JPH03189644A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity, the preservable property with age and pressure resistance by specifying the silver chloride content of the silver halide particles in all emulsion layers to a specific value or below and subjecting the layers to gold sensitization and further specifying the gelatin content in the photosensitive material to a specific value or below. CONSTITUTION:This photographic sensitive material is formed by providing respective silver halide emulsion layers which are at least blue-, green- and red photosensitive on a base and, confining the silver chloride content of the silver halide particles in all the emulsion layers to <=70mol% and subjecting the layers to the gold sensitization. Further, the total content of the gelatin contained in the photosensitive material is specified to <=7.5g/m<2>. Silver chlorobromide is usable for this silver halide and aureate chloride, etc., are usable for the gold sensitization.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, and in particular a silver halide color photographic light-sensitive material that is highly sensitive, has excellent storage stability over time, pressure resistance, and processing variation resistance. Regarding.

[Background of the invention]

In recent years, there has been an increasing demand for higher sensitivity for various purposes including improving the productivity of photographic prints.

In particular, with the spread of printers capable of exposing 15,000 to 20,000 sheets per hour, the demand for higher sensitivity has become higher, and various measures have been taken to meet this demand.

As one method, International Publication Patent WO37-0453
No. 4 had gold sensitization applied to silver chloride to achieve high sensitivity, but it was found that sensitivity fluctuations and increased fog during storage over time were problems. Regarding Capri, especially in the case of color photographic paper, it is required that the white background density be low, and if the storage stability deteriorates over time, the product will not be able to maintain uniformity, which will hinder work in the photo lab. , which is a fatal flaw. or,
Research Disclosure, 1976, No.
, 15159, JP-A-60-80840, JP-A No. 62-1
As described in No. 78239, when gold sensitization is applied to silver halide with a low silver chloride content, high sensitivity is achieved, and the sensitivity is stable and there is no increase in fog during storage over time. Understood.

However, these techniques have the disadvantage of lacking pressure resistance.

When a photosensitive material is subjected to mechanical pressure in a printer or automatic processor, pressure is also applied to the silver halide grains in the material through gelatin, which is a binder for the silver halide grains, resulting in changes in photographic properties. occurs, pressure desensitization,
This causes phenomena such as pressure blurring. In particular, in the case of high-speed printers, the moving speed of the photosensitive material is faster, making it easier to receive stronger pressure. This phenomenon has been well known as the photographic pressure effect.

Pressure may be applied to the photosensitive material either in a dry state or in a wet state during development processing.

Therefore, it cannot be said that the effect will be sufficient unless the pressure resistance in both conditions is improved.

For this reason, attempts have been made to provide photosensitive materials that are less affected by pressure. For example, in JP-A-5313923, the coupler-containing layer contains a high boiling point solvent of 20% by weight or more of the binder, and in JP-A-57-12133, a coupler and a conversion emulsion are used;
No. 618 describes heterocyclic compounds in U.S. Patent No. 2,960,4.
No. 04 discloses a method using polyhydric alcohol, but no satisfactory effect has been obtained.

By the way, after exposure of silver halide color photographic materials,
Color development, bleaching and fixing, or bleach-fixing, washing with water or stabilizing treatment are performed, and finally drying with hot air.In recent years, there has been an emphasis on energy conservation, and attempts have been made to lower the temperature of the processing solution and the drying temperature. However, the former has not been realized because sufficient color density cannot be obtained. In addition, the latter causes problems such as insufficient drying and sticking of the photosensitive materials to each other. It is known that this problem can be solved by reducing the amount of gelatin contained in the photographic material.
There is a drawback that the sensitivity of the silver halide color photographic light-sensitive material is lowered, and when the pH of the color developing solution fluctuates, the gradation of the dye image fluctuates greatly.

In color photographic materials, yellow magenta,
The gradation balance of the three primary colors of cyan is extremely important for neutral (neutral color) reproduction. The gradation of the portion (highlight portion) where the color development density is relatively low is particularly important, and if the gradation changes as described above, it will cause extremely inconvenient problems in terms of color reproduction.

As a result of intensive studies, the present inventors surprisingly found that by gold-sensitizing silver halide grains containing a certain amount of silver chloride and regulating the amount of gelatin contained in the silver halide photographic light-sensitive material. The present invention has been developed based on the discovery that the above problems can be solved.

[Object of the present invention]

The purpose of the present invention is as described above; to solve the problems of the prior art;
The object of the present invention is to provide a silver-rhodanide color photographic light-sensitive material that has high sensitivity, excellent storage stability over time and pressure resistance, and is stable against fluctuations in the pH of a color developing solution.

[Structure of the invention]

The above object of the present invention is to provide at least a blue-sensitive layer on a support.
In a silver rhodanide color photographic light-sensitive material having green-sensitive and red-sensitive silver rhodanide emulsion layers, all the silver halide grains in the silver rhodanide emulsion layers are chlorinated. This is achieved by making the silver halide color photographic material contain 70 mol% or less of silver, gold sensitization, and the total amount of gelatin contained in the silver halide color photographic material being 7.5 g/m' or less.

[Specific structure of the invention]

The halide grains of the present invention are silver halide grains having a silver chloride content of 70 mol% or less, and may be any of silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chlorobromoiodide, etc. That's fine, but
Silver chlorobromide is preferred.

When used in a blue-sensitive silver halide emulsion layer, the silver chloride content is particularly preferably 5 mol% or more and 20 mol% or less. When used in green-sensitive and red-sensitive silver halide emulsion layers, the silver chloride content is particularly preferably 15 mol% or more and 60 mol% or less. Either case is particularly preferable in terms of suppressing an increase in fog during storage over time.

The grain size of the silver halide grains used in the present invention is 1 μm.
The following is good. The average particle size is expressed as follows.

In the case of cubic silver halide grains, the grain size of silver halide grains is determined by the length of its side, and in the case of grains with shapes other than cubes such as spheres, the grain size is calculated by converting it into a cube having the same volume. The average particle size 7 is expressed by the following equation where ri is the particle size on each side of the particle and ni is the number of particles having the particle size ri.

Σn1ri r″′Σn1 The grain size distribution of the silver halide grains used in the present invention may be polydisperse or monodisperse, but it is more preferably a monodisperse emulsion. means an emulsion in which the coefficient of variation in the grain size distribution of silver halide grains contained in the emulsion is 22% or less, preferably 15% or less.The coefficient of variation is the breadth of the grain size distribution. The above particle size can be measured by various methods commonly used in the technical field for the above purpose.Typical methods include:
Loveland's [Particle Size Analysis Method J A, S.

T.M., Symposium on Light Microscopes, 1955, pp. 94-122, or chapter 2 of ``Theory of the Photographic Process'', co-authored by Mies and James, 3rd edition, published by Macmillan Publishing Co., Ltd. (1966). It is described in.

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Alternatively, the halide ions and silver ions may be generated by sequentially and simultaneously adding the halide ions and silver ions while controlling the pH and pAg in the mixing pot, taking into consideration the critical growth rate of the silver halide crystals.

By this method, monodisperse silver halide grains with regular crystal shapes and nearly uniform grains can be obtained.

The crystal phase of the silver halide grains according to the present invention is - For boat fishing,
Cubic particles are used, but particles with regular crystal shapes such as octahedrons and tetradecahedrons obtained by the presence of various compounds during the particle growth process, and particles with these shapes can also be used. The crystals may have rounded corners or cores, or may have irregular crystal shapes such as spherical or plate shapes.

In these particles, any ratio of the (1001 plane to the (111) plane) can be used. Also, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion of the present invention is optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holoporacyanine dyes, hemicyanine dyes, tyryl dyes, hemioxanol dyes, etc. are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetofuzole nucleus, pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: and these. These include a nucleus in which an aromatic hydrocarbon ring is fused to the nucleus. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbyl acid group can be applied.

Examples of the sensitizing dye used in the blue-sensitive silver halide emulsion layer of the present invention include West German Patent No. 929.080, US Patent No. 2,231,658, US Pat.
2゜503,776, 2,519.001, 2,912.329, 3゜656.959, 3
, No. 672,897, No. 3,694.217, No. 4,025.349, No. 4,046.572, British Patent No. 1,242.588, Japanese Patent Publication No. 14030/1973, No. 52-24844 Examples include those listed in the No. In addition, useful sensitizing dyes used in green-sensitive/N silver chloride emulsions include, for example, U.S. Pat. No. 1,939.
No. 201, No. 2,072.908, No. 2,739.1
No. 49, No. 2,945.763, British Patent No. 505.9
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 79 and the like. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat. .629, same 2
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 776.280. Furthermore, US Patent 2
, 213.995, 2,493.748, 2,
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 519.001 and West German Patent No. 929.080 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive halogen emulsions.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.

Examples of dyes that do not themselves have a spectral sensitizing effect, or substances that do not substantially absorb visible light and exhibit supersensitization, are used together with sensitizing dyes, such as aromatic organic acid formaldehyde condensates ( For example, US Patent 3,4
No. 37.510) cadmium salts, azaindene compounds, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. No. 2,933.390,
3,635.721). The combinations described in US Pat. Nos. 3,615,613, 3,615,641, 3,617,295, and 3,635,721 are particularly useful.

In the silver halide color photographic light-sensitive material of the present invention, all the silver halide emulsions in the blue-sensitive layer, green-sensitive layer and red-sensitive layer must be gold-sensitized. If even one layer is not gold sensitized, fog will increase during storage of the result, and the fog of the layer to which gold sensitization has been applied will also increase.

For gold sensitization in the present invention, a gold sensitizer having an oxidation number of +1 or +3 is used. Typical examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold, etc. It will be done.

The amount of gold sensitizer added varies depending on various conditions, but the preferable amount is 5 x 10-' to 5 per mole of silver halide.
X 10-' mol, preferably 2 X 10-'
'~I X 10-' mol, more preferably 2.6X
10-e to 9X 10-' moles.

The gold sensitizer may be added at any stage in the production process of silver genide emulsion, but it is preferable to add the gold sensitizer at any stage between the completion of formation of silver genide and the end of chemical sensitization.

Further, in the present invention, a gold sensitizer may be used in combination with a sulfur sensitizer.

As the sulfur sensitizer, known ones can be used.

For example, sulfur sensitizers that can be used include thiosulfate,
Examples include allylthiocarbamide thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine.

The sulfur sensitizer may be added in an amount that sensitizes silver halide, and there is no particular limitation, but as a guide, in the case of sodium thiosulfate, it is preferably IX per mole of silver halide.
to-' to l x 10-' mol, more preferably 2
It can be contained in an amount of X 10-' to 8 X 10-' moles.

In addition to lime-treated gelatin, gelatin according to the present invention includes acid-treated gelatin, Bulletin of Society of Science of 7 Otograph ("Bull, Soc, Sci, Phot, Japan)"
Enzyme-treated gelatin as described in No. 16.30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

The amount of gelatin coated on the silver halide color photographic light-sensitive material is 7.5 g/m" or less, but more preferably 6.0 g/m" to 7-0 g/m" from the viewpoint of pressure resistance. .

If it is less than 6.0 g/m'', the stability against pH fluctuations of the developer will be slightly impaired.

In the silver halide grains of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide can be controlled by using a silver halide solvent as necessary during production. .

Examples of the silver halide solvent include ammonia, thioether, thiourea, thiourea derivatives such as 411-substituted thio atom, and imidazole derivatives. Regarding thioethers, see US Pat. No. 3,271゜157, US Pat.
No. 90.387, No. 3,574.628, etc. may be referred to.

Preferably, noble metal ions are added to the interior of the silver halide grains of the present invention.

The noble metal salt is preferably an iridium salt, a rhodium salt, a gold salt, a cadmium salt, or a lead salt, and particularly an iridium salt is more preferable. The amount of these noble metal salts added is preferably from lo-9 to lO1 mole per mole of silver halide;
More preferred is 10-' moles.

The silver halide grains of the present invention may have unnecessary soluble salts removed after grain formation. Alternatively, it may be left as is.

When removing the salts, any of the long-known Nordel water washing methods, dialysis methods, coagulation water washing methods, etc. can be used.

The silver halide color photographic light-sensitive material of the present invention has the following features:
It is preferable to contain a compound represented by:

General formula [■] In the formula, R and R2 are each a hydrogen atom, a halogen atom, a carboxylic acid group (including its salt), a sulfonic acid group (
), mercapto group, alkylthio group, acyl group, carbamoyl group, acylamino group, acyloxy group, alkylcarbonyl group, sulfonamido group, aminosulfonyl group, alkylsulfonyl group, alkylsulfinyl group, -2 ■ ■ each, Represents a hydrogen atom, a halogen atom, an amino group, a hydroquine group, a carboxylic acid group (including its salt), or a sulfonic acid group (or its salt).

n represents an integer of 0 to 3. ] represents a monovalent group selected from

R1 represents a halogen atom or a monovalent group.

n and n2 each represent an integer of 0 to 4, n represents an integer of 0 to 3, the sum of nl+12 represents an integer of 1 to 4, and the sum of nl+n and n represents an integer of 1 to 4.

Specific examples of the compound represented by the general formula CI) are listed below, but the present invention is not limited thereto.

-5 -6 ■ -8 -9 -10 1 -11! -12 -21 ■ -22 -13 -14 ■ 3 ■ -24 -15 -16 ■ -25 ■ -26 ■ 7 ■ 8 ■ 7 ■ 8 ■ 9 ■ 0 ■ -29 ■ -30 SIJ3N＆Nt+≧υ2 and i3 In order to incorporate the compound represented by general formula (1) into the silver halide photographic material of the present invention, it can be dissolved in water or an organic solvent miscible with water (for example, methanol, ethanol, etc.). , or dissolved in an organic solvent (which may not be miscible with water) and then dispersed in a hydrophilic colloid,
It can be added as a solution or dispersion. The amount added is preferably 1.0XlO per mole of silver halide.
-' to 1.0 mol, more preferably 1.2X 1
0-'~1. OX is 10 moles. The addition may be made at any time from the preparation of the silver halide emulsion to the time of coating, but preferably from the end of chemical ripening of the silver halide emulsion to the time of coating.

The addition site may be any layer of the light-sensitive silver halide emulsion layer and/or the non-light-sensitive hydrophilic colloid layer.

Layers constituting the silver halide color photographic light-sensitive material of the present invention include, in addition to the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer. Layers such as a subbing layer, an intermediate layer, an ultraviolet absorbing layer, a protective layer, and an antihalation layer can be provided as necessary.

In particular, the non-photosensitive layer containing the compound represented by the general formula (1) of the present invention may be applied in advance or may be applied simultaneously with the above-mentioned constituent layers. Preferably, it is coated in advance in terms of color turbidity and storage stability over time.

When the silver halide emulsion of the present invention is used in a color photographic light-sensitive material, aromatic primary
A dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized product of a grade amine developer (for example, a p-phenylenediamine derivative or an aminophenol derivative). The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above combinations.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable.

Dye-forming couplers can be used as development accelerators, bleach accelerators, developing agents, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants,
Compounds that release photographically useful 7-ragments such as chemical sensitizers, spectral sensitizers, and desensitizers can be included.

Colored couplers that have a color correction effect on these dye-forming couplers or I>IR that release development inhibitors during development and improve image sharpness and image graininess.
A coupler may also be used in combination.

In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different type of dye may be used. It may also be one that forms a pigment.

Instead of the DIR coupler, or in combination with the coupler,
A DIR compound which undergoes a coupling reaction with an oxidized form of a developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valence group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction at the base circle separated by the coupling reaction ( (referred to as timing DIR couplers and timing DIR compounds). Also, depending on the purpose, inhibitors that can be dispersed after release and those that are not so dispersible can be used alone or in combination. A colorless coupler that undergoes a coupling reaction with an oxidized aromatic primary amine developer, but does not form a dye, can also be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, various acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta dye-forming coupler, 5-pyrazolone couplers, pyrazolopenzimidazole couplers, pyrazoloazole couplers, and acylacetonitrile couplers can be preferably used.

As the cyan dye-forming coupler, naphthol couplers and 7-enol couplers can be preferably used.

In addition to the above-mentioned compounds, various photographic additives can be added to the silver halide photographic material containing the silver halide emulsion of the present invention.

Examples include ultraviolet absorbers (e.g. benzophenone compounds, benzotriazole compounds, etc.),
Development accelerators (e.g. l-aryl-3-virazolidone compounds, etc.), surfactants (e.g. alkylnaphthalene sulfonates, alkyl succinate ester sulfonates,
itaconate, polyalkylene oxide compounds, etc.)
, water-soluble anti-irradiation dyes (e.g. azo compounds, styryl compounds, oxonol compounds, anthraquinone compounds, triphenylmethane compounds, etc.)
, film property improvers (e.g. glycerin, polyalkylene glycol, polymer latex, solid or liquid paraffin, etc.), color clouding preventive agents (diffusion-resistant hydroquinone compounds, etc.), dye image stabilizers (e.g. hydroquinone derivatives, gallic acid derivatives, etc.) , phenolic compounds, hydroxychroman compounds, polyalkylpiperidine compounds, aromatic amine compounds, etc.), water-soluble or oil-soluble optical brighteners, ground color tone regulators (oil-soluble coloring dyes, etc.), and the like.

Dye-forming couplers that do not need to be adsorbed onto the surface of silver halide crystals Colored couplers DIR couplers DIR
compounds, image stabilizers, color cast 9 inhibitors, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. In the oil-in-water emulsion dispersion method, various methods for dispersing hydrophobic additives such as couplers can be applied, and usually a high boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low boiling point and/or A stirrer, a homogenizer, a colloid mill, a 70-git mixer,
It may be emulsified and dispersed using a dispersion means such as an ultrasonic device, and then added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

The ratio of high boiling point organic solvent to low boiling point organic solvent is 1:0.1~
It is preferable that l:50, more preferably l:1 to 1:20.

Examples of high boiling point solvents include phenol derivatives that do not react with the oxidized form of the developing agent, 7-tar acid alkyl esters, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters, etc. with a boiling point of 150°C or higher. Organic solvents are used.

Low-boiling or water-soluble organic solvents that can be used with or in place of high-boiling solvents are described in U.S. Patent No. 2,801.171;
Examples include those described in No. 2,949.360. Organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene, and water-soluble organic solvents include acetone. , methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl ether, phenoxyethanol, and the like.

Surfactants can be used as dispersing aids, such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfonates, alkylsulfates, alkylphosphates, sulfosuccinates, and sulfoalkylsulfonates. Anionic surfactants such as polyoxyethylene alkylphenyl ether, nonionic surfactants such as steroidal saponins, alkylene oxide derivatives and glycidol derivatives, amino acids, aminoalkylsulfonic acids, and alkyl betaines. It is preferred to use amphoteric surfactants such as cationic surfactants such as quaternary ammonium salts, and cationic surfactants such as quaternary ammonium salts.

As a latex dispersion method, for example, US Pat.
．． No. 363, No. 4,214.047, No. 4,203.
No. 716, No. 4゜247.627, JP-A-49-74
No. 538, No. 51-59942, No. 51-59943
The method described in No. 54-32552 is preferred.

Any known method can be used for developing the photographic material containing the silver halide emulsion of the present invention.

Each processing step is usually carried out by immersing the photosensitive material in a processing solution, but other methods include, for example, a spray method in which the processing solution is supplied in the form of a spray, and a method in which the material is brought into contact with a carrier impregnated with the processing solution. A web method, a method of performing viscous development processing, etc. may be used.

The color development process includes a color development process, a bleaching process, a fixing process, a water washing process if necessary, and/or
Alternatively, a stabilization treatment step is carried out, but instead of a treatment step using a bleach solution and a treatment step using a fixer solution, a bleach-fixing geography step can be carried out using a l-bath bleach-fix solution, or a color development It is also possible to carry out a monobath processing step using a one-bath development, bleaching, fixing and fixing processing solution in which bleaching and fixing can be carried out in one bath.

In combination with these treatment steps, a pre-dural treatment step, its neutralization step, a stop and fixation geography step, a post-dural treatment step, etc. may be performed. In these treatments, instead of the color development process, an activator treatment process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution, or an activator treatment process may be performed instead of the monobath process. Beta treatment, bleaching, and fixing treatments may be performed simultaneously.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these embodiments.

Example 1 Four types of silver chlorobromide emulsions having the average grain size and silver chloride content shown in Table 1 below were produced by the Chondral double jet mixing method described in JP-A No. 54-48521. did. All silver halide grains were single-coat-1. For emulsions A and B, sodium thiosulfate was added at 6 x 10-' mol per mol of silver halide, and chloroauric acid was added at 3.5 x 10-' mol per mol of silver halide. In addition, chemical sensitization was carried out, and blue sensitization was carried out by adding the following blue sensitizing dye (BSD-1) in an amount of 4.3×10 −' mol per mol of silver halide.

This silver halide emulsion also contains 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene C3TB-1 as a stabilizer per mole of silver halide! , I
X 10-" moles were added.Each emulsion was designated as A-1 and B below.
-1.

On the other hand, emulsion B-2 was prepared by chemically sensitizing emulsion B by removing only the chloroauric acid.

Next, for emulsions C and D, sodium thiosulfate was added to lXl0-' mol per mol of silver halide, chloroauric acid was added to 6 x 10-' mol per mol of silver halide, and green sensitizing dye (GSD-1) was added. 2 per mole of silver halide
10-'mol of X was added to sensitize the green color.

In this silver halide emulsion, 1.5TB-1 was added per mole of silver halide. 10-'' moles of OX were added.Each emulsion is hereinafter referred to as C-1 and D-1.

On the other hand, a chemically sensitized emulsion was prepared by removing only the chloroauric acid from the emulsion, and designated as D-2.

Furthermore, for emulsions C and D, sodium thiosulfate was added at 2 X 10-' mol per mol of silver halide, chloroauric acid was added at 1 X 10-' mol per mol of silver halide, and red sensitizing dye (BSD-1) was added to 9 per mole of silver 10genide
10-'mol of X was added to red sensitize.

Further, 5TB-1 was added to this silver halide emulsion in an amount of 1.5×10 −' mol per mol of 7S silver halide. Each emulsion is hereinafter referred to as C-3 and D-3.

On the other hand, a chemically sensitized emulsion was prepared by removing only the chloroauric acid from the emulsion, and designated as D-4.

(BSD-1) (G S D -1') Each layer of the structure shown below is formed on a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the first layer side of the other side. A multilayer silver halide color photographic material was prepared. The coating solution was prepared as follows.

First layer coating liquid Yellow coupler (Y-1) 26.5g, dye image stabilizer (ST-t) 10.0g, additive (IQ
-1) 0.46g and high boiling point organic solvent (DNP) l
Add and dissolve ethyl acetate 60+a (2) in Og, and add this solution to 1
A yellow coupler dispersion was prepared by emulsifying and dispersing the mixture in 220 mQ of a 0% gelatin aqueous solution using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The second to seventh layer coating solutions were also the same as the first layer coating solution.5U-2 and 5U-3 were used as coating aids, and H-1 and H-2 were used as hardeners.

T DOP (Dioctyl 7 tallate) NP (Dinonyl phthalate) DIDP (diisodecyl phthalate) Q-1 H υ■ Q-2 tl ltl l-1 )L)311)υ3h U-1 U-2 Sample number i- prepared in this way The following evaluations were conducted.

1 to 26 were subjected to wedge exposure using a high-sensitivity photosensitive needle KS-7 type (manufactured by Konica Corporation), and the reflection densities of the yellow magenta and cyan dye images obtained by performing the development process shown below were measured using PDA-65.
Sensitivity (density 1.
The reciprocal number S) of the exposure amount giving 0 was determined.

The relative sensitivity of each sample is shown when each sensitivity of sample number 1-1 is set as 100.

Processing process Time Temperature color development 3 minutes 30 seconds 33°C bleach fixing
1 minute 30 seconds 33°C water washing
Dry for 3 minutes at 30-35°C
2 minutes at 60-80°C The formulations of the color developing solution and bleach-fixing solution used are as follows.

Color developer pure water 800m (2 ethylene glycol l 5mQ benzyl alcohol 15IIQ Whitex B B (50% aqueous solution) 2m (1
(Fluorescent brightener; manufactured by Sumima Kagaku Kogyo Co., Ltd.) Hydroquineluamine sulfate 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline sulfate p-toluenesulfonic acid potassium carbonate ( (anhydrous) Potassium sulfite (anhydrous) Potassium bromide Potassium chloride l-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) Add water to make 112, then add sulfuric acid or hydroxide to pH -10
, 1.

Bleach-fix solution Ethylenediaminetetraacetic acid-disodium-dihydrate Ammonium sulfite (40% aqueous solution) Ammonium thiosulfate (70% aqueous solution) Ethylenediaminetetraacetic acid iron (II[) g 4.5g 10.0g 2g g 0.2g 1. 0g mQ Lium 5g 5m12 50m12 Sodium salt 90g■ Storage stability over time A portion of the sample prepared above was stored at 50℃ and relative humidity 8
After storage under 0% conditions for 6 days, it was exposed through an optical wedge and processed according to the processing steps described above. The reflection densities of the yellow magenta and cyan dye images were measured on the processed samples using a PDA-65 densitometer, and the sensitivity (reciprocal of the exposure that gave a density of 1.0) and minimum density (Dmin) were determined.
and the sensitivity difference (ΔS) with the sample that is not stored over time, Dm
This shows the variation in in (Δwin).

ΔDmin= (Dmin after storage conditions) (Dmin before storage conditions) ■ Pressure resistant when drying After leaving the sample at 25°C and 140% RH for 2 hours, use a pole point needle with a sphere diameter of 0.1m+n perpendicular to the sample surface. The sample surface was moved in parallel at a speed of 1 CIII/sec, while at the same time a load of 0 to 100 g was applied continuously to the pole point needle, and the same development process as in the sensitivity/gradation test was performed. Record the load on the pole point needle when the yellow, magenta, and cyan densities increase due to pressure. In this case, the larger the load value, the greater the pressure resistance during drying.

■Pressure resistance when wet Yellow after development The sample was uniformly exposed so that the color density of magenta and cyan was 0.1 to 0.3, and the sample was color-developed at 35°C using the above-mentioned color developer. While performing this, a Pole Point needle with a spherical diameter of 0.3 + m is placed perpendicular to the sample surface in the color developing solution, and while the sample surface is moved in parallel at a speed of 1 cm/sec, the Pole Point needle is set at 0 to 50 mm at the same time.
Except for applying a load of g continuously.
Perform the same development process as in the gradation test, and record the load on the pole point needle when the yellow, magenta, and cyan density increases due to pressure. In this case as well, the larger the load value, the better the pressure resistance when wet is evaluated.

■ Stability of color developer against pH fluctuations After exposing the sample prepared above through an optical wedge, the color developer used in the processing step was adjusted to pH 9.7 and IO25 using sulfuric acid or sodium hydroxide. It was developed and processed. The processing steps after bleach-fixing are the same as those described above.

The yellow, magenta and cyan reflection densities of the treated samples were measured using a PDA-65 densitometer to determine characteristic curves.

The gradation γ (gradation of reflection density 0.2 to 0.7) of each sample was determined, and the variation in gradation (Δγ) was shown.

Δγ-(γ of sample treated with pH 10.5 color developer
) - (γ of sample treated with pH 9.7 color developer) As is clear from Table 3, the silver halide emulsions of the blue-sensitive layer, green-sensitive layer and red-sensitive layer were gold sensitized. A sample of the present invention (sample number 1-io, 18. 23
-26) are highly sensitive, have excellent storage stability and pressure resistance, and have stable gradations even when the pH of the color developing solution changes.

In addition, in sample numbers 1-to and 18.23 to 26, when the total gelatin amount coated was 6.0 to 7.0 g/m'', the pressure resistance and gradation stability against pH fluctuations of the color developer were It can be seen that it is particularly superior in terms of sex.

Example-2 Monodisperse c as shown in Table-4 was prepared in the same manner as in Example-1.
1. Chemical sensitization was performed in the same manner as B-2, and each
2, F-1, F-2, G-1, G-2, H-1 and H-
It was set as 2.

Emulsion 1. D-1 of Example-1 for J, K and L;
Chemical sensitization was performed in the same manner as D-2, D-3, and D-4, and each was subjected to 1-1.1-2.1-3. I-4, Jl, J-2,
J-3, 1-4, ni-1, ni-2, ni-3°K-4, L
-1, L-2, L-3 and L-4.

A multilayer silver halide color photographic material was prepared in the same manner as in Example 1 using each emulsion. However, the compound of Ichimonna CI) was added to the fourth and fifth layers as shown in Table 5.

Subsequently, the same treatments and evaluations as in Example 1 were performed, and the results are shown in Table 6.

However, regarding the sensitivity, the sensitivity of sample number 2-1 was set to 10
It is expressed as relative sensitivity when it is set to 0.

As is clear from Table 6, the silver halide emulsions of the blue-sensitive layer, green-sensitive layer, and red-sensitive emulsion were gold-sensitized, and the silver chloride content in the silver halide grains was 70%.
Samples of the present invention with a total gelatin amount of 7.5 g/m" or less (sample number 2-6.8.10.12-2)
1) has high sensitivity, long shelf life, pressure resistance, and P of color developer.
All of the resistance to H fluctuation is excellent.

From the comparison of sample number 2-6.8.10.12 of the present invention,
The silver chloride content of the silver halide grains contained in the blue-sensitive layer is 20 mol % or less, or the silver chloride content of the silver halide grains contained in the green-sensitive layer or the red-sensitive layer is 60 mol %. % or less, the increase in fog during storage over time is suppressed, which is more preferable.

In addition, in sample numbers 2-14 to 21, the fourth layer and the sixth layer
By adding the compound represented by Ichimonana CI) to the layer, the sensitivity fluctuation during storage over time is improved, and the p of the color developer is improved.
It can be seen that the stability of the gradation against H fluctuations is more excellent.

Furthermore, in place of emulsion H-1 in the first layer of sample number 2-12, a blue-sensitive emulsion was prepared by chemically sensitizing an emulsion with a silver chloride content of 4 mol % in the same manner as B-1 in Example-1. The sample used was a sample in which a green-sensitive emulsion was chemically sensitized in the same manner as D-1 in Example-1, using an emulsion with a silver chloride content of 12 mol % instead of emulsion L-1 in the third layer. In place of emulsion L-3 in the fifth layer, a red-sensitive emulsion chemically sensitized in the same manner as D-3 in Example-1 was used, and the same emulsion with a silver chloride content of 12 mol % was used. As a result of processing and evaluation, the effect of the present invention was recognized, but the anti-fogging effect during storage over time was slightly smaller than that of Sample No. 2-12.

Claims (1)

[Claims] In a silver halide color photographic light-sensitive material comprising at least blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers on a support, the silver halide in all the silver halide emulsion layers is The particles contain 70 mol% or less of silver chloride,
Furthermore, the silver halide color photographic material contains 7.5 g/g of total gelatin.
A silver halide color photographic light-sensitive material characterized by having a silver halide of m^2 or less.