JPH095951A - Silver halide color photographic sensitive material and image forming method - Google Patents

Abstract

PURPOSE: To improve the of gradation balance caused by the reduction of color development time by specifying the gradation of yellow, magenta, and cyan colors obtained by 2 kinds of developing processings. CONSTITUTION: The gradations of the yellow, magenta, and cyan colors obtained by the 2 kinds of development processings A' and B' different from each other in a developing time are allowed to satisfy the following conditional expressions; 0.8<=γA'(C)/γB'(C)<=1.2, 0.8<=γA'(M)/γB'(M)<=1.2, 0.8<=γA'(Y)/γB'(Y)<=1.2, where γA'(Y) and γB'(C) and the like are the yellow gradation obtained by the development processing A' and the cyan gradation obtained by the development processing B' and the like. The development processings A' and B' are executed for color developing times of 3min-3min 15sec and 50-70sec, respectively, and at a color developing temperature of 37-39 deg.C and 43-47 deg.C, respectively, by using the color developing solution containing 2-methyl-4-[N-ethyl-N-(β-hydroxyethyl)- amino] aniline as a color developing agent in an amount of 15-20mmol/l and 35-40mmol/l, respectively, and not any silver halide solvent represented by the formula.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material suitable for rapid processing and a color image forming method. More specifically, it improves the deterioration of gradation balance due to shortening of color development time, The present invention relates to a silver halide color photographic light-sensitive material and a color image forming method capable of obtaining an image having the same gradation in both the processing and the rapid processing which are currently widely used.

[0002]

2. Description of the Related Art The development processing time of a color negative photosensitive material is
It was significantly accelerated by the Kodak C-41 treatment introduced in 1972, and the wet treatment time without a drying step was 17 minutes and 20 seconds. In addition, the wet processing time of the CN-16FA processing of Fuji Photo Film Co., Ltd., which has been recently introduced into the minilab market, is 8 minutes and 15 seconds due to further speeding up.

Even when the processing speed is increasing, it takes about 30 minutes to finish even the fastest finishing in-store processing (so-called minilab) when the user requests the printing of the negative photosensitive material photographed, and the majority of the processing. The current situation is to force users to visit the photo shop twice. In the current system of color negative and color paper, further shortening of the development processing time is desired in order to meet the demand of the user who wants to visit the photo shop only once.

Conventional development processing time has been shortened mainly in the desilvering step after the color development processing step. Taking the above-mentioned C-41 processing and CN-16FA processing as examples,
The color development time of the former is 3 minutes 15 seconds and that of the latter is 3 minutes 5
Seconds, there is almost no change in color development time. In the CN-16FA processing, the color development time accounts for about 40% of the total development processing time.
In order to significantly shorten the development processing time, it is extremely difficult to reduce the color development time.

On the other hand, C-41 processing and development processing compatible with it (for example, CN-16FA processing) are now widespread all over the world. In order to be introduced to the market, this rapid process is required to be compatible with the C-41 process. Normally, a color negative light-sensitive material is composed of several color-sensitive silver halide emulsion layers and is designed so that the gradation balance of each emulsion layer is optimal when developed.
When rapid processing was performed with a shortened color development time, the gradation balance was lost and the color reproducibility was significantly deteriorated.

A processing method for obtaining similar gradations even if development processing is carried out at different color development times is disclosed in, for example, Japanese Patent Application Laid-Open No. HEI-2.
No. 2553. According to the processing method,
Equivalent gradation can be obtained by changing the processing temperature, the concentration of the color developing agent in the color developing solution and the color developing time.
Specifically, in Example 1 of the patent, the treatment temperature was 38 ° C.,
Color developing agent concentration: 15 mmol / l, color developing time: 3 minutes 15 seconds (conceivable to be equivalent to C-41 processing)
The gradation equivalent to the gradation (gamma value) obtained in the above is the processing temperature of 38 ° C., the concentration of the color developing agent is 150 mmol / liter,
It is shown that a color development time of 1 minute and 30 seconds is obtained.

However, the shortening of the color developing time by the processing method is because the concentration of the color developing agent exceeds 100 mmol / liter, so that the self-coupling reaction of the color developing agent in the liquid is remarkably promoted and after storage. The change in photographic property due to the decrease in the concentration of the color developing agent
Coloring of the light-sensitive material due to the product of the self-coupling reaction is increased. Further, the amount of the color developing agent remaining in the light-sensitive material after the development processing increases, and when the light-sensitive material is stored indoors, the density (stain) of the unexposed areas remarkably increases.

In order to avoid the above problems, the concentration of the color developing agent is set to 80 mmol / l or less and the processing temperature is set to 40 ° C. or more, so that the color developing processing time is 1 minute 3 minutes.
When the time is shortened to 0 seconds or less, the diffusion of the color developing agent becomes rate-determining, and the development of the lower layer (emulsion layer on the side closer to the support) is lower than the development of the upper layer (emulsion layer on the side far from the support) of the light-sensitive material. Due to the delay, the gradation balance between the upper layer and the lower layer was lost, and the color reproducibility was significantly deteriorated.

[0009]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to improve the deterioration of gradation balance due to the shortening of the color development time, and to achieve the ultra-rapid development which is widely used at present and shortens the color development time. The present invention relates to a silver halide color photographic light-sensitive material and a color image forming method capable of obtaining an image having an equivalent gradation in any of the treatments.

[0010]

The above objects of the present invention have been achieved by the following method. (1) Color development time in a silver halide color photographic light-sensitive material having at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer on a support. When the following two types of development processing A'and development processing B'which are different from each other are carried out, the gradations of yellow, magenta and cyan obtained by the two types of development processing satisfy the following conditional expressions: Silver halide color photographic light-sensitive material. 0.8 ≦ γ _B ′ (C) / γ _A ′ (C) ≦ 1.2 0.8 ≦ γ _B ′ (M) / γ _A ′ (M) ≦ 1.2 0.8 ≦ γ _B ′ ( Y) / γ _A ′ (Y) ≦ 1.2 (γ _A ′ (Y), γ _A ′ (M) and γ _A ′ (C) are yellow, magenta, and
Represents the gradient of cyan, γ _B ′ (Y), γ _B ′
(M) and γ _B ′ (C) represent gradations of yellow, magenta, and cyan, respectively, when development processing B ′ is performed. (Development treatment A ′) Color development time is 3 minutes to 3 minutes 15 seconds, the temperature of the color developing solution is 37 to 39 ° C., and 2-methyl-4- [N-ethyl-N is used as a color developing agent. -(Β-
A development process characterized in that the color development process is carried out using a color development solution containing 15 to 20 mmol / L of hydroxyethyl) amino] aniline and containing substantially no silver halide solvent. (Development processing B ′) Color development time is 50 to 70 seconds,
The temperature of the color developing solution is 43 to 47 ° C., the color developing solution contains 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline in an amount of 35 to 40 mmol / liter, and The following silver halide solvent (I-
A development process characterized in that color development is performed using a color developer containing 1) of 1 to 3 mmol / liter.

[0011]

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(2) The halogen according to (1), wherein the red-sensitive silver halide emulsion layer contains a silver halide emulsion having an average silver iodide content of 0.1 to 10 mol%. Silver halide color photographic light-sensitive material. (3) The average silver iodide content of the silver halide emulsion is 0.5.
The silver halide color photographic light-sensitive material as described in (2) above, wherein the content is from 5.0 to 5.0 mol%. (4) The average aspect ratio of the silver halide emulsion is 5 to 1
The silver halide color photographic light-sensitive material as described in (2), which is 0. (5) The red-sensitive silver halide emulsion layer is composed of three layers of high-sensitivity, medium-sensitivity and low-sensitivity red-sensitive silver halide emulsion layers, and the medium-sensitivity red-sensitive silver halide emulsion layer contains the silver halide emulsion. Any one of (2) to (4) characterized in that
6. The silver halide color photographic light-sensitive material according to the above item. (6) A transparent magnetic recording layer is provided on the side opposite to the silver halide emulsion layer with the support interposed therebetween (1) and (5).
The silver halide color photographic light-sensitive material according to any one of 1. (7) The silver halide color photographic light-sensitive material according to any one of (1) to (6) is characterized in that a color image is formed by performing the following development processing A or development processing B. Color image forming method. (Development Processing A) Color development time is 150 to 200 seconds, color developing solution temperature is 37 to 40 ° C., color developing agent concentration is 15 to 20 mmol / liter, and a silver halide solvent is used. A development process characterized by using a color developer which does not substantially contain. (Development Treatment B) Color development time is 25 to 90 seconds, the temperature of the color developing solution is 40 to 60 ° C., the concentration of the color developing agent is 25 to 80 mmol / liter, and the following general formula (I ) A developing process characterized by using a color developing solution containing at least one silver halide solvent represented by General formula (I)

[0013]

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R1, R2, R3, R4 and R5 are each independently a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group,
It represents a substituted or unsubstituted thioureido group, a substituted or unsubstituted amino group, a hydroxy group, an alkoxy group, a sulfonyl group or an acyl group. However, R1, R2, R3, R4 and R5 are not a hydrogen atom, an unsubstituted thioureido group, an unsubstituted amino group and a hydroxy group at the same time.
R1 and R3, R2 and R4, R3 and R5, and R4 and R5 may form a ring. However, R1, R2, R3, at least one of R4 and _{R5, -SO 3 M, -CO 2 Y} , amino group, at least one-substituted aliphatic hydrocarbon group for a hydroxy group, an aryl group, a heterocyclic It represents a ring group, a substituted thioureido group, a substituted amino group, an alkoxy group, a sulfonyl group or an acyl group. M and Y represent a hydrogen atom, ammonium, an alkali metal, or an alkaline earth metal.

Next, the general formula (I) used in the present invention will be described in detail. In the general formula (I), the aliphatic hydrocarbon group represented by R1 to R5 is a linear, branched or cyclic alkyl group (for example, methyl, ethyl, isopropyl, n
-Propyl, t-butyl, n-octyl, n-decyl,
n-hexadecyl, cyclopropyl, cyclopentyl,
Cyclohexyl, 2-sulfoethyl, sulfomethyl, 3
-Sulfopropyl, 2,3-disulfopropyl, carboxymethyl, 2-carboxyethyl, 1-carboxyethyl, 3-carboxypropyl, 1,2-dicarboxyethyl, 1,3-dicarboxypropyl, 2,3- Dicarboxypropyl, 1-carboxy-2-methylpropyl, 1-carboxy-3-methylbutyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl,
1,2-dihydroxyethyl, 3-hydroxypropyl, 1,3-dihydroxypropyl, 2,3-dihydroxypropyl, aminomethyl, 2-aminoethyl, 1-
Aminoethyl, 1,2-diaminoethyl, 3-aminopropyl, 1,3-diaminopropyl, 2,3-diaminopropyl, 1-carboxy-2-hydroxyethyl, 1
-Carboxy-2-hydroxypropyl, 2-carboxy-2-hydroxyethyl, 1-carboxy-3-hydroxypropyl, 2-amino-1-carboxyethyl,
2-amino-1-carboxypropyl, 2-amino-2
-Carboxyethyl, 1-carboxy-2-methylthioethyl, 1-carboxy-2-methylthiopropyl, 1
-Carboxy-3-methylthiopropyl, 1-carboxy-2-ethylthioethyl, 1-carboxy-3-ethylpropyl, 2- (5-imidazolyl) -1-carboxyethyl, 1-carboxy-2-mercaptoethyl, 2
-Aminocarbonyl-1-carboxyethyl, 2-N,
N-dimethylaminoethyl, 2-N, N-diethylaminoethyl, 2-N, N-dimethylaminopropyl, etc.),
Alkenyl groups (eg, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups (eg, pyropagyl, 3
-Pentynyl, etc.), an aralkyl group (eg, benzyl,
4-sulfobenzyl, 4-carboxybenzyl, etc.) and the like.

In the general formula (I), the aryl group represented by R1 to R5 is a monocyclic or condensed ring aryl group, and is phenyl, 4-sulfophenyl, 4-carboxyphenyl, 2
-Carboxy-4-sulfophenyl, naphthyl and the like can be mentioned.

In the general formula (I), the heterocyclic group represented by R1 to R5 is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of nitrogen atom, oxygen atom and sulfur atom. It is a base. These may be monocyclic or may form a condensed ring with another aromatic ring. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group, and examples thereof include a pyridyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, a thienyl group, a furyl group and a benzothiazolyl group.

In the general formula (I), the thioureido groups represented by R1 to R5 include unsubstituted thioureido, N-methylthioureido, N-phenylthioureido, N-sulfoethylthioureido, N-carboxymethylthioureido, N-carboxyethyl thioureido etc. are mentioned.

In the general formula (I), the amino group represented by R1 to R5 is an unsubstituted amino group or an alkylamino group (eg, methylamino, ethylamino, isopropylamino, 2-hydroxyethylamino, 2 -Carboxyethylamino, carboxymethylamino, 2-sulfoethylamino, 2-aminoethylamino, 2-N, N-dimethylaminoethylamino, 2-N, N-diethylaminoethylamino, aminomethylamino, etc.) , Preferably an unsubstituted amino group, a 2-sulfoethylamino group,
A carboxymethylamino group and a 2-carboxyethylamino group.

Examples of the alkoxy group represented by R1 to R5 in the general formula (I) include methoxy, ethoxy, isopropoxy, 2-hydroxyethoxy, 2-aminoethoxy, 2-carboxyethoxy and 2-sulfoethoxy. And the like, and preferably methoxy, ethoxy, 2-sulfoethoxy, and 2-carboxyethoxy.

Examples of the sulfonyl group represented by R1 to R5 in the formula (I) include methanesulfonyl group, ethanesulfonyl group, hydroxyethanesulfonyl group, paratoluenesulfonyl group, phenylsulfonyl group, methoxyethanesulfonyl group and An aminoethane sulfonyl group etc. are mentioned.

Examples of the acyl group represented by R1 to R5 in the general formula (I) include acetyl, benzoyl, formyl,
Pivaloyl and the like can be mentioned.

In the general formula (I), R1 and R3, R2 and R4, R3 and R
5, R4 and R5 may form a ring, and examples thereof include a pyrrolidine ring, an imidazolidine ring, a triazine ring, and an oxazolidine ring.

The aliphatic hydrocarbon moiety represented by R1 to R5 in the general formula (I), the aryl moiety, the heterocyclic moiety, the thioureido moiety, the amino moiety, the alkoxy moiety, the sulfonyl moiety, the acyl moiety and R1 and R3. , R2 and R4, R3 and R5, R4 and
The ring formed by R5 may have a substituent, and examples of the substituent include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl, ethyl, isopropyl, n-). Propyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl, etc., alkenyl group (eg, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (eg, propargyl, 3-pentynyl, etc.), aralkyl group (eg, benzyl, Phenethyl etc.), aryl groups (eg phenyl, naphthyl, 4-methylphenyl etc.), heterocyclic groups (eg pyridyl, furyl, imidazolyl, piperidyl, morpholyl etc.), alkoxy groups (eg methoxy, ethoxy, butoxy etc.),
Aryloxy group (eg phenoxy, 2-naphthyloxy etc.), sulfamoyl group (eg unsubstituted sulfamoyl group, N, N-dimethylsulfamoyl, N-phenylsulfamoyl etc.), carbamoyl group (eg unsubstituted carbamoyl, N , N-diethylcarbamoyl, N-phenylcarbamoyl etc.), thiocarbamoyl group (eg unsubstituted thiocarbamoyl, N, N-diethylthiocarbamoyl, N-phenylcarbamoyl etc.), sulfonyl group (eg mesyl, tosyl etc.), sulfinyl group (Eg, methylsulfinyl, phenylsulfinyl, etc.), an alkyloxycarbonyl group (eg, methoxycarbonyl,
Ethoxycarbonyl etc.), aryloxycarbonyl group (eg phenoxycarbonyl etc.), acyl group (eg acetyl, benzoyl, formyl, pivaloyl etc.), acyloxy group (eg acetoxy, benzoyloxy etc.), phosphoric acid amide group (eg N, N -Diethylphosphoric acid amide, etc.), alkylthio group (eg methylthio, ethylthio etc.), arylthio group (eg phenylthio etc.), cyano group, thiosulfonic acid group, sulfinic acid group,
Mercapto group, phosphono group, nitro group, sulfino group,
Examples thereof include an ammonio group, a phosphonio group (eg, trimethylammonio), a hydrazino group, and the like. When there are two or more substituents, they may be the same or different.

In the general formula (I), R1, R2, R3, R4 and R5
At least one of -SO ₃ M, -CO ₂ Y, at least an amino group (for example, unsubstituted amino, methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, acetamino, etc.) and a hydroxy group. one substituted aliphatic hydrocarbon group, an aryl group, a heterocyclic group, a substituted thioureido group, a substituted amino group, an alkoxy group, represents a sulfonyl group and an acyl group, preferably -SO ₃ M, -CO ₂ Y , at least one substituted aliphatic hydrocarbon group of unsubstituted amino group, a substituted thioureido group, a substituted amino group, more preferably -SO ₃ M
And it represents a -CO ₂ at least one in substituted aliphatic hydrocarbon group of Y. In addition, M and Y represent a hydrogen atom, ammonium (eg, unsubstituted ammonium, triethylammonium, tetramethylammonium, etc.), alkali metal (eg, sodium, potassium, etc.) and alkaline earth metal (eg, calcium, magnesium, etc.), Preferred are hydrogen atom, ammonium and alkali metal, and more preferred are hydrogen atom and sodium. The most preferable M is sodium, and the most preferable Y is a hydrogen atom.

The preferred combinations of R1, R2, R3, R4 and R5 in formula (I) are described below.

In the general formula (I), R1, R2, R3, R4 and R5
Are each independently a hydrogen atom, an aliphatic hydrocarbon group, a substituted thioureido group and a substituted amino group, R1, R2, R
3, at least one of R4 and R5 is -SO ₃ M, -CO ₂ Y
And an aliphatic hydrocarbon group substituted with at least one of an unsubstituted amino group, a substituted thioureido group and a substituted amino group. Further, in the general formula (I), R1, R2,
R3, R4 and R5 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R1, carbon atoms at least one substituted with -SO ₃ M and -CO ₂ Y of R2 and R5 1-10 Is preferably an alkyl group of Also most preferred
As a combination of R1, R2, R3, R4 and R5, R1 and R2 are hydrogen atoms or an alkyl group having 1 to 5 carbon atoms (for example, methyl, ethyl, etc.), R3 and R4 are hydrogen atoms, and R5 Is an alkyl group having 1 to 5 carbon atoms substituted with at least one of -SO ₃ M and -CO ₂ Y (eg, 2-sulfoethyl, carboxymethyl, 2-carboxyethyl, etc.)
It is.

Specific examples of the compounds represented by formula (I) are shown below, but the invention is not limited thereto.

[0029]

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[0030]

[Chemical 6]

[0031]

[Chemical 7]

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

[Chemical 12]

These compounds are disclosed, for example, in JP-A-64-35.
Method described in Japanese Patent No. 550, Synthesis, 24
3-292 (1973), Journal of the American Chemical Society (J. Am. Chem. Soc.),
It can be easily synthesized with reference to Vol. 69, 2136 (1967) and the like.

The amount of the silver halide solvent of the present invention used in the color development processing B is 0.1 per liter of the processing solution.
The amount is preferably in the range of mmol to 10 mmol, more preferably in the range of 0.3 to 5.0, and most preferably in the range of 0.8 to 3.0.

If the amount of the silver halide solvent added is less than 0.1 mmol, the effect of the present invention becomes small and the development delay of the red-sensitive emulsion layer occurs. And the silver development in the unexposed area increases.

The light-sensitive material of the present invention may be provided with at least one of each of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer on a support, The number of silver halide emulsion layers and non-light-sensitive layers is not particularly limited. A typical example is a silver halide photographic light-sensitive material having at least two color-sensitive layers comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Material, the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to either of red light and red light. In a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is, in order from the support side, a red light-sensitive layer and a green light-sensitive layer. A color layer and a blue-sensitive layer are provided in this order. The entire hydrophilic colloid layer including these color-sensitive emulsion layers is called a "photosensitive layer". Preferred maximum spectral sensitivity wavelengths of each layer are, for example, 420 to 480 nm for the blue-sensitive layer and 520 to 5 nm for the green-sensitive layer.
80 nm, and the red-sensitive layer is 520 to 580 nm. A non-light-sensitive layer such as an intermediate layer of each layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, JP-A-61-43748 and JP-A-5-43748 are used.
9-113438, 59-134440, 61
No. 20037 and No. 61-20038, a coupler, a DIR compound, etc. may be contained, and a color mixing inhibitor may be contained as is usually used. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Further, JP-A Nos. 57-112751, 62-200350, and 6
2-206541, 62-206543, etc., a low-sensitivity emulsion layer on the side remote from the support,
A high sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) /, or BH / BL / GL / GH / RH / RL, or B
They can be installed in the order of H / BL / GH / GL / RL / RH. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more light-sensitive than the middle layer. A preferred example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged and three layers having different sensitivities are sequentially reduced toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layer / High-sensitivity emulsion layer /
The low-speed emulsion layers may be arranged in this order. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four layers or more, the arrangement may be changed as described above. In order to improve color reproducibility, US Pat. Nos. 4,663,271 and 4,705,74
4, No. 4,707,436, JP-A-62-160.
B described in the specifications of Nos. 448 and 63-89850.
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L, GL, and RL, adjacent to or in proximity to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The gradation degree in the present invention is obtained as follows. First, a standard white light source (black-body radiation 4800
After exposing the test light-sensitive material with a wedge (light source having an energy distribution of ° K) and performing the specified development processing, red,
The absorption densities of cyan, magenta and yellow are measured through a green filter and a blue filter to obtain a characteristic curve. From the obtained characteristic curves, the absorption densities of cyan, magenta, and yellow were fog +0.2, +0.
The points of 5, +1.0, +1.5, and +2.0 are plotted respectively, and after linearly approximating these points by the method of least squares, tan θ with respect to the angle θ from the horizontal axis is defined as the gradation degree γ of the photosensitive material. By definition, γ of cyan, magenta, and yellow are defined as γ (C), γ (M), and γ (Y), respectively.

The light-sensitive material of the present invention has the gradations γ _A ′ (C), γ _A ′ (M) and γ _A ′ (Y) of cyan, magenta and yellow after the development processing A ′ of the present invention. And the gradation degree γ _B ′ after the development processing B ′ of the present invention is performed.
(C), γ _B ′ (M) and γ _B ′ (Y) satisfy the following conditional expressions.

0.8 ≦ γ _B ′ (C) / γ _A ′ (C) ≦ 1.2 0.8 ≦ γ _B ′ (M) / γ _A ′ (M) ≦ 1.2 0.8 ≦ γ _B '(Y) / γ _A ' (Y) ≦ 1.2

More preferably, 0.9 ≦ γ _B ′ (C) / γ _A ′ (C) ≦ 1.1 0.9 ≦ γ _B ′ (M) / γ _A ′ (M) ≦ 1.10. The conditional expression of 9 ≦ γ _B ′ (Y) / γ _A ′ (Y) ≦ 1.1 is satisfied.

If this condition is not satisfied, the tint of the print obtained from the color negative developed by at least one of the developing treatments A'and B'is destroyed, and it is not possible to obtain a color reproduction that can be appreciated. .

In the present invention, γ _A ′ (C), γ _A ′
(M), γ _A ′ (Y), γ _B ′ (C), γ _B ′ (M),
γ _B ′ (Y) is preferably 0.50 to 1.00, more preferably 0.60 to 0.90, and particularly preferably 0.65 to 0.80.

In the present invention, any commercially available color paper may be used for printing. The preferred gradation of color paper is about 2.7 ± 0.1 in colorimetric density. (For the colorimetric density, see page 387, "Basics of Photographic Engineering" edited by The Photographic Society of Japan, "Gin-Salt Photograph").

Next, the silver halide emulsion used in the red-sensitive emulsion layer of the present invention will be described in detail. The silver halide emulsion of the present invention is silver iodobromide or silver iodochlorobromide, preferably silver iodobromide. The average silver iodide content is preferably 0.1 to 10 mol%, more preferably 0.5 to 10.
It is 5.0 mol%, and most preferably 1.0 to 3.0 mol%.

If the average silver iodide content is less than 0.1 mol%, a satisfactory photosensitivity cannot be obtained, while 10 mol%
If it is larger than this, the effect of promoting development by the silver halide solvent becomes small, and if it exceeds 30 mol%, almost no effect is observed.

The silver halide grains of the present invention are preferably used in a light-sensitive material having a layer structure in which a red-sensitive emulsion layer is composed of three layers of high sensitivity, medium sensitivity and low sensitivity, and which red-sensitive emulsion layer is used. However, it is particularly preferable to use it for the medium-sensitive layer, and most preferably for the medium-sensitive layer and the low-sensitive layer.

From the standpoint of promoting development with a silver halide solvent, the silver halide grains of the present invention are preferably tabular. In the tabular silver halide emulsion used in the present invention, the aspect ratio means the ratio of diameter to thickness of silver halide grains. Here, the diameter means the diameter of a circle having an area equal to the projected area of a grain when the silver halide emulsion is observed with a microscope or an electron microscope. Therefore, the aspect ratio of 2 or more means that the diameter of this circle is twice or more the thickness of the particles.

In the tabular silver halide grains used in the silver halide emulsion of the present invention, the grain size is 2 times the grain thickness.
It is at least 3 times, preferably 3 to 20 times, more preferably 4 to 15 times, particularly preferably 5 to 10 times. The proportion of tabular silver halide grains in the projected area of all silver halide grains is 50% or more, preferably 70% or more, particularly preferably 85% or more.

The tabular silver halide grains have a diameter of 0.02 to 20 μm, preferably 0.3 to 10.0.
.mu.m, particularly preferably 0.4 to 5.0 .mu.m. The thickness of the particles is preferably 0.5 μm or less. Here, the tabular silver halide grain diameter refers to the diameter of a circle having an area equal to the projected area of the grains. The thickness of the grains is represented by a distance between two parallel planes constituting the tabular silver halide grains.

In the present invention, more preferred tabular silver halide grains have a grain diameter of 0.3 μm or more and 10.0 μm or more.
m or less, the particle thickness is 0.3 μm or less, and the average (diameter / thickness) is 5 or more and 10 or less. If it is more than this, the photographic performance may be abnormal when the photosensitive material is bent, wrapped tightly, or touches a sharp object, which is not preferable. More preferably the particle diameter is 0.4
This is the case of a silver halide emulsion in which grains having a size of not less than μm and not more than 5.0 μm and having an average (diameter / thickness) of not less than 5 account for 85% or more of the total projected area of all silver halide grains.

The tabular silver halide emulsion used in the present invention is described by Cugnac and Chatean and Duffin in "Photogra.
phic Emulsion Chemistry "(Focal Press, New York 1
966) pp. 66-72, and APHTrivelli, WFSmith
Ed., "Phot. Journal", 80 (1940), p. 285, which is described in JP-A-58-113927 and JP-A-58-11392.
It can be easily prepared by referring to the methods described in JP-A Nos. 8 and 58-127921.

The tabular silver halide grains of the present invention can be chemically sensitized if necessary. For chemical sensitization, see, for example, "Die Grundlagen der Photographi" edited by H. Frieser.
schen Prozesse mit Silberhalogeniden "(Akademische
Verlagsgesellschaft. 1968) pages 675 to 735 can be used.

That is, compounds containing chalcogen capable of reacting with active gelatin or silver (for example, thiosulfates, thioureas, mercapto compounds, rhodanins, selenoureas, phosphine selenides, phosphine tellurides, etc.) ) Using a chalcogen; a reduction sensitization using a reducing substance (eg, stannous salt, amines, hydrazine derivative, formamidinesulfinic acid, silane compound);
A noble metal sensitization method using a noble metal compound (for example, a complex salt of a metal of Group VIII of the periodic table such as Pt, Ir, and Pd other than a gold complex salt) or the like can be used alone or in combination.

Specific examples of these are the chalcogen sensitization methods described in US Pat. Nos. 1,574,944 and 2,27.
No. 8,947, No. 2,410,689, No. 2,7
Nos. 28,668 and 3,656,955, etc., and reduction sensitization methods are described in U.S. Pat. Nos. 2,419,974, 2,983,609 and 4,054,458. US Patent No. 2,399,0 discloses noble metal sensitization.
No. 83, No. 2,448,060, British Patent No. 61
No. 8,061 and the like. In particular, from the viewpoint of saving silver, the tabular silver halide grains of the present invention are preferably gold sensitized or chalcogen sensitized, or a combination thereof.

The tabular silver halide grains of the present invention can be spectrally sensitized with a methine dye or the like, if necessary. Another feature of the tabular silver halide grains of the present invention is that the spectral speed is high in addition to the improvement in sharpness described above. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

Examples of useful sensitizing dyes include German Patent No. 929,080 and US Pat. No. 2,493,748.
No. 2,503,776 and No. 2,519,00
No. 1, No. 2,912,329, No. 3,656,9
No. 59, No. 3,672,897, No. 4,025
No. 349, British Patent No. 1,242,588, Japanese Patent Publication No. Sho 4
There can be mentioned those described in JP-A No. 4-143030.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,5
No. 22,052, No. 3,527,641, No. 3,
Nos. 617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,814,609,
No. 4,026,707, British Patent No. 1,344,2
No. 81, Japanese Patent Publication No. 43-4936, and No. 53-12375
JP-A-52-109925, JP-A-52-11061
No. 8.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . Azoles,
For example, benzothiazolium salts, nitroimidazoils, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted);
Heterocyclic mercapto compounds, for example, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; carboxyl group and sulfone group, etc. The above-mentioned heterocyclic mercapto compounds having a water-soluble group; thioketo compounds such as oxadolinthione; azaindenes such as triazaindenes and tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) Tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and many other compounds known as antifoggants or stabilizers can be added. For more detailed examples of these and methods of using them, see, for example, U.S. Patent Nos. 3,954,474 and 3,982,944.
7, No. 4,021,248 or JP-B-52-28660 can be referred to.

The emulsion of the present invention is preferably a monodisperse emulsion. The monodisperse emulsion according to the present invention is an emulsion having a grain size distribution with a variation coefficient relating to the grain size of silver halide grains of 0.25 or less. Here, the coefficient of variation is a value obtained by dividing the standard deviation regarding the particle size by the average particle size. That is,
When the grain size of individual emulsion grains is ri and the number is ni, the average grain size is

Average particle size = Σrini / Σni

And its standard deviation is

Standard deviation = Σ (ri−F) ² / Σni r: average particle size

It is defined as The term "individual grain size" as used in the present invention refers to a silver halide emulsion prepared by T. James (T.
H. James) et al., "The Theory of the Photographic Process"
Process) 3rd edition, pages 36-43, published by Macmillan (1
966), which is the diameter equivalent to the projected area corresponding to the area projected when microscopically photographed by a method well known in the art (usually electron microscope photography) as described in 966). Here, the projected equivalent diameter of a silver halide grain is defined by the diameter of a circle equal to the projected area of a silver halide grain as shown in the above-mentioned book. Therefore, even when the shape of the silver halide grains is other than spherical (for example, cubic, octahedral, tetradecahedral, tabular, potato-like), the average grain size r and its deviation S can be obtained as described above. is there.

The coefficient of variation relating to the grain size of silver halide grains is 0.25 or less, preferably 0.20 or less,
It is more preferably 0.15 or less.

The tabular silver halide emulsion of the present invention is particularly preferably a monodisperse hexagonal tabular silver halide emulsion described in JP-A-63-151618. Here, the hexagonal tabular silver halide grains are {1,1,
The shape of the 1} plane is hexagonal, and the ratio of adjacent sides is 2 or less. Here, the adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. The hexagonal tabular silver halide grains of the present invention may have some rounded corners as long as the ratio of adjacent sides is 2 or less. The length of a side when the corner is rounded is represented by the distance between the intersections of the straight line portion of the side and the line obtained by extending the straight line portion of the adjacent side. It is preferable that 1/2 or more of each side forming the hexagon of the hexagonal tabular grain of the present invention is substantially a straight line, and particularly 4/5 or more is substantially a straight line. In the present invention, the ratio of adjacent sides is preferably 1 to 1.5.

The hexagonal tabular silver halide emulsion of the present invention comprises
The hexagonal tabular silver halide grains comprise a dispersion medium and silver halide grains, and account for 50% or more, preferably 70% or more, more preferably 90% or more of the total projected area of the silver halide grains. .

The distribution of silver iodide in the grain may be uniform throughout the grain, the silver iodide content may be different between the inside of the grain and the surface layer, or different iodide may be present inside the grain. It may be a so-called multiple structure with several layers of silver content.

The method for producing a hexagonal tabular silver halide emulsion is as follows:
Reference may be made to US Pat. No. 4,797,354. As a method for producing a monodisperse hexagonal tabular silver halide emulsion, the production process is divided into nucleation, Ostwald ripening and grain growth. At the time of nucleation, pBr is 1.0 to
The supersaturation conditions (temperature, gelatin concentration, addition rate of silver salt aqueous solution and alkali halide aqueous solution, pBr, iodide ion) that keeps 2.5 and creates as many nuclei (tabular grain nuclei) as possible having parallel twin planes Content, stirring speed, p
H, silver halide solvent amount, salt concentration, etc.) are used for nucleation. During the Ostwald ripening, the temperature and pB are set so that grains other than the tabular grain nuclei formed during nucleation are extinguished, and only tabular grain nuclei grow and nuclei with good monodispersity are obtained.
r, pH, gelatin concentration, silver halide solvent amount, etc. are adjusted. During grain growth, hexagonal tabular silver halide grains having a desired aspect ratio and grain size can be obtained by adjusting pBr and the amount of added silver ions and halogen ions. At the time of grain growth, the addition rate of silver ions and halogen ions is set to 30 to 1 of the critical crystal growth rate.
It is preferably set to 00%.

In the emulsion of the present invention, 50% of the number of silver halide grains preferably contains 10 or more dislocations per grain. The average particle dislocation is, for example, JFHamil
ton, Phot.Sci.Eng., 11, 57 (1967) and T.Shiozawa, J.So
c. Phot. Sci Japan, 35, 213 (1972), which can be observed by a direct method using a transmission electron microscope at low temperature. That is, silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for observation with an electron microscope to prevent damage (print-out, etc.) by electron beams. Observation is performed by a transmission method while the sample is cooled. At this time,
Since the thicker the particle, the more difficult it is for an electron beam to pass through, a high-pressure type (200 μm-thick particles
KV) can be observed more clearly using an electron microscope. From the photograph of the grains obtained by such a method, the position and number of dislocations for each grain when viewed from the direction perpendicular to the main plane can be used.

The positions of dislocations in the tabular grains of the present invention occur from the distance of x% of the length from the center of the tabular grain in the major axis direction to the side to the side. This value of x is preferably 1
0 ≦ x <100, more preferably 30 ≦ x <98
And more preferably 50 ≦ x <95. At this time, the shape formed by connecting the positions where the dislocations start is close to a particle shape, but may not be a perfect shape and may be distorted. The direction of the transition line is from the center to the side, but it often meanders. Regarding the number of dislocations in the tabular grain of the present invention, it is preferable that 50 number% or more of grains containing 10 or more dislocations are present. More preferably, the number of particles containing 10 or more dislocations is 80% by number or more,
In particular, particles having 20 or more dislocations in an amount of 80% by number or more are preferable.

Further, in the silver halide grains in which 50% by number or more of the silver halide grains preferably used in the tabular silver halide grains of the present invention contain 10 or more dislocations per grain, the silver halide grains are The relative standard deviation of the individual silver iodide contents is particularly preferably 30% or less, more preferably 20% or less. The silver iodide content of each emulsion grain can be measured, for example, by analyzing the composition of each grain using an X-ray microanalyzer. Here, the "relative standard deviation of the silver iodide content of each grain" means, for example, the silver iodide content when the silver iodide content of at least 100 emulsion grains is measured by an X-ray microanalyzer. It is a value obtained by multiplying the value obtained by dividing the standard deviation by the average silver iodide content by 100. A specific method for measuring the silver iodide content of individual emulsion grains is described in, for example, European Patent 147,868A.

If the relative standard deviation of the silver iodide content of each grain is large, the appropriate point of chemical sensitization of each grain is different, and it becomes impossible to bring out the performance of all emulsion grains.
Further, the relative standard deviation of the number of dislocations between grains also tends to be large. There may or may not be a correlation between the silver iodide content Yi (mol%) of each grain and the sphere equivalent diameter Xi (micron) of each grain, but it is desirable that there is no correlation.

Regarding the structure relating to the halogen composition of the tabular grains, X-ray diffraction, EPMA (also called XMA) method (method of scanning silver halide grains with an electron beam to detect the silver halide composition), ESCA This can be confirmed by combining a method (also called XPS) (method of irradiating X-rays to disperse photoelectrons emitted from the particle surface) and the like. In the present invention, the particle surface is defined as 50% from the surface.
A region up to a depth of about A. The halogen composition in such a region can usually be measured by the ESCA method. The inside of a particle refers to a region other than the above-mentioned surface region.

An emulsion comprising tabular grains having dislocation lines described above is disclosed in JP-A-63-220238 and Japanese Patent Application No. 2-31.
It can be prepared based on the method described in JP0862. The silver halide emulsion of the present invention preferably has a narrow grain size distribution, and is prepared through the steps of nucleation-Ostwald ripening and grain growth.
The method described in No. 51618 can be preferably used. However, the silver iodide content of individual grains of the emulsion tends to be non-uniform unless particularly controlled precisely.

In order to make the silver iodide content of individual grains of the emulsion uniform, it is important to make the size and shape of the grains after Ostwald ripening as uniform as possible. Further, in the growth stage, the silver nitrate aqueous solution and the alkali halide aqueous solution are added by the double jet method while keeping the pAg constant in the range of 6.0 to 10.0. It is preferable that the supersaturation degree of the solution therein is high. For example, it is desirable to perform the addition at a relatively high degree of supersaturation such that the growth rate of the crystal is 30 to 100% of the critical crystal growth rate by a method as described in U.S. Pat. No. 4,242,445. .

The dislocation of the tabular grain of the present invention can be controlled by providing a specific high iodine phase inside the grain. Specifically, it is obtained by preparing substrate particles, then providing a high iodine phase, and covering the outside with a phase having a lower iodine content than the high iodine phase. here,
In order to make the silver iodide content of each grain uniform, it is important to appropriately select the conditions for forming the high iodine phase.

It is important that the internal high iodine phase is not uniformly deposited on the plane of the tabular grains of the substrate, but rather is localized. Such localization may occur at any location on the main plane, side, side, or corner of the flat plate. Further, the internal high iodine phase may be selectively epitaxially coordinated at such a site. As a method for this purpose, a so-called conversion method in which an iodide salt is added alone, or, for example, JP-A-59-133540.
JP-A-58-108526, JP-A-59-162
Epitaxial bonding methods such as those described in No. 540 can be used. At that time, selecting the following conditions is effective for making the silver iodide content of each grain uniform. That is, pAg when iodide salt is added
Is preferably in the range of 8.5 to 10.5, and 9.0 to 10.
A range of 5 is especially preferred. The temperature is preferably maintained in the range of 50 ° C to 30 ° C. Regarding the addition of the iodide salt, it is preferable to add 1 mol% or more of the iodide salt with respect to the total amount of silver over a period of 30 seconds to 5 minutes under a sufficiently stirred condition.

The properties of silver halide grains can be controlled by allowing various compounds to be present in the silver halide precipitation forming process. Such compounds may be initially present in the reactor. In addition, according to the conventional method, 1
Alternatively, it can be added together with two or more salts. U.S. Pat. Nos. 2,448,060 and 2,628,
167, 3,737,313, 3,772,0
No. 31, Research Disclosure, 134
Vol., June 1975, 13452,
Copper, iridium, lead, bismuth, cadmium, zinc (eg chalcogen compounds of sulfur, selenium and tellurium),
The properties of silver halide can be controlled by the presence of compounds such as compounds of gold and Group VII noble metals during the silver halide precipitation process. Tokiko Sho 58-
1410, by Moisar et al., Journal of Photographic Science, 25, 197
As described on pages 7, 19-27, silver halide emulsions can reduce and sensitize the interior of grains during precipitation.

In the tabular grains used in the present invention,
Silver halides having different compositions may be joined by epitaxial joining, or may be joined with a compound other than silver halide such as silver rhodanide or lead oxide. These emulsion grains are described, for example, in US Pat.
4,684, 4,142,900, 4,45
9,353, British Patent 2,038,792, U.S. Patents 4,349,622, 4,395,478.
Issue No. 4,433,501 Issue 4,463,087
Issue 3, Issue 3,656,962, Issue 3,852,067
And JP-A-59-162540.

The tabular silver halide emulsion of the present invention is usually chemically sensitized. The chemical sensitization is performed after the formation of the silver halide emulsion.
The emulsion may be washed with water during the chemical sensitization. Regarding chemical sensitization, see Research Disclosure, No.
No. 17643 (December 1978: p. 23) and No. 1
8716 (November 1979: right column, p. 648), pAg 5-10, pH 5-8, and temperature 30-.
The reaction can be carried out at 80 ° C. using sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers.

The tabular silver halide emulsion of the present invention is preferably chemically sensitized in the presence of a spectral sensitizing dye. A method of chemically sensitizing in the presence of a spectral sensitizing dye is described in, for example, U.S. Patent Nos. 4,425,426 and 4,442.
No. 201, JP-A-59-9658 and 61-1031
No. 49, 61-133941 and the like. As the spectral sensitizing dye to be used, any spectral sensitizing dye may be used as long as it is a spectral sensitizing dye generally used for a silver halide photographic light-sensitive material. The spectral sensitizing dye is described in Research Disclosure, No. 17643, pp. 23-24 and N
o. 18716, page 648, right column to page 649, right column. The spectral sensitizing dye may be used alone or as a mixture of several kinds.

The spectral sensitizing dye may be added at any time before the start of chemical sensitization (at the time of grain formation, at the end of grain formation, after washing with water), during the chemical sensitization or at the end of the chemical sensitization. Is preferably after the grain formation and before the chemical sensitization or at the end of the chemical sensitization. The amount of the spectral sensitizing dye to be added is optional, but is preferably 30 to 100% of the saturated adsorption amount, and more preferably 50 to 90%.

The tabular silver halide emulsion of the present invention is usually spectrally sensitized. The spectral sensitizing dyes to be used are described in the above two Research Disclosures as described above. The emulsion in which the spectral sensitizing dye is present during the chemical sensitization as described above may or may not additionally contain the same or different type of dye for spectral sensitization.

The emulsion of the present invention may be used alone in the light-sensitive emulsion layer, or two or more kinds of emulsions having different average grain sizes may be used in combination. When two or more types of emulsions are used, they may be used in different layers, but are preferably used in a mixture with the same photosensitive layer. When two or more kinds of emulsions are used, an emulsion having an average aspect ratio specified in the present invention and an emulsion having an average aspect ratio not used may be used. As mentioned above, the use of a mixture of emulsions provides gradation control, control of graininess from low to high exposure areas,
And the dependence on color development (e.g., from the viewpoints of the dependence on the composition of the developer such as time and color developing agent, sodium sulfite, etc., and the control of pH (dependency), etc.) The emulsion of the present invention is disclosed in JP-A-60-143332. , Id.
The relative standard deviation of the silver iodide content between grains described in No. 2 is particularly preferably 20% or less.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
It is silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides. Particularly preferred is about 2 mol%
To silver iodobromide or silver iodochlorobromide containing up to about 10 mol% of silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having regular crystal forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The grain size of silver halide is about 0.2 μm or less, but the projected area diameter is about 10 μm.
It may be a large size grain up to the above, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (R
D) No. 17643 (December 1978), 22-23
Page, "I. Emulsion prepar
nation and types) "and No. 1 of the same.
No. 8716 (November 1979), p. 648; 307
105 (November 1989), pp. 863-865, and "Physics and Chemistry of Photography" by Grafkid, published by Paul Montel (P. Glafkides, Chemie et P.).
hisique Photographique, Pa
ul Montel, 1967), Duffin, "Emulsion Chemistry", published by Focal Press (GF Duffi).
n, Photographic Emulsion C
chemistry (Focal Press, 196)
6)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating P
photographic Emulsion, Foca
1 Press, 1964).

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in JP-A No. 1989-2000 are also preferable. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. A method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-13354.
No. 2. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm.
5-20 nm is particularly preferred.

The silver halide emulsion usually used is one subjected to physical ripening, chemical ripening and spectral sensitization. The additives used in such a process are Research Disclosure No. 17643, ibid. No. 18716 and the same No.
No. 307105, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. U.S. Pat. No. 4,082,553.
No. 626,498, JP-A-59-214852, and JP-A-59-214852, in which a silver halide grain and a colloidal silver are coated with a light-sensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. Can be used preferably. The term "silver halide emulsion having a fogged inside or surface of a grain" means a silver halide emulsion which can be uniformly (non-imagewise) developed irrespective of unexposed portions and exposed portions of the photosensitive material.
A method for preparing silver halide grains having the inside or the surface of the grains fogged is described in U.S. Pat. No. 4,626,498;
-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. The silver halide having the inside or surface of the grain covered is silver chloride,
Any of silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is 0.01 to 0.75 μm, particularly 0.05 to 0.6 μm.
m is preferred. The grain shape is not particularly limited, and may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or the number of silver halide grains is ± 40% of the average grain size). %).

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average grain size (average value of circle-equivalent diameter of projected area) of 0.01 to 0.5 μm, and 0.02 to
2 μm is more preferable. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized nor spectral sensitization. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer. The coated silver amount of the light-sensitive material of the present invention is 8.0 g.
/ M ² or less are preferred, 6.0 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 648 page right column page 866 2. Sensitivity enhancer Page 648, right column 3. 3. Spectral sensitizers, pages 23 to 24, right column at page 648 to pages 866 to 868 supersensitizers, right column at page 649 Brightener page 24 page 647 page right column page 868 5. Antifoggants page 24-25 page 649 right column pages 868-870 Stabilizer 6. 6. Light absorber, page 25-26, page 649, right column-page 873, filter dye, page 650, left column, UV absorber 7. Anti-stain agent Page 25, right column, page 650, left column to page 872, right column. Dye image stabilizer page 25 page 650 page left column page 872 9. Hardener page 26 page 651 left column pages 874 to 875 10. Binder page 26 page 651 left column pages 873-874 11. Plasticizers and lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 13. Static 27 pages 650 pages right column 876-877 Inhibitors 14. Matting agent 878-879

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with the formaldehyde described in No. 7 and No. 4,435,503. Nos. 4,740,454 and 4,788,132 in the photosensitive material of the present invention.
It is preferable to contain a mercapto compound described in JP-A-62-18539 and JP-A-1-283551. Compounds which release a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by the development processing described in JP-A-1-106052. Is preferably contained. The light-sensitive material of the present invention may be added to International Publication WO88 / 047.
No. 94, JP-A No. 1-502912, or dyes described in EP 317,308A, U.S. Pat. No. 4,420,555, and JP-A-1-259358. preferable. Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. supra. 1764
3, VII-CG, and VII-CG. 307105, VII-
It is described in the patents described in C to G. Examples of yellow couplers include US Pat. No. 3,933,501.
No. 4,022,620, 4,326,02
No. 4, No. 4,401,752, No. 4,248,9
No. 61, Japanese Patent Publication No. 58-10739, British Patent Nos. 1 and 4
25,020, 1,476,760, U.S. Pat. Nos. 3,973,968, 4,314,023,
No. 4,511,649, European Patent No. 249,473.
Those described in No. A, etc. are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
No. 35730, No. 55-118034, No. 60-18
Those described in US Pat. No. 5951, US Pat. No. 4,500,630, US Pat. No. 4,540,654, US Pat. The cyan coupler that can be used in the present invention,
Examples thereof include phenol-based and naphthol-based couplers, and U.S. Pat. Nos. 4,052,212 and 4,146,39.
No. 6, No. 4,228,233, No. 4,296,2
No. 00, No. 2,369,929, No. 2,801,
No. 171, No. 2,772, 162, No. 2,89
No. 5,826, No. 3,772,002, No. 3,7
No. 58,308, No. 4,334,011, No. 4,
No. 327,173, West German Patent Publication No. 3,329,729.
No., European Patent Nos. 121,365A and 249,45
3A, US Pat. Nos. 3,446,622 and 4,3.
No. 33,999, No. 4,775,616, No. 4,
No. 451,559, No. 4,427,767, No. 4,690,889, No. 4,254,212, No. 4,296,199, and JP-A No. 61-42658. The couplers mentioned are preferred. Furthermore, JP-A-64-5
No. 53, No. 64-554, No. 64-555, No. 64
The pyrazoloazole couplers described in -556 and the imidazole couplers described in U.S. Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye forming couplers are found in US Pat. No. 3,451,82.
No. 0, No. 4,080, 211, No. 4, 367, 2
No. 82, No. 4,409,320, No. 4,576.
No. 910, British Patent No. 2,102,137, European Patent No. 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable. A colored coupler for correcting unnecessary absorption of a coloring dye is described in Research Disclosure No.
17643, Item VII-G, ibid. VII of 307105-
Section G, U.S. Pat. No. 4,163,670, JP-B-57-
39413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368.
Those described in the above item are preferred. Also, US Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group. Compounds that release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler releasing a development inhibitor is described in RD17643, VII-F and No. 307105, Patents described in Section VII-F, JP-A-57-151944, 57-15423.
No. 4, No. 60-184248, No. 63-37346.
No. 63-37350, U.S. Pat. No. 4,248,96.
Those described in Nos. 2 and 4,782,012 are preferred. As a coupler which releases a nucleating agent or a development accelerator in an image form during development, British Patent No. 2,097,14
No. 0, No. 2,131,188, JP-A-59-157.
Nos. 638 and 59-170840 are preferred. Also, Japanese Patent Application Laid-Open Nos. 60-107029 and 60-2
52340, JP-A-1-44940, 1-456
Compounds described in No. 87 which release a fogging agent, a development accelerator, a silver halide solvent, and the like by an oxidation-reduction reaction with an oxidized form of a developing agent are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618, etc .;
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. , A ligand releasing coupler described in US Pat. No. 4,555,477, a coupler releasing a leuco dye described in JP-A-63-75747, and a fluorescent dye described in US Pat. No. 4,774,181. Examples thereof include releasing couplers.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like. Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, Bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate,
Bis (1,1-di-ethylpropyl) phthalate), phosphoric acid or phosphonic acid esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, Tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-Ethylhexylphenylphosphonate), benzoates (eg, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecaneamide, N, N-diethyllauramide),
N-tetradecylpyrrolidone), alcohols or phenols (eg, isostearyl alcohol, 2,4
-Di-tert-amylphenol), aliphatic carboxylic esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (N, N- Dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or more, preferably 50 ° C. or more and about 160 ° C. or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, Ethoxyethyl acetate, dimethylformamide and the like. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,54.
1, 230 and the like.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-257747 are used.
272248, and 1,2-benzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various antiseptics or antifungal agents such as 2- (4-thiazolyl) benzimidazole. Suitable supports that can be used in the present invention are described, for example, in RD. No. 17643, page 28, ibid. 18716
No. 647, right column to page 648, left column; 307
105, p.879, published by JIII Journal of Technical Disclosure No. 94-6023. Preferable examples of the support include triacetate support (TAC), polyester support, polyethylene naphthalate support and the like. In the light-sensitive material of the present invention, the film swelling speed T _1/2 of the entire hydrophilic colloid layer having the emulsion layer is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means the film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days).
To 25 μm is preferable, and 12 to 22 μm is more preferable.
m, particularly preferably 15 to 20 μm. The film swelling rate T _1/2 can be measured according to a method known in the art. For example, A Green (A. Gr
een) and others in Photographic Science and Engineering (Photogr. Sci. E.
ng. ), Vol. 19, No. 2, pp. 124-129, which can be measured by using a swellometer (swelling meter) of the type. T _1/2 was treated with a color developer at 30 ° C. for 3 minutes and 15 seconds. 90% of the maximum swollen film thickness that reaches at time is the saturated film thickness,
It is defined as the time required to reach 1/2 of the saturated film thickness.

The swelling ratio of the color photographic light-sensitive material of the present invention in a developing solution is preferably 2.3 or more in order to accelerate the diffusion of the developing agent. More preferably, 2.4 or more 4
It is the following. Particularly preferably, it is 2.4 or more and 3 or less.
If it is too large, the diffusion distance becomes long, and development may be delayed. In the present invention, the swelling ratio in the developer is a value obtained by dividing the film thickness after swelling in the developer (the thickness of the photographic layer on the side having the photosensitive layer with respect to the support) by the dry film thickness. . The measurement of the swollen film thickness in the developer is described in A. Green and GI
P. Levenso, J. Phot. Sci., 20, 205 (1972)
Can be performed by the method described in (1). That is, 38 ° C. It can be determined from the equilibrium value of the swollen film thickness in the heated developer. As the developer, for example, the formulations described in the examples can be used. The developer A is used for the measurement of the swelling ratio defined in the present invention. Membrane swelling speed T _1/2
The swelling ratio and the swelling ratio can be adjusted by adding a film hardening agent to gelatin as a binder or changing aging conditions after coating.

The photosensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 2.5
〜6.0 is preferred. The silver halide color photographic light-sensitive material of the present invention is described in JP-B-2-32615 and JP-B-3-39.
When applied to the lens-fitted film unit described in Japanese Patent No. 784 or the like, it is effective because the effect is more easily exhibited.

The present invention is also applicable to a silver halide photographic light-sensitive material having a transparent magnetic recording layer in the back layer. Conventionally, the silver halide photographic light-sensitive material only provided image information at the time of shooting or printing,
As disclosed in Japanese Patent Laid-Open No. 4-68336 and Japanese Patent Laid-Open No. 4-73737, by providing a transparent magnetic recording layer on the entire surface of a light-sensitive material, the date and time of shooting, weather, reduction / enlargement ratio, etc. The shooting conditions, the number of reprints, the portion to be zoomed, a message, development, print conditions, etc. can be input to the sensitive material, and can also be input to a video device such as a TV / video. In that case, remove the effect of dust due to electrification, improve the slipperiness of the film,
It is desirable to eliminate the effect of curls containing the support.

The transparent magnetic recording layer used in the present invention will be described. The magnetic particles used in the present invention are γFe ₂ O ₃
Such as ferromagnetic iron oxide, Co-deposited γFe ₂ O ₃ , Co-deposited magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite or the like can be used. Co deposition γFe ₂ O ₃ and other Co
Deposited ferromagnetic iron oxide is preferred. The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization ([sigma] s) of the ferromagnetic material is preferably 400 to 3000 Oe, and particularly preferably 600 to 3000 Oe. The ferromagnetic particles may be surface-treated with silica and / or alumina or an organic material. Further, magnetic particles are disclosed in JP-A-6-161.
The surface may be treated with a silane coupling agent or a titanium coupling agent as described in No. 032. Further, magnetic materials described in JP-A-4-259911 and 5-81652, the surface of which is coated with an inorganic or organic substance, can also be used.

Next, the binder used for the magnetic particles is
Thermoplastic resins, thermosetting resins, radiation curable resins, reactive resins, acids, alkalis or biodegradable polymers, natural polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures described in JP-A-4-219569. Can be used. The Tg of the above resin is -40 ° C to 300 ° C, and the weight average molecular weight is 20,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based cross-linking agent include isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, tolylene diisocyanate). Examples thereof include a reaction product of 3 mol of isocyanate and 1 mol of trimethylolpropane), and polyisocyanate produced by condensation of these isocyanates, and they are described in, for example, JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the above-mentioned binder, a kneader, a pin type mill, an annular type mill, etc. are preferable and a combination thereof is also preferable, as in the method described in JP-A-6-35092. JP-A-5-08828
The dispersant described in 3 or other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μ to 10 μ, preferably 0.2 μ to 5 μ, and more preferably 0.3 μ to 3 μ. The weight ratio of magnetic particles to binder is preferably less than 0.1.
It is composed of 5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount as a magnetic substance is 0.005 to 3 g / m ² , preferably 0.01 to ² g
/ M ² , more preferably 0.02 to 0.5 g / m ² . The magnetic recording layer used in the present invention can be provided on the back surface of the photographic support by coating or printing and provided in the entire surface or in a stripe shape. As a method for applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze,
Impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion and the like can be used.
The coating liquid described in No. 6 is preferable.

The magnetic recording layer has improved lubricity, curl adjustment,
It may have functions such as antistatic, anti-adhesion and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. The binder used at this time may be the same as the binder described above for the magnet layer, and preferably the same binder as the binder for the magnet layer. For the light-sensitive material having a magnetic recording layer, see US Pat. Nos. 5,336,589 and 5,250,404.
No. 5,229,259, No. 5,215,874
, EP 466130.

Next, the polyester support used in the present invention will be described. For details, including a sensitive material, a treatment, a cartridge, an example, and the like, which will be described later, are described in JIII Journal of Technical Disclosure, Official Gazette No. 94-6023 (1994. 3.15). The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components, and the aromatic dicarboxylic acid is 2,6-
Examples thereof include naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, and diols as (poly) ethylene glycol, cyclohexanedimethanol, bisphenol A, and biphenol. Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is 2,6-naphthalenedicarboxylic acid of 0.1.
It is a polyester containing ~ 1.0. Among them, polyethylene 2,6-naphthalate is particularly preferred. The average molecular weight range is about 5000 to 200,000.
The Tg of the polyester of the present invention is 50 ° C. or higher.
Furthermore, Tg is preferably 90 ° C. or higher.

Next, the polyester support is subjected to a heat treatment at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg−20 ° C. or higher and lower than Tg in order to prevent the curling tendency. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. This heat treatment time is 0.1 hours or more and 1500 hours or less, and more preferably 0.5 hours or more and 200 hours or less. The heat treatment of the support may be performed in the form of a roll, or may be performed while being transported in the form of a web. Irregularities may be imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), and after the application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. To prevent light piping, Mitsubishi Chemical
The purpose can be achieved by mixing commercially available dyes for polyester such as aresin and Kayaset manufactured by Nippon Kayaku.

In the present invention, surface treatment is preferable in order to bond the support and the light-sensitive material constituting layer. Surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, and the like. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.
Next, the undercoating method will be described. It may be a single layer or a multilayer of two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including copolymers starting from monomers selected from maleic anhydride, as a starting material, Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcin and p-chlorophenol. In the undercoat layer, as a gelatin hardening agent, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine) are used. Etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. Inorganic particles such as SiO ₂ , TiO ₂ and matting agent or polymethylmethacrylate copolymer particles (0.
01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferable antistatic agent is Z
nO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ ,
The volume resistivity of at least one selected from SiO ₂ , MgO, BaO, MoO ₃ , and V ₂ O ₅ is 10 ⁷ Ω-cm.
Or less, more preferably 10 < ⁵ > [Omega] -cm or less, grain size 0.001 to 1.0 [mu] m crystalline metal oxide or a composite oxide thereof (Sb, P, B, In, S, Si,
C) and further, sol-like metal oxides or fine particles of composite oxides thereof. The content in the light-sensitive material is preferably 5 to 500 mg / m ² , and particularly preferably 1
It is a 0~350mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is from 1/300 to 10
0/1 is preferable, and 1/100 to 100 is more preferable.
/ 5.

The light-sensitive material of the present invention preferably has a slip property. The slipperiness is preferably used on both the photosensitive layer surface and the back surface. The preferred sliding property is a dynamic friction coefficient of 0.25.
It is 0.01 or more below. The measurement at this time represents a value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25 ° C., 60% RH). In this evaluation, even when the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level.
The slip agent that can be used in the present invention is polyorganosiloxane, higher fatty acid amide, higher fatty acid metal salt, ester of higher fatty acid and higher alcohol, and the like. Siloxane polydiethyl siloxane, polystyryl methyl siloxane, polymethyl phenyl siloxane, etc. can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The photosensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be a compound that dissolves in the treatment or a treatment-soluble matting agent, and it is preferably used at the same time. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)),
Polystyrene particles are preferred. 0.8 as particle size
10 to 10 μm is preferable, and the particle size distribution is preferably narrow, and the total particle number is 9 to 9 times the average particle size 0.9 to 1.1 times.
It is preferable that 0% or more is contained. It is also preferable to add fine particles of 0.8 μm or less at the same time in order to enhance the matting property. For example, polymethyl methacrylate (0.2
μm), poly (methyl methacrylate / methacrylic acid =
9/1 (molar ratio, 0.3 μm)), polystyrene particles (0.25 μm), colloidal silica (0.03 μm)
Is mentioned.

Next, the film cartridge used in the present invention will be described. The cartridge used in the present invention may be made of metal or synthetic plastic as a main material. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the cartridge of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations, betaine-based surfactants or polymers can be preferably used. As these antistatic patrones, JP-A 1-312537 and 1
-312538. Especially at 25 ° C, 2
The resistance at 5% RH is preferably 10 ¹² Ω or less. Usually, Patrone is made of plastic in which carbon black, pigments, etc. are kneaded in order to impart a light-shielding property. The size of the cartridge may be the same as it is now, or if the current cartridge diameter of 25 m / m is set to 22 m / m or less, it is effective for downsizing the camera. The volume of the cartridge case is 30 cm ³ or less, preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

Further, a patrone used in the present invention may be one that rotates the spool to feed the film. Further, a structure may be employed in which the leading end of the film is housed in the patrone main body, and the leading end of the film is sent out from the port portion of the patrone by rotating the spool shaft in the film sending direction. These are disclosed in U.S. Pat. No. 4,834,306 (corresponding to JP-A-1-306845) and JP-A-4-11525.
No. 1 (US Pat. No. 5,226,613).
The photographic film used in the present invention may be a so-called raw film before development or a developed photographic film. Further, the raw film and the developed photographic film may be housed in the same new cartridge, or may be different cartridges.

Color developing processing A of the present invention will be described below. The color development time of the color development processing A of the present invention is 15
It is 0 second or more and 200 seconds or less, preferably 165 seconds or more and 195 seconds or less. The color development time depends on the type and concentration of the developing agent in the processing solution, halogen ion (especially Br ⁻ )
It can be changed depending on the concentration, the temperature of the processing solution, the pH, and the like.

The developing agent in color development processing A of the present invention is 2
-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N- (3-hydroxypropyl) amino] aniline, 2-methyl-4 -[N-ethyl-N- (4-hydroxybutyl) amino] aniline, preferably 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline, which is a developing agent. The concentration is 15 millimole or more and 20 millimole or less, preferably 15 millimole or more and 18 millimole or less, per liter of the treatment liquid.

[0117] Bromide ion concentration, Br from a silver halide color photographic material ^- and elution, Br is replenished in the color developing solution ^- is determined by the amount, to keep the photographic properties during continuous processing stably Per milliliter of the treatment liquid is 9 mmol or more and 14 mmol or less, preferably 10
It is not less than 13 mmol and not more than 13 mmol.

The replenisher for the color developing solution preferably has a bromide ion concentration reduced to 0.004 mol / liter or less from the viewpoint of reducing the replenishment amount, and particularly has a bromide ion concentration of 0.002 mol / liter or less. Is preferred. The replenishing amount is 700 ml or less, preferably 200 ml or more and 600 ml or less per 1 m ² of the light-sensitive material.

The temperature of the treatment liquid is 37 ° C. or higher and 40 ° C. or lower.

The pH of the treatment liquid is 9.9 or more and 10.3 or less, preferably 10.0 or more and 10.2 or less.

Further, the color developing treatment A contains substantially no silver halide solvent of the present invention. The term "substantially free of" means that the concentration is not more than the concentration at which the silver halide solvent of the present invention does not exhibit the effect, and it may be contained in a trace amount due to mixing from the subsequent step. 05 mmol / liter or less, preferably 0-0.01 mmol / l
It is liter, and most preferably contains no liter.

Further, a hydroxylamine having a substituent described in JP-A-3-158849 and JP-A-3-174152 may be contained as a preservative, and hydroxylamine having a sulfoalkyl group as a substituent is particularly preferable. Those containing are preferred. Further, as a chelating agent, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-
1,1-diphosphonic acid, 4,5-dihydrosibenzene-
Those containing 1,3-disulfonic acid are preferred.

Specifically, a color negative film processing agent, CN-16 or CN-1 manufactured by Fuji Photo Film Co., Ltd.
6X, CN-16Q, CN-16FA color developers and color development replenishers, or Eastman Kodak color negative film processing agents C-41, C-41.
Color developing solutions of B and C-41RA can be preferably used.

Color development processing B of the present invention will be described below. The color development time of the color development processing B of the present invention is 2
5 seconds or more and 90 seconds or less, preferably 35 seconds or more 7
It is 5 seconds or less, and most preferably 45 seconds or more and 65 seconds or less.

The color developing time of the present invention is a time including the crossover time (time from the exit of the color developing solution to the processing solution of the next step). The shorter the crossover time is, the better the processing is. 2 seconds or more and 10 seconds or less are preferable, and 3 seconds or more and 7 seconds or less are more preferable in terms of device performance.

The color developing time can be changed in the same manner as in the color developing treatment A depending on the type and concentration of the developing agent in the processing solution, the halogen ion (special Br) concentration, the temperature of the processing solution, the pH and the like.

The developing agent in color development processing B of the present invention is p
-Phenylenediamine derivatives, preferable representative examples of which are shown below. (D-1) 2-methyl-4- [N-ethyl-N- (β
-Hydroxyethyl) amino] aniline (D-2) 2-methyl-4- [N-ethyl-N- (3
-Hydroxypropyl) amino] aniline (D-3) 2-methyl-4- [N-ethyl-N- (4
-Hydroxybutyl) amino] aniline (D-4) 2-methyl-N, N-diethyl-p-phenylenediamine (D-5) 2-methyl-4- [N-ethyl-N- (β
-Methanesulfonamidoethyl) amino] aniline (D-6) 2-methoxy-4- [N-ethyl-N-
(Β-Hydroxyethyl) amino] aniline (D-7) 4-amino-3-methoxy-N, N-bis (3-hydroxypropyl) aniline (D-8) 4-amino-3-isopropoxy-N,
N-bis (β-hydroxyethyl) aniline (D-9) 1- (β-hydroxyethyl) -5-amino-6-methyl-indoline (D-10) 1,2,3,4-tetrahydro-1-
(3,4-dihydroxybutyl) -2,2,4,7-tetramethyl-6-amino-quinoline (D-11) 1,2,3,4-tetrahydro-1- (β
-Hydroxyethyl) -4-hydroxymethyl-6-amino-7-methyl-quinoline

In the color development processing B of the present invention, D-
1, D-2, D-3, D-6, D-7, D-8, D-1
0, D-11 are particularly preferable, and D-1, D-2, D-3
Is more preferable, and D-1 is the most preferable.

The concentration of the developing agent is 25 to 80 mmol, preferably 25 to 60 mmol, more preferably 27 to 50 mmol, and most preferably 30 to 45 per liter of the processing solution. It is below millimolar.

Within the concentration range of the developing agent, two or more kinds of the developing agents may be used in combination.

In the color development processing B of the present invention, bromide ion (Br ⁻ ) is particularly important as an antifoggant,
The Br ^- concentration is 15 mmol or more and 60 mmol or less, preferably 16 mmol or more and 4 per liter of the treatment liquid.
It is 2 mmol or less, and particularly preferably 16 mmol or more and 35 mmol or less.

If necessary, I ⁻ or Cl ⁻ may be contained as a halogen ion other than Br ⁻ . From the viewpoint of reducing the replenishment amount, the replenisher for the color developing solution preferably has a bromide ion concentration reduced to 0.004 mol / liter or less, and particularly preferably a bromide ion concentration of 0.002 mol / liter or less. The replenishing amount is 600 ml or less, preferably 100 ml or more and 500 ml or less, and particularly preferably 130 ml or more and 400 ml or less per 1 m ² of the light-sensitive material.

The temperature of the treatment liquid is 40 ° C. or higher and 60 ° C. or lower, preferably 42 ° C. or higher and 55 ° C. or lower, and particularly preferably 43 ° C. or higher and 50 ° C. or lower.

The pH of the treatment liquid is 9.9 or more and 11.0 or less, preferably 10.0 or more and 10.5 or less.

Further, as described above, at least 1 part of the silver halide solvent of the present invention is used in the color development processing B of the present invention.
Contains seeds.

In the color developing solution of the present invention, compounds which directly preserve the aromatic primary amine color developing agent are disclosed in JP-A-63-5341, JP-A-63-106655 and JP-A-4-144446. Various hydroxylamines described in JP-A-63-43138, hydrazines and hydrazides described in JP-A-63-146041, and phenols described in JP-A-63-45743. , 63-4
[Alpha] -hydroxyketones and [alpha] -aminoketones described in No. 4656, various sugars described in No. 63-36244, and the like can be contained. In addition, in combination with the above compound, JP-A-63-4235, JP-A-63-24254,
No. 63-21647, No. 63-146040, No. 6
3-27841 and 63-25654, etc., monoamines, 63-30845, 63-14.
640, 63-43139 and the like diamines, 63-21647, 63-26655 and 63-46655, and polyamines 63.
No. 53551, Nitroxy Radicals, 63
The alcohols described in -43140 and 63-53549, the oximes described in 63-56654, and the tertiary amines described in 63-239447 can be used. Other preservatives include JP-A-57
Nos. 44148 and 57-53749, various metals, 59-180588, salicylic acids, 54-3582, alkanolamines, and 56-94349, polyethyleneimines. If desired, the aromatic polyhydroxy compounds described in US Pat. No. 3,746,544 and the like may be contained.
Particularly preferred preservatives are described in JP-A-3-144446.
The hydroxylamines represented by the general formula (I) of the above-mentioned No. 1, among which compounds having a sulfo group or a carboxy group are preferable.

Others In the color developing solution of the present invention, various additives described in JP-A-3-144446 can be used. For example, examples of buffers for maintaining pH include carbonic acid, phosphoric acid, boric acid, hydroxybenzoic acid and the like on page 6 of the publication (9), upper right column, line 6 to lower left column, line 1. As a chelating agent, the lower left column, line 2 to the lower right column, 18 on the same page
Of the various aminopolycarboxylic acids, phosphonic acids, and sulfonic acids of the line, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N, N, N ', N '-Tetrakis (methylenephosphonic acid) and catechol-3,5-disulfonic acid are preferable. Examples of the development accelerator include various additives described on page 9, lower left column, line 19 to page 10, upper right column, line 7 of the same publication. Examples of the antifoggant include halide ions described in the same publication, page (10), upper right column, line 8 to lower left column, line 5;
Organic antifoggants may be mentioned. If necessary, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid may be added.

When the color developing solution of the present invention is used for processing in an automatic developing machine, it is preferable that the area (opening area) in which the color developing solution comes into contact with air is as small as possible. For example, when the aperture ratio is a value obtained by dividing the opening area (cm ² ) by the volume of the developer (cm ³ ), the aperture ratio is preferably 0.01 cm ^-1 or less, and
It is more preferably 005 cm ^-1 or less. The color developing solution can be regenerated and used. Regeneration of the color developing solution means that the used developing solution is subjected to anion exchange resin or electrodialysis, or a processing chemical called a regenerant is added to increase the activity of the color developing solution and to use it again as a color developing solution. That is. In this case, the regeneration rate (ratio of the overflow solution in the replenisher) is preferably 50% or more,
It is particularly preferably 70% or more. As a process using the color developing solution regeneration, the overflow solution of the color developing solution is regenerated and then used as a replenishing solution. As a method for regenerating the color developing solution, it is preferable to use an anion exchange resin. Particularly preferred anion exchange resin compositions and resin regeneration methods include those described in DIAION Manual (I) (14th edition, 1986) issued by Mitsubishi Kasei Co., Ltd. Further, among the anion exchange resins, resins having the compositions described in JP-A-2-952 and 1-281152 are preferable.

In the present invention, the light-sensitive material is subjected to color development processing and then desilvering processing. Specific examples of the desilvering treatment include the following. Bleach-fix Bleach-wash-fix Bleach-bleach-fix Bleach-wash-bleach-fix Bleach-bleach-fix Bleach-fix

Examples of the bleaching agent used in the processing solution having a bleaching ability include aminopolycarboxylic acid iron (III) complexes, persulfates, bromates, hydrogen peroxide, and red blood salts. The polycarboxylic acid (III) complex can be most preferably used. The ferric iron complex salt used in the present invention may be added and dissolved as a complexed iron complex salt in advance, and the complex forming compound and the ferric iron salt (for example, ferric sulfate, ferric chloride) may be added. Iron, ferric bromide, iron (III) nitrate, iron (III) ammonium sulfate, etc.) may coexist to form a complex salt in a liquid having a bleaching ability. The complex-forming compound may be slightly in excess of the amount required for complex formation with ferric ion, and when it is added in an excess amount, it is usually 0.01 to 1
It is preferable to make it excessive in the range of 0%.

In the present invention, as the compound forming the ferric complex salt in the liquid having a bleaching ability, ethylenediaminetetraacetic acid (EDTA), 1,3-propanediaminetetraacetic acid (1,3-PDTA), Diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) iminodiacetic acid, nitrilotriacetic acid, N- (2-carboxyethyl) iminodiacetic acid, N- (2-Carboxymethyl) iminodipropionic acid, β-alanine diacetic acid, 1,
4-diaminobutane tetraacetic acid, glycol ether diamine tetraacetic acid, N- (2-carboxyphenyl) iminodiacetic acid, ethylenediamine-N- (2-carboxyphenyl) -N, N ', N'-triacetic acid, ethylenediamine-
N, N'-disuccinic acid, 1,3-diaminopropane-
N, N'-disuccinic acid, ethylenediamine-N, N'-
Examples thereof include dimaleonic acid and 1,3-diaminopropane-N, N′-dimalonic acid, but are not particularly limited thereto.

The concentration of the ferric complex salt in the processing solution having a bleaching ability is appropriately in the range of 0.005 to 1.0 mol / liter, preferably 0.01 to 0.50 mol / liter. , And more preferably 0.02-0.3
It is in the range of 0 mol / liter. The concentration of the ferric complex salt in the replenisher for the processing solution having bleaching ability is preferably 0.005 to 2 mol / liter, more preferably 0.01 to 1.0 mol / liter.

Various compounds can be used as a bleaching accelerator in the bath having bleaching ability or the pre-bath thereof. For example, compounds having a mercapto group or a disulfide bond described in U.S. Pat. No. 3,893,858, German Patent 1,290,812, JP-A-53-95630 and Research Disclosure No. 17129 (July 1978). And Japanese Patent Publication No. 45-8506, Japanese Patent Laid-Open Nos. 52-20832, 53-3
2735, U.S. Pat. No. 3,706,561 and the like, and thiourea compounds or halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

Other bleaching baths applicable to the present invention include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride). Alternatively, a rehalogenating agent such as iodide (eg, ammonium iodide) can be included. PH of borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, malonic acid, succinic acid, glutaric acid, etc. It is possible to add one or more kinds of inorganic acids and organic acids having a buffering capacity and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine. Further, the bath having a bleaching ability may contain various other fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol.

The bleach-fixing solution and the fixing agent component in the fixing solution are
Known fixing agents, ie, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate; ethylenebisthioglycolic acid, 3,6-dithia-1,8-
It is a water-soluble silver halide dissolving agent such as a thioether compound such as octanediol, a mesoionic compound and thioureas, and these can be used alone or as a mixture of two or more. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfate and sodium thiosulfate, is preferred. The amount of fixing agent per liter is
The amount is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol. Sulfites (or bisulfites and metabisulfites) as preservatives in bleach-fix and fixers
It is desirable to contain 0.08 to 0.4
Mol / l, more preferably 0.1-0.3 mol / l
It is preferable to contain liter. By using this concentration range and further using the final bath of the present invention, not only the magnetic recording performance was remarkably improved, but also desirable results were shown in terms of image storability. The bleach-fixing solution or the fixing solution is a sulfite as described above as a preservative (for example, sodium sulfite, potassium sulfite,
Release of sulfite ion such as ammonium sulfite), bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite) In addition to containing the compound, aldehydes (benzaldexide, acetaldehyde, etc.), ketones (acetone, etc.), ascorbic acids, hydroxylamines, etc. can be added as necessary.

Further, a bleaching solution, a bleach-fixing solution, and a fixing solution may be added with a buffering agent, a fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like, if necessary. In the bleaching solution and the bleach-fixing solution used in the present invention, the preferred pH range is 4.5.
It is -6.2 and more preferably 5-6. Magnetic recording performance may not be sufficiently exhibited at a pH higher or lower than the main pH. In the case of a fixer, the pH is 5-8.
A degree is desirable.

Bleaching solution, bleach-fixing solution, used in the present invention,
The replenishing amount of the fixing solution is 50 to 200 per 1 m ² of the light-sensitive material.
0 ml. Particularly preferably 100 to 100
It is 0 ml. Further, washing water as a post-bath or overflow solution of a stabilizing bath may be replenished as necessary.
The processing temperature of the bleaching solution, the bleach-fixing solution and the fixing solution is 20 to 50 ° C.
And preferably 30 to 45 ° C. Processing time is 1
It is 0 second to 3 minutes, preferably 20 seconds to 2 minutes. In terms of speeding up, it is most preferably 20 seconds to 1 minute 30 seconds. The shorter the desilvering time, the more remarkable the effect of the present invention.

A processing solution having a bleaching ability is particularly preferably subjected to aeration during processing because the photographic performance can be kept extremely stable. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector. When blowing air, it is preferable to release air into the liquid through a diffuser having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Z-1 issued by Eastman Kodak Company
21, Youth Process C-41 3rd Edition (198)
2 years), and the matters described on pages BL-1 to BL-2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is strengthened, and the processing is carried out as described in JP-A-3-33847, page 8, upper right column, line 6 The contents described in the second row from the lower left column can be used as they are.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. Specific examples of the method for strengthening stirring include a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and JP-A-62-1834.
A method of increasing the stirring effect using the rotating means of No. 61, and further moving the light-sensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. Examples thereof include a method for improving the method and a method for increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

After the treatment step with the fixer and / or the bleach-fixer, a washing treatment step is usually carried out. It is also possible to use a simple processing method in which after the treatment with the treatment liquid having the fixing ability, the stabilizing treatment using the stabilizing liquid is carried out without substantially washing with water. The washing water used in the washing step and the stabilizing solution used in the stabilizing step may contain various surfactants in order to prevent water droplet unevenness during drying of the processed light-sensitive material. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

The washing water and the stabilizing solution may contain various antibacterial agents and antifungal agents in order to prevent generation of water stains and molds generated in the processed light-sensitive material. Further, it is preferable to add various chelating agents to the wash water and the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetraacetic acid and diethylenetriamine-N, N, N ', N'-tetramethylene. Examples thereof include organic phosphonic acids such as phosphonic acid, and hydrolysis products of maleic anhydride polymers described in European Patent 345172A1. It is also preferable that the preservative that can be contained in the fixing solution or the bleach-fixing solution is contained in the washing water and the stabilizing solution.

The stabilizing solution used in the stabilizing step is a processing solution for stabilizing the dye image, such as an organic acid or pH 3 to
6, a solution containing an aldehyde (for example, formalin or glutaraldehyde), or the like. The stabilizing solution may contain all compounds that can be added to the washing water, and if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, and hardeners. Agents such as alkanolamines described in U.S. Pat. No. 4,786,583 can be used.

In the present invention, it is preferable that the stabilizing solution does not substantially contain formaldehyde as a stabilizer for the dye image. The term "substantially free of formaldehyde" means that the total amount of free formaldehyde and its hydrate is 0.003 mol or less per liter of the stabilizing solution. By using such a stabilizing solution, it is possible to suppress the scattering of formaldehyde vapor during processing. In this case, for the purpose of stabilizing the magenta dye, it is preferable that the formaldehyde substitute compound is present in the stabilizing solution, the bleaching solution or its prebath (for example, a preparation bath).

Preferred compounds as the formaldehyde substitute compound are hexamethylenetetramine and its derivatives, formaldehyde bisulfite adducts, N-methylol compounds and azolylmethylamine compounds. In addition to stabilizing the magenta dye, these preferable compounds suppress the generation of yellow stain over time.

Hexamethylenetetramine and its derivatives include "Beilsteins Handbook Der.
Organischen Chemie (Beilsteins Handbuch der
Organishen Chemie) Volume II Supplement 26, P.200-P.
The compounds described in 212 can be used, but in particular:
Hexamethylenetetramine is preferred. Further, as the formaldehyde bisulfite addition product, sodium formaldehyde bisulfite is preferable.

The N-methylol compound is preferably an N-methylol compound of pyrazole or its derivative, an N-methylol compound of triazole or its derivative, or an N-methylol compound of urazole or its derivative. Specific examples of these N-methylol compounds include 1-hydroxymethylpyrazole, 1-hydroxymethyl-2-methylpyrazole, 1-hydroxymethyl-2,4-dimethylpyrazole, 1-hydroxymethyl-1,2,4. -Triazole, 1-hydroxymethylurazole and the like can be mentioned. Of these, particularly preferred are 1-hydroxymethylpyrazole and 1-hydroxymethyl-1,2,4-triazole. N above
The methylol compound can be easily synthesized by reacting an amine compound having no methylol group with formaldehyde or paraformaldehyde. When the above N-methylol compound is used, it is preferable that an amine compound having no methylol group is allowed to coexist in the treatment liquid, and it is preferable that the N-methylol compound is present at a molar concentration of 0.2 to 10 times.

As the azolylmethylamine compound,
1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine and 1,4-bis (pyrazol-1-ylmethyl) piperazine may be mentioned, which may be combined with an azole such as 1,2,4-triazole or pyrazole. Combined use (Patent application 3
No. 159918), the image stability is high and the formaldehyde vapor pressure is low, and thus it is particularly preferable. The addition amount of the formaldehyde substitute compound is 0.003 to 0.2 mol, preferably 0.005 to 0.05 mol, per liter of the treatment liquid. Two or more of these formaldehyde substitute compounds may be used in combination in the bath.

The pH of the stabilizing solution is preferably from 3 to 9, more preferably from 4 to 7. The washing process and stabilization process are
A multi-stage countercurrent system is preferable, and the number of stages is preferably 2 to 4. The replenishing amount is 1 to 50 times, preferably 1 to 30 times, more preferably 1 to 50 times the amount brought in from the previous bath per unit area.
10 times. Regarding the washing and stabilizing steps carried out in the present invention, the contents described in JP-A-3-33847, page 11, lower right column, line 9 to page 12, upper right column, line 19 can be preferably carried out. .

As the water used in the washing step and the stabilizing step, tap water can be used, but water and halogen deionized to have Ca and Mg ion concentrations of 5 mg / liter or less by an ion exchange resin or the like. It is preferable to use water that has been sterilized by an ultraviolet sterilization lamp or the like. Further, by using a method in which the overflow solution of the washing step or the stabilizing step is caused to flow into a bath having a fixing ability as a pre-bath,
It is preferable because the amount of waste liquid can be reduced.

In the process of the present invention, in order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenishing solution. The specific method for replenishing water is not particularly limited, but among them, JP-A 1-2
The monitor water tank different from the bleaching tank described in No. 54959 and No. 1-254960 is installed, the evaporation amount of water in the monitor water tank is obtained, and the evaporation amount of water in the bleaching tank is calculated from the evaporation amount of this water. However, a method for replenishing the bleaching tank with water in proportion to this evaporation amount and Japanese Patent Application Nos. 2-46743 and 2-477.
The evaporation correction method using a liquid level sensor or an overflow sensor described in Nos. 77, 2-47778, 2-47779, and 2-117792 is preferable. The water for correcting the evaporation of each treatment liquid may be tap water, but it is preferable to use deionized water or sterilized water which is preferably used in the above washing step.

[0161]

EXAMPLES The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples unless it exceeds the gist of the present invention. (Example 1) 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 100
After drying 2 parts by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy Co.) as an ultraviolet absorber, 300 ° C.
After being melted at, it was extruded from a T-die, stretched 3.3 times at 140 ° C, then stretched 3.3 times at 130 ° C, and heat-fixed at 250 ° C for 6 seconds to form a 90 μm thick PEN.
I got a film. The PEN film has a blue dye, a magenta dye, and a yellow dye (public technical report: I-1, I-4, I-6, I-24, I-26, I-26 described in the official gazette number 94-6023). 27, II-5)
Was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled.

2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both sides thereof, and then gelatin 0.1 g / m ² and sodium α-sulfodione on each side. -2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p
-Chlorophenol 0.2 g / m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂
CH ^₂ 0.012g / m _2, polyamide - epichlorohydrin polycondensate was coated an undercoat solution ^{0.02g / m 2 (10cc / m} 2, a bar coater used), provided with a subbing layer hotter side at the time of stretching. Dry 1
The test was carried out at 15 ° C for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C). 3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat.

3-1) Coating of antistatic layer A tin oxide-antimony oxide composite having an average particle size of 0.005 μm has a specific resistance of 5 Ω · cm and is a dispersion of fine particle powder (secondary agglomerated particle size of about 0.08 μm). 0.2 g / m ^2, gelatin 0.05g / m ^2, (C
H ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 1
0) Oxyethylene-p-nonylphenol 0.005 g / m ²
And resorcinol. 3-2) Coating of magnetic recording layer 3-poly (degree of polymerization: 15) Cobalt-γ-iron oxide coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area: 43 m ² / g; Long axis 0.14μm, single axis 0.03μm, saturation magnetization 89emu / g, Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface is treated with silicon oxide aluminum oxide with 2% by weight of iron oxide) 0.06g / m ² diacetyl cellulose 1.2 g / m ² (dispersion of the iron oxide was carried out using an open kneader and a sand _{mill), C 2 H 5 C (} CH 2 OCONH-C 6 H 3 (CH 3) NCO) as a curing agent ₃
0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, cyclohexanone as a solvent,
A magnetic recording layer having a thickness of 1.2 μm was obtained. Abrasive aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) as matting agents, respectively
It was added to 10 mg / m ² . Drying was carried out at 115 ° C for 6 minutes.
° C). X- write saturation magnetization moment of the magnetic recording layer of the D color density increment of about 0.1 of ^B, also the magnetic recording layer is 4.2 emu / g, coercive force 7.3 × 10 ⁴ A / m, the squareness ratio in (blue filter) Was 65%.

3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ C
OOC ₄₀ H ₈₁ (compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H
(Compound b, 9 mg / m ² ) mixture was applied. In addition, this mixture is xylene / propylene monomethyl ether (1/1)
The mixture was melted at 105 ° C. in water, and dispersed by pouring into propylene monomethyl ether (10-fold amount) at room temperature, and then dispersed in acetone (average particle size: 0.01 μm) and then added. As a matting agent, silica particles (0.3 μm) and abrasive 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (aluminum oxide (0.15 μm) coated with 15% by weight) are each 15 mg / m ² . And dried at 115.
C. for 6 minutes (115 ° C. for all rollers and conveyors in the drying zone). The sliding layer had a dynamic friction coefficient of 0.06 (stainless steel hard ball of 5 mmφ, load of 100 g, speed of 6 cm / min), a static friction coefficient of 0.07 (clip method), and a dynamic friction coefficient of 0.12 between the emulsion surface and the sliding layer which will be described later. .

4) Coating of Photosensitive Layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was multilayer coated to prepare a color negative film.
This is designated as Sample 101.

(Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye The numeral corresponding to each component indicates the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer.

First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion A Silver 0.45 ExS-1 6.0 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.0 × 10 ^-4 ExC-1 0.15 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion B Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.10 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion C Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion D Silver 0.15 Silver iodobromide emulsion E Silver 0.10 Silver iodobromide emulsion F Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion G Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion H Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion I Silver 0.09 Silver iodobromide emulsion J Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion K Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion L Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property, each layer may be provided with W-1 to W-3, B-4 to B-. 6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0182]

[Table 1]

In Table 1, (1) Emulsions I to K were subjected to reduction sensitization at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Emulsions A to H were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. ing. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the example of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains using a high voltage electron microscope. (5) Emulsion K is a double-structured grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) of the aqueous solution was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The material was dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the fine dye particles were 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP549,489A. The average particle size was 0.06 μm.

[0186]

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[0187]

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[0188]

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[0189]

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[0190]

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[0191]

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[0192]

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[0193]

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[0194]

[Chemical 21]

[0195]

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[0196]

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[0197]

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[0198]

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[0199]

[Chemical formula 26]

[0200]

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[0201]

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Next, Samples 102 to 108 were prepared in the same manner except that the average silver iodide (AgI) content of the silver iodobromide emulsion B of the fourth layer of Sample 101 was changed as shown in Table 2. Created. The obtained sample was subjected to wedge exposure with white light, and the development processing A-1 and the development processing B-1 shown below were performed.
I went.

(Development processing A-1)

Next, the composition of the treatment liquid will be described. (Color developer) Tank solution (g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N -Ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.6 (15.7 mmol) Water was added to 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05

(Bleaching Solution) Tank Solution and Replenishing Solution Common (Unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH ₃ ). _{2 N-CH 2 -CH 2 -SS} -CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) was added to 15.0 ml water 1.0 l pH (adjusted with aqueous ammonia and nitric acid) 6.3

(Bleach-fixing solution) Tank solution (g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (700 g / l) 240.0 ml Ammonia water (27%) ) 6.0 milliliters Add water 1.0 liter pH (adjust with ammonia water and acetic acid) 7.2

(Washing Solution) Common to Tank Solution and Replenishing Solution Tap water was used as H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400). Water was passed through a mixed bed column filled with to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg / liter of sodium diisocyanurate dichloride and 0.15 g / liter of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

Development Process B-1 Process and Composition of Processing Solution Processing Process Temperature Time Color Development 45 ° C. 60 sec Bleach Fixing 40 ° C. 60 sec Washing with water (1) 40 ° C. 20 sec with water washing (2) 40 ° C. with 20 sec water washing (3) 40 ℃ for 20 seconds Drying 80 ℃ for 60 seconds (Washing was carried out in the 3 tank countercurrent system from (3) to (1).)

Liquid composition (color developer) Tank liquid (g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1diphosphonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 2.4 Potassium iodide 1.3 mg Disodium N, N -Bis (sulfonate ethyl) hydroxylamine 10.0 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 (37.6 mmol) Water was added to 1.0 liter pH (potassium hydroxide 10.05 (bleach-fixer) (unit mol) ethylenediamine- (2-carboxyphenyl) -N, N ', N'-triacetic acid 0.17 ferric nitrate nonahydrate 0.15 ammonium thiosulfate 1.25 ammonium sulfite 0.10 Metacarboxybenzenesulfinic acid 0.05 Add water to 1.0 liter pH (acetic acid and ammonia 5.8 (wash water) Same composition as described in Treatment A-1

After the treatment, the absorption densities of cyan, magenta and yellow of each sample were measured to obtain a characteristic curve.
From the obtained characteristic curve, the gradation degrees γ _A (C), γ _A of cyan, magenta, and yellow after the development processing A-1 was carried out
(M), γ _A (Y), and cyan, magenta, and yellow gradations γ _B (C), γ after development processing B-1 is performed.
_B (M) and γ _B (Y) are calculated, and γ _B (C) / γ
_A (C), γ _B (M) / γ _A (M), γ _B (Y) / γ _A
The value of (Y) was calculated.

Further, development processing B-2 was carried out in the same manner except that the compound (I-3) of the present invention was added in an amount of 1.0 mmol / liter to the color developer of development processing B-1.
Similarly, the ratio to the gradation after the development processing A-1 was calculated. Table 2 shows the obtained results.

[0212]

[Table 2]

From the results of Table 2, by adding the silver halide solvent of the present invention, (γ _B (C) / γ _A (C))
Value is 0.8 to 1.2, which shows that the development delay of the lower layer is improved and an image with good color reproducibility can be obtained.

On the other hand, the silver halide solvent of the present invention is (γ
_B (M) / γ _A (M)) and (γ _B (Y) / γ
_It has almost no effect on the value of _A (Y)).

When the average AgI content is 0.5 to 5.0 mol%, the value of (γ _B (C) / γ _A (C)) is 0.9.
It is ~ 1.1, which is more preferable.

Example 2 Compound (I-1) of the invention in the developing treatment B-2 of Example 1
Was developed in the same manner as in Example 3 except that the silver halide solvent was replaced with an equimolar amount (1.0 mmol / liter). _B (C) / γ _A (C) was determined. Table 3 shows the obtained results.
Shown in

[0219]

[Table 3]

Example 3 An experiment was carried out in the same manner as Experiment A12 of Example 1 except that the addition amount of the compound (I-1) of the present invention in the development treatment B-2 was changed as shown in Table 5. C01 to C08 were carried out, and the obtained results are shown in Table 4.

[0219]

[Table 4]

From the results shown in Table 5, the compound of the present invention (I-
When the addition amount of 1) is 0.3 to 5.0 mmol / liter, the value of (γ _B (C) / γ _A (C)) is 0.90 to 1.
It turns out that 10 is more preferable. Further, when the added amount was 20 mmol / liter or more, the fog density in the unexposed area remarkably increased.

Example 4 An experiment was conducted in exactly the same manner as in Development Processing B-2 of Experiment A12 of Example 1 except that the color developing time and the temperature of the color developing solution were changed as shown in Table 5. Table 5 shows the obtained results.

[0222]

[Table 5]

As is clear from these results, the ratio of gradation is less than 0.2 in a short development time of 25 to 90 seconds.
An image of 8 or more and 1.2 or less was obtained, that is, an image with good color reproducibility was obtained by rapid processing.

Example 5 Samples 501 to 507 were prepared in the same manner as in Sample 105 of Example 1 except that only the diameter / thickness ratio (average aspect ratio) was changed as shown in Table 6, and Experimental Example 1 Developing processes A-1, B-1, and B-2 were performed, and the ratio of the cyan density tonality (γ _B (C) / γ _A (C)) was obtained. Table 6 shows the obtained results.

[0225]

[Table 6]

From these results, it is understood that the effect of the present invention is greatest when the average aspect ratio is 5 or more and 10 or less.

Example 6 Table 7 shows the average silver iodide (AgI) contents of the silver iodobromide emulsions A, B and C of the third, fourth and fifth layers of the sample 101 of Example 1.
Sample 601 was made in exactly the same manner except that it was changed as shown in
To 610, and the development processes A-1 and B- of Example 1 are performed.
1 and B-2 are carried out, and the gradation ratio of the cyan density (γ
_B (C) / γ _A (C)) was obtained. The obtained results are shown in Tables 7 and 8.

[0228]

[Table 7]

[0229]

[Table 8]

From these results, it is understood that the silver iodobromide of the present invention may be used in any red-sensitive emulsion layer, but it is particularly preferable to use it in the medium-speed red-sensitive emulsion layer.

Example 7 Samples 101 and 104 of Example 1 were prepared to have a width of 24 mm and a width of 160 cm.
Further, two 2 mm square perforations are provided at a distance of 5.8 mm at a position 0.7 mm from the width direction on one side of each sample. 32mm for these two sets
Created with spacing, US Pat. No. 5,296,8
87 of FIG. 1 to FIG. 7 was housed in a plastic film cartridge.

For these samples, heads having a head gap of 5 μm and a turn number of 2000 were used for input / output from the coated surface side of the magnetic recording layer.
The FM signal was recorded at a feed rate of 0 mm / s.

After recording the FM signal, the photosensitive layer side was subjected to wedge exposure with white light, and then the following development processing A-2 and B-
30 was carried out. Each developing process was run by a cine-type automatic developing machine (until the cumulative replenishment amount of the color developing solution became three times the tank capacity).

After the processing, the gradation degrees γ _A of cyan, magenta, and yellow after development processing A-2 was carried out for each sample
(C), γ _A (M), γ _A (Y), and development treatment B-30
Γ _B (C), γ _B (M), γ after performing
_{Calculate B} (Y), γ _B (C) / γ _A (C), γ _B (M)
The values of / γ _A (M) and γ _B (Y) / γ _A (Y) were calculated.

Next, in the sample after development processing B-30, the signal was read at the same speed as when the signal was recorded by the above head, and the ratio of the number of bits in which an error occurred to the number of input bits. (Error rate) was calculated. If this error rate is 0.1% or more, it is NG, and it is 0.05% or less, preferably 0.01% or less. If it is lowered in this way, practical problems will disappear.

Further, the silver halide solvents shown in Table 9 were added to the color developer, tank solution and replenisher of Development Treatment B-30 in the same manner except that 0.8 and 1.0 mmol / liter were added, respectively. Development processes B-31 and B-32 are carried out to obtain γ _B (C) / γ _A (C) and γ _B (M) / γ.
_A (M), γ _B (Y) / γ _A (Y), and the error rate were obtained. Table 9 shows the obtained results.

[0237]

[Table 9]

From the results shown in Table 9, the present invention was able to obtain an image with good color reproducibility even during running processing.
It has also been found that the present invention significantly reduces magnetic recording read errors.

(Processing Step and Liquid Composition of Development Processing A-2) (Processing Step) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C. 23 ml 17 liters Bleach 50 seconds 38.0 ° C. 5 ml 5 liters Bleaching fixing 50 seconds 38.0 ° C-5 liters fixing 50 seconds 38.0 ° C 16 ml 5 liters Water washing 30 seconds 38.0 ° C 34 ml 3.5 liters Stability (1) 20 seconds 38.0 ° C-3 liters Stability (2) 20 seconds 38.0 ° C 20 ml 3 liter Dry 1 min 30 sec 60 ° C * Replenishment amount per 35 mm width of photosensitive material 1.1 m (equivalent to 24 Ex. 1) Stabilizer is countercurrent method from (2) to (1) The overflow of washing water was introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank. I was allowed to flow in. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the bleach-fixing step, the amount of the bleach-fixing liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm width of the photosensitive material. 2.5 ml, 2.0 ml, 1 m, respectively.
0 ml and 2.0 ml. Also,
The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.1 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Disodium N, N-bis (sulfonate ethyl) hydroxylamine 8.0 10.7 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.8 6.5 Water was added to 1.0 liter 1.0 Liter pH (prepared with potassium hydroxide and sulfuric acid) 10.05 10.15

(Bleaching solution) Tank solution (g) Replenishing solution (g) 1,3-Diaminopropaneferric acid ammonium ferric acid monohydrate 130 195 Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 50 75 Acetic acid 40 60 Water 1.0 liter 1.0 liter pH [prepared with ammonia water] 4.4 4.4

(Bleaching Fixing Tank Solution) A 15:85 (volume ratio) mixture of the above bleaching tank solution and the following fixing tank solution. (PH 7.0)

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml 840 ml Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water 1.0 liter 1.0 liter pH [prepared with aqueous ammonia and acetic acid] 7.4 7.45

(Washing Water) The same composition as in Example 1 of the present application was used.

(Stabilizing Solution) The tank solution and the replenishing solution have the same formulation (unit: g) sodium p-toluenesulfinate 0.03 1,2-benzisothiazolin-3-one 0.05 polyoxyethylene-p-monononylphenyl ether (average polymerization 10) 0.2 Succinic acid 1.0 Sodium chlorinated isocyanurate 0.02 Add water to 1000 ml pH (with ammonia / sulfuric acid) 6.5

(Processing Process and Liquid Composition of Development Process B-30) (Processing Process) Process Processing Time Processing Temperature Replenishment Volume * Tank Capacity Color Development 60 seconds 45.0 ° C 260 ml 5 liter Bleach 20 seconds 45.0 ° C 130 ml 3 liter Settling 40 seconds 45.0 ℃ 100 ml 5 liters Water wash (1) 15 seconds 45.0 ℃ -1 liter Water wash (2) 15 seconds 45.0 ℃ -1 liter Water wash (3) 15 seconds 45.0 ℃ 400 ml 1 liter Dry 45 80 ℃ * Replenishment amount per 1 m ² of light-sensitive material (4 tank counter-current multi-stage cascade for washing from (3) to fixing)

The composition of the processing liquid is shown below. (Color developer) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 4.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 3.3 Sodium sulfite 3.9 6.5 Potassium carbonate 37.5 39.0 Potassium bromide 2.0-Potassium iodide 1.3 mg-Disodium N, N-bis (sulfonate ethyl) hydroxylamine 12.0 17.0 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.5 15.0 Water was added to 1.0 liter 1.0 Liter pH (prepared with potassium hydroxide and sulfuric acid) 10.05 10.25

(Bleaching solution) Tank solution (mol) Replenishing solution (mol) 1,3-diaminopropanetetraacetic acid ferric salt ammonium monohydrate 0.33 0.50 ferric nitrate nonahydrate 0.30 4.5 ammonium bromide 0.80 1.20 Ammonium nitrate 0.20 0.30 Acetic acid 0.67 1.0 Add water 1.0 liter 1.0 liter pH [Prepared with ammonia water] 4.5 4.0

(Fixer) Common to tank and replenisher (g) Ammonium sulfite 28 Ammonium thiosulfate aqueous solution (700 g / liter) 280 ml Imidazole 15 Ethylenediaminetetraacetic acid 15 1.0 liter pH with water (prepared with ammonia water and acetic acid) 5.8

(Washing Water) The same composition as the washing water described in Example 1 of the present application was used.

(Stabilizer) The stabilizer used had the same composition as the stabilizer described in A-2.

Example 8 The color developing agent 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate of Example 1 was added to D-3, D-7 and D-10. When the same molar amount was changed and the same evaluation as in Example 1 was performed, the effect of the present invention was confirmed as in Example 1.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 7/407 G03C 7/407 7/413 7/413

Claims (8)

[Claims] 1. At least one layer each on a support,
In a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, the following two types of development processing A'and development processing having different color development times are carried out. A silver halide color photographic light-sensitive material characterized in that, when B ′ is carried out, the gradations of yellow, magenta and cyan obtained by the two types of development processes satisfy the following conditional expressions. 0.8 ≦ γ _B ′ (C) / γ _A ′ (C) ≦ 1.2 0.8 ≦ γ _B ′ (M) / γ _A ′ (M) ≦ 1.2 0.8 ≦ γ _B ′ ( Y) / γ _A ′ (Y) ≦ 1.2 (γ _A ′ (Y), γ _A ′ (M) and γ _A ′ (C) are yellow, magenta, and
Represents the gradient of cyan, γ _B ′ (Y), γ _B ′
(M) and γ _B ′ (C) represent gradations of yellow, magenta, and cyan, respectively, when development processing B ′ is performed. (Development treatment A ′) Color development time is 3 minutes to 3 minutes 15 seconds, the temperature of the color developing solution is 37 to 39 ° C., and 2-methyl-4- [N-ethyl-N is used as a color developing agent. -(Β-
A development process characterized in that the color development process is carried out using a color development solution containing 15 to 20 mmol / L of hydroxyethyl) amino] aniline and containing substantially no silver halide solvent. (Development processing B ′) Color development time is 50 to 70 seconds,
The temperature of the color developing solution is 43 to 47 ° C., the color developing solution contains 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline in an amount of 35 to 40 mmol / liter, and The following silver halide solvent (I-
A development process characterized in that color development is performed using a color developer containing 1) of 1 to 3 mmol / liter. Embedded image 2. A halide according to claim 1, wherein the red-sensitive silver halide emulsion layer contains a silver halide emulsion having an average silver iodide content of 0.1 to 10 mol%. Silver color photographic light-sensitive material. 3. The silver halide color photographic light-sensitive material according to claim 2, wherein the average silver iodide content of the silver halide emulsion is 0.5 to 5.0 mol%. 4. The silver halide color photographic light-sensitive material according to claim 2, wherein the silver halide emulsion has an average aspect ratio of 5 to 10. 5. The red-sensitive silver halide emulsion layer is composed of three layers of high-sensitivity, medium-sensitivity and low-sensitivity red-sensitive silver halide emulsion layers, and the middle-sensitivity red-sensitive silver halide emulsion layer is said silver halide emulsion. 2 to 4 are contained.
The silver halide color photographic light-sensitive material according to any one of 1. 6. The silver halide color according to claim 1, further comprising a transparent magnetic recording layer on the opposite side of the silver halide emulsion layer with the support interposed therebetween. Photographic material. 7. A silver halide color photographic light-sensitive material according to any one of claims 1 to 6 is subjected to the following development processing A or development processing B to form a color image. And a color image forming method. (Development Processing A) Color development time is 150 to 200 seconds, color developing solution temperature is 37 to 40 ° C., color developing agent concentration is 15 to 20 mmol / liter, and a silver halide solvent is used. A development process characterized by using a color developer which does not substantially contain. (Development Treatment B) Color development time is 25 to 90 seconds, the temperature of the color developing solution is 40 to 60 ° C., the concentration of the color developing agent is 25 to 80 mmol / liter, and the following general formula (I ) A developing process characterized by using a color developing solution containing at least one silver halide solvent represented by General formula (I) R1, R2, R3, R4 and R5 are each independently a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, a substituted or unsubstituted thioureido group, a substituted or unsubstituted amino group, a hydroxy group, an alkoxy group. Represents a sulfonyl group or an acyl group. However, R1, R2, R3, R4 and R5 are not a hydrogen atom, an unsubstituted thioureido group, an unsubstituted amino group and a hydroxy group at the same time. Also, R1 and R
3, R2 and R4, R3 and R5, R4 and R5 may form a ring. However, at least one of R1, R2, R3, R4 and R5 is
SO ₃ M, -CO ₂ Y, amino group, aliphatic hydrocarbon group substituted with at least one of hydroxy group, aryl group, heterocyclic group, substituted thioureido group, substituted amino group, alkoxy group, sulfonyl group or acyl Represents a group. M and Y represent a hydrogen atom, ammonium, an alkali metal, or an alkaline earth metal. 8. The color image forming method according to claim 7, wherein the addition amount of the silver halide solvent in the development treatment B is 0.3 to 5.0 mmol per liter of the color developing solution. .