JPH06242531A - Silver halide color photographic sensitive material and production thereof - Google Patents

Abstract

PURPOSE:To provide a color photographic sensitive material improved in sharpness, graininess and sensitizing processing aptitude and having improved production stability. CONSTITUTION:In the color photographic 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 on a supporting body, at least one of layers contains >=2 kinds of platelike silver halide emulsions different in average particle diameter or contains the platelike silver halide emulsion and a regular emulsion in at least one of layers and further a compound expressed by a formula. In the formula, R1 is hydrogen atom, aliphatic group, aromatic group, heterocyclic group, amino group, hydroxy group, alkoxy group, alkyl thio group, carbamoyl group, halogen atom, cyano group, carboxyl group or alkoxycarbonyl group, each of R2 and R3 is hydrogen atom, aliphatic group, aromatic group or heterocyclic group and (n) is an integer 3-5.

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, and more particularly to a color photographic light-sensitive material excellent in sharpness, graininess and sensitizing processability and improved in manufacturing stability. is there.

[0002]

2. Description of the Related Art In recent years, the demands on the performance of color photographic light-sensitive materials have become more and more stringent, and it has been desired to improve multi-faceted and comprehensive photographic characteristics such as high sharpness, smooth graininess, and vivid and faithful color reproduction. There is. In particular, in the case of reversal color photographic light-sensitive materials for photographing, so-called sensitization processing is performed to extend the processing time of the first development and sensitization is performed, and it is strongly required to improve gradation and color balance in the sensitization processing. .

Many studies have been conducted on means for improving sharpness and graininess, for example, JP-A-62-18.
No. 556, it is possible to improve the sharpness and graininess by using monodisperse tabular silver halide.
No. 3-151618 discloses a method for preparing the above monodisperse tabular silver halide emulsion. JP-A-2-2560
In No. 43, the sharpness and graininess can be improved by monodispersing even the intergranular iodide distribution of tabular silver halide grains, and EP-0514743A1 specifies the tabularity and provides a high monodispersity. It is disclosed that the sharpness can be improved by using tabular silver halide grains having a certain degree.

Although the monodisperse tabular silver halide emulsion is effective for improving the sharpness and graininess, it has a problem that the gradation becomes hard and a rich contrast cannot be realized especially in the sensitized development processing. It was As a method of controlling the gradation while utilizing the advantages of a monodisperse tabular silver halide emulsion, a method of mixing tabular silver halide emulsions having different sizes can be considered. For example, JP-A-1-27174 can be used.
No. 2 is disclosed. Further, a method of mixing a tabular silver halide emulsion and a regular grain emulsion is also effective in controlling gradation and is disclosed in, for example, JP-A-3-121444.

However, when tabular silver halide grain emulsions are mixed with each other, or when tabular silver halide grain emulsions and regular grain emulsions are mixed, production stability is improved, especially when the emulsions are dissolved before coating. There is a problem that fogging increases or sensitivity decreases with the passage of time, which is a serious obstacle to the production of stable and excellent quality products.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a color photographic light-sensitive material having improved sharpness, graininess and suitability for sensitization and improved production stability, and a method for producing the same.

[0007]

The objects of the present invention are: 1) having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer on a support. A color photographic light-sensitive material, characterized in that at least one layer contains two or more kinds of tabular silver halide emulsions having different sizes and a compound represented by the general formula (I). 2) In a color photographic light-sensitive material having a red light-sensitive silver halide emulsion layer, a green light-sensitive silver halide emulsion layer and a blue light-sensitive silver halide emulsion layer on a support, at least one tabular halogenated material A silver halide color photographic light-sensitive material containing a silver emulsion and a regular emulsion and containing a compound represented by formula (I), 3) at least one layer in size The method of manufacturing a silver halide color photographic material containing a different tabular silver halide emulsion of two or more, the compounds of general formula (I) 50
4. A method for producing a silver halide color photographic light-sensitive material, which comprises adding to each tabular silver halide emulsion at a temperature of ℃ or more, and then mixing the two or more tabular silver halide emulsions. ) In a method for producing a silver halide color photographic light-sensitive material containing a tabular silver halide emulsion and a regular emulsion in at least one layer, a compound of the general formula (I) is added at a temperature of 50 ° C. or higher to a tabular silver halide emulsion and It is achieved by a method for producing a silver halide color photographic light-sensitive material, which comprises adding to a regular emulsion and then mixing the silver halide emulsion. General formula (I)

[0008]

[Chemical 5] In the formula, R ₁ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, a hydroxy group, an alkoxy group, an alkylthio group, a carbamoyl group, a halogen atom, a cyano group, a carboxy group or an alkoxycarbonyl group. , R
₂ and R ₃ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and n represents an integer of 3-5.

The photosensitive material of the present invention will be described in more detail below. The tabular silver halide grains of the present invention have a tabularity of 5 or more as defined by the formula (II). (Equation-II) (Flatness) = (Grain diameter) / (Grain thickness) ² Grain thickness is the distance (μm) between two substantially parallel planes constituting the tabular grain, and the grain diameter is It is represented by the diameter (μm) of a circle having an area equal to the projected area. Flatness is 8
The above is preferable, and 16 or more is more preferable. In the tabular silver halide grains of the present invention, 95% or more of all grains preferably have a tabularity of 5 or more, and 97% or more of grains preferably have a tabularity of 5 or more.
It is most desirable that 9% or more of the grains have a tabularity of 5 or more. The tabular silver halide grains of the present invention have an aspect ratio defined by the grain diameter / grain thickness ratio of 2 or more. The aspect ratio is preferably 2 or more and 50 or less, and more preferably 3 or more and 30 or less.

The tabular silver halide grain of the present invention is preferably a monodisperse emulsion having a relative variation coefficient of grain diameter distribution of 20% or less. The relative coefficient of variation of the particle diameter distribution is defined as the standard deviation of the particle diameter divided by the average value multiplied by 100. In the tabular silver halide grains of the present invention, the relative variation coefficient of grain diameter distribution is preferably 16% or less, and most preferably 10% or less. The tabular silver halide grain of the present invention is preferably a multi-structure grain having phases having different halogen compositions inside the grain. In particular, it is preferable to have a phase having a high iodine content inside the particles. Further, the halogen composition distribution between grains is preferably uniform, and the relative standard deviation of the iodide content of each grain is preferably 20% or less, more preferably 15% or less.

The monodisperse tabular emulsion can be prepared, for example, by the method described in US Pat. No. 4,797,354. Further US Pat. No. 514777
No. 1, No. 5147772, and No. 514777.
No. 3 shows that a good monodisperse emulsion can be obtained by using a polyethylene oxide block copolymer, and in that method, for example, Pluronic ^™ (P
LURONIC ^™ ) -31R1 compound (PL
-1) is used. This compound is 100% by weight or less, preferably 20% by weight, with respect to the amount of silver used for tabular nucleus formation in the process of forming tabular grains of silver halide.
Used below. Further, it is preferable to add the above amount before the start of grain formation, and it may be added additionally in the process of growing tabular grains. It may also be added only during the grain formation process. Further, as shown below, various polyethylene oxide block copolymers can be used to prepare an emulsion composed of tabular grains having a similarly low dispersity.

In the photographic light-sensitive material of the present invention, particularly useful compounds for preparing a silver halide emulsion are the hydrophobic polyalkylene oxide represented by the following general formula (II) and the following general formula (III). Is a polymer having a hydrophilic polyalkylene oxide block polymer component represented by General formula (II)

[0013]

[Chemical 6] General formula (III)

[0014]

[Chemical 7] In the formula, R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (for example, methyl, chloromethyl, ethyl, n-butyl),
It represents an aryl group having 6 to 10 carbon atoms (for example, phenyl or naphthyl), and n represents an integer of 1 to 10. Where n
When = 1, R ¹ does not become a hydrogen atom. R ² represents a hydrogen atom or a lower alkyl group having 4 or less carbon atoms (eg, hydroxymethyl, carboxymethyl) substituted with a hydrophilic group (eg, hydroxy group, carboxyl group).

X and y represent the number of repetitions of each unit (number average degree of polymerization). For x and y, depending on the structure of the polymer,
Although the preferable range is different, x is 2 to 1000,
Preferably 3 to 500, y is 1 to 100
It is 0, preferably 2 to 400. The ratio of the components of the general formulas (II) and (III) in the block polymer may vary depending on the hydrophilicity / hydrophobicity of each unit and the type of emulsion prepared, but roughly speaking, the weight ratio is 4: 4.
It is within the range of 96 to 96: 4. Particularly preferred among the hydrophobic polyalkylene oxides of the general formula (II) are polypropylene oxides (R ¹ = methyl group, n = 1), and among the hydrophilic polyalkylene oxides of the general formula (III) are preferred. Polyethylene oxide (R ² = hydrogen atom), polyglycerol (R ² = CH ₂ OH), and particularly preferred is polyethylene oxide.

With respect to the polymer having the above block copolymer component in the molecule, a compound having polypropylene oxide-polyethylene oxide as a typical component as a block copolymer component will be described in more detail below. Representative examples of the polymer used in the present invention can be represented by the following general formulas (IV) to (XI). General formula (IV)

[0017]

[Chemical 8] General formula (V)

[0018]

[Chemical 9] General formula (VI)

[0019]

[Chemical 10] General formula (VII)

[0020]

[Chemical 11] General formula (VIII)

[0021]

[Chemical 12] General formula (IX)

[0022]

[Chemical 13] General formula (X)

[0023]

[Chemical 14] General formula (XI)

[0024]

[Chemical 15] Among the above general formulas (IV) to (XI), x, x ', x'', x
“″, Y, y ′, y ″, y ′ ″ represent the number of repetitions of each unit, and the preferred range is x in the general formulas (II) and (III),
Same as y. R ³ represents a monovalent group, specifically a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group, and preferably a substituted or unsubstituted lower alkyl group (having 6 or less carbon atoms). Specific examples of R ³ include methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, chloromethyl group, methoxycarbonylmethyl group, N-methyl N-ethylaminoethyl group,
An N, N-diethylaminoethyl group can be mentioned.

L represents a trivalent or tetravalent linking group.
Specific examples of L (“chemical formula 16” and “chemical formula 17”) are shown below, but the invention is not limited thereto.

[0026]

[Chemical 16]

[0027]

[Chemical 17] Specific examples (Tables 1 and 2) of polymers having a block polymer component in the molecule used in the present invention are shown below.
The present invention is not limited to these.

[0028]

[Table 1]

[0029]

[Table 2] Specific examples of the above polymers used in the present invention,
For general description and specific examples of preparation of silver halide emulsions using this type of polymer, see, for example, European Patent Publication Nos. 513722, 513723, 513724,
513725, 513742, 513743, 5180
66 can be mentioned.

In the first and third inventions, at least one layer contains two or more tabular silver halide emulsions having different average grain sizes. The grain diameter of the tabular silver halide emulsion is preferably 0.2 μm or more and 5.0 μm or less, more preferably 0.3 μm or more and 3.0 μm or less. The difference in average grain size between two or more tabular silver halide emulsions to be mixed is 0.1 μm or more and 3.0 μm or less in terms of grain diameter. The difference in average grain size between two or more types of tabular silver halide emulsions to be mixed is preferably 0.2 μm or more and 2.0 μm or less in terms of grain diameter.

When two or more tabular silver halide emulsions having different average grain sizes are mixed, the average grain size can be determined so that two or more maximum values appear in the grain diameter distribution curve of the mixed emulsion. preferable. At least one of tabular silver halide emulsions having different average grain sizes is preferably a monodisperse emulsion having a variation coefficient of grain diameter of 20 or less, more preferably 16% or less, further preferably 10% or less. More preferably, all the emulsions to be mixed have the above-mentioned monodispersity.

In the second and fourth inventions, at least one layer contains a tabular silver halide emulsion and a regular emulsion. A regular emulsion is an emulsion composed of normal crystal grains having no twin plane. There is no particular limitation on the particle shape, but for example, cubic, tetradecahedral, octahedral, and spherical particles are common. Cubes or tetradecahedrons having a (100) face ratio of 60% or more or grains having rounded corners and / or sides are particularly desirable.

The regular grains of the present invention are preferably monodisperse emulsions having a relative variation coefficient of grain diameter distribution of 20% or less, more preferably 16% or less, and 1
It is preferably 0% or less. The regular particles of the present invention are preferably multi-structured particles having phases having different halogen compositions inside the particles. In particular, it is preferable to have a phase having a high iodine content inside the particles. Further, the halogen composition distribution between grains is preferably uniform, and the relative standard deviation of the iodide content of each grain is preferably 20% or less, more preferably 15% or less.

In the first invention, at least one layer of the compound of the present invention contains two or more tabular silver halide emulsions having different average grain sizes and a compound represented by the general formula (I). The layer containing the compound represented by formula (I) is preferably an emulsion layer, and more preferably an emulsion layer containing two or more tabular silver halide emulsions having different average grain sizes. Further, it may be contained in the non-photosensitive intermediate layer, but in that case, it is preferably added to both the emulsion layer and the intermediate layer.

In the second invention, the compound of the present invention contains a tabular silver halide emulsion and a regular emulsion in at least one layer and a compound represented by the general formula (I). The layer containing the compound represented by formula (I) is preferably an emulsion layer, and more preferably an emulsion layer containing a tabular silver halide emulsion and a regular emulsion. Further, it may be contained in the non-photosensitive intermediate layer, but in that case, it is preferably added to both the emulsion layer and the intermediate layer. The light-sensitive material of the present invention contains a compound represented by the general formula (I), and is an azaindene compound which has been widely used as a stabilizer, for example, compound F.
You may use together with -1.

In the first and second inventions, the compound represented by the general formula (I) may be added to individual emulsions, at the time of mixing emulsions, or at the time of mixing with couplers and other additives, or It may be added to the finished emulsion after mixing,
Addition to individual emulsions is desirable. When they are added to individual emulsions, it is desirable that they be further added during the emulsion mixing, during the mixing with the coupler or other additives, or after the mixing. An azaindene compound other than the general formula (I), for example, F-1 may be additionally added.

In the third and fourth inventions, the compound represented by the general formula (I) is added to each emulsion.
Further, it is desirable to add further during mixing of the emulsion, during mixing with the coupler or other additives, or after mixing. An azaindene compound other than the general formula (I), for example, F-1 may be additionally added.

Next, the general formula (I) will be described in detail.

In the general formula (I), the aliphatic group represented by R ₁ is preferably an aliphatic group having 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, An alkenyl group, an alkynyl group, and an aralkyl group. Examples of the alkyl group, alkenyl group, alkynyl group and aralkyl group include methyl group, ethyl group, isopropyl group, t-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group and cyclopentyl group. , Cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group, propargyl group, 3-pentynyl group, and benzyl group.

In the general formula (I), the aromatic group represented by R ₁ preferably has 6 to 30 carbon atoms,
Particularly, it is a monocyclic or condensed-ring aryl group having 6 to 20 carbon atoms, for example, a phenyl group or a naphthyl group. In formula (I), the heterocyclic group represented by R ₁ is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. 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, for example, a pyridyl group, an imidazolyl group, a quinolyl group, a benzimidazolyl group, a pyrimidyl 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 amino group represented by R ₁ may be substituted. Examples of the substituent include an alkyl group (eg, methyl, ethyl, butyl) and an acyl group (eg, acetyl, methanesulfonyl).
Specific examples of the substituted amino group include a dimethylamino group,
They are a diethylamino group, a butylamino group, and an acetylamino group. In formula (I), specific examples of the alkoxy group represented by R ₁ include a methoxy group, an ethoxy group, a butoxy group, and a heptadecyloxy group.

In the general formula (I), specific examples of the alkylthio group represented by R ₁ include, for example, a methylthio group,
Examples thereof include ethylthio group and butylthio group. In the general formula (I), the carbamoyl group represented by R ₁ can have one or two alkyl or aryl groups having 1 to 20 carbon atoms as a substituent. Specific examples of the substituted carbamoyl group include a methylcarbamoyl group, a dimethylcarbamoyl group, an ethylcarbamoyl group and a phenylcarbamoyl group. In the general formula (I), R
Specific examples of the alkoxycarbonyl group represented by ₁ are a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. In formula (I), specific examples of the halogen atom represented by R ₁ are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (I), R ₂ and R ₃ may be the same or different. The aliphatic group, aromatic group or heterocyclic group represented by R ₂ and R ₃ has the same meaning as R ₁ . In the general formula (I), preferably R ₁ represents a hydrogen atom, an alkyl group, an aryl group or an alkylthio group, R ₂ and R ₃ represent a hydrogen atom, and n is 3
Or represents 4. More preferably in the general formula (I), R ₁ represents a hydrogen atom, an alkyl group or an alkylthio group, R ₂ and R ₃ represent a hydrogen atom, and n is 3
Or represents 4.

Specific examples of the compound of the present invention are shown in the following "Chemical formula 18" to "Chemical formula 20", but the compound of the present invention is not limited thereto.

[0045]

[Chemical 18]

[0046]

[Chemical 19]

[0047]

[Chemical 20] The compound represented by the general formula (I) is already known in the following literatures, such as Bulow and Haas.
Berichte, 42, 4638 (1907).
Vol. 43 and p. 375 (1910), Allen (Al
Len) et al. Org. Chem. , 24 volumes 79
6 (1959), Bull. By DeCat and Dormael. Soc. Ch
im. Belg. 60:69 (1951) and Cook et al., Rec. Trav. Che
m. , 69, page 343 (1950) and the like.

Next, the difference between the known case of using the compound of the general formula (I) and the present invention will be explained.

Conventionally, tetrazaindene compounds have been widely used as fog inhibitors and stabilizers. For example, Japanese Examined Patent Publication No. 32-9432, U.S. Pat. No. 2716062,
Nos. 2,444,607 and 2,566,659 and JP-A-3-13934 describe that a tetrazaindene compound is effective as a fog inhibitor for a silver halide light-sensitive material. In addition, Japanese Examined Japanese Patent Publication No.
The publication discloses that the combined use of a resorcinol compound or a hydroxynaphthalene compound with a tetrazaindene compound enhances the effects of stabilizing photographic performance and suppressing fogging.

However, among the tetrazaindene compounds in these known examples, the compound represented by the general formula (I) is particularly effective for the production stability of a light-sensitive material using a tabular silver halide emulsion. Not disclosed.
In order to improve the change with time in the state where the mixed emulsion is dissolved, particularly when tabular silver halide emulsions having different average grain sizes are mixed and used, or when tabular silver halide emulsion and regular emulsion are mixed and used. It was an unexpected finding that the compound of the general formula (I) is particularly effective, which cannot be easily analogized from the conventional knowledge. Further, the above-mentioned known examples do not disclose a manufacturing method in which the compound of the general formula (I) is added at a certain temperature or more before mixing two or more kinds of emulsions. When the compound represented by formula (I) is added to the emulsion, it can be added in the form of an aqueous solution.

In the third and fourth inventions, the temperature of the emulsion when the compound represented by the general formula (I) is added is 50 ° C. or higher, particularly preferably 58 ° C. or higher. The time of addition may be any time during the preparation of the emulsion, but it is preferably after the chemical sensitization or during the chemical sensitization. When a sensitizing dye is added to the emulsion, it is preferable to add the compound represented by formula (I) and then add the sensitizing dye. The addition amount of the compound represented by formula (I) is 1 × 10 ⁻⁵ mol or more and 2 × 1 per 1 mol of silver halide in the emulsion.
It is preferably 0 ^-3 mol or less, more preferably 1 x 10 ^-4 mol or more and 1 x 10 ^-2 mol or less.

In the first and third inventions, when the compound represented by the general formula (I) is added to the two types of tabular silver halide emulsions, the addition amount is 1 mol of silver halide. It is desirable to calculate according to the following formula. (X _s × R _s / R ₁ ) × 0.4 <X ₁ <(X _s × R _s /
R ₁ ) × 1.1 where X _s is the addition amount of the compound represented by the general formula (I) to the emulsion having a small average grain size, and X ₁ is the general formula (I) to the emulsion having a large average grain size. The addition amount of the compound represented, R _s represents the grain diameter of the emulsion on the small average grain size side, and R ₁ represents the grain diameter of the emulsion on the large average grain size side.

The amount of the compound of the formula (I) added to each emulsion is (X _s × R _s / R ₁ ) × 0.6 <X ₁ <(X _s × R _s /
It is more preferable that R ₁ ) × 0.9. When three or more tabular silver halide emulsions are mixed, it is preferable that the amounts of the compounds of formula (I) added to the respective emulsion grains satisfy the above relationships.

In the second and fourth inventions, the addition amount of the compound represented by the general formula (I) to the tabular silver halide emulsion and the regular emulsion is such that the addition amount per surface area of each emulsion grain is the regular emulsion. It is desirable to determine that the number is larger than that of the tabular emulsion. The amount of the compound of the formula (I) added to the tabular silver halide emulsion and the regular emulsion is 1.5 in the regular emulsion as compared with the tabular emulsion in the addition amount per surface area of each emulsion grain.
It is more desirable to determine so that it is more than twice, and more preferably more than twice.

The light-sensitive material of the present invention has a red light-sensitive silver halide emulsion layer, a green light-sensitive silver halide emulsion layer and a blue light-sensitive silver halide emulsion layer on a support. It is preferable that each sensitivity color layer is composed of three or more sub-layers having different sensitivities. Preferred specific examples of the layer structure of the light-sensitive material of the present invention are shown below, but the present invention is not limited thereto. That is, from the support side, 1st layer: antihalation layer 2nd layer: intermediate layer 3rd layer: intermediate layer (containing colloidal silver or fogged fine grain silver halide) 4th layer: low-sensitivity red photosensitive emulsion layer 5th layer : Middle speed red photosensitive emulsion layer 6th layer: High sensitivity red photosensitive emulsion layer 7th layer: Intermediate layer 8th layer: Intermediate layer (containing colloidal silver or fogged fine grain silver halide) 9th layer: Low sensitivity green Photosensitive emulsion layer 10th layer: Medium sensitivity green photosensitive emulsion layer 11th layer: High sensitivity green photosensitive emulsion layer 12th layer: Intermediate layer 13th layer: Yellow filter layer 14th layer: Low sensitivity blue photosensitive emulsion layer Fifteenth layer: Medium sensitivity blue photosensitive emulsion layer Sixteenth layer: High sensitivity blue photosensitive emulsion layer Seventeenth layer: First protective layer Eighteenth layer: Second protective layer Nineteenth layer: Third protective layer Same color sensitivity Of the silver coating amount of each layer when it is composed of 3 or more layers with different sensitivity In this case, when the total amount of silver in the color-sensitive layer is 100%, the high-sensitivity layer is preferably 15 to 45%, the medium-sensitivity layer is 20 to 50%, and the low-sensitivity layer is 20 to 50%. . It is desirable that the coating amount of silver in the high-sensitivity layer be smaller than the coating amount of silver in the middle and low-sensitivity layers.

In the above-mentioned constitution in which each color-sensitive layer is composed of three or more sub-layers having different sensitivities, the layer in which the tabular silver halide emulsion and the regular emulsion are mixed is used for each medium sensitivity and / or low sensitivity. It is preferably a sensitivity emulsion layer. The layer to be used by mixing the tabular silver halide emulsion is not particularly limited.

The average silver iodide content of the silver halide emulsion contained in the red light-sensitive silver halide emulsion layer is higher than the average silver iodide content of the silver halide emulsion contained in the green light-sensitive silver halide emulsion layer. High is preferred. When each color-sensitive layer is composed of a plurality of sublayers having different sensitivities, the average silver iodide content of each photosensitive emulsion layer is the average silver iodide content of each sublayer having the color sensitivity. It is an average value obtained by weighted averaging the silver coating amount of the layer separation.

When each color-sensitive layer is composed of a plurality of sub-layers having different sensitivities, it is desirable that the sub-layers with lower sensitivity have a higher silver iodide content. Especially the red-sensitive layer has different sensitivity.
In the case of two separate layers, the silver iodide content of the most sensitive red-sensitive sublayer is 1.0 mol% to 5 mol more than the silver iodide content of the least sensitive red-sensitive sublayer. % Is particularly preferred.

The light-sensitive material of the present invention is not particularly limited in the number and order of layers of the silver halide emulsion layer and the non-light-sensitive layer.
In general, the unit photosensitive layers are arranged in order from the support side in the order of red color sensitive layer, green color sensitive layer, and blue color sensitive layer. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that photosensitive layers having different color sensitivities are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes, for example, JP-A-61-43.
748, 59-113438, 59-1134
No. 40, No. 61-20037, No. 61-20038, the coupler and the DIR compound may be contained, and the color mixture inhibitor may be contained as it is usually used.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448,
BL, GL, described in the specification of 63-89850.
It is preferable that the RL has a multilayer effect donor layer (CL) having a spectral sensitivity distribution different from that of the main photosensitive layer and is disposed 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 light-sensitive material.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pages 22-23,
"I. Emulsion preparation
ion and types) ”and ibid. 187.
16 (November 1979), page 648, ibid. 307
105 (November 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chemieet P.
hisque Photographaque Pa
ul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, 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 Ph
otographic Emulsion, Focal
It can be prepared using the method described in Press, 1964).

Monodisperse emulsions are described, for example, in US Pat.
The method described in 4,628, 3,655,394 and British Patent 1,413,748 can be used. The tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photographic Science), for example.
14th Engineering,) Volume 14,
248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,43
It can be easily prepared by the method described in 3,048, 4,439,520 and US Pat. No. 2,112,157.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, No. 17643. 18716 and the same No. No. 307105, and the relevant parts are summarized in the table below. U.S. Pat. No. 4,082,553
No. 4,626,498, JP-A-59-2148.
The fogged silver halide grains and colloidal silver described in No. 52 can be preferably used for the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,4.
98 and JP-A-59-214852.

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. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the average grain size of these fogged silver halide grains, but the average grain size of 0.01 to
0.75 μm, particularly 0.05 to 0.6 μm is preferable.
The grain shape is not particularly limited and may be regular grains or a polydisperse emulsion, but monodisperse grains are preferable.

A non-photosensitive unfogged fine grain silver halide emulsion can also be used in the present invention. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment. The unfogged 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. Further, the average grain size (average value of circle equivalent diameter of projected area) is preferably from 0.01 to 0.5 μm, more preferably from 0.02 to 0.2 μm, in the same manner as in the case of ordinary photosensitive silver halide. Can be prepared. in this case,
The surface of the silver halide grain does not need to be optically sensitized nor spectrally sensitized. However, before adding this to the coating solution, triazole-based,
It is preferable to add a known stabilizer such as an adenindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

The amount of silver coated on the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable.

Known photographic additives that can be used in the present invention are described in the above-mentioned three Research Disclosures, and the related portions are shown in the following table.

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column to pages 866 to 868, supersensitizer, page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Antifoggant, pages 24 to 25, page 649, right column, pages 868 to 870, stabilizer 6. Light absorber, pages 25 to 26, page 649, right column to page 873, filter dye, page 650, left column, ultraviolet absorber 7. Anti-staining agent Page 25 Right column Page 650 Left column Page 872 Right column 8. Dye image stabilizer page 25 page 650 page left column page 872 9. Hardener 26 pages 651 left column 874 to 875 10. Binder pages 26 pages 651 left column 873 to 874 pages 11. Plasticizers and lubricants page 27 650 right columns 876 pages 12. Coating aids, 26 to 27 Page 650 page right column 875 to 876 surface active agent 13. static, page 27 page 650 right column 876 to 877 page inhibitor 14. matting agent page 878 to 879 To prevent deterioration of photographic performance due to formaldehyde gas U.S. Pat. Nos. 4,411,987 and 4,
It is preferable to add to the light-sensitive material a compound capable of immobilizing by reacting with formaldehyde described in No. 435,503. The light-sensitive material of the present invention can be incorporated into US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Application Laid-Open No. 1-1060.
It is preferable to include a compound described in No. 52, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing. International Publication WO88
No. 04794, Dyes or EP No. 317,308A dispersed by the method described in JP-A-1-502912.
No. 4,420,555, Japanese Patent Laid-Open No. 1-25
It is preferable to incorporate the dye described in No. 9358.
Various color couplers can be used in the light-sensitive material of the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-CG, and the same No. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in EP 249,473A are preferred.

As the magenta coupler, 5-pyrazolone type compounds and pyrazoloazole type compounds are preferable, for example, US Pat. Nos. 4,310,619 and 4,351,89.
7, EP 73,636, US Pat. No. 3,06
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, 61-72238 and 60.
-35730, 55-118034, 60-1
Those described in US Pat. No. 8,5951, US Pat. No. 4,500,630, US Pat. No. 4,540,654, US Pat. No. 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers. For example, US Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4 are cited. , 296,200,
No. 2,369,929, No. 2,801,171
No. 2, No. 2,772,162, No. 2,895,82
No. 6, No. 3,772,002, No. 3,758,3
08, 4,334,011, 4,327,
No. 173, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A,
US Pat. Nos. 3,446,622 and 4,333,9
No. 99, No. 4,775, 616, No. 4,451,
No. 559, No. 4,427, 767, No. 4,69
No. 0,889, No. 4,254,212, No. 4,2
Those described in 96,199 and JP-A No. 61-42658 are preferable. Furthermore, JP-A-64-553 and JP-A-64-553
-554, 64-555 and 64-556, and pyrazoloazole couplers described in U.S. Pat.
The imidazole couplers described in No. 8,672 can also be used.

Typical examples of polymerized dye-forming couplers are, for example, US Pat. Nos. 3,451,820, 4,080,211, 4,367,282, and 4,409. No. 320, No. 4,576,910,
British Patent No. 2,102,137, European Patent 341,
188A.

As couplers in which the color forming dye has an appropriate diffusibility, 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.

Colored couplers for correcting unwanted absorption of color-forming dyes are Research Disclosure N.
o. 17643, Item VII-G, ibid. 307105
VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,92.
9, U.S. Pat. No. 4,138,258, and U.S. Pat. No. 1,14.
Those described in 6,368 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181 and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler which releases the development inhibitor is the above-mentioned R
D17643, VII-F section and No. 30710
5, the patents described in VII-F, JP-A-57-15
1944, 57-154234, 60-184.
No. 248, No. 63-37346, No. 63-37350.
U.S. Pat. Nos. 4,248,962 and 4,782,0.
Those described in No. 12 are preferable.

For example, R. D. No. 11449 and 24
241, the bleaching accelerator releasing coupler described in JP-A No. 61-201247 is effective for shortening the processing time having a bleaching ability, and particularly, the light-sensitive material using the tabular silver halide grains described above. The effect is great when added to. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent 2,097,
140, 2,131,188, JP-A-59-15.
Those described in 7638 and 59-170840 are preferable. Moreover, JP-A-60-107029 and JP-A-60-
252340, JP-A-1-44940, and 1-45.
Compounds which release a fogging agent, a development accelerator, and a silver halide solvent by an oxidation-reduction reaction with an oxidized product of a developing agent described in 687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat.
Competitive couplers as described in US Pat. No. 4,427, for example US Pat.
No. 283,472, No. 4,338,393, No. 4,310,618, and multi-equivalent couplers, such as JP-A-60-185950 and JP-A-62-24252.
REDOXOXIDE COMPOSITION RELEASE COUPLERS
R coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Nos. 173,302A and 313,30
8A couplers releasing a dye that recolors after release, ligand releasing couplers described in U.S. Pat. No. 4,555,477, couplers releasing leuco dyes described in JP-A-63-75747, such as U.S. Pat. Patent No. 4,774,
Examples thereof include couplers releasing a fluorescent dye described in No. 181. 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 medium agent used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in the oil-in-water dispersion method is 1
Specific examples of the high boiling point organic solvent having a temperature of 75 ° C. or higher 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-diethylpropyl) 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), benzoic acid esters (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amide (Eg, N, N-diethyldodecane amide, N, N-
Diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg bis (2-ethylhexyl) sebacate, Dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg N, N-dibutyl-2-butoxy-5-ter).
t-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2 -Ethoxyethyl acetate, dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in, for example, US Pat. No. 4,19.
No. 9,363, West German Patent Application (OLS) No. 2,541,
274 and 2,541,230. The color light-sensitive material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-272.
No. 248 and JP-A No. 1-80941, for example 1,2-benzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2- It is preferable to add various preservatives or antifungal agents such as phenoxyethanol and 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. 1871
6, page 647, right column to page 648, left column, and No. 6 of the same. Three
07105, page 879.

In the photographic material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and 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, can be measured by using a swellometer (swelling meter) of the type, and T _1/2 is treated with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness reached at that time is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling rate T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swelling film thickness under the conditions described above, using the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3- Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluene Examples include sulfonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include such a development inhibitor or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents. Agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be mentioned as representative examples.

Next, processing liquids and processing steps of the color reversal light-sensitive material of the present invention other than color development will be described. Among the processing steps of the color reversal light-sensitive material of the present invention, the steps from black development to color development are as follows.

1) Black-white development-washing-reversal-color development 2) Black-white development-water washing-light reversal-color development 3) Black-white development-water washing-color development Steps 1) to 3) are all US patents. 4,8
In place of the rinse process described in No. 04,616, it is possible to simplify the process and reduce waste liquid.

Next, the steps after color development will be described. 4) Color development-adjustment-bleach-fixing-washing-stable 5) Color development-washing-bleaching-fixing-washing-stable 6) Color development-adjusting-bleaching-washing-fixing-washing-stable 7) Color development-washing -Bleaching-washing-fixing-washing-stable 8) Color development-bleaching-fixing-washing-stable 9) Color development-bleaching-bleach-fixing-washing-stable 10) Color development-bleaching-bleach-fixing-fixing-washing-stable 11) Color development-bleaching-washing-fixing-washing-stable 12) Color development-adjusting-bleaching fixing-washing-stable 13) Color developing-washing-bleaching fixing-washing-stable 14) Color development-bleaching fixing-washing- Stable 15) Color development-fixing-bleach-fixing-washing-stable 4) to 15), the washing step immediately before the stabilizing step may be omitted, or conversely the final stabilizing step may be omitted. Good. Any one of the above steps 1) to 3) and any one of steps 4) to 15) are connected to form a color reversal step.

Next, the processing liquid in the color reversal processing step of the present invention will be described.

Known developing agents can be used in the black and white developing solution used in the present invention. As a developing agent,
For example, dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-
3-pyrazolidone), aminophenols (eg N
-Methyl-p-aminophenol), 1-phenyl-3
-Pyrazolines, ascorbic acid and US Pat.
The heterocyclic compounds such as 1,2,3,4-tetrahydroquinoline ring and indrene ring described in No. 67,872 can be used alone or in combination.

The black-and-white developing solution used in the present invention may include, if necessary, preservatives (eg, sulfite, bisulfite), buffers (eg, carbonate, boric acid, borate, alkanolamine), alkaline agents. (Eg, hydroxide, carbonate), dissolution tablet (eg, polyethylene glycols,
Contains these esters), pH adjusters (eg organic acids such as acetic acid, sensitizers (eg quaternary ammonium salts), development accelerators, surfactants, defoamers, hardeners, viscosity imparting agents) Can be made.

The black-and-white developing solution used in the present invention must contain a compound acting as a silver halide solvent.
The sulfite, which is usually added as a preservative, plays the role. The sulfite and other silver halide solvents that can be used include, for example, KSCN and NaSC.
N, K ₂ SO ₃ , Na ₂ SO ₃ , K ₂ S ₂ O ₅ , Na ₂
It can be exemplified _{S 2 O 5, K 2 S} 2 O 3, Na 2 S 2 O 3. The pH value of the developer thus adjusted is selected to an extent sufficient to provide the desired density and contrast, but is in the range of about 8.5 to about 11.5.

In order to carry out a sensitizing process using such a black-and-white developing solution, it is usually necessary to extend the time by up to about 3 times the standard process. At this time, if the processing temperature is raised, the extension time for the sensitization processing can be shortened. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, the contact area with the air in the processing tank is reduced to evaporate the liquid,
It is preferable to prevent air oxidation.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0. 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82 is available.
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps,
For example, it is preferably applied in all steps of bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The reversal bath used for black and white development may contain a known fogging agent. That is, for example, stannous ion-organic phosphoric acid complex salt (US Pat. No. 3,617,28)
No. 2), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-32616), stannous ion-aminopolycarboxylic acid complex salt (US Pat. No. 1,20).
9,050) stannous ion complex salts such as borohydride compounds (US Pat. No. 2,984,567), heterocyclic amine borane compounds (US Pat. No. 1,0).
11,000), such as a boron compound.
The fogging bath (reversal bath) has a wide pH range from the acidic side to the alkaline side, and has a pH of 2 to 12, preferably 2.5 to 10, and particularly preferably 3 to 9. Instead of the reversal bath, a light reversal treatment by re-exposure may be performed, and the reversal step can be omitted by adding the fogging agent to the color developing solution.

The silver halide color photographic light-sensitive material of the present invention is subjected to bleaching treatment or bleach-fixing treatment after color development. These treatments may be carried out immediately after the color development without passing through other processing steps, in order to prevent unnecessary post-development and air fog and to reduce the carry-in of the color developing solution to the desilvering process. Also, in order to wash out and detoxify the sensitizing dyes, dyes and other sensitive material parts contained in the photographic light-sensitive material and the color developing agent impregnated in the photographic light-sensitive material, stop, adjust, and wash with water after color development processing. A bleaching treatment or a bleach-fixing treatment may be carried out after the treatment steps such as.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. A typical bleaching agent is an iron (III) complex salt,
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc. Can be used. Among these, aminopolycarboxylic acid iron (II) complexes including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminepropanetetraacetic acid iron (III) complex salts.
I) Complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following specifications. For example, U.S. Pat. No. 3,893,858, West German Patents 1,290,812, and 2,059,988,
JP-A Nos. 53-32736, 53-57831, 53-37418, 53-72623, 53-
No. 95630, No. 53-95631, No. 53-104
No. 232, No. 53-124424, No. 53-1416
23, 53-28426, Research Disclosure No. 17129 (July 1978), a compound having a mercapto group or a disulfide group;
Thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5.
Thiourea derivatives described in No. 61; West German Patent No. 1,12
7,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,
No. 430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40,943, 49-59,644, 53-94,927, and 54-35, 727, 5
Compounds described in JP-A Nos. 5-26,506 and 58-163,940; bromide ions can be used. Of these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of having a large accelerating effect, and particularly, US Pat. No. 3,893,8
58, West German Patent 1,290,812, JP-A-53
The compounds described in -95,630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specifically, for example, acetic acid, propionic acid and hydroxyacetic acid are preferable.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Use of thiosulfates Are generally used, and ammonium thiosulfate is most widely used. Further, for example, a combination of thiosulfate, thiocyanate, thioether compound and thiourea is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening the stirring, a method of causing a jet of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461. Method to improve the effect, further moving the photosensitive material while contacting the emulsion surface with the wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. 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, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, it is possible to remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath of such a conveying means, and it is highly effective in preventing the deterioration of the performance of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range.
Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage counterflow method is described in the Journal of the Societ.
y of Motion Picture and T
Evolution Engineers Volume 64,
P. 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the above document, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria are propagated, and the produced floating substances adhere to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, JP-A-62-288,83 has been proposed.
The method of reducing calcium ion and magnesium ion described in No. 8 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and benzotriazole are also described by Hiroshi Horiguchi in "Bacterial and Antifungal Agents". Chemistry "(1986)
Sankyo Publishing, Sanitary Technology Society, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Microbial and Antifungal Encyclopedia" (1986) Can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on, for example, the characteristics of the light-sensitive material and the intended use, but generally 15 to 45 ° C. and 20 seconds to 10 seconds.
Minutes, preferably at 25-40 ° C. for 30 seconds-5 minutes. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No. 57-8543,
All known methods described in JP-A-58-148344 and JP-A-60-220345 can be used.

In addition, the washing treatment may be followed by a further stabilizing treatment. As an example thereof, a stabilizing agent containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, may be used. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, n-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath. The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in US Pat. No. 3,342,597,
Schiff base type compounds described in U.S. Pat. No. 3,342,599, Research Disclosures 14,850 and 15,159, aldol compounds described in U.S. Pat. No. 13,924, metals described in U.S. Pat. No. 3,719,492. Examples thereof include salt complexes and urethane compounds described in JP-A No. 53-135628.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are, for example, JP-A-56-64339 and 57-57.
-144547 and 58-115438. Various treatment liquids in the present invention are 10 ° C to 5 ° C.
Used at 0 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

[0108]

【Example】

(Embodiment 1) Hereinafter, the present invention will be specifically described with reference to embodiments, but the present invention is not limited thereto. Preparation of Samples 111 to 119 Samples 111 to 1 having the following basic constitution on a cellulose triacetate film support having a thickness of 127 μm and having an undercoat.
Made nineteen. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use. First layer: antihalation layer Black colloidal silver 0.2 g Gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g High boiling organic solvent Oil- 1 0.1 g Microcrystalline solid dispersion of Dye E-1 0.1 g Second layer: Intermediate layer Gelatin 0.4 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High boiling organic solvent Oil -3 0.1 g Dye D-4 0.8 mg Third layer: intermediate layer Yellow colloidal silver Silver amount 0.05 g Gelatin 0.4 g Fourth layer: low-sensitivity red photosensitive emulsion layer Monodisperse cubic emulsion A (average particle size) 0.3 μm, size variation coefficient 12%, AgI content 4 mol%) Silver amount 0.4 g Monodisperse cubic internal latent image type emulsion B (average particle size 0.26 μm, size variation coefficient 8%, AgI content 3 mol) %) Silver 0.2 g Gelatin 0.6 g Coupler C-1 0.12 g Coupler C-2 0.05 g Coupler C-6 0.004 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g Fifth layer: Medium speed red photosensitive emulsion layer Monodisperse tetradecahedral emulsion C (average particle size 0.4 μm, size variation coefficient 14%, AgI content 4 mol%) Silver amount 0.5 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-6 0.01 g High boiling organic solvent Oil-2 0.1 g Additive P-1 0.1 g Sixth layer: High-sensitivity red light-sensitive emulsion layer Monodisperse tabular emulsion D (average grain size 0.6 μm, size variation coefficient 12%, AgI content 2 mol%) silver amount 0.4 g gelatin 1.1 g coupler C-3 0.7 g Coupler C-6 .04 g Additive P-1 0.1 g Seventh layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-I 2.6 mg High boiling organic solvent Oil-1 0.02 g Dye D- 5 0.02 g Eighth layer: Intermediate layer Yellow colloidal silver Silver amount 0.02 g Gelatin 1.0 g Additive P-1 0.2 g Color mixing inhibitor Cpd-A 0.1 g Compound Cpd-C 0.1 g Ninth layer: Low-sensitivity green light-sensitive emulsion layer Cubic emulsion E (average particle size 0.2 μm, size variation coefficient 22%, AgI content 3 mol%) Silver amount 0.2 g Monodisperse cubic emulsion F (average particle size 0.25 μm, size Variation coefficient of 13%, AgI content 3 mol%) Silver amount 0.2 g Monodisperse cubic internal latent image type emulsion G (average particle size 0.26 μm, size variation coefficient 8%, AgI content 3 mol%) Silver amount 0 .2g Gelatin 0.5g Coupler C 4 0.1 g Coupler C-7 0.05 g Coupler C-8 0.2 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.04 g Compound Cpd-J 10 mg Compound Cpd-L 0.02 g High-boiling point organic solvent Oil-1 0.1 g High-boiling point organic solvent Oil-2 0.1 g 10th layer: Medium speed green photosensitive emulsion layer Monodisperse cubic emulsion H (average particle size 0 0.4 μm, size variation coefficient 7%, AgI content 3 mol%) Silver amount 0.4 g Internally fogged silver iodobromide emulsion (average grain size 0.2 μm, size variation coefficient 14%, AgI content 1 mol) %) Silver amount 0.04 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.2 g Coupler C-8 0.1 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.05 g Compound Cpd-L 0.05 g High boiling point organic solvent Oil-2 0.01 g Eleventh layer: high-sensitivity green photosensitive emulsion layer Monodisperse tabular emulsion I ( Average particle size 0.7 μm, size variation coefficient 18%, AgI content 2 mol%) Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.3 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd-B 0.08g Compound Cpd-E 0.02g Compound Cpd-F 0.04g Compound Cpd-K 5 mg Compound Cpd-L 0.02g High boiling organic solvent Oil-1 0.02g High boiling organic solvent Oil- 2 0.02 g 12th layer: Intermediate layer Gelatin 0.6 g Compound Cpd-L 0.05 g High boiling point organic solvent Oil-1 0.05 g 13th layer: Yellow filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Color mixing inhibitor Cpd-A 0.01 g Compound Cpd-L 0.01 g High boiling point organic solvent Oil-1 0.01 g Dye E-2 microcrystalline solid dispersion 0. 05g 14th layer: low-sensitivity blue light-sensitive emulsion layer Monodisperse cubic emulsion J (average grain size 0.3 μm, size variation coefficient 18%, AgI content 3 mol%) Silver amount 0.2 g Monodisperse cubic emulsion K (average Particle size 0.4 μm, size variation coefficient 13%, AgI content 3 mol%) Silver amount 0.3 g Gelatin 0.8 g Coupler C-5 0.2 g Coupler C-6 0.1 g Coupler C-10 0.4 g Fifteen layers: Medium-sensitivity blue light-sensitive emulsion layer Monodisperse tabular emulsion L (average particle size 0.6 μm, size variation coefficient 12%, AgI content 2.5 mol%) Silver amount 0.4 g Gelatin 0.9 g Coupler C -50. g Coupler C-6 0.1 g Coupler C-10 0.6 g 16th layer: High-sensitivity blue-sensitive emulsion layer Emulsion M Silver amount 0.5 g Gelatin 1.2 g Coupler C-5 0.1 g Coupler C-6 0. 1 g Coupler C-10 0.6 g High boiling point organic solvent Oil-2 0.1 g 17th layer: 1st protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber Agent U-5 0.3 g Formalin scavenger Cpd-H 0.4 g Dye D-1 0.15 g Dye D-2 0.05 g Dye D-3 0.1 g Eighteenth layer: second protective layer Colloidal silver Silver amount 0. 1 g Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g 19th layer: third protective layer Gelatin 0.4 g Polymethylmethacrylate (average grain size 1 ． 5 μm) 0.1 g Methyl methacrylate and acrylic acid 4: 6 copolymer (average particle size 1.5 μm) 0.1 g Silicone oil 0.03 g Sea surface active agent W-1 3 mg Sea surface active agent W-2 0. In addition to the above composition, an additive F- was added to all emulsion layers.
1-F-8 were added. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer.

Further, as an antiseptic and antifungal agent, phenol, 1,
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, p-benzoic acid butyl ester were added.

Table 3 Spectral sensitized emulsion names of emulsions A to L Sensitizing dye added Amount added per mol of silver halide (g) A S-2 0.025 S-3 0.25 S-8 0. 01 B S-1 0.01 S-3 0.25 S-8 0.01 C S-1 0.01 S-2 0.20 S-3 0.01 D S-2 0.01 S-30 .10 S-8 0.01 E S-4 0.5 S-5 0.1 F S-4 0.4 S-5 0.1 G S-4 0.4 S-5 0.1 H S- 4 0.2 S-5 0.06 S-9 0.05 IS S-4 0.3 S-5 0.07 S-9 0.1 J S-6 0.07 S-7 0.24 K S -6 0.04 S-7 0.19 L S-6 0.04 S-7 0.18 M S-6 0.04 S-7 0.15

[0111]

[Chemical 21]

[0112]

[Chemical formula 22]

[0113]

[Chemical formula 23]

[0114]

[Chemical formula 24]

[0115]

[Chemical 25]

[0116]

[Chemical formula 26]

[0117]

[Chemical 27]

[0118]

[Chemical 28]

[0119]

[Chemical 29]

[0120]

[Chemical 30]

[0121]

[Chemical 31]

[0122]

[Chemical 32]

[0123]

[Chemical 33]

[0124]

[Chemical 34] Sample 11 shown in Table 5 was prepared by using each emulsion shown in Table 4.
1-119 were created. The characteristic values of the emulsions in Table 4 are as defined in the specification.

[0125]

[Table 4] The emulsions of the 16th layer are shown in Table 5, and
119 was created. The emulsion to be added to the 16th layer and the completed emulsion after mixing the emulsion were melted at 40 ° C. before being coated and
Stirred for 0 minutes. Furthermore, the 16th of Samples 111 to 119
The completed emulsion of the layer was coated at 40 ° C. with stirring for 16 hours while it was still dissolved. The name of each coated sample is Sample 12
1 to 129. All the finished emulsions of the layers other than the 16th layer were remade and coating was carried out with a dissolution stirring time of 30 minutes.

Table 5 Sample No. 17th Layer Emulsion ^* Emulsion Mixing Ratio Sample 111 EM11 112 EM12 113 EM13 / EM14 1/1 114 EM15 / EM16 1/1 115 EM15 / EM17 1/1 116 EM15 / EM18 1/1 117 EM15 / EM19 1/1 118 EM22 119 EM25 / EM28 1/1 Samples 111 to 119 and 121 to 129 were allowed to stand for 10 days at a temperature of 30 ° C. and a relative humidity of 60%, then exposed to light and subjected to the following development treatment, Dmax, Γ (6 ') and RMS granularity were determined. Dmax and Γ are the maximum density and gradation obtained by ordinary sensitometry, respectively. Γ (6 ′) is defined as the absolute value of the slope of the exposure amount that gives a density of 1.0 and the exposure amount that is 0.5 (Log amount) less than that. The RMS granularity is a value obtained by measuring the RMS value at a density of 1.0 with an aperture of 48 μmΦ by a conventional method.

Then, the time of the first development processing was extended to 8 ', and the same processing was carried out to perform sensitometric evaluation.
The obtained gradation is Γ (8 ′).

Samples 111-119 and 121-129
Of the yellow image of each sample of Dmax, Γ (6 ′), Γ
Table 8 shows (8 ') and RMS granularity. Development processing conditions: Processing time Temperature First development 6 minutes 38 ° C Water washing 2 minutes 38 ° C Inversion 2 minutes 38 ° C Color development 6 minutes 38 ° Pre-bleaching 2 minutes 38 ° C Bleaching 6 minutes 38 ° C fixing 4 Min 38 ° C water wash 4 min 38 ° C final rinse 1 min 25 ° C The composition of each treatment liquid was as follows. [First developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 1.5 g Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0 g Sodium sulfite 30 g Hydroquinone / potassium monosulfonate 20 g Potassium carbonate 15 g sodium bicarbonate 12 g 1-phenyl-4-methyl-4-hydroxymethyl 1.5 g-3-pyrazolidone potassium bromide 2.5 g potassium thiocyanate 1.2 g potassium iodide 2.0 mg diethylene glycol 13 g water 1000 ml pH 9.60 The pH was adjusted with sulfuric acid or potassium hydroxide. [Inversion liquid] Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 3.0 g Stannous chloride dihydrate 1.0 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 The pH was adjusted with acetic acid or sodium hydroxide. [Color developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 2.0 g Sodium sulfite 7.0 g Trisodium phosphate / dihydrate 36 g Potassium bromide 1.0 g Potassium iodide 90 mg Sodium hydroxide 3.0 g Citrazine acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 11 g 3,6-dithiaoctane -1,8-diol 1.0g Water was added and 1000 ml pH 11.80 pH was adjusted with sulfuric acid or potassium hydroxide. [Pre-bleaching] Ethylenediamine tetraacetic acid / disodium salt / dihydrate 8.0 g Sodium sulfite 6.0 g 1-Thioglycerol 0.4 g Sodium formaldehyde bisulfite adduct 30 g Water was added 1000 ml pH 6.20 pH is Adjusted with acetic acid or sodium hydroxide. [Bleach] Ethylenediaminetetraacetic acid / sodium salt / dihydrate 2.0 g Ethylenediaminetetraacetic acid / Fe (III) / ammonium / dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g Water 1000 ml pH 5 The .70 pH was adjusted with nitric acid or sodium hydroxide. [Fixer] Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 The pH was adjusted with acetic acid or aqueous ammonia. [Final rinse] 1,2-benzisothiazolin-3-one 0.02 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Polymaleic acid (average molecular weight 2,000) 0.1 1000 ml pH 7.0 with addition of water

[0129]

[Table 6] As is clear from Table 6, the sample using the monodisperse tabular silver halide grains has excellent graininess. Further, the sample using the monodisperse emulsion alone has an appropriate gradation, especially the gradation in the sensitization process, but the sample containing the emulsion has an appropriate gradation. However, in the sample in which the compound A-1 is not used, especially when the emulsion is mixed, the fluctuations of Dmax and Γ are large and unstable with the passage of time in the dissolved state of the coating solution. Therefore, the tabular emulsion of the present invention can be mixed, and only the sample containing the compound A-1 has excellent image quality and can be stably produced. (Example 2) This example shows how the effects of the present invention are exhibited depending on the type and amount of stabilizer added. The emulsions shown in Table 7 were prepared.

[0130]

[Table 7] Further, the amount of the stabilizer was changed as shown in Table 8, and the emulsions 31 to 31 were changed.
42 was created.

[0131]

[Table 8] Samples 211 to 219 were prepared by coating two layers having the same constitution as the sixth layer and the nineteenth layer of Sample 111 in this order on an undercoated cellulose triacetate film support having a thickness of 127 μm. However, the emulsion of the emulsion layer was changed as shown in Table 9.
The emulsion in the emulsion layer of each sample was melted at 40 ° C. after preparation and aged for 30 minutes before coating.

[0132] Further, the emulsions of the emulsion layers of the samples 211 to 218 were melted at 40 ° C., and after 16 hours, they were coated to prepare samples 221 to 228, respectively. Samples 211 to 218 and 221 to 228 were placed at a temperature of 30 ° C. and a relative humidity of 60.
% For 10 days, then exposed to light and subjected to the same development process as in Example 1 to determine Dmax and S _1.0 . However,
The processing time of the first development was set to 10 minutes in order to accurately detect the change in fogging. Dmax and S _1.0 are the maximum concentration and relative sensitivity obtained by ordinary sensitometry, respectively. Samples 211-218 and 221-2
Table 10 shows the Dmax and S1.0 of the cyan image of each of the 28 samples.

[0133]

[Table 10] As is clear from Table 10, the stabilizers A-1 and A-2 of the present invention remarkably improve the change with time in the dissolved state of the emulsion (reduction in Dmax and decrease in sensitivity due to increase in fog). Further, by optimally defining the addition amount, the sensitivity can be improved and the change in the performance of the emulsion in the dissolved state can be minimized. (Example 3) This example shows how the degree of the effect of the present invention varies depending on the timing and method of addition of the stabilizer.

Emulsions EM-43 to 48 were prepared by changing the addition timing of the compound A-1 from the emulsions EM37 and EM38 of Example 2 as shown in Table 11.

Table 11 Emulsion No. Grain Characteristics Compound A-1 Addition Time / Emulsion Temperature at Addition EM37 After Chemical Sensitization Before Sensitizing Dye Addition / Emulsion Temperature 63 ° C. EM38 〃 / 〃 EM43 Same chemical sensitization as EM37 After completion After adding sensitizing dye / Emulsion temperature 63 ° C EM44 Same as EM38 〃 / 〃 EM45 Same as EM37 〃 / Emulsion temperature 40 ° C EM46 Same as EM38 〃 〃 EM47 Same as EM37 Compound A-1 not added EM48 EM38 Samples 231-236 were prepared by changing the emulsion of the emulsion layer from the sample 214 of the same example 2 as shown in Table 12. The emulsion in the emulsion layer of each sample was melted at 40 ° C. after preparation and aged for 30 minutes before coating.

Further, the emulsions in the emulsion layers of the samples 214, 231 to 234 were melted at 40 ° C., and after 16 hours, they were coated to prepare samples 224, 241-244, respectively.

Samples 214, 231-234 and 22
Samples Nos. 4, 241-244, temperature 30 ° C., relative humidity 60
% For 10 days, then exposed to light and subjected to the same development process as in Example 1 to determine Dmax and S _1.0 . However,
The processing time of the first development was set to 10 minutes in order to accurately detect the change in fogging. Dmax and S _1.0 are the maximum concentration and relative sensitivity obtained by ordinary sensitometry, respectively.

Samples 214, 231-234 and 22
Table 12 shows the Dmax and S _1.0 of the cyan color image of each of the samples Nos. 4, 241-244.

[0139]

[Table 12]

[0140]

[Table 13] As is clear from Table 13, by adding the stabilizer A-1 at a temperature of 50 ° C. or higher, changes with time in the dissolved state until the emulsion is coated (a decrease in Dmax and a decrease in sensitivity due to an increase in fog) ) Can be significantly improved. The effect becomes more remarkable by adding the compound A-1 after the chemical sensitization and before the addition of the sensitizing dye. (Example 4) This example shows the effect of the present invention on the stability of the emulsion in a dissolved state when the tabular emulsion and the regular emulsion are mixed.

The emulsions shown in Table 14 were prepared.

[0142]

[Table 14] Further, the amount of the stabilizer was changed as shown in Table 15, and the emulsion 53 was changed.
~ 59 was created.

The fifth layer and the nineteenth layer of Sample 111 were placed on a subbed 127 μm thick cellulose triacetate film support.
Samples 411 to 4 were prepared by applying two layers having the same constitution as the layers in this order.
17 was created. However, the emulsion of the emulsion layer was changed as shown in Table 16. The emulsion in the emulsion layer of each sample was melted at 40 ° C. before preparation coating and aged for 30 minutes.

Table 15 Emulsion name Grain characteristics Stabilizer type Stabilizer addition amount ^* EM51 F-1 9 × 10 ^-4 EM52 F-1 12 × 10 ^-4 EM53 Same as EM51 A-1 9 × 10 ^-4 EM54 EM52 Same as A-1 12 × 10 ^-4 EM55 Same as EM52 A-1 20 × 10 ^-4 EM56 Same as EM52 A-1 9 × 10 ^-4 EM57 Same as EM51 None EM58 Same as EM52 None Table 16 Sample name Emulsion layer Emulsion composition Sample 411 EM51 alone 412 EM52 alone 413 EM51 / EM52 (1/1 mixture) 414 EM53 / EM54 (1/1 mixture) 415 EM53 / EM55 (1/1 mixture) 416 EM53 / EM56 (1/1 mixture) 417 EM57 / EM58 (1/1 mixture) Further, the emulsions in the emulsion layers of the samples 411 to 417 were dissolved at 40 ° C., After aging for 16 hours, coating was performed to prepare samples 421 to 427, respectively.

Samples 411-417 and 421-427
Each sample was allowed to stand for 10 days at a temperature of 30 ° C. and a relative humidity of 60%, exposed to light, and subjected to the same development treatment as in Example 1 to obtain Dma.
x and S _1.0 were determined. However, the processing time of the first development was set to 10 minutes in order to accurately detect the change in fogging. Dmax and S _1.0 are the maximum concentration and relative sensitivity obtained by ordinary sensitometry, respectively.

Samples 411-417 and 421-427
Table 17 shows the Dmax and S _1.0 of the cyan color image of each sample.

[0147]

[Table 17] As is clear from Table 17, when a tabular emulsion and a regular emulsion are mixed, the performance greatly changes with time in the dissolved state before coating. The stabilizer A-1 of the present invention remarkably improves such changes over time in the dissolved state of the emulsion (decrease in Dmax and decrease in sensitivity due to increase in fog). Further, by optimally defining the addition amount, the sensitivity can be improved and the change in performance with time in the emulsion dissolved state can be suppressed to a minimum. (Example 5) This example shows how the degree of the effect of the present invention varies depending on the timing and method of addition of the stabilizer.

Emulsions EM-59 to 62 were prepared by changing the addition timing of the compound A-1 from the emulsions EM53 and EM54 of Example 4 as shown in Table 18.

Table 18 Emulsion No. Grain characteristics Compound A-1 Addition time / Emulsion temperature during addition EM53 After completion of chemical sensitization Before addition of sensitizing dye / Emulsion temperature 63 ° C. EM54 〃 / 〃 EM59 Same as EM53〃 / Emulsion Temperature 40 ° C. EM60 Same as EM54 〃 〃 EM61 Same as EM53 No compound A-1 added EM62 Same as EM54 〃 Same as in Example 4, except that the emulsion of the emulsion layer was changed as shown in Table 19 to obtain Sample 511. ~ 513 was created. The emulsion in the emulsion layer of each sample was melted at 40 ° C. after preparation and aged for 30 minutes before coating.

Further, the emulsions of the emulsion layers of the samples 414, 511 to 513 were melted at 40 ° C., and after 16 hours, they were coated to prepare samples 424, 521 to 523, respectively. Samples 414, 511-513 and 424, 5
1 of each sample of 21 to 523 at a temperature of 30 ° C. and a relative humidity of 60%
After leaving it for 0 days, it was exposed to light and subjected to the same development treatment as in Example 1 to determine Dmax and S _1.0 . However, the processing time of the first development was set to 10 minutes in order to accurately detect the change in fogging. Dmax and S _1.0 are the maximum concentration and relative sensitivity obtained by ordinary sensitometry, respectively.

Samples 414, 511-513 and 42
Table 20 shows the Dmax and S _1.0 of the cyan color image of each of the samples Nos. 4,521 to 523.

[0152]

[Table 19]

[0153]

[Table 20] As is clear from Table 20, by adding the stabilizer A-1 at a temperature of 50 ° C. or higher, changes with time in a dissolved state until the emulsion is coated (a decrease in Dmax and a decrease in sensitivity due to an increase in fog) ) Can be significantly improved. The effect becomes more remarkable by adding the compound A-1 after the chemical sensitization and before the addition of the sensitizing dye. Example 6 This example shows the advantage of mixing tabular grains and regular grains.

Sample 611 was prepared by changing the emulsion of the 15th layer from the sample 116 of Example 1 as shown in Table 21.

Table 21 Sample No. 15th layer emulsion 116 Emulsion L alone 611 Emulsion L and tetradecahedral regular grain emulsion mixture (ratio 2/1) Development processing was carried out in the same manner as in Example 1, and Γ (6 ′) And Γ (8 ′) were obtained. The results obtained are shown in Table 22.

[0156] As is clear from Table 22, although the gradation of the sample 116 including the tabular grain emulsion alone is hardened by the sensitization treatment, by mixing the regular grain emulsion, it is possible to alleviate the gradation hardening in the sensitization treatment. A preferable gradation can be obtained even by the sensitization process.

Although the monodisperse tabular emulsions used in the above examples were prepared by using the block copolymer PL-1 at the time of grain formation, the same excellent results were obtained even when the following polymers PL-2 to 8 were used. can get.

[0158]

[Chemical 35]

[0159]

[Chemical 36]

[0160]

[Chemical 37]

[0161]

[Chemical 38]

[0162]

[Chemical Formula 39]

[0163]

[Chemical 40]

[0164]

[Chemical 41] (Embodiment 7) The effects of the present invention were similarly exhibited in the light-sensitive material having the following constitution. First layer: Antihalation layer Gray colloidal silver 0.34 Gelatin 2.40 Second layer: Intermediate layer Gelatin 1.20 Third layer: Low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.60 Silver bromide Lippmann emulsion Silver amount 0.06 Gelatin 0.90 Coupler C-1 0.20 High boiling point organic solvent oil-1 0.10 Compound Cpd-M (Chemical formula name shown in [Chemical Formula 1] below) 0.05 Fourth layer: High sensitivity Red-sensitive emulsion layer Emulsion B Silver amount 0.50 Fine grain silver iodobromide emulsion (AgI 4.8%) Silver amount 0.05 Gelatin 1.50 Coupler C-1 0.90 High boiling point organic solvent oil-1 0.40 Fifth layer: Intermediate layer Gelatin 0.60 Compound Cpd-M (Chemical formula name shown in [Chemical formula 1] below) 0.16 D-6 (Chemical formula name shown in the following [Chemical formula 2]) 0.65 Sixth layer: Intermediate Layer Gelatin 0.60 7th layer: Low sensitivity green Emulsion layer Emulsion C Silver amount 0.45 Gelatin 0.90 Coupler C-11 0.20 Coupler C-7 0.07 High boiling point organic solvent oil-2 0.11 Eighth layer: High sensitivity green sensitive emulsion layer Emulsion D Silver amount 0.45 Silver bromide Lippmann emulsion Silver amount 0.07 Fine grain silver iodobromide emulsion (AgI 4.8%) Silver amount 0.05 Gelatin 1.50 Coupler C-11 0.60 Coupler C-7 0. 25 High boiling point organic solvent oil-2 0.40 9th layer: intermediate layer gelatin 0.60 10th layer: intermediate layer gelatin 0.60 Compound Cpd-M (chemical formula name shown in the following [Chemical Formula 1]) 0.11 D -7 (chemical formula name shown in [Chemical Formula 2] below) 0.27 Eleventh layer: low-sensitivity blue-sensitive emulsion layer Emulsion E Silver amount 0.45 Gelatin 0.90 Coupler C-5 0.18 High boiling organic solvent oil- 1 0.06 Compound Cpd-M ( Chemical formula name shown in the following [Chemical formula 1] 0.05 12th layer: High-sensitivity blue-sensitive emulsion layer Emulsion F Silver amount 0.55 Silver bromide Lippmann emulsion Silver amount 0.07 Fine grain silver iodobromide emulsion (AgI 4. 8%) Silver amount 0.05 Gelatin 2.40 Coupler C-5 1.55 High boiling point organic solvent oil-1 0.50 13th layer: 1st protective layer UV absorber U-6 ([Chemical formula 3] below) Chemical formula name shown 0.38 Ultraviolet absorber U-7 (chemical formula name shown in [Chemical Formula 3] below) 0.13 Compound Cpd-M (chemical formula name shown in the following [Chemical Formula 1]) 0.07 Gelatin 1.40 14 layers: Second protective layer Gelatin 0.97 Silver bromide Lippmann emulsion Silver amount 0.12 Yellow colloidal silver Silver amount 0.003 Gelatin hardening agent H-2 (Chemical formula name shown in [Chemical Formula 4] below) 0.31 [ 1] Cpd-M N '-{2- [4-h hydroxyphen Nirusuruhoniru) phenoxy] dodecanoyl}-N-[4
-(2-Pentyroxy) phenyl] hydrazine (N'-
{2- [4-hydroxyphenylsulfon
yl) phenoxy] dodecanoyl} -N-
[4- (2-pentyloxy) phenyl] hy
Drazine) [Chemical Formula 2] D-6 1,3-bis [(1- {4-carboxyphenyl} -3-methyl-2-pyrazolin-5-one (4)] trimethineoxonol (1,3-bis)
[(1-carboxyphenyl} -3-meth
yl-2-pyrazolin-5-one (4)] t
rimthineoxonol) D-7 4- (4- (butanesulfonamidophenyl) -3-cyano-5-furfurylidene-2,5-dihydro-2-furanone (4- (4- (butanesul
fonamidophenyl) -3-cyano-5
-Furfurylidene-2,5-dihydrr
o-2-furanone) [Chemical Formula 3] U-6 2- (2H-benzotriazol-2-yl) -4,6-bis (1,1-dimethyl-propyl) phenol (2- (2H-benzotriazol-2
-Yl) -4,6-bis (1,1-dimethyl)
-Propyl) phenol) U-7 3- (di-n-dihexylamino) allylidene malononitrile (3- (di-n-dihexyla)
mono) allylidenemalononitr
ile) [Chemical Formula 4] H-2 bis (vinylsulfonyl) methane

[0165]

As described in detail above, according to the present invention, it is possible to provide a color photographic light-sensitive material which has improved sharpness, graininess and suitability for sensitization and improved production stability, and a method for producing the same.

Claims (4)

[Claims] 1. A color photographic light-sensitive material having a red light-sensitive silver halide emulsion layer, a green light-sensitive silver halide emulsion layer and a blue light-sensitive silver halide emulsion layer on a support, and at least one of them has an average grain size. A tabular silver halide emulsion different from each other and containing a compound represented by the general formula (I). General formula (I) In the formula, R ₁ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, a hydroxy group, an alkoxy group, an alkylthio group, a carbamoyl group, a halogen atom, a cyano group, a carboxy group or an alkoxycarbonyl group. , R
₂ and R ₃ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and n represents an integer of 3-5. 2. A color photographic light-sensitive material having a red light-sensitive silver halide emulsion layer, a green light-sensitive silver halide emulsion layer and a blue light-sensitive silver halide emulsion layer on a support, and at least one layer of tabular halogen. A silver halide color photographic light-sensitive material containing a silver halide emulsion and a regular emulsion and containing a compound represented by formula (I). General formula (I) In the formula, R ₁ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, a hydroxy group, an alkoxy group, an alkylthio group, a carbamoyl group, a halogen atom, a cyano group, a carboxy group or an alkoxycarbonyl group. , R
₂ and R ₃ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and n represents an integer of 3-5. 3. A method for producing a silver halide color photographic light-sensitive material containing at least two tabular silver halide emulsions having different sizes in at least one layer, wherein the compound of the general formula (I) is added at a temperature of 50 ° C. or higher. The method for producing a silver halide color photographic light-sensitive material, which comprises adding to the tabular silver halide emulsion, and then mixing the two or more tabular silver halide emulsions. General formula (I): In the formula, R ₁ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, a hydroxy group, an alkoxy group, an alkylthio group, a carbamoyl group, a halogen atom, a cyano group, a carboxy group or an alkoxycarbonyl group. , R
₂ and R ₃ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and n represents an integer of 3-5. 4. A method for producing a silver halide color photographic light-sensitive material containing a tabular silver halide emulsion and a regular emulsion in at least one layer, wherein the compound of the general formula (I) is tabular halogen at a temperature of 50 ° C. or higher. A method for producing a silver halide color photographic light-sensitive material, which comprises adding to a silver halide emulsion and a regular emulsion, and then mixing the silver halide emulsion. General formula (I): In the formula, R ₁ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, a hydroxy group, an alkoxy group, an alkylthio group, a carbamoyl group, a halogen atom, a cyano group, a carboxy group or an alkoxycarbonyl group. , R
₂ and R ₃ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and n represents an integer of 3-5.