JPH0545759A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To ensure high sensitivity and improved graininess and to suppress sensitization due to scratch by incorporating a silver halide emulsion subjected to reduction sensitization and contg. a specified compd. into at least one of emulsion layers and a specified compd. into a protective layer. CONSTITUTION:A silver halide emulsion subjected to reduction sensitization during production and contg. at least one of compds. represented by formulae I-III is incorporated into at least one of emulsion layers and a compd. represented by formula IV into a protective layer. In the formulae I-TV, each of R, R<1> and R<2> is an aliphatic or arom. group, etc., M is a cation, Lis a divalent combining group, m is 0 or 1, R11 is 1-3C alkyl, R12 is 1-3C alkyl or 1-2C alkoxy and n is a cardinal number of 0-2,000.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having high sensitivity, good graininess and less scratch sensitization. ..

[0002]

2. Description of the Related Art The basic performance required for a silver halide emulsion for photography is high sensitivity, low fog and fine grain.

In order to increase the sensitivity of the emulsion, (1) increase the number of photons absorbed by one grain, and (2) increase the efficiency of conversion of photoelectrons generated by light absorption into silver clusters (latent images). It is necessary to increase the developing activity and (3) to effectively utilize the latent image thus formed. Increasing the size increases the number of absorbed photons in one particle, but deteriorates the image quality. Increasing the development activity is also an effective means for increasing the sensitivity, but in the case of parallel type development such as color development, grain deterioration is generally accompanied. In order to increase the sensitivity without degrading graininess, it is most preferable to increase the efficiency of converting photoelectrons into a latent image, that is, increase the quantum sensitivity.

In order to enhance the quantum sensitivity, it is necessary to eliminate inefficient processes such as recombination and latent image dispersion as much as possible.
It is known that a method of reduction sensitization in which a small silver nucleus having no developing activity is formed inside or on the surface of silver halide is effective in preventing recombination.

In addition, James et al. Have conducted a kind of reduction sensitization by performing a kind of reduction sensitization in which a coating film of a gold / sulfur-sensitized emulsion is degassed in vacuum and then heat-treated in an atmosphere of hydrogen gas. It was found that the sensitivity can be increased at a low fog level as compared with reduction sensitization. This sensitization method is well known as hydrogen sensitization, and is effective as a sensitization means on a laboratory scale. Furthermore, hydrogen sensitization is actually used in the field of astrophotography.

Attempts at reduction sensitization have been studied for a long time. Carroll, US Pat. No. 2,48
In No. 7,850, the tin compound became Lowe.
Disclosed in US Pat. No. 2,512,925 that polyamine compounds are useful as reduction sensitizers, and Fallens (Farence) et al in British Patent No. 789,823 that thiourea dioxide compounds are useful as reduction sensitizers. Furthermore C
ollier is Photographic
Science and Engineering
Volume 23, page 113 (1979) compares the properties of silver nuclei produced by various reduction sensitization methods. She has dimethylaminoborane, stannous chloride, hydrazine,
The method of high pH aging and low pAg aging was adopted. The method of reduction sensitization is further described in US Pat.
No. 201, 254, No. 3,779, 777, No. 3,
No. 930,867.

With respect to not only the selection of reduction sensitizers but also the method of using reducing agents, JP-B-57-33572 and 58-1.
No. 410 and JP-A No. 57-179835. Further, regarding a technique for improving the preservability of reduction-sensitized emulsions, JP-A-57-82831 and 60-17 are also applicable.
No. 8445. In spite of many studies as described above, the width of increase in sensitivity was insufficient as compared with hydrogen sensitization in which a photosensitive material was treated with hydrogen gas under vacuum. This is Journalof Image
g Science 29: 233 (1985) by Moisar et al.

The prior art of reduction sensitization has not been sufficient for the recent demand for a photographic light-sensitive material having high sensitivity and high image quality. The means of hydrogen sensitization also has a drawback that the sensitizing effect is lost if the light-sensitive material is left in the air after hydrogen sensitization. It is difficult to use this sensitizing method in the case of a photographic light-sensitive material which cannot use a special device.

[0009]

Under such circumstances, an emulsion having high sensitivity and good graininess is disclosed in JP-A 1-273034.
Japanese Patent No. 3242187 discloses a silver halide emulsion to which a thiosulfonic acid compound was added during the manufacturing process.

However, it has been revealed that when the above-mentioned halogenated emulsion is used in a color light-sensitive material, it has high sensitivity and excellent graininess, but has a defect that scratch sensitization occurs. Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivity, good graininess and less scratch sensitization.

[0011]

The objects of the present invention can be achieved by the following constitutions.

In a silver halide color photographic light-sensitive material, each having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, red-sensitive silver halide emulsion layer and protective layer on a support, said emulsion At least one compound selected from the compounds represented by the general formulas (I), (II) and (III) is subjected to reduction sensitization to at least one of the layers during the production process of the silver halide emulsion. A silver halide color photographic light-sensitive material containing a halogenated emulsion added to 1. and a compound represented by the general formula (IV) shown in Chemical formula 28 below in the protective layer.

(I) R-SO ₂ S-M (II) R-SO ₂ S-R ¹ (III) R-SO ₂ S-L _m -SSO ₂ -R ^{2 In the} formula, R, R ¹ and R ² may be the same or different and represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds of the general formulas (I) to (III) may be polymers containing a divalent group derived from the structure represented by (I) to (III) as a repeating unit. If possible, R, R ¹ , R ² and L may be bonded to each other to form a ring.

In the general formula (IV), R ₁₁ is an alkyl group having 1 to 3 carbon atoms, and R ₁₂ is an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 2 carbon atoms. N is one of the cardinal numbers from 0 to 2000.

The present invention will be described in detail below.

The silver halide emulsion manufacturing process involves grain formation.
It is roughly divided into processes such as desalting, chemical sensitization, and coating. Grain formation is divided into nucleation, ripening, and growth. These steps are not performed uniformly, but the order of the steps is reversed, or the steps are repeated. The fact that reduction sensitization is carried out during the manufacturing process of a silver halide emulsion basically means that it may be carried out at any process. The reduction sensitization may be carried out at the initial stage of grain formation, that is, during nucleation, physical ripening, or during growth, and may be carried out prior to chemical sensitization such as gold sensitization and / or sulfur selenium sensitization. It may be performed after chemical sensitization. When chemical sensitization is performed in combination with gold sensitization, it is preferable to carry out reduction sensitization prior to chemical sensitization so that unfavorable fog does not occur. Most preferred is the method of reduction sensitization during the growth of silver halide grains. Here, the term "during growth" refers to a method in which the silver halide grains are physically ripened or subjected to reduction sensitization while they are growing by the addition of a water-soluble silver salt and a water-soluble alkali halide. It also means that a method of further growing after performing reduction sensitization in the state of containing is also included.

The reduction sensitization of the present invention is a method of adding a known reducing agent to a silver halide emulsion, pAg 1 called silver ripening.
Either a method of growing or aging in a low pAg atmosphere of ˜7 or a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

Known reduction sensitizers are stannous salts, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. In the present invention, these known compounds can be selected and used, and two or more kinds of compounds can be used in combination. Stannous chloride, thiourea dioxide and dimethylamine borane are preferred compounds as the reduction sensitizer. The addition amount of the reduction sensitizer depends on the emulsion production conditions, so it is necessary to select the addition amount, but it is 10 ^-7 to 10 ^-3 per mol of silver halide.
A molar range is suitable.

The reduction sensitizer may be dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain formation or before or after chemical sensitization. It may be added at any stage of the emulsion production process, but the method of addition during grain growth is particularly preferred. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time for particle formation. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and grains may be formed using these aqueous solutions. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times with the grain formation or to continuously add it for a long time.

The thiosulfonic acid compounds of the general formulas (I), (II) and (III) will be described in more detail.
^{When 1} and R ² are aliphatic groups, it is a saturated or unsaturated, linear, branched or cyclic, aliphatic hydrocarbon group, preferably an alkyl group having 1 to 22 carbon atoms and 2 carbon atoms. To 22 alkenyl groups and alkynyl groups, which may have a substituent. As an alkyl group,
For example, methyl, ethyl, propyl, butyl, pentyl,
Hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, t-butyl can be mentioned.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

The aromatic group of R, R ¹ and R ² includes a monocyclic or condensed ring aromatic group, preferably having 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl. These may be substituted.

The heterocyclic group for R, R ¹ and R ² is
A 3- to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium, and tellurium, and having at least one carbon atom, preferably 3 to 6
Member rings are preferred, for example pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, oxadiazole, An example is the thiadiazole ring.

Substituents for R, R ¹ and R ² include, for example, alkyl groups (eg methyl, ethyl, hexyl), alkoxy groups (eg methoxy, ethoxy, octyl), aryl groups (eg phenyl, naphthyl, tolyl). ), A hydroxy group, a halogen atom (eg, fluorine, chlorine, bromine, iodine), an aryloxy group (eg, phenoxy), an alkylthio group (eg, methylthio, butylthio), an arylthio group (eg, phenylthio), an acyl group (eg, acetyl). , Propionyl, butyryl, valeryl), a sulfonyl group (eg, methylsulfonyl,
Phenylsulfonyl), acylamino group (for example, acetylamino, benzoylamino), sulfonylamino group (for example, methanesulfonylamino, benzenesulfonylamino), acyloxy group (for example, acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, amino group, -SO ₂ SM group (M represents a monovalent cation),
An example is a —SO ₂ R ¹ group.

The divalent linking group represented by L is C,
An atom or an atomic group containing at least one selected from N, S and O. Specifically, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S.
Each of-, --NH--, --CO--, SO _2-, etc. or a combination thereof.

L is preferably a divalent aliphatic group or a divalent aromatic group. The divalent aliphatic group of L for example _{- (CH 2) n - (} n = 1~12), -CH 2 -CH = CH-CH 2 -, -CH 2 C three CCH ₂ -,

[0029]

[Chemical 2] Examples thereof include a xylylene group. Examples of the divalent aromatic group of L include a phenylene group and a naphthylene group.

These substituents may be further substituted with the above-mentioned substituents.

M is preferably a metal ion or an organic cation. Examples of the metal ion include lithium ion, sodium ion and potassium ion. Examples of the organic cation include ammonium ion (for example, ammonium, tetramethylammonium, tetrabutylammonium), phosphonium ion (tetraphenylphosphonium), and guanidyl group.

When the general formulas (I) to (III) are polymers, examples of the repeating units are as follows.

[0033]

[Chemical 3] These polymers may be homopolymers or copolymers with other copolymerizable monomers.

Specific examples of the compounds represented by the general formula (I), (II) or (III) are shown in Chemical formulas 4 to 13, but not limited thereto.

[0035]

[Chemical 4]

[0036]

[Chemical 5]

[0037]

[Chemical 6]

[0038]

[Chemical 7]

[0039]

[Chemical 8]

[0040]

[Chemical 9]

[0041]

[Chemical 10]

[0042]

[Chemical 11]

[0043]

[Chemical formula 12]

[0044]

[Chemical 13] The compounds of the general formulas (I), (II) and (III) are described in JP-A-54-1019; British Patent 972, 211;
al of Organic Chemistry (Journal of Organic Chemistry) 53
Volume 396 (1988) and Chemical Ab.
59 volumes of tracts (Chemical Abstracts),
It can be easily synthesized by the method described or cited in 9776e.

The compound represented by the general formula (I), (II) or (III) is 10 ^-7 to 10 per mol of silver halide.
^It is preferable to add ^-1 mol. From 10 ^-6 to 1
An addition amount of 0 ^-2 , particularly 10 ^-5 to 10 ^-3 mol / mol Ag is preferable.

In order to add the compounds represented by the general formulas (I) to (III) during the production process, a method which is usually used when an additive is added to a photographic emulsion can be applied. For example, a water-soluble compound is prepared as an aqueous solution having an appropriate concentration, and a water-insoluble or sparingly-soluble compound is a suitable organic solvent miscible with water, such as alcohols, glycols, ketones, esters, and amides. Then, it can be dissolved in a solvent that does not adversely affect the photographic characteristics and added as a solution.

The compound represented by formula (I), (II) or (III) may be added at any stage during grain formation of a silver halide emulsion, before or after chemical sensitization.
Preferred is a method in which the compound is added before or during reduction sensitization. Particularly preferred is the method of addition during grain growth.

It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time for grain formation. Further, the compounds (I) to (III) are added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide,
Particles may be formed using these aqueous solutions. Further, it is also a preferable method to add the solutions of the compounds (I) to (III) in several times along with the formation of particles or to continuously add them for a long time.

The most preferred compound of the present invention has the general formula (I).

Next, the polymerized silicone compound represented by the general formula (IV) will be described. Effective silicone polymers include, for example, commercially available silicones such as trialkyl and trialkoxy end-capped dialkyl polysiloxanes, such as dimethyl polysiloxane, diethyl polysiloxane, trimethoxy end-capped dimethyl polysiloxane and triethoxy end-capped dimethyl polysiloxane. Contains oil. These silicone compounds have a molecular weight of 162 to 150,000, preferably 10,000 to 20.
000 and the viscosity at 25 ° C. is 2 to 100000 centistokes, preferably 200 to 800 centistokes.

Generally, the silicone polymer is added to the protective layer, which is the outermost layer of the photographic film, as an aqueous dispersion in the presence of a suitable dispersant, preferably a nonionic dispersant. Aqueous dispersions containing 35% by weight of silicone polymer are preferred, but dispersions containing 1 to about 50% by weight of polymer are suitable.

The amount of the silicone polymer added is 0.05 to 5% based on the solid weight of the outermost protective layer of the photographic film.
Is preferred.

Suitable dispersants which do not have a deleterious effect on the photographic emulsions are generally of the nonionic type, for example alkylphenyl polyethylene glycol ethers such as nonylphenyl polyethylene glycol ether, undecylphenyl polyethylene glycol ether, undecyl. Phenyl polyethylene glycol ethers, alkyl and alkylphenyl polyether alcohols such as isooctylphenyl polyethoxy ethanol, nonyl phenyl polyethoxy ethanol, tetradecyl polyethoxy ethanol. Other suitable dispersants are those described in U.S. Pat. No. 2,400,532 to Saponin and Blake (Blake), i.e., oxyalkylene ethers of hexitol ring dehydration products, such as 2 to 3 divided in three chains. Polyoxyethylene sorbitan monolaurates, monostearates, monooleates containing 20 oxyethylene groups; salts of alkyl-substituted aryloxyalkylene ether sulfonates, such as Baldsiefen US Pat. No. 2,600,831. Includes sodium P-tert-octylphenoxyethoxyethyl sulfonate as disclosed herein; sodium dodecyl, tetradecyl and octadecyl sulfate and dioctyl esters of sodium sulfosuccinate. Certain soaps, such as sodium morpholine oleate sodium stearate, can also be used as dispersants. These dispersants are used in an amount of 1 to about 50% by weight, preferably 2 to 20% by weight, based on the weight of the silicone compound.

In addition to adding a silicone compound to the outermost protective layer of the photographic film in the form of a dispersion, the silicone polymer is a suitable organic solvent such as amyl acetate, ethyl acetate,
It can be added in benzene, carbon tetrachloride, ethyl ether, perchlorethylene, petroleum ether, xylene and the like. Of course, the organic solvent must not adversely affect the physical or photographic properties of the photographic film.

The light-sensitive material of the present invention is provided with at least one layer of blue-sensitive layer, green-sensitive layer, silver halide emulsion layer of red-sensitive layer and non-photosensitive layer on a support. It should be. A typical example is a silver halide photographic light-sensitive material having a photosensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support, The photosensitive layer is a unit photosensitive layer having color sensitivity to blue light, green light, and red light, respectively, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally The red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer are installed in this order from the body side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

A non-photosensitive layer 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.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
No. 61-20037, No. 61-20038, for example, a coupler and a DIR compound may be contained, and a color mixing inhibitor may be contained as is usually used. ..

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of emulsion layers can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
For example, JP-A-57-112751, JP-A-62-200.
No. 350, No. 62-206541, No. 62-20654
As described in No. 3, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
For example, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / high-sensitivity red photosensitive layer (RH) ) / Low-sensitivity red photosensitive layer (RL) order or BH / BL / GL / GH / R
H / RL order or BH / BL / GH / GL / RL /
It can be installed in the order of RH.

Further, as described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest photosensitivity, the middle layer is the silver halide emulsion layer having a lower photosensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer.

In addition, for example, high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. Also, in the case of four layers or more, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
No. 63-89850, for example,
It is preferable to dispose a donor layer (CL) having a multi-layer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layers of BL, GL, and RL, adjacent to or close to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.

The silver halide grains other than the silver halide grains according to the present invention will be described below.

The preferable silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides. About 2 mol% is particularly preferred.
To silver iodobromide or silver iodochlorobromide containing up to about 10 mol% silver iodide.

The silver halide grains in a photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
For example, it may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pages 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid.
716 (November 1979), page 648, ibid. Thirty
7105 (Nov. 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chemieet.
Phisique Photographie, P
aulMontel, 1967), "Photoemulsion 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).

For example, US Pat. No. 3,574,628
No. 3,655,394 and British Patent No. 1,41
The monodisperse emulsion described in 3,748 is also preferable.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described, for example, by Gatov, Photographic Science and Engineering (Gutoff, Photog.
radical Science and Engine
ering), Vol. 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
4,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent 2,112,157.

The crystal structure is uniform, and the inside and the outside may have different halogen compositions, and may have a layered structure. Also, silver halides having different compositions are joined by epitaxial joining. Or it may be bonded to a compound other than silver rhodan and lead oxide, for example. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain or a type having a latent image in both the surface and the inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
A shell type internal latent image type emulsion can be used. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-133.
No. 542. The thickness of the shell of this emulsion varies depending on, for example, the development treatment, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are Research Disclosure No. 17643, the same No. 18716 and No. 18716. No. 307105, and the corresponding portions are summarized in Table A below.

The light-sensitive material of the present invention comprises a light-sensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having different characteristics of at least one of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The obtained silver halide grains and colloidal silver can be preferably used in 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 which enables uniform (non-imagewise) development 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. 4,626,498,
It is described in JP-A-59-214852.

The silver halide forming the inner core of the core / shell type silver halide grain in which the inside of the grain is fogged may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.75 μm.
m, particularly preferably 0.05 to 0.6 μm. The grain shape is not particularly limited and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or number of silver halide grains are ± 40 of the average grain size). %) Is preferable.

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is not fogged in advance. ..

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferably silver iodide,
The content is 0.5 to 10 mol%.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains.

The silver coating amount of 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 also described in the above three Research Disclosures, and the related portions are shown in Table X below.

Table A Additive Types 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, pages 866 to 868, supersensitizer, page 649, right column, 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Fogging prevention pages 24 to 25 pages 649 right column 868 to 870 pages agents and stabilizers 6. Light absorber, page 25-26, page 649, right column, page 873, filter dye, ~ page 650, left column, ultraviolet absorber 7. Stain page 25 right column page 650 left column page 872 Inhibitor to right column 8. Dye image Page 25 Page 650 Left column Page 872 Stabilizer 9. Hardener 26 pages 651 left column 874-875 pages 10. Binder page 26 page 651 left column 873 to 874 page 11. Plasticizers and lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static Page 27 Page 650 Right column 876-877 Page 14 Inhibitor 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being added to the light-sensitive material.

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 Laid-Open No. 1-1060
It is preferable to contain a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, as described in No. 52, regardless of the amount of developed silver produced by the development processing.

The light-sensitive material of the present invention has the international publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-25935.
It is preferable that the dye described in No. 8 is contained.

Various color couplers can be used in 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 compounds and pyrazoloazole compounds are preferable, and examples thereof include US Pat. Nos. 4,310,619 and 4,35.
No. 1,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432, 3,725,067, Research Disclosure No. 24220 (198
June 4), JP-A-60-33552, Research Disclosure No. 24230 (June 1984)
Mon), JP-A-60-43659, JP-A 61-72238.
No. 60-35730, No. 55-118034,
No. 60-185951, U.S. Pat. No. 4,500,63.
No. 0, No. 4,540, 654, No. 4,556, 6
No. 30, those described in International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
52,212, 4,146,396, and 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, No. 249,453A, US Patent Nos. 3,446,622 and 4,333,999.
No. 4,775,616, No. 4,451,55
9, No. 4,427,767, No. 4,690,8
89, 4,254,212 and 4,296,4
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable. Furthermore, JP-A-64-553 and 64-55
Nos. 4, 855 and 64-556, and pyrazoloazole-based couplers described in U.S. Pat. No. 4,818,6.
The imidazole couplers described in No. 72 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 2,102,137, European Patent 341,1
88A.

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. 30710
5, section VII-G, U.S. Pat. No. 4,163,670,
Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,9
29, 4,138,258, British Patent 1,1.
Those described in No. 46,368 are preferable. Further, a coupler described in US Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are RD1 described above.
7643, Item VII-F and No. 307105, V
Patents described in paragraph II-F, JP-A-57-15194
No. 4, No. 57-154234, No. 60-184248.
Nos. 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

For example, R. D. No. 11449 and 2
The bleaching accelerator releasing couplers described in JP-A No. 4241 and JP-A No. 61-201247 are effective in 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 it is added to. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59.
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Also preferred are compounds that release, for example, a fogging agent, a development accelerator and a silver halide solvent by a redox reaction with an oxidized product of a developing agent described in JP-A-45687.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat. No. 4,13.
Competitive couplers described in U.S. Pat. No. 4,427, for example, multiequivalent couplers described in U.S. Pat. Nos. 4,283,472, 4,338,393 and 4,310,618, such as JP-A- 60-185950, JP-A-62-242
No. 52 DIR redox compound releasing coupler,
DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, EP Nos. 173,302A and 313,
308A, a coupler that releases a dye that recolors after release, for example, a ligand-releasing coupler described in U.S. Pat. No. 4,555,477, a coupler that releases a leuco dye described in JP-A-63-75747, U.S. Pat. No. 4,7
Examples thereof include couplers that release the fluorescent dye described in JP-A-74,181.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027. Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphonic acid Esters (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di- - ethylhexyl phenyl phosphonate), benzoic acid esters (e.g., 2
-Ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amic acid (e.g. N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (For example, isostearyl alcohol, 2,4-di-t
ert-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
Examples thereof include butoxy-5-tert-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, for example, 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, 2-ethoxyethyl acetate, dimethylformamide are mentioned.

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. 4,1.
99,363, West German Patent Application (OLS) No. 2,54
No. 1,274 and No. 2,541,230.

The color light-sensitive material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-125747.
No. 272248 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.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

Suitable supports that can be used in the present invention are, for example, those described in RD. No. 17643, page 28, ibid.
18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

In the light-sensitive 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, et al., Photographic Science and Engineering (Photogr. Sci. E)
ng. ), Vol. 19, No. 2, pp. 124-129, and can be measured by using a swellometer (swelling meter) of the type. T _1/2 was treated with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness that reaches at time is the saturated film thickness,
It is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed 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 can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. The back layer preferably contains, for example, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. .. The swelling ratio of this back layer is preferably 150 to 500%.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid.
18716, 651 left column to right column, and the same No. 307
Development processing can be carried out by a usual method described on page 880-881.

The color developing solution used in 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 a typical example thereof is 3-methyl-4-.
Amino-N, N-diethylaniline, 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 sulphates, hydrochlorides or p-toluenesulphonates. Among these, especially 3-metal-
4-Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. Two or more kinds of these compounds can be used in combination depending on the purpose.

The color developing solution is, for example, a pH buffering agent such as an alkali metal carbonate, boric acid solution or phosphate,
It usually contains a development inhibitor or an antifoggant such as a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as aminos, dye forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, 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.

When the reversal process is carried out, the black and white development is usually carried out before the color development. In this black and white developer,
Dihydroxybenzenes such as hydroquinone, 3 such as 1-phenyl-3-pyrazolidone
The known black-and-white developing agents of pyrazolidones or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination. The pH of these color developer and black-and-white developer is 9
Generally, it is -12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed,
Generally, it is 3 liters or less per 1 square meter of the light-sensitive material, and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment amount is reduced, it is preferable to prevent the evaporation and air oxidation of the liquid by reducing the contact area of the processing liquid with air.

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 aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, The slit development processing method described in JP-A-63-216050 can be mentioned. Reducing the aperture ratio is not limited to both color development and black and white development,
Subsequent steps, such as bleaching, bleach-fixing, fixing, washing,
It is preferably applied in all steps of stabilization.
Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a color developing agent at a high concentration. it can.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. 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. Examples of bleaching agents include polyvalent metal compounds such as iron (III), peracids (in particular, sodium persulfate is suitable for color negative films for motion pictures), quinones,
Nitro compounds are used. Typical bleaching agents are iron (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol etherdiaminetetraacetic acid aminopolycarboxylic acid. Acids or complex salts such as citric acid, tartaric acid and malic acid can be used. Of these, ethylenediaminetetraacetic acid iron (III) complex salts,
Aminopolycarboxylic acid iron (III) complex salts including iron (III) complex salts of 1,3-diaminopropanetetraacetic acid and 1,3-diaminopropanetetraacetate are preferable from the viewpoint of rapid treatment 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 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 bleaching accelerators are described in the following specifications: For example, U.S. Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988.
JP-A-53-32736 and JP-A-53-57831.
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53-95631, No. 53-.
No. 104232, No. 53-124424, No. 53-1
No. 41623, No. 53-28426, Research Declosure No. 17129 (July 1978), a compound having a mercapto group or a disulfide group; a thiazolidine derivative described in JP-A-50-140129; JP-B-45-8506, JP-A-52-208.
32, No. 53-32735, U.S. Pat. No. 3,70.
Thiourea derivatives described in 6,561; West German Patent No. 1,
127,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410, and 2,74.
No. 8,430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40, 943 and 49-59, 644.
No. 53-94, 927, 54-35, 727.
No. 55, No. 55-26, 506, No. 58-163, 940.
Compounds described in No. 1; 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.
93,858, West German Patent 1,290,812, and JP-A-53-95,630 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 photographing.

In addition to the above compounds, the bleaching agent and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred 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 preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Is most commonly used, with ammonium thiosulfate being the most widely used. It is also preferable to use a thiosulfate solution in combination with, for example, a thiocyanate salt, a thioether compound, or thiourea. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent 29476.
The sulfinic acid compounds described in No. 9A are preferable. Furthermore,
It is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2- It is preferable to add 0.1 to 10 mol / liter of an imidazole such as methylimidazole.

The total time of the desilvering process is preferably short as 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 step, it is preferable that the stirring is strengthened as much as possible. As a concrete 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, and stirring using a rotating means of JP-A-62-183461. A method to improve the effect, further a method to improve the stirring effect by moving the light-sensitive material while bringing the emulsion surface into contact with the wiper blade provided in the solution and making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such 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 effect 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, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration 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 light-sensitive material (for example, depending on the material used such as coupler), the application, and further, for example, the rinsing water temperature, the number of rinsing tanks (the number of stages), the countercurrent, the countercurrent replenishment method, etc. It can be set in a wide range according to various conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is
Society of Motion Pictu
re and Television Vision
rs vol. 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, for example, bacteria propagate, and the produced suspended matter adheres to the photosensitive material. The problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, Japanese Patent Application Laid-Open No.
The method for reducing calcium ion and magnesium ion described in 2-288,838 can be used very effectively. Also, for example, isothiazolone compounds, siabendazoles, chlorine-based bactericides of chlorinated sodium isocyanurate, and the like described in JP-A-57-8542, such as benzotriazole, by Horiguchi "The Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing,
Hygiene Technology Association, “Microbial Sterilization, Sterilization, and Antifungal Technology” (19
1982) It is also possible to use the bactericides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can be set variously 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 in the range of 25-40 ° C and 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-58-14834 and JP-A-60-220345 can be used.

In addition, the washing treatment may be followed by a further stabilizing treatment. As an example of the stabilizing treatment, a stabilizing agent containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing is used. You can mention the bath. Examples of dye stabilizers include formalin, aldehydes such as 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 resulting from the washing with water and / or the supplementation of the stabilizing solution can be reused in another step such as a desilvering step.

For example, in processing using an automatic processor,
When each of the above treatment liquids 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, US Pat.
Indoaniline compounds described in No. 342,597, for example, No. 3,342,599, Research Disclosure No. 14, 850 and the same No. 15,159
Examples thereof include the Schiff base type compounds described in JP-A No. 13-324, the aldol compounds described in JP-A No. 13,924, the metal salt complexes described in US Pat. No. 3,719,492, and the urethane compounds described in JP-A-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 described, for example, in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° 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.

The silver halide light-sensitive material of the present invention comprises
For example, U.S. Pat. No. 4,500,626, JP-A-60
-133449, 59-218443, 61-
It can also be applied to the photothermographic materials described in 238056 and European Patent 210,660A2.

Examples will be shown below for further description. Example 1 Average iodine content is 20 mol%, average equivalent spherical diameter is 0.8 μm
As a seed crystal of the double twinned crystal particles, the core-shell ratio is 1: in the aqueous gelatin solution by the control double jet method.
2. An emulsion composed of twin grains having an average equivalent spherical diameter of 1.2 μm was formed so that the iodine content of the shell would be 2 mol%.

After grain formation, the emulsion was redispersed at 40 ° C. under the conditions of pAg 8.9 and pH 6.3 by subjecting it to an ordinary desalting water washing step. The emulsion thus prepared is designated as _Em- 1. On the other hand, 1 minute before the start of shell formation, the thiosulfone oxides 1-10, 1-2 and 1-16 shown below were added to the addition amount reaction pots shown in Table 1-1 shown in Table 1. the emulsion was subjected to particle formation and E _m -2~4.

When grains are formed in the same manner as E _m -1, one minute after the start of shell formation, the following reduction sensitizers 2-A, 2-B,
2-C was added in the amount shown in Table 1-2 shown in Table 1 to give an emulsion _Em.
The -5~E _m -7 were prepared.

Further, when the same particle formation as for E _m -1 is carried out, the thiosulfonic acid compounds 1-10, 1-2 and 1-16 are added 1 minute before the start of shell formation, and 1 minute after the start of shell formation. Emulsion E shown in Table 1-3 shown in Table 1 by a method of adding optimum amounts of reduction sensitizers 2-A, 2-B and 2-C.
We have created a _{m -8~E m} -16.

[0134]

[Table 1] Emulsions 1 to 16 thus prepared were optimally sensitized with gold and sulfur using sodium thiosulfate and chloroauric acid to prepare chemically sensitized emulsions.

Sample 101, which is a multilayer color light-sensitive material having the following composition, was prepared on an undercoated cellulose triacetate film support. (Rough formation of photosensitive layer) The coating amount is shown in units of g / m ² . However, for silver halide and colloidal silver, g / m ^{2 of} silver
Of the sensitizing dye and the number of moles per mole of silver halide in the same layer. First layer: antihalation layer Black colloidal silver Silver coating amount 0.2 Gelatin 2.2 UV-1 0.1 UV-2 0.2 Cpd-1 0.05 Solv-1 0.01 Solv-2 0.01 Solv-3 0.08 Second layer: intermediate layer Fine grain silver bromide (sphere equivalent diameter 0.07 μ) Silver coating amount 0.15 Gelatin 1.0 Cpd-2 0.2 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, sphere equivalent diameter 0.7 μ, variation coefficient of sphere equivalent diameter 14%, tetrahedral grains) Silver coating amount 0.26 Silver iodobromide emulsion ( AgI 4.0 mol%, internal high AgI type, sphere-equivalent diameter 0.4 μ, coefficient of variation of sphere-equivalent diameter 22%, tetrahedral grains) Silver coating amount 0.2 Gelatin 1.0 ExS-1 4.5 × 10 ^{-4 ExS-2 1.5 × 10 -4} ExS-3 0.4 × 10 -4 ExS-4 0 ^{3 × 10 -4 ExC-1 0.33} ExC-2 0.009 ExC-3 0.023 ExC-6 0.14 Layer 4: Second Red-sensitive emulsion layer Silver iodobromide emulsion (AgI 16 mol%, Internal high AgI type, equivalent sphere diameter 1.0 μ, variation coefficient of equivalent sphere diameter 25%, plate-like particles, diameter / thickness ratio 4.0) Silver coating amount 0.55 Gelatin 0.7 ExS-1 3 × 10 ^{− 4} ExS-2 1 × 10 ⁻⁴ ExS-3 0.3 × 10 ⁻⁴ ExS-4 0.3 × 10 ⁻⁴ ExC-3 0.05 ExC-4 0.10 ExC-6 0.08 Fifth layer : Third red-sensitive emulsion layer Silver iodobromide emulsion I (high internal AgI type, spherical equivalent diameter 1.2 μ, variation coefficient of spherical equivalent diameter 28%) Silver coating amount 0.9 Gelatin 0.6 ExS-12 × ^{10 -4 ExS-2 0.6 × 10} -4 ExS-3 0.2 × 10 -4 ExC-4 0.07 ExC-5 0.06 Sol -1 0.12 Solv-2 0.12 Sixth layer: Intermediate layer Gelatin 1.0 Cpd-4 0.1 Seventh layer: First green emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, Internal high AgI type, equivalent spherical diameter 0.7μ, variation coefficient of equivalent spherical diameter 14%, tetrahedral grains) Silver coating amount 0.2 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, spherical Equivalent diameter 0.4 μ, variation coefficient of spherical equivalent diameter 22%, tetrahedral grain) Silver coating amount 0.1 Gelatin 1.2 ExS-5 5 × 10 ⁻⁴ ExS-6 2 × 10 ⁻⁴ ExS-7 1 × 10 ⁻⁴ ExM-1 0.41 ExM-2 0.10 ExM-5 0.03 Solv-1 0.2 Solv-5 0.03 Eighth layer: second green emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high iodine type, equivalent sphere diameter 1.0 μ, variation coefficient of equivalent sphere diameter 25%, plate-like particles, diameter / Thickness ratio 3.0) Silver coating amount 0.4 Gelatin 0.35 ExS-5 3.5x10 ^-4 ExS-6 1.4x10 ^-4 ExS-7 0.7x10 ^-4 ExM-1 0.09 ExM-3 0.01 Solv-1 0.15 Solv-5 0.03 9th layer: intermediate layer gelatin 0.5 10th layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion II (internal high AgI type, sphere equivalent diameter 1.2μ, variation coefficient of sphere equivalent diameter 28%) Silver coating amount 1.0 Gelatin 0.8 ExS-5 2 × 10 ^-4 ExS-6 0.8 × 10 ^-4 ExS-7 0.8 × 10 ⁻⁴ ExM-3 0.01 ExM-4 0.04 ExC-4 0.005 Solv-1 0.2 11th layer: Yellow filter layer Cpd-3 0.05 Gelatin 0.5 Solv- 1 0.1 12th layer: intermediate layer gelatin 0.5 Cpd-2 0.1 13th layer: 1st blue Emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high iodine type, spherical equivalent diameter 0.7 μ, variation coefficient of spherical equivalent diameter 14%, tetrahedral grains) Silver coating amount 0.1 Silver iodobromide emulsion ( AgI 4.0 mol%, internal high iodine type, sphere equivalent diameter 0.4 μ, variation coefficient of sphere equivalent diameter 22%, tetrahedral grain) Silver coating amount 0.05 gelatin 1.0 ExS-8 3 × 10 ⁻⁴ ExY-1 0.53 ExY-2 0.02 Solv-1 0.15 14th layer: 2nd blue sensitive emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high AgI type, equivalent spherical diameter 1) 0.0μ, variation coefficient of equivalent spherical diameter 16%, tetradecahedral grain) Silver coating amount 0.19 Gelatin 0.3 ExS-8 2 × 10 ^-4 ExY-1 0.22 Solv-1 0.07 Fifteenth layer: Intermediate layer Fine grain silver iodobromide (FAgI 2 mol%, uniform type, equivalent spherical diameter of 0.13 μ) Silver coating amount 0.2 Gelatin 0.36 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion III (internal high AgI type, equivalent spherical diameter 1.2 μ, variation coefficient of equivalent spherical diameter 28%) Silver coating Amount 1.0 Gelatin 0.5 ExS-8 1.5 × 10 ^-4 ExY-1 0.2 Solv-1 0.07 17th layer: 1st protective layer Gelatin 1.8 UV-1 0.1 UV- 2 0.2 Solv-1 0.01 Solv-2 0.01 18th layer: 2nd protective layer Fine grain silver bromide (sphere equivalent diameter 0.07μ) Silver coating amount 0.18 Gelatin 0.7 Polymethylmethacrylate particles (Diameter 1.5 μ) 0.2 W-1 0.02 H-1 0.4 Cpd-5 1.0 S-1 0.01 The structural formula of the compound used in Sample 101 is shown in Chemical formula 14 to
Shown in Chemical formula 27.

Samples 102 to 116 were prepared in the same manner as in Sample 101 except that the silver iodobromide emulsion I of the fifth layer, the silver iodobromide emulsion II of the tenth layer, and the silver iodobromide emulsion III of the sixteenth layer were changed.
Was produced.

For samples 101 to 116, the 18th
Samples 117 to 116 were prepared in exactly the same manner as Samples 101 to 116, except that the silicone polymer S-2 of the present invention was used instead of the silicone polymer added to the layer (the amount added was the same).
132 was created.

Further, except that the silicone polymer added to the 18th layer for Samples 101 to 116 was replaced with the silicone polymer S-3 of the present invention (the addition amount was the same),
Samples 133 to 14 in exactly the same manner as Samples 101 to 116
8 was created.

These samples were exposed for sensitometry and subjected to the following color development processing. The treated sample was subjected to concentration measurement with a red filter, a green filter and a blue filter. Regarding the result of photographic performance, the sensitivity of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer was 10 for the sensitivity of Sample 101, respectively.
It was expressed as a relative sensitivity when 0 was set.

Furthermore, these samples were made 10 times with a needle having a diameter of 1 mm.
After scratching with a weight of g, the same color development processing as described above was performed to evaluate scratches and fog. The evaluation was performed by the 10-point method, and the worst scratch fogging was set to 10 and the best one was set to 1.

The above results are shown in Table 1-4 shown in Tables 2-4.

[0142]

[Table 2]

[0143]

[Table 3]

[0144]

[Table 4] Treatment process Temperature (℃) Time 1. Pre-bath 27 ± 1 10 seconds 2. Backing removal 27-385 seconds and spray water washing 3. Color development 41.1 ± 0.1 3 minutes 4. Stop 27-38 30 seconds 5. Bleach acceleration 27 ± 1 30 seconds 6. Bleach 38 ± 1 3 minutes 7. Washing with water 27-38 1 minute 8. Stationary 38 ± 12 minutes 9. Washing with water 27-38 2 minutes 10. Stability 27-38 10 seconds Prescription of each processing solution 1. Pre-bath treatment value 27-38 ° C water 800 ml Borax (decahydrate) 20.0 g Sodium sulfate (anhydrous) 100 g Sodium hydroxide 1.0 g Water added 1.00 liter pH (27 ° C) 9.25 3. Color development processing value Water at 27-38 ° C 850 ml Kodak anti-calcium No.4 2.0 ml Sodium sulfite (anhydrous) 2.0 g Eastman Antifog No.9 0.22 g Sodium bromide (anhydrous) 1.20 g Sodium carbonate ( Anhydrous) 25.6 g Sodium bicarbonate 2.7 g Color developing agent; 4- (N-E 4.0 g Cyl-N- (β-methanesulphonmamidoethyl) -m-toluidine Water added 1.00 liter pH (27 ° C) 10.20 4. Stopping treatment value 21 to 38 ° C water 900 ml 7.0 N sulfuric acid 50 ml Water is added to 1.00 liter pH (27 ° C) 0.9 5. Bleach accelerating treatment treatment value Water 900 ml Sodium metabisulfite (anhydrous) 10.0 g Glacial acetic acid 25.0 ml Sodium acetate 10.0 g EDTA-4Na 0.7 g PBA 5.5 g Water was added. 1.0 liter pH (27 ° C.) 3.8 ± 0.2 PBA stands for 2-dimethylaminoethylisothiourea dihydrochloride.

6. Bleaching solution Treatment value 24-38 ° C water 800 ml Gelatin 0.5 g Sodium persulfate 33.0 g Sodium chloride 15.0 g Sodium monophosphate (anhydrous) 9.0 g Phosphoric acid (85%) 2.5 ml Water In addition 1.0 liter pH (27 ° C.) 2.3 ± 0.2 8. Fixed process value Water at 20-38 ° C 700 ml Kodak anti-calcium No.4 2.0 ml 58% ammonium thiosulfate solution 185 ml Sodium sulfite (anhydrous) 10.0 g Sodium bicarbonate 8.4 g Add water 1.00 liter pH (27 ° C) 6.5 10. Stabilizing value 21-27 ° C water 1.00 ml Kodak Stabilizer 0.14 ml Additive Formalin (37.5% solution) 1.50 ml Example 2 The light-sensitive material of Example 1 was similarly exposed to the following color. When development was carried out and the sensitivity, fog and scratch fog of each color-sensitive layer were evaluated, the same results as in Example 1 were obtained. Processing Method Color development processing was carried out at 38 ° C. according to the following processing steps.

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Settling 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds It was the street. Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2 0.4 g 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 g Water was added to 1.0 liter pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid Ferric ammonium salt 100 0.0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water added 1.0 liter pH 6.0 Fixer ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Thio Ammonium sulfate aqueous solution (70%) 75.0 ml Sodium bisulfite 4.6 g Water was added to 1.0 liter pH 6.6 Stabilizing solution Formalin (40%) 2.0 ml Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.3 g Water In addition, as is clear from Tables 1 to 4 shown in Tables 2 to 4, it is understood that the light-sensitive material of the present invention has the effect of sensitization with almost no deterioration in scratch fogging.

[0147]

[Chemical 14]

[0148]

[Chemical 15]

[0149]

[Chemical 16]

[0150]

[Chemical 17]

[0151]

[Chemical 18]

[0152]

[Chemical 19]

[0153]

[Chemical 20]

[0154]

[Chemical 21]

[0155]

[Chemical formula 22]

[0156]

[Chemical formula 23]

[0157]

[Chemical formula 24]

[0158]

[Chemical 25]

[0159]

[Chemical formula 26]

[0160]

[Chemical 27]

[0161]

[Chemical 28]

Claims (1)

[Claims] 1. A support having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and
In a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer and a protective layer, at least one of the emulsion layers is subjected to reduction sensitization in the process for producing the silver halide emulsion, and the compound represented by the general formula (I) Containing a halogenated emulsion to which at least one compound selected from the compounds represented by formulas (II) and (III) was added during the production process, and containing the compound represented by the general formula (IV) in the protective layer. A silver halide color photographic light-sensitive material characterized in that (I) in _{R-SO 2 S-M (} II) R-SO 2 S-R 1 (III) R-SO 2 S-L m -SSO 2 -R 2 Formula, R, R ^1, R ² are the same However, they may be different and represent an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds of the general formulas (I) to (III) may be polymers containing a divalent group derived from the structure represented by (I) to (III) as a repeating unit. If possible, R, R ¹ , R ² and L may be bonded to each other to form a ring. General formula (IV): In the formula, R ₁₁ is an alkyl group having 1 to 3 carbon atoms, R ₁₂ is a member selected from the group consisting of an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 2 carbon atoms, and n Is 0
It is one of the bases of 2000.