, Alkyl group, alkenyl group, aralkyl group, alkoxy group, alkoxycarbonyl group, anilino group, acylamino group, ureido group, cyano group, nitro group,
Represents a sulfonamide group, sulfamoyl group, carbamoyl group, aryl group, carboxy group, sulfo group, hydroxy group, alkanesulfonyl group, and has general formulas (7), (8), (9), (]1) and (13)
In the formulas (7), (1), (12) and (13), k represents an integer from 0 to 2, and the general formulas (7), (10) and In (11), R6 represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, or an aryl group, and is represented by the general formula (12) and (
13), B represents an oxygen atom or -N (Ra represents the same meaning as defined above), and the one-layer HIBIT group has the general formula (2A), (2B), (3)
, has the same meaning as the general formula defined in (4) and (5). However, the number of carbon atoms is different. However, in general formulas (2A), (2B) and (3), -
The total number of carbon atoms contained in the molecular biohazard R, is 1 to 32, in general formula (4), the number of carbon atoms contained in R2 is 1 to 32, and in general formula (5), R3 and R4
The total number of carbon atoms contained in is 0 to 32. When R5 and R5 represent an alkyl group, they may be substituted or unsubstituted, chain-like or cyclic. Examples of the substituent include the substituents listed when R1=R4 is an alkyl group. When R1 and R6 represent an aryl group, the aryl group may be substituted. Examples of the substituent include the substituents listed for R+ to R4 or the aryl group. Among the above diffusible DIR compounds, general formula (2A), (
Those having a leaving group represented by 2B), (2E) or 4) are particularly preferred. The yellow image-forming coupler residue represented by A in general formula (1) includes pivaloylacetanilide type, benzoylacetanilide type, malondiester type,
malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malon ester monoamide type,
Coupler residues of the benzothiazolylacetate type, benzoxacylylacetamide type, benzoxacylylacetate type, malon diester type, benzimidaprilylacetamide type or benzimidazolylacetate-1 type, in U.S. Pat. No. 3,841,880 Coupler residues derived from heterocycle-substituted acetamides or heterocycle-substituted acetates included or U.S. Pat. No. 3,770,4
No. 46, British Patent No. 1,459.171, West German Patent (
OLS) No. 2.503.099, Japanese Unexamined Patent Publication No. 1973-13
No. 9738 or Research Disclosure 157
Examples thereof include coupler residues derived from acylacetamides described in No. 37 and heterozygous coupler residues described in US Pat. No. 4,046,574. The magenta image-forming coupler residue represented by A includes a 5-oxo-2-pyrazoline nucleus, pyrazolo-(1,5
-a) Coupler residues having a benzimidazole core or a cyanoacetophenone type coupler residue are preferred. The cyan image-forming coupler residue represented by A is preferably a coupler residue having a Fe, '-l or α-naphthol nucleus, or an indacylon or pyrazolotriazole coupler residue. Furthermore, the effect as a DIR coupler is the same even if the coupler does not substantially form a dye after coupling with the oxidized form of the developing agent and releasing the development inhibitor. Coupler residues of this type represented by A include U.S. Pat.
No. 2,213, No. 4.088,491, No. 3.6
32,345, 3.958,993 or 3
, 961.9599, and the like. Next, preferred specific examples of DIR compounds that can be used in the present invention are listed. However, as a matter of course, the DIR of the present invention
The compounds are not limited to those shown below. CIHs to sH+t(tJ u IJ D-14 01I ll -OH D-21 C+zHzs00CCHCOOC+zllzsl I 1M JOt D-29 All 0■ H 0■ N″N CI!H□OCOCHCOOC1tHgs , ID-37 0■ IJ ID・- 41 0I+ 8 2 ~ D-47 C+ ffl[ztcONH N=N Il 0H H II NO□ NU. Hs ut These compounds are described in U.S. Pat.
3, 227.554, 3,617,291, 3,858,993, 4,149,886, 3
, No. 933,500, Japanese Patent Publication No. 57-56837, Japanese Patent Publication No. 13239-1983, British Patent No. 2,072,363, British Patent No. 2,070,266, Research Disclosure No. 21228 of December 1981, etc. It can be easily synthesized by the method described. The amount of the diffusible DIR compound of the present invention to be added is generally preferably 2X10-' to 2XLO-' moles, more preferably lx104 to lX10-' moles, per mole of silver in the emulsion layer. Next, the development suppressing effect (hereinafter referred to as DIR effect D) in the present invention will be explained.
a f f) can be evaluated by the following method. A photosensitive material sample (n
[) and (IV) were created. Sample (■): Silver iodobromide spectrally sensitized to green sensitivity (silver iodide 6
mole %, average particle size 0.413 μm) and exemplary couplers (
A gelatin coating solution containing 0.07 mol of M-1) per mol of silver was used, the amount of coated silver was 1.1 g/the amount of gelatin coating was 3
．． A protective layer (gelatin coating liquid) was applied thereon so that the amount of gelatin applied was 0.8 g/m. Sample (■): Silver iodobromide spectrally sensitized to green sensitivity (silver iodide 6
mole% average particle size 0.48 μm) and exemplary coupler (M
-1) per mole of silver and an exemplary diffusivity D
A gelatin coating solution containing 0.004 mol of IR compound (D-11) per mol of silver was applied in an amount of 1.1 g/mol of silver.
rrr, gelatin was coated so that the amount of gelatin applied was 3.0 g/nf, and the same gelatin protective layer as the above sample (I) was further coated. In addition to the above, each layer contains a gelatin hardening agent and a surfactant. Samples (III) and (IV) were exposed to white light using a wedge and then processed according to the processing method of Example 1 described later, except that the development time was 2 minutes and 40 seconds. If the sensitivity of the sample (Iff) is SF and the sensitivity of the sample (IV) is S, then the diffusible DIR compound (D-11) in the coupler (M-1) system
) development suppression effect [) jl , 1°11 is D”II
It is expressed as mrr-Δ5==s, -8D. The diffusivity D in the coupler (M-12) system was evaluated in the same manner as above except that the coupler was changed from the exemplary coupler (M-1) to the exemplary coupler (M-12).
Development inhibitory effect of IR compound (D-1) D””xet
We can find t. However, all sensitivities were set as the logarithm (-1ogE) of the reciprocal of the exposure amount at the density point of fog density +0.3. In addition, the amount of the diffusible DIR compound added is adjusted so that the TIE imparted to other layers is approximately the same depending on the type of compound.
Modify and evaluate. The value obtained through this evaluation was used as a measure of the effect of suppressing the phenomenon. In the present invention, as long as the ratio of the development suppressing effect determined by the diffusible DIR compound, coupler A, and coupler B satisfies the relationship D''-tt/D^.1.≦0.70. , each of the two couplers can be selected from a wide range of structures. Table 2 shows some values of D”att / DAatt when a diffusible DIR compound and two colorless couplers are combined. A specific example is shown below. As can be seen from this table, for example, the combination of B-1 and B-2 corresponds to the structure of the present invention and is a preferable combination, but B-5, B-7, B-
13 can be said to be an inappropriate combination in the present invention. D″*tr/DAatt: Can the object of the present invention be achieved with 50.70? Preferably, D”att/D
Aatt≦0.50, more preferably D”
It is preferable that err/D Aart:i; 0.30. According to studies conducted by the present inventors, it has been found that in selecting couplers A and B for the preferred implementation of the present invention, the combination of these can be predicted to some extent based on the coupling reaction rate. That is, it can be said that it is preferable to select one fast-reacting coupler and one slow-reacting coupler, which are distinguished by measuring relative coupling rates as described below. The coupling reaction rate of couplers is determined in the color image obtained by mixing two types of couplers M and N, which give different dyes that can be clearly separated from each other, and adding the mixture to a silver halide emulsion for color development. can be determined as a relative value by measuring the amount of each pigment. If the maximum concentration of coupler M (DM) □10, the color development of the concentration DM in the middle stage, and the color development of coupler N (DN), □1, DN, then the reaction activity of the double force puller. The ratio RM/RN is expressed by the following formula. That is, in a silver halide emulsion containing mixed couplers,
The value of the coupling activity ratio RM/RN can be determined from the slope of the straight line obtained by plotting several pairs of DM and DN obtained by applying various stages of exposure and color development on two orthogonal axes. . By using a fixed coupler N and determining the value of RM/RN for various couplers as described above, a relative value of the coupling reaction rate, that is, a relative coupling reaction rate value can be determined. According to the study by the present inventor, "Coupler A" of the present invention
corresponds to a slow-reacting coupler and [coupler BJ corresponds to a fast-reacting coupler. The amounts of "Coupler A" and "Coupler B" of the present invention are:
Although there is no particular restriction, it is preferable that the amount of "Coupler B" in the layer containing the diffusible DIR compound be 5 to 50 mol%, particularly preferably 10 to 35 mol%, of the total amount of colorless couplers in the layer. . As the yellow dye-forming coupler used in the present invention, known acylacetanilide couplers can be preferably used. Among these, hendoylacetanilide and piparoylacetanilide compounds are advantageous. Specific examples of yellow coloring couplers that can be used include, for example, U.S. Pat.
No. 65,506, No. 3.408.194, No. 3,
No. 551,155, No. 3,582,322, No. 3
, No. 725,072, No. 3,89L445, West German Patent No. 1.547,868, West German Application Publication No. 2,219,9
No. 17, No. 2,261,361, No. 2,414,00
No. 6, British Patent No. 1.425,020, Special Publication No. 1973-
No. 10783, JP-A No. 47-26133, 4B-
No. 73147, No. 50-6341, No. 50-8765
No. 0, No. 50-123342, No. 50-130442
No. 51-21827, No. 51-102636,
No. 52-82424, No. 52-115219, No. 5
No. 8-95346, etc. As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacilloy couplers, and the like can be used. Specific examples of magenta color-forming couplers that can be used include, for example, U.S. Pat. No. 2,600.188, U.S. Pat.
No. 3.419; 391, No. 3.519, 42
No. 9, No. 3,558,319, No. 3.582.3
No. 22, No. 3,615.506, No. 3,834,
No. 908, No. 3,891,445, West German Patent No. 1,8
No. 10.464, West German Patent Application (OL S) 2,408
, No. 665, No. 2,417,945, No. 2,418,
No. 959, No. 2,424.467, Special Publication No. 1977-1960
No. 31, JP-A-49-74027, JP-A No. 49-7402
No. 8, No. 49-129538, No. 50-60233, No. 50-159336, No. 51-20826, No. 51-26541, No. 52-42121, No. 52-
No. 58922, No. 53-55122, patent application No. 55-1
Examples include those described in No. 10943. Phenol or naphthol couplers are commonly used as cyan dye-forming couplers. Specific examples of cyan color-forming couplers that can be used include, for example, U.S. Pat.
No. 3,730, No. 2,474,293, No. 2.8
No. 01,171, No. 2.895,826, No. 3.
No. 476, 563, No. 3,737,326, No. 3
．． No. 758,308, specification No. 3.893.044, JP-A-47-37425, JP-A No. 50-10135,
50-25228 boat, 50-112038, 5
Couplers described in Japanese Patent Application Publication No. 0-117422, Japanese Patent Application Publication No. 50-130441, etc., and couplers described in Japanese Patent Application Laid-open No. 58-98731 are preferred. Next, specific examples of preferred couplers used in the present invention will be listed, but the couplers are not limited thereto. -I Y-2 I The silver halide emulsion used in the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, silver chloride, etc. Any emulsion commonly used in silver halide emulsions can be used, but silver bromide, silver iodobromide, and silver chloride iodobromide are particularly preferred. The following margin - ('r,'',',,,. ゛Shadow; The obtained particles may be used. The particles may be grown all at once, or may be grown after forming seed particles. Seed particles The method of making and growing may be the same or different. Silver halide emulsions can be made by mixing halide ions and ions at the same time, or by mixing one in a solution where the other is present. Alternatively, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions can be generated by sequentially and simultaneously adding them to a mixing pot while controlling the pH and I)Ag. This method yields halogenated root particles with regular crystal shape and nearly uniform particle size.Conversion methods may be used at any step in the formation of AgX to change the halogen composition of the particles. Good. Known silver halide solvents such as ammonia, thioether, thiourea, etc. can be present during the growth of silver halide grains. Cadmium Metal ions are added using at least one selected from salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts (including complex salts). inside and/or
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere. Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disc
Losure (hereinafter sometimes abbreviated as RD) can be carried out based on the method described in No. 17643, Section 3. The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer. The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain. The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (100) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. The size of silver halide grains is 0.05 to 30μ, preferably 0.1 to 30μ.
20μ can be used. Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). A particle with a value of 0.20 or less when divided by the average grain size.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with a shape other than spherical. This indicates the diameter when the image is converted into a circular image with the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used. The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions. Silver halide emulsions can be chemically sensitized by conventional methods. Namely, sulfur aggravation method, selenium aggravation method, reduction aggravation method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination. Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as enhancing dyes. Aggravating pigments may be used alone, or two or more types may be used in combination. In addition to sensitizing dyes, dyes that do not themselves have spectral sensitizing effects, or compounds that do not substantially absorb visible light, and superchromatic sensitizers that enhance the sensitizing effects of sensitizing dyes, may be included in the emulsion. good. Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, heminocyanine dyes, steryl dyes and hemioxanol dyes are used. Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment. Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographs may be taken during chemical ripening, at the end of chemical ripening, and/or after chemical ripening and before coating a silver halide emulsion. Compounds known in the art as antifoggants or stabilizers can be added. It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin H? b Conductors, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives,
Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as single or copolymers may also be used. The photographic emulsion layer and other hydrophilic colloid layers of a light-sensitive material using a silver halide emulsion as described above are made of a binder (or
The film can be hardened by using one or more hardening agents that crosslink molecules (protective colloid) and increase film strength. The hardening agent can be added in an amount that can harden the Idemitsu material to the extent that it is not necessary to add a hardening agent to the processing solution, but it is also possible to add a hardening agent to the processing solution. For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3 ,5-
Triacryloyl-hexahydro-5-)riazine, 1
, 3-vinylsulfonyl-2-propatur, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-3-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. Or they can be used in combination. A plasticizer can be added to the silver halide emulsion layer and/or other wood-philic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in item A of RD 17643. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (
(e.g. vinyl acetate), acrylonitrile, olefins,
Styrene etc. alone or in combination, or together with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid,
A polymer containing a combination of hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used. Among dye-forming couplers, colored couplers, image stabilizers, color capping inhibitors, ultraviolet absorbers, fluorescent brighteners, etc. that do not need to be adsorbed onto the surface of silver halide crystals, hydrophobic compounds can be prepared using the solid dispersion method or latex dispersion. Various methods can be used, such as the method, oil-in-water emulsion dispersion method, etc., and can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. For the oil-in-ice emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied.
Usually, it is dissolved in a high boiling point solvent with a boiling point of about 150°C or higher, if necessary in combination with a low boiling point and/or water-soluble organic solvent, and stirred in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. Rice cooker, homogenizer, colloid mill,
It may be emulsified and dispersed using a dispersion means such as a flow lift mixer or an ultrasonic device, and then added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion. Examples of high-boiling point solvents include phenol salts that do not react with the oxidized form of the developing agent, phthalic acid alkyl esters, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, and trimesic acid esters with a boiling point of 150'. An organic solvent of C or higher is used. Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene. When dye-forming couplers, colored couplers, image stabilizers, color anti-capillary agents, ultraviolet absorbers, fluorescent whitening agents, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be added to hydrophilic colloids as an alkaline aqueous solution. It can also be done by 4 people. Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used. The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable. The color anti-capri agent may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer. An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in RD No. 17643, Section 2 J. Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain ultraviolet absorbers to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to ultraviolet rays. good. In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material. When a dye or an ultraviolet absorber is contained in the woody colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer. Compounds that change the developability, such as development accelerators and development retarders, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. A compound that can be preferably used as a development accelerator is RD 17
A compound described in No. 643 (7) XXI section B-D,
The development retardant is a compound described in Section XXI, Section E of No. 17643. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes. The emulsion layer of photographic light-sensitive materials is made of polyalkylene oxide or diluents such as its ethers, esters, and amines, thioether compounds, thiomorpholine necks, quaternary ammonium compounds, and urethane derivatives for the purpose of increasing sensitivity, contrast, or promoting development. urea derivatives, imidazole derivatives, etc. A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds which can preferably be used as fluorescent brighteners are described in RD 17643, item 7. The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These dyes and/or emulsion layers may contain dyes that flow out of the light-sensitive material or are bleached during development. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. In the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material, reduction of gloss of the light-sensitive material, improvement of writeability,
A capping agent can be added for the purpose of preventing photosensitive materials from sticking to each other. Any matting agent can be used, but examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resin, polycarbonate, and styrene. and copolymers thereof. The particle size of the cloak agent is preferably 0.05 μ to 1.0 μ. The amount added is preferably 1 to 300 .mu./d. A lubricant can be added to the photosensitive material to reduce sliding friction. An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. Preferably used antistatic agents that may be used are the compounds described in RD 17643 χ■. The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material may be coated with coating properties, antistatic properties, slipperiness properties, emulsification dispersion,
Various surfactants can be used for the purpose of preventing adhesion and improving photographic properties (development acceleration, hardening, aggravation, etc.). The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g. polyethylene, polypropylene,
Flexible reflective supports such as paper laminated with ethylene/butene copolymer), synthetic paper, etc., semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. These include films made of , flexible supports made of these films with reflective layers, glass, metals, ceramics, etc. After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface.
It may be applied through one or more subbing layers to improve antihalation properties, frictional properties, and/or other properties. When coating photosensitive materials, thickeners may be used to improve coating properties.For example, thickeners, such as hardeners, have quick reactivity and can be added to the coating solution in advance to cause gelation before coating. For materials that may cause such problems, it is preferable to mix them using a static mixer or the like immediately before application. As a coating method, extrusion coating and curtain coating, which can coat two or more types of layers at the same time, are particularly used, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected. Examples of surfactants include, but are not limited to, natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyridine, and others. Heterocycles, cationic surfactants such as phosphoniums or sulfoniums, anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric esters, phosphoric esters, amino acids, aminosulfonic acids, amino acids, etc. Ampholytic surfactants such as sulfuric or phosphoric esters of alcohols may also be added. In addition, for the same purpose, a fluorine-based surfactant may be used.To obtain a dye image using the light-sensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. In addition, a bleach-fixing process can be performed using a one-bath bleach-fixing solution, or a monobath processing process using a one-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be performed in one bath. You can also do In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development treatment step, an activator treatment step may be performed in which a color developing agent or its precursor is contained in the material and the development treatment is performed with an activator solution.
Activator processing can be applied to the monobus processing. Among these processes, typical processes are shown below. (These treatments are carried out as the final step, which is either a water washing process, a water washing process, or a stabilization process.) Color development process - Bleach process Constant fixation process - Color development process - Bleach-fixing process Processes: Pre-hardening process - Color development process - Stop fixing process - Washing process - Bleaching process Constant fixation process - Washing process - Post-hardening process - Color development process - Washing process - Supplementary information Color development process - Stop process - Bleach process Constant fixation process/activator process - Bleach-fix process/Activator process - Bleaching process Constant fixation process/Monobath process Processing temperature is usually 10°C It is selected in the range of ~65℃,
The temperature may exceed 65°C. Preferably, the treatment is carried out at 25°C to 45°C. A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenylezine amine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, such as salt bridge acids, sulfates, p-)luenesulfonates, sulfites, oxalates, benzenesulfonates, etc. I can do it. These compounds are generally about 0.0% for color developer IE.
A concentration of 1 to 30 g, more preferably color developer II!
It is used at a concentration of about 1 to 15 g. If the amount added is less than 0.1 g, sufficient color density cannot be obtained. Examples of the aminophenol-based developer include 0-aminophenol, p-aminophenol, 5-aminophenol,
These include 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-], 4-dimethyl-benzene, and the like. Particularly useful primary aromatic amine color developers include N, N-
A dialkyl-p-phinidine diamine compound,
Alkyl groups and phenyl groups may be substituted or unsubstituted. Among them, particularly useful compound examples include N-N-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, and N. N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amino Aniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3 −
Examples include methylaniline-p-)luenesulfonate. Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials. In this case, it is also possible to treat the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment. The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. It can also contain various additives, such as benzyl alcohol, alkali metal halides, such as potassium bromide or potassium chloride, or a moderating agent such as citrazic acid, and a preservative such as hydroxylamine or sulfite. Furthermore, various antifoaming agents and surfactants, and organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be contained. The pH of the color developing solution used in the present invention is usually 7 or more,
Preferably it is about 9-13. In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or hexose, pyrogallol-1,
3-dimethyl ether etc. may be contained. Various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution used in the present invention. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminopentaacetic acid,
-organic phosphonic acids such as hydroxyethylidene-1,1-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane-1, Examples include phosphonocarboxylic acids such as 2,4-)licarponic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds. The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately. As a bleaching agent, a metal complex salt of an organic acid is used, such as a polycarboxylic acid, an aminopolycarboxylic acid, or an organic acid such as oxalic acid or citric acid, which is coordinated with a metal ion such as cobalt or copper. It will be done. Among the above organic acids, the most preferable afJ is polycarboxylic acid or aminopolycarboxylic acid. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-N, Nl, N'-) 1) vinegar'fl, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid , iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, and the like. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaching agents have a concentration of 5 to 450 g/jl, more preferably 20 to 2
50 g/j! Use with. In addition to the above bleaching agent, the bleaching solution may contain a sulfite as a preservative, if necessary. Alternatively, it may be a bleaching solution containing an ethylenediaminetetraacetate iron (I[[) complex salt bleaching agent and containing a large amount of a halide such as ammonium bromide. In addition, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used. The bleaching solution used in the present invention includes JP-A No. 46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770,910, JP-A No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added. The pH of the bleach solution used is 2.0 or higher, but -C has a pH of 4.0 or higher.
It is used between 0 and 9.5, preferably between 4.5 and 8.0, and most preferably between 5.0 and 7.0. A fixer having a commonly used composition can be used. As a fixing agent, a compound that reacts with silver halide to form a water-soluble complex salt, such as a thiosulfate such as potassium thiosulfate, sodium thiosulfate, or ammonium thiosulfate, or potassium thiocyanate, which is used in ordinary fixing processing, may be used. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, and thioether. These fixatives are 5
It is used in an amount of 71 g/It or more, within a range that can dissolve it, but it is generally used in an amount of 70 to 250 g/It. Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank. The bleaching solution and/or fixing solution may contain various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. These agents may be contained alone or in combination of two or more. Furthermore, various fluorescent brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, hardening agents such as water-soluble aluminum salts, An organic solvent such as methanol, dimethylsulfamide/dimethylsulfur oxide, etc. can be contained as appropriate. The pH of the fixer is used at 3.0 or higher, but generally it is 4.
．． 5 to 10, preferably 5 to 9.5, most preferably 6 to 9. Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process. The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fix solution consisting of an ethylenediaminetetraacetate iron (I [I) complex salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixer, or conversely, a composition such as ammonium bromide, etc. Bleach-fix solutions containing a large amount of halides, iron ethylenediaminetetraacetate (
m) A special bleach-fix solution having a composition consisting of a combination of an if salt bleach and a large amount of a halide such as ammonium bromide can also be used. As the halide,
In addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. Examples of the halogenation-limited adhesive that can be included in the bleach-fix solution include the fixing agents described in the above-mentioned fixing process. The concentration of the fixing agent and the pH buffer and other additives that can be contained in the bleach-fixing solution are the same as in the above-mentioned fixing process. The bleach-fix solution has a pi (pi) of 4.0 or more, but is generally used with a pi of 5.0 to 9.5, preferably 6.0 to 8.
．． 5, most preferably 6.5 to 8.5. In the following margin [Examples] Specific examples of the present invention will be described below. However, it goes without saying that the embodiments of the present invention are not limited to these embodiments. In all the examples shown below, unless otherwise specified, the amount added in the silver halide color photographic light-sensitive material is shown per point, and the amounts of silver halide and colloids are shown in terms of silver. Example 1 A multilayer color negative photographic material (Sample No. 1) was prepared by coating the following layers on a cellulose triacetate film. 1st layer: Antihalation layer 2nd layer: Intermediate layer gelatin -・-・-・-12 g/m 3rd layer: Low sensitivity red-sensitive emulsion layer 4th layer: High sensitivity red-sensitive emulsion 5th layer: Intermediate layer gelatin −・・−・−・・−・−0.08g
/ m 6th layer: Low window green sensitive layer 7th layer: High sensitivity green sensitive layer 8th layer: Yellow filter single layer 9th layer: Low sensitivity blue sensitive layer ■ ) (Silver iodide 6 mol %) ---・・0.50 g/
tri 10th layer: High-temperature blue layer 11th layer: 1st protective layer 1 Fine grain silver iodobromide emulsion -4,5X lo'' g /=(
Gelatin ・－・・・・・・・・・－0,80g
/m 12th layer: 2nd protective layer Each emulsion layer contains 4-hydroxy-6-methyl-1,3,3a in addition to the above composition. 7-tetrazaindene 1-phenyl-5-mercapto
In addition to the above composition, gelatin hardeners H-1 and H-2, surfactants, etc. were added to each layer. Margin below 1'ε- B5-1 ZH5 C00C) IZCHC,,H. C,)l. BS-2 Sensitizing dye-1 Sensitizing dye-■ Sensitizing dye-■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ V-1 4t19([) C-10H F-10H CI+□=CIICIIzCII□5OZCIl =CH
2Na 'C1 Regarding the sample (1) prepared in this way, Table 3 below,
As shown in Table 4, the diffusivity D of the 7th layer or the 6th layer
Sample (2) with different IR compound and colorless coupler
(13) was created. Regarding the above samples (1) to (13), the following ■. ■We conducted an evaluation. ■ 1.1. Analysis of E: Each sample was exposed to blue light, green light, red light and white light through a wedge and processed through the following processing steps to obtain a dye image. To of this green light-exposed sample was measured with green light, γA
G, where TN is 10 when exposed to white light, and γ
AG~γN represents the magnitude of interimage effect (IIEIli effect) experienced by the green-sensitive silver halide emulsion layer, and T9 when a sample exposed to red light was similarly measured using red light.
If TN is γAR/γN, γAR/γN represents the magnitude of the IIE effect that the red-sensitive silver halide emulsion layer receives, and similarly, TAB/γN represents the magnitude of the IIE effect that the blue-sensitive silver halide emulsion layer receives.
E represents the magnitude of the effect. The larger the IIE effect received, the larger γA/γN becomes. T1; Let D be the density at an exposure point (Δlog E=1.O) that is 10 times the exposure amount at a density point with fog +0.3:
r=(D-(fog+0.3))/1.0. ■ Moisture resistance analysis: Samples (1) to (13) were left at 40"C for 10 days at a relative humidity of 80%, subjected to moisture resistance treatment, and then passed through a wedge together with untreated samples. The sample was exposed to light and developed in the same way as in ■.The difference between the sensitivity of the sample subjected to moisture resistance treatment (S, ) and the sensitivity of the untreated sample (So), △S, is defined as the desensitization width due to moisture resistance treatment. It is shown in Tables 3 and 4. Desensitization width Δ5 = So -3° Here, the sensitivity is the exposure amount (fog density + 0.3 density)
Let the sensitivity S be the logarithm of the reciprocal of G), that is, -1og E. Naturally, it is said that the smaller the desensitization width S, the better the moisture resistance. Processing steps (38° C.) Color development 2 minutes 40 seconds Bleaching 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Stabilization 3 minutes 15 seconds The composition of the processing solution used in each processing step is as follows. [Color developer] 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.15g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5g potassium hydroxide 1.0g Add water to make 11. [Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100. g Ethylenediaminetetraacetic acid 2 ammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0mj! Add water to make the solution 11, and adjust the pH to 6.0 using aqueous ammonia. [Fixer] Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make 11, and adjust to pH -6.0 using acetic acid. Margin below π8 1. ), as shown in Table 3, those that satisfy the constitution of the present invention,
The combination of couplers gives a diffusible DIR compound II
It can be seen that the E and IIE values are large, and the storage stability under high humidity is good. [Effects of the Invention] Therefore, the combination of a diffusible DIR compound and a coupler as shown in the structure of the present invention emphasizes the IIE effect,
It can be seen that the objectives of improving color reproducibility and increasing the storage stability of photosensitive materials under high humidity conditions were achieved. Patent applicant Roku Konishi Photo Industry Co., Ltd. Agent Patent attorney Toru Takatsuki Procedural amendment form) % formula % 2. Name of the invention Silver halide color photosensitive material 3. Relationship with the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 6, Subject of amendment Specification

Claims (1)

[Scope of Claims] A red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a blue-sensitive silver halide emulsion containing a yellow coupler on a support. At least one layer of the emulsion layer contains a compound that reacts with an oxidized form of a developing agent to release a diffusible development inhibitor or development inhibitor precursor (diffusible DIR compound D); A silver halide color photosensitive material characterized by containing two or more colorless couplers that satisfy the following relationship: [Conditions] The development inhibitory effect D^A_e_f_f of the "diffusible DIR compound D" in the "coupler A" system and the development inhibitory effect D^B_e_f of the diffusible DIR compound D in the "coupler B" system
_f has a relationship of D^B_e_f_f/D^A_e_f_f≦0.70.