JPS6336237A - Silver halide photographic sensitive material having excellent processing stability - Google Patents

Abstract

PURPOSE:To obtain the titled material capable of rapidly processing the photosensitive material and having improved image preservability and processing stability by dispersing a coupler capable of forming a cyan coloring matter in a high b.p. org. solvent having a specific dielectric constant. CONSTITUTION:The red sensitive emulsion layer of the color photographic sensitive material contains a silver halide particle having >=90mol% silver chloride content and a compd. which has an improved processing stability and is shown by formula I. Further, in said layer, the coupler capable of forming the cyan coloring matter which is shown by formula II is dispersed in the high b.p. org. solvent having <=6.0 dielectric constant which is improved the image preservability, such as preferably, a phthalic acid ester or a phosphoric acid ester. In the formula, Q is an atomic group necessary to forming 1,3,4-exadiazole ring and 1,3,4-thiazole ring, etc., M is H or an alkali metal, etc., R1 is 2-6C alkyl group, R2 is a ballast group, Z is H or a group capable of cleaving by reacting with an oxidant of a developing agent.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material.
The present invention relates to a silver halide photographic material that is suitable for rapid processing, has excellent image storage stability, and has good processing stability.

[Background of the Invention] In recent years, the industry has developed a silver halide photographic material that can be processed quickly, has high image quality, has excellent dye image storage stability, has excellent processing stability, and is low cost. In particular, silver halide photographic materials that can be rapidly processed are desired.

In other words, silver halide photographic materials are processed continuously in automatic processing machines installed at each processing laboratory. It is now required to process and convert the information to the user, and in recent years it has even become necessary to convert it within a few hours after receiving it, and the need for rapid processing is increasing. Furthermore, shortening of processing time improves production efficiency and makes it possible to reduce costs, so there is a need to develop rapid processing.

In order to achieve rapid processing, approaches have been taken from two aspects: photosensitive materials and processing solutions. Regarding color development processing, attempts have been made to increase the temperature, increase pi-1, increase the concentration of color-forming crude drugs, and it is also known to add additives such as development accelerators.

As the development accelerator, 1-phenyl-3-pyrazolidone described in British Patent No. 811.185, U.S. Patent No. 2,4
N-methyl-p-aminephenol described in No. 17,514, and N, N, N' described in JP-A-50-15554.

Examples include N'-tetramethyl-p-phenylenediamine.

However, these methods often fail to achieve sufficient speed and result in performance deterioration such as increased fog.

On the other hand, it is known that the shape, size, and composition of silver halide grains in silver halide emulsions used in photosensitive materials greatly affect development speed, etc., and the halogen composition has a particularly large effect, and high chloride halogen It has been found that especially when silver oxide is used, a significantly high development rate is exhibited.

On the other hand, in order to form a dye image using a silver halide color photographic light-sensitive material, an aromatic primary amine color developing agent is usually used to form a dye image on the silver halide particles in the exposed silver halide color photographic light-sensitive material. When reducing, it is itself oxidized, and this oxidized product reacts with a coupler previously contained in the silver halide color photographic light-sensitive material to form a dye. A three-layer coupler that forms three pigments, yellow, magenta, and cyan, is normally used as a coupler in order to perform color reviewing using a subtractive color method.

The dye image of the silver halide color photographic light-sensitive material obtained as described above may be stored by being exposed to light for a long time, or may be exposed to light for a short time but stored in a dark place for a long time. It is known that the color changes and fades significantly depending on the storage conditions. In general, the former type of color change is called photochromic color fading or bright color color change, and the latter type of color change is called chromatic color color fading or dark color color fading. Fading color,
It is necessary to keep the degree of fading to a minimum.

The basic properties required of each coupler are firstly that it has high solubility in high-boiling organic solvents, has good dispersibility and dispersion stability in silver halide emulsions, and does not easily precipitate. , that good photographic properties can be obtained, and that the resulting dye image has fastness to light, heat, moisture, etc. In particular, in cyan couplers, improvement of heat and humidity resistance (fading resistance) has become an important issue in recent years.

However, conventionally commonly used examples include:
JP-A-47-37425, JP-A No. 50-10135, JP-A No. 5゜-25228, JP-A No. 50-112038, JP-A No. 50-112038;
No. 50-117422, No. 50-130441, U.S. Patent No. 2,369,929, U.S. Patent No. 2,423.730,
The cyan couplers disclosed in Japanese Patent Nos. 2,434,272, 2,474,293, and 2,698.794 are unsatisfactory because of their poor fading properties, especially their dark fading properties.

For this reason, various cyan couplers have been studied to improve the photobleaching properties, and for example, U.S. Pat.
No. 95,826, JP-A-50-112038, JP-A No. 53
2,5-diacylamino cyan coupler J disclosed in No. 109630 and No. 55-163537:
and U.S. Patent Boxes 3,772,002 and 4,443.
A phenolic cyan coupler having an alkyl group having 2 or more carbon atoms at the 5th position, which is described in , No. 536, etc., was discovered as a cyan coupler having excellent dark fading properties. Especially regarding the latter phenolic cyan coupler,
As described in No. 205447, the dielectric constant is 6.
When used in combination with a high boiling point organic solvent having a boiling point of 0 or less, a silver halide photographic light-sensitive material having excellent light fading properties, dark fading properties, dispersion stability, etc. can be obtained.

Therefore, in order to produce a silver halide photographic material that can be rapidly processed and has excellent light fading resistance, dark fading resistance, dispersion stability, etc., a phenol having an alkyl group having 2 or more carbon atoms at the 5th position is used. The dielectric constant of the cyan coupler is 6.0.
It is conceivable to dissolve it in the above-mentioned high boiling point organic solvent and incorporate it into the high chloride silver halide layer.

Incidentally, silver halide photographic materials are generally processed continuously in various developing laboratories such as laboratories while replenishing replenishers. It is difficult to keep it constant, and there is a problem that photographic characteristics (particularly gradation fluctuations) fluctuate due to changes in the composition of the processing liquid. This problem has become even more serious as processing liquids have become less replenishable in recent years.

In particular, when a phenolic coupler having an alkyl group with 2 or more carbon atoms at the 5th position is used in a high chloride silver halide layer, the photographic properties may change significantly due to changes in the composition of the processing solution and fluctuations in conditions. It has become clear that the problems of poor processing stability and stable photographic performance are serious.

Processing stability here refers to the degree of variation in sensitometry with respect to one degree change in the pH of the processing solution composition and the contamination of other compounds other than the processing solution composition.

In particular, it is almost impossible to completely eliminate contamination of the bleach-fixer with the developer, even if you set a strict replenishment rate, prevent evaporation, and eliminate substances eluted from the photosensitive material. Close to , especially for roller conveyance and automatic a! In machines, the amount of bleach-fix solution mixed into the developer solution varies significantly depending on the processing claw and the method of squeezing, and if the processing solution replenishment rate decreases, the rotation speed of the processing solution will decrease.
Furthermore, the reality is that there are differences in the contamination rate.

Furthermore, although the color developer is maintained at a high pH, IIH fluctuations in the color developer are unavoidable due to the amount of replenisher replenishment during continuous operation, air oxidation, etc.

Changes in photographic performance (in most cases, increased fog and gradation changes) due to contamination of the bleach-fix solution into the color developer and H fluctuations in the color developer can result in stable and good color and gradation reproduction. This is a major obstacle to implementation.

For the reasons mentioned above, it is extremely difficult to avoid contamination with bleach-fix solution and IIH fluctuations. It is desired to develop a silver halide photographic material having excellent resistance to contamination and resistance to pH fluctuation. In addition, in silver halide color photographic light-sensitive materials, a dye image is formed by color development processing after exposure, and a coupler is contained using high chloride silver halide suitable for the above-mentioned rapid processing. In silver halide color photographic light-sensitive materials, the rate of production of the oxidized product of the color developing agent is often faster than the reaction in which the oxidized product and the coupler undergo a coupling reaction to form a dye. For this reason, a large amount of oxidized developing agent exists, and this oxidizes the latent image nuclei formed by exposure to light, causing latent image bleaching. This seems to be the cause of the increased processing variability of the material.

In particular, high chloride silver halide has a high development rate, but generally has poor latent image bleaching resistance due to an oxidized product of the developing agent produced in excess. Furthermore, if the above-mentioned low dielectric constant and high boiling point organic solvent with a dielectric constant of 6.0 or less is used as a coupler solvent, image preservation is excellent, but since the oxidized form of the developing agent is slowly incorporated into the oil, the developing agent It is thought that the degree of excess of the oxidant increases dramatically, resulting in a system in which latent image bleaching is very likely to occur, resulting in the deterioration of the processing stability. Furthermore, it has been confirmed that when a conventionally used high-boiling organic solvent with a high dielectric constant such as dibutyl phthalate is used, the effect on the dye image is negligible.

[Object of the invention] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a silver halide photographic light-sensitive material that is suitable for rapid processing, has excellent image storage stability, and has good processing stability. Our goal is to provide the following.

[Structure of the Invention] As a result of extensive research by the present inventors, the object of the present invention is to form a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support. In a silver halide photographic light-sensitive material having a photographic constituent layer including a silver emulsion layer, the red-sensitive silver halide emulsion layer contains silver halide grains having a silver chloride content of 90 mol % or more, and further contains the following general Contains a compound represented by formula [S], and contains a cyan dye-forming coupler represented by general formula [I] below, dispersed using a high boiling point organic solvent with a dielectric constant of 6.0 or less. It has been found that this can be achieved by using a silver halide photographic light-sensitive material.

General formula [S] (wherein, Q is a 1,3.4-oxadiazole ring, 1.3
．． Represents an atomic group necessary to form a 4-thiadiazole ring or a 1,3,5-triazine ring. M represents a hydrogen atom, an alkali metal atom, or an ammonium group.

) General formula [I] (In the formula, R1 represents an alkyl group having 2 to 6 carbon atoms.

R2 represents a ballast group. Z does not represent a hydrogen atom or a group that can be separated by reaction with the oxidized product of the color developing agent.

) [Specific structure of the invention] Hereinafter, the configuration of the present invention will be specifically explained.

In the silver halide photographic material of the present invention, the red-sensitive silver halide emulsion layer contains a compound represented by the general formula [S].

In the general formula [S], the 1,3゜4-oxadiazole ring, 1.3.4-thiadiazole ring, and 1,3.5-t-lyazine ring formed by Q are any substitutable substituents. Including those with groups. Examples of substitutable groups include alkyl groups, aryl groups, alkenyl groups, cycloalkyl groups, mercapto groups, amine groups, acylamino groups, sulfonamide groups, and heterocyclic groups. Further, examples of the alkali metal atom represented by M include a sodium atom and a potassium atom.

Among the compounds represented by the general formula [S] according to the present invention,
Preferred examples include compounds represented by the following general formula [SA].

General formula [SA] In the formula, Z represents an oxygen atom or a sulfur atom.

RA is a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, -8R,, -NH802
Represents RAtF or a heterocyclic group. Here, RAI and RA2 represent a hydrogen atom, an alkyl group, or an aryl group, and RA3 and RA'l- each represent an alkyl group or an aryl group. Further, M represents a hydrogen atom, an alkali metal atom or an ammonium group.

RA, RA, , RAZ in general formula [SA]
.

Examples of the alkyl group represented by R, 43, and RA4- include a methyl group, benzyl group, ethyl group, and propyl group, and examples of an aryl group include a phenyl group and a naphyl group. represents the group of In addition, RBI and R[3□ are RA+ in the general formula [SA], respectively.
and represents a group having the same meaning as RA-L.

Specific examples of compounds represented by the general formula [S] are shown below, but the present invention is limited to these.
], for example, chemical and pharmaceutical picolethane (Q hemica
l and PharmaceuNcalBul
letin) (Tokyo) 261. 314
(1978), JP-A-55-79436, Berichte.
3erichte der [) eutsc
hen Q hemischenGesellsdr
aft) 82, 121 (1948), U.S. Patent No. 2.843.491, U.S. Patent No. 3,017,270
No., British Patent No. 940.169, JP 51-102
No. 639, Journal of American Chemical
Society, 44.1502-1510, etc., and can be synthesized according to the methods described in these documents.

In order to contain the compound represented by the general formula [S] according to the present invention (hereinafter referred to as compound [S]) in the silver halide emulsion layer according to the present invention, water or an organic solvent optionally miscible with water can be used. It may be added after being dissolved in (for example, methanol, ethanol, etc.). Compound [S] may be used alone, or in combination with another compound represented by the general formula [S], another stabilizer other than the compound represented by the general formula [S], or a fog suppressant. It's okay.

The timing of adding the compound [S] is before the formation of silver halide grains, during the formation of silver halide grains, from after the completion of silver halide grain formation to before the start of chemical ripening, during chemical ripening, at the end of chemical ripening, It may be applied at any time from the end of chemical ripening to the time of application. Preferably, it is added during chemical ripening, at the end of chemical ripening, or after the end of chemical ripening and before the time of coating. The entire amount may be added at one time, or may be added in multiple portions.

It can be added directly to the silver halide emulsion or silver halide emulsion coating solution, or it can be added to the coating solution for the adjacent non-photosensitive hydrophilic colloid layer to prevent J stiffness during multilayer coating. may be contained in the silver halide emulsion layer according to the present invention.

There is no particular restriction on the amount of addition, but it is usually 1 x 10-6 mol to 1 x 10-1 mol per liter of silver halide.
It is preferably added in an amount of 1 x 10-5 mol to 1 x 10-2 mol.

Some of the compounds [S] according to the present invention are compounds known in the art as stabilizers or antifoggants. For example, British Patent No. 1.273.030, Japanese Patent Publication No. 58-9936, Japanese Patent Publication No. 60-27010, Japanese Patent Application Publication No. 102639-1980, Japanese Patent Application Publication No. 22416-1987,
There are descriptions in JP-A-55-59463, JP-A-55-79436, J: and JP-A-59-232342, etc. However, in the above-mentioned known documents, although there are descriptions regarding fog suppression and emulsion stabilization, the effects of the present invention, i.e., silver halide grains with a high silver chloride content, a specific cyan coupler, and a specific high boiling point, are described. It has not been known in the past that this method is effective against processing fluctuations that occur during color development processing of silver halide color photographic photosensitive materials containing organic solvents.

Compound [S] is generally known as a compound that exhibits effects such as fog suppression while also desensitizing and suppressing visual images. (Eds.), Corona Publishing, 1979, 0195, etc.) The application of these compounds to the system of the present invention to improve processing stability is a completely unexpected effect. there were.

The reason why this seemingly unique effect occurs has not yet been elucidated, but if we consider the mechanism, we will find the following.

As mentioned above, color development is the so-called "silver development" in which exposed silver halide is reduced to silver by a color developing agent.
and a so-called "color development" process in which the oxidized color developing agent produced by the above reaction and the dye-forming coupler undergo a coupling reaction to produce a dye. However, the silver halide emulsion with a high silver chloride content according to the present invention,
The system in which the dye-forming couplers of the present invention are combined is a system in which the "silver development" process is very fast and the "color development" process is slow. Therefore, the oxidized form of the color developing agent produced during "silver development" is present at a high concentration around the silver halide grains. In this case, the oxidized product of the color developing agent, which is present in large amounts, bleaches the "latent image" formed on the silver halide grains by exposure, leaving it in a state where it cannot be developed. '' may occur, resulting in a decrease in color density. Considering this, it is possible to explain why simply using an emulsion with a high silver chloride content does not improve the color development as expected. Considering that the "latent image" is strengthened and becomes difficult to bleach by using S], the effect of the present invention is also obvious.Also, the composition of the silver halide particles according to the present invention is It is more preferable to contain silver bromide in an amount of 0.5 to 5 mol %, but this required silver bromide may also be related to "latent image reinforcement".

The above considerations are just speculations, and the facts are still unknown.

The red-sensitive silver halide emulsion layer of the silver halide photographic light-sensitive material of the present invention contains silver halide grains having a silver chloride content of 90 El % or more.

The silver halide grains of the present invention have a silver chloride content of 90 mol% or more, a silver bromide content of 10 mol% or less,
The silver iodide content is preferably 0.5 mol% or less. More preferably, the silver bromide content is 0.5 to 5 mol%.
silver chlorobromide.

The silver halide grains of the present invention may be used alone, or
It may be used in combination with other silver halide grains having different compositions. Further, it may be used in combination with silver halide grains having a silver chloride content of 10 mol % or less.

In addition, in the silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more according to the present invention, the silver chloride content in the total silver halide grains contained in the emulsion layer is The proportion of silver halide grains of 90 mol% or more is 60% by weight or more, preferably 80% by weight or more.

The composition of the silver halide grains of the present invention may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. Further, when the composition inside and outside the particle is different, the composition may change continuously or discontinuously.

The particle size of the silver halide grains of the present invention is not particularly limited, but in consideration of other photographic performance such as rapid processability and sensitivity, it is preferably 0.2 to 1.6 μm1, more preferably 0.
．． It is in the range of 25 to 1.2 μm.

Note that the particle size can be measured by various methods commonly used in the technical field. A typical method is Loveland's [Particle Size Analysis Method J
(A, S, T, M, Symposium Online 1~・
Microscopy, 1955.

(pp. 94-122) or Theory of the Photographic Process (co-authored by Mies and James, 3rd edition, published by Macmillan Publishing Co., Ltd.)
1966) No. 21? )It is described in.

The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse, monodisperse or monodisperse.

Preferably, the silver halide grains are monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain size distribution. The coefficient of variation here is a coefficient indicating the breadth of the particle size distribution, and is defined by the following equation.

Here, ri represents the particle size on each side of the particle, and ni represents the number thereof.

The grain size here refers to the diameter in the case of spherical silver halide grains, and in the case of grains with shapes other than cubic or spherical, the diameter when the projected image is converted to a circular image of the same area. .

The silver halide grains used in the emulsion of the present invention can be prepared by acidic method.
It may be obtained by either the neutral method or the ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced.

The method of creating and growing the seed particles may be the same or different.

Further, the soluble silver salt and the soluble halogen salt may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferable. Furthermore, as a form of simultaneous mixing method,
I) A! described in No. 4-4.8521 etc. +-Chondrold-double jet method can also be used.

Furthermore, if necessary, a silver halide solvent such as thioether may be used.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.

Also, U.S. Patent No. 4.183.756, U.S. Patent No. 4,22
No. 5,666, JP-A No. 55-26589, Special Publication No. 55-Sho.
Specifications such as No.-42737, The Journal ΔB.
Photographic Science LJ, Photog
r, 5ci), 21.

39 (1973), etc., by the method described in the literature such as
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can also be prepared and used. Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

The silver halide grains used in the emulsion of the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Alternatively, metal ions can be added using lead salts to be included inside the particles and/or on the particle surface, and by placing them in a suitable reducing atmosphere.
Reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

Emulsion containing silver halide grains according to the present invention (hereinafter referred to as
In the emulsion of the present invention), unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left in the emulsion.

In the case of removing the salts, it can be carried out based on the method described in Research Disclosure v-17643.

The silver halide grains used in the emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains. Preferably, the particles are particles on which latent images are mainly formed.

The emulsion of the present invention is chemically sensitized by conventional methods.

In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensing methods can be used alone or in combination.

In the present invention, for example, a chalcogen sensitizer can be used as a chemical sensitizer. Chalcogen sensitizer is a general term for sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and for photography, sulfur sensitizers and selenium sensitizers are preferred. Examples of sulfur sensitizers include thiosulfate, allylthiocarbazide, thiourea, allyl isoselenocyanate,
Examples include cystine, p-toluenethiosulfonate, and rhodanine. Other U.S. Patent Nos. 1,574,944, 2.410,689, 2.278.947, 2.728.668, 3.501.313, 3.656.955 , West German Publication (OLS)
) No. 1,422,869, JP-A-56-24937
Sulfur sensitizers described in Japanese Patent No. 55-45016 and the like can also be used. The amount of sulfur sensitizer added is p
It varies over a considerable range depending on various conditions such as the H1 temperature and the size of silver halide grains, but as a rough guide, it is preferably about 10 -7 mol to 10 -1 mol per mol of silver halide.

Selenium sensitizers can be used instead of sulfur sensitizers, but examples of selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas,
Selenides such as selenoketones, selenoamides, selenocarboxylic acid salts and esters, selenobosphates, diethyl selenide, and diethyl diselenide can be used, and specific examples thereof are described in U.S. Pat. No. 1,574.
, No. 944, No. 1,602,592, No. 1, 623
．． No. 499 specification.

Furthermore, reduction sensitization can also be used together. The reducing agent is not particularly limited, but examples include stannous chloride, thiourea dioxide, hydrazine, and polyamine.

Moreover, noble metal compounds other than gold, such as palladium compounds, etc. can also be used in combination.

The silver halide grains of the present invention may contain a gold compound. As for the gold compound, the oxidation number of gold may be +1 or +3, and various types of gold compounds are used. Typical examples include chlorauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, te]-lacyano auric azide, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, Gold selenide etc.

The gold compound may be used to sensitize silver halide grains, or may be used so as not to substantially contribute to sensitization.

The amount of the gold compound added varies depending on various conditions, but as a guideline, it is from 10-8 mol to 10-1, preferably from 10-7 mol to 10-2 mol, per mol of silver halide. These compounds may be added at any time during silver halide grain formation, during physical ripening, during chemical ripening, or after completion of chemical ripening.

The emulsion of the present invention can be spectrally sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more.

Next, the cyan dye-forming coupler represented by the following general formula [I] used in the present invention will be explained in detail.

General formula [I] (In the formula, R1 represents a straight chain or branched alkyl group having 2 to 6 carbon atoms, Z represents a hydrogen atom or a group that leaves by a coupling reaction, and R2 represents a ballast group. ) In the present invention, the straight chain or branched alkyl group having 2 to 6 carbon atoms represented by R1 in the general formula [I] is, for example, a methyl group, an ethyl group, a propyl group, or a butyl group.

In general formula [I], the ballast group represented by R2 has a size and shape that imparts sufficient bulk to the coupler molecule to substantially prevent the coupler from diffusing from the layer to which it is applied to other layers. It is an organic group having Typical ballast groups include alkyl or aryl groups having 8 to 32 total carbon atoms. These alkyl groups and aryl groups may have a substituent, and examples of the substituent for this aryl group include an alkyl group, an aryl group, an alkoxy group, an allyloxy group, a carboxy group, an acyl group, an ester group, Examples include hydroxy group, cyano group, nitro group, carbamoyl group, carbonamide group, alkylthio group, arylthio group, sulfonyl group, sulfonamide group, sulfamoyl group, and halogen, and substituents for alkyl groups exclude alkyl groups. The substituents listed above for the aryl group may be mentioned.

Preferable examples of the ballast group include the following general formula %, where R3 represents an alkyl group having 1 to 12 carbon atoms, and A
r represents an aryl group such as a phenyl group, and this aryl group may have an @ substituent. Examples of the substituent include an alkyl group, a hydroxy group, an alkylsulfonamide group, and the most preferable one is a branched alkyl group such as a t-butyl group.

The group that leaves upon coupling defined by 7 in the general formula [I] determines the number of equivalents of the coupler and influences the reactivity of the coupling, as is well known to those skilled in the art. Typical examples include halogens such as chlorine and fluorine, aryloxy groups, substituted and unsubstituted alkoxy groups, acyloxy groups, sulfonamide groups, arylthio groups, heteroylthio groups, heteroyloxy groups, sulfonyloxy groups, and carbamoyloxy groups. Groups, etc.

More specific examples include JP-A Nos. 50-10135, 50-120334, and 50-13044.
No. 1, No. 54-48237, No. 51-146828
No. 54-14736, No. 47-37425, No. 50-123341, No. 58-95346, Japanese Patent Publication No. 4G-36894, U.S. Patent No. 3.476, 563,
It is described in the respective publications No. 3,737,316 and No. 3,227,551.

Next, specific examples of the coupler represented by the general formula [■] will be shown, but the coupler is not limited thereto.

The cyan dye-forming coupler of the present invention represented by the above general formula [I] usually has a content of I x 10- per mole of silver halide.
3 moles to 1 mole, preferably I x 10-" moles to 8
It can be used in the range of X10'' moles.

In the present invention, in addition to the cyan dye-forming coupler represented by the general formula [I], in the red-sensitive silver halide emulsion layer,
Further, if desired, a conventionally known cyan dye-forming coupler may be used in combination, but in this case, the total amount of the cyan dye-forming coupler represented by general formula [I] and other cyan dye-forming couplers must be within the above range. It is better to do so.

In the present invention, the high boiling point organic solvent with a dielectric constant of 6.0 or less used to disperse and contain the cyan coupler represented by the general formula [I] is, for example, a phthalate ester or phosphorus having a dielectric constant of 6.0 or less. These include esters such as acid esters, organic acid amides, ketones, and hydrocarbon compounds. Preferably, it is a high boiling point organic solvent with a dielectric constant of 6.0 or lower and 1.9 or higher and a vapor pressure of 0.5 mmH (+ or lower) at 100°C.Also more preferably, phthalate esters or These are phosphoric acid esters.Furthermore, the high boiling point organic solvent may be a mixture of two or more types.

Note that the dielectric constant referred to in the present invention refers to the dielectric constant at 30°C.

Examples of phthalic acid esters advantageously used in the present invention include those represented by the following general formula [a].

General formula [a] R4 and R5 each represent an alkyl group, an alkenyl group or an aryl group. However, the total number of carbon atoms in the groups represented by R4 and R5 is 8 to 32, preferably 16 to 24.

The alkyl group represented by R4 and R5 in general formula [a] may be linear or branched, such as a butyl group, hexyl group, 2-ethylhexyl group, 3.5.5-t-rimedylhexyl group, and octyl group. , nonyl group, tetradecyl group, hexadecyl group, octadecyl group, etc. R4
The aryl group represented by and R5 is, for example, a phenyl group, a naphthyl group, etc., and the alkenyl group is, for example, a hexenyl group, a heptenyl group, an ophtadecenyl group, etc.

These alkyl groups, alkenyl groups and aryl groups include those having single or multiple substituents.

In the above, R4 and R5 are preferably alkyl groups, such as 2-ethylhexyl group, 3.5.5-trimethylhexyl group, n-octyl group, n-nonyl group, etc.

The phosphoric acid ester is represented by the following general formula [bl].

General formula [bl R,0-P-OR.

OR? R6, R7 and R8 each represent an alkyl group, an alkenyl group or an aryl group. However, the total number of carbon atoms represented by R6, R7 and R8 is 24 to 54
It is.

The alkyl groups represented by R6, R7 and R8 in the general formula [b] are linear or branched, such as butyl group, pentyl group, hexyl group, 2-ethylhexyl group,
Nonyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, nonadecyl group, etc., and aryl groups include, for example, phenyl group, naphthyl group, etc.
Examples of the alkenyl group include hexenyl group, heptenyl group, and octadecenyl group.

These alkyl groups, alkenyl groups and aryl groups include those having single or multiple substituents. Preferably R6, R7 and R8 are alkyl groups, such as 2-ethylhexyl group, n-octyl group, 3.5.
Examples include 5-trimedhexyl group, n-nonyl group, n-decyl group, 5ec-decyl group, 5ec-dodecyl group, t-octyl group, and the like.

Typical specific examples of high boiling point organic solvents used in the present invention are shown below, but the present invention is not limited thereto.

General formula [a] General formula [bl R,0-P-OR.

OR.

These organic solvents are used in a proportion of 25 to 150 weight percent relative to the cyan dye-forming coupler of the present invention. Preferably 50 to 100% by weight based on coupler
It is.

The high boiling point organic solvent used in the present invention has a dielectric constant of 6
．． Any high boiling point organic solvent having a boiling point of 0 or less can be used, but high boiling point organic solvents represented by the general formulas [a] and [bl are preferred.

A cyan coupler according to the present invention represented by formula [I] (hereinafter referred to as a cyan coupler according to the present invention) and a high boiling point organic solvent having a dielectric constant of 6.0 or less (hereinafter referred to as a high boiling point organic solvent according to the present invention) ), the method used for ordinary cyan dye-forming couplers can be similarly applied, and the cyan coupler according to the present invention may be dispersed and contained using the high boiling point organic solvent according to the present invention.

In the present invention, in order to disperse the cyan coupler according to the present invention in a silver halide emulsion using the high boiling point organic solvent according to the present invention, the cyan coupler according to the present invention is added to the high boiling point standby solvent used in the present invention or After dissolving the high boiling point organic solvent used in the present invention in a mixed solvent with a low boiling point organic solvent used as necessary as shown below, it is mixed with an aqueous gelatin solution containing a surfactant, and then a stirrer, a homogenizer, Colloid mill, flow jet mixer,
After emulsifying and dispersing using a dispersion means such as an ultrasonic dispersion device,
It may be added to the silver halide emulsion, but a step of removing the low boiling point organic solvent may be included after or simultaneously with the dispersion.

Examples of low-boiling organic solvents that can be used in combination as necessary include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexane, tetrahydrofuran, methyl alcohol,
Acetonitrile, dimethylbormamide, dioxane,
Examples include methyl ethyl ketone, methyl isobutyl ketone, diethylene glycol monoacetate, acederacetone, nitromethane, carbon tetrachloride, and chloroform.

In the present invention, the ratio of the high boiling point organic solvent and the low boiling point organic solvent according to the present invention is 1:0.1 to 1:50, and more preferably 1:50 to 1:50.
:1 to 1:20 is preferable.

The silver halide emulsion layer of the silver halide photographic light-sensitive material of the present invention contains an oxidized product of an aromatic primary amine developer (for example, a p-phenylene diamine derivative, an amine phenol derivative, etc.) and a cup in the color development process. A dye-forming coupler is used that undergoes a ring reaction to form a dye. 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, a cyan coupler according to the present invention is used in the red-sensitive emulsion layer, and if desired, other cyan dye-forming couplers are used. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

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. Furthermore, even if these dye-forming couplers are 4-equal, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions need to be reduced. 2. Either is acceptable. Dye-forming couplers can be combined with the oxidized form of a developing agent to produce development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, Compounds that release photographically useful fragments 1 - such as spectral sensitizers and desensitizers can be included. Colored couplers that have a color correction effect on these dye-forming couplers, or DIR that releases a development inhibitor during development and improves 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. In place of the DIR coupler, or in combination with the coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the 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 valent group, and the intramolecular nucleophilic reaction within the door that J:removes during the coupling reaction,
Included are those in which the inhibitor is bonded so as to be released by an intramolecular electron transfer reaction or the like (referred to as timing DIR couplers and timing DIR compounds). Further, 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, acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Preferably, it is a compound represented by the following general formula [Y].

General Formula [Y] In the formula, RIY' represents a halogen atom or an alkoxy group. R2Y represents a hydrogen atom, a halogen atom, or an alkoxy group which may have a substituent.

RaY is an acylamino group that may have a substituent, an alkoxycarbonyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an arylsulfonamide group,
It represents an alkylureido group, an arylureido group, a succinimide group, an alkoxy group or an aryloxy group.

Z+Y does not represent a group that can be separated upon coupling with an oxidized color developing agent.

Specific examples of yellow dye-forming couplers that can be used include British Patent No. 1.077, 874, Japanese Patent Publication No. 45-40757, Japanese Patent Publication No. 1031-1981, Japanese Patent Publication No. 47-26133, Japanese Patent Publication No. 48-94432, Japanese Patent Publication No. 50-1989. -87650, 51-
No. 3631, No. 52-115219, No. 54-994
No. 33, No. 54-133329, No. 56-30127
No. 2,875,057, U.S. Patent No. 3,253,
No. 924, No. 3゜265.506, No. 3,408.1
No. 94, No. 3,551,155, No. 3,551,
No. 156, No. 3,664.8111, No. 3.72
5.072, 3.730.722, 3.8
91.445, 3,900, 483, 3.9
No. 29.484, No. 3.933.500, No. 3.97
3,968tan, 3.990.896, 4.0
No. 12.259, No. 4.022.620, No. 4
, No. 029,508, No. 4,057,432, No. 4,057,432, No. 4,057,432, No.
4.106.942, 4,133,958, 4,269.936, 4,286,053,
4,304,845, 4.314,023,
These are described in No. 4,336,327, No. 4,356.258, No. 4,386.155, No. 4,401,752, etc.

In the present invention, as the magenta coupler, the well-known 5
-Pyrazolone couplers, pyrazoloazole couplers, etc. can be preferably used.

More preferred are couplers represented by the following general formula [P] or [a].

General Formula [P] ■ Ar In the formula E, Ar represents an aryl group, RF represents a hydrogen atom or a substituent, and R12 represents a substituent. Y is a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent, and W is -N+-1-1-N+-(CO-
(N atom is bonded to the carbon atom of the pyrazolone nucleus) or -N
It represents HCONH-, and m is an integer of 1 or 2.

] General formula [A] Za represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Za may have a substituent.

X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, Ra represents a hydrogen atom or a substituent.

Examples of the substituent represented by Ra include a halogen atom,
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group,
Spiro compound residue, organic hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group , sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, aryldio group, and heterocyclic dio group.

These include, for example, U.S. Patent No. 2,600. ．． No. 788,
Same No. 3,061,432, Same No. 3,062,653, Same No. 3.127゜269, Same No. 3.311.476
No. 3,152,896, No. 3.419,39
1tan, same No. 3.519.1129, same No. 3.555.
No. 318, No. 3,684,514, No. 3.888
．． No. 680, No. 3,907,571, No. 3,92
No. 8,044, No. 3.930, No. 861, No. 3.9
Specifications such as No. 30.866 and No. 3.933.500, JP-A No. 49-29639, No. 49-111631, No. 49-129538, No. 50-13041, No. 52-58922, No. 55-62454, No. 55-
No. 118034, No. 56-38043, No. 57-35
858, 60-23855, British Patent No. 1,247,493, Belgian Patent No. 769.116
No. 792,525, West German Patent No. 2,156,11
Specifications of No. 1, Japanese Patent Publication No. 46-60479, Japanese Patent Publication No. 1973
No. 9-125732, No. 59-228252, No. 5
No. 9-162548, No. 59-171956, No. 6
No. 0-33552, No. 60-43659, West German Patent No. 1, No. 070.030, and US Patent No. 3.725.
It is described in each specification etc. of No. 067.

The cyan coupler according to the present invention can be used with conventionally known cyan dye-forming couplers to the extent that it does not contradict the purpose of the present invention. Preferred cyan dye-forming couplers that can be used in combination include couplers represented by the following general formula [E] or [F].

General Formula [E] In the formula, R1 represents an aryl group, a cycloalkyl group, or a heterocyclic group. R2 represents an alkyl group or a phenyl group. R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

R1, R2, and R3 may further have a substituent. Zl
represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

General Formula [F] In the formula, R4F represents an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, nonyl group, etc.). R5
F represents alkyl M (eg, methyl group, ethyl group, etc.). R6 represents a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine@), or an alkyl group (eg, methyl group, ethyl group, etc.).

R4, F, and R5F may further have a substituent.

22F represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

These cyan couplers are described in U.S. Patent No. 2.306.4.
No. 10, No. 2.356.475@, No. 2.362.
No. 598, No. 2,367.531, No. 2,369
, No. 929, No. 2,423, 730, No. 2,47
No. 4,293, No. 2,476.008, No. 2,4
No. 98,466, No. 2,545,687, No. 2,
728, 660, same No. 2.772.162, same No. 2
, 895,826, 2,976.146, 3.002.836, 3.419, 390, 3.446.622, 3.476, 563 ,
3.737.316, 3.758.308, 3.839,044, British Patent No. 478,99
No. 1, No. 945,542, No. 1□084.480
No. 1,377.233, No. 1, 388.0
24 and 1.543.040, as well as JP-A-47-37425 and JP-A-50-10135,
No. 50-25228, No. 50-112038, No. 5
No. 0-117422, No. 50-130441, No. 51
-6551, 51-37647, 51-528
No. 28, No. 51-108841, No. 53-109
No. 630, No. 54-48237, No. 54-66129
No. 54-131931, No. 55-32071, No. 59-146050, and No. 59-31953.

The yellow dye-forming coupler and the magenta dye-forming coupler are usually present in each silver halide emulsion layer in amounts ranging from 1.times.10@-3 mole to 1 mole per mole of silver halide, respectively.
Preferably, it can be used in a range of 1×10 −2 mol to 1×10 −1 mol.

The above dye-forming couplers are usually dissolved in a high boiling point organic solvent with a boiling point of about 150°C or higher, if necessary in combination with a low boiling point and/or water-soluble organic solvent, and then interfacially dissolved in a hydrophilic binder such as an aqueous gelatin solution. After emulsifying and dispersing using an activator,
It may be 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.

Examples of high boiling point organic solvents include phenol derivatives, phthalate esters, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters, etc. that do not react with the oxidized form of the developing agent.
An organic solvent having a temperature of 50° C. or higher is used.

Examples of low boiling point organic solvents that may be used as necessary include:
Examples include ethyl acetate, cyclohexanol, methyl ether ketone, and the like.

Examples of surfactants that can be used in the present invention include alkylbenzene sulfonates, alkylnaphthalene sulfones 11, alkyl sulfates, sulfosuccinates, alkyl phosphates, sulfosuccinates, and sulboalkyl polyols. Anionic surfactants such as xyethylene alkylphenyl ethers, nonionic surfactants such as styroid saponins, alkylene oxide derivatives and glycidol derivatives, amphoteric surfactants such as amino acids, aminoalkylsulfonic acids and alkyl betaines, etc. Surfactants, cationic surfactants such as quaternary ammonium salts and the like can be used. Specific examples of these surfactants can be found in the “Surfactant Handbook” (Sangyo Tosho,
(1966) and [Emulsifier/emulsifying equipment research/technical data collection] (For chemical general theory, other hydrophobic compounds such as hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, optical brighteners, etc.) may be added as necessary. can be added at the same time.

The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative film, a positive film, or a color photographic paper. In particular, when a color photographic paper intended for direct viewing is used, the method of the present invention can be used. The effects of this will be effectively demonstrated.

The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic materials, in order to perform subtractive color reproduction, a photographic coupler is usually used.
It has a structure in which a silver halide emulsion layer containing magenta, yellow, and cyan couplers and a non-light-sensitive layer are laminated on a support in an appropriate number and order of layers. The order may be changed as appropriate depending on the important performance and purpose of use.

When the silver halide photographic light-sensitive material of the present invention is a multicolor light-sensitive material, the specific layer structure includes a support, a yellow dye image-forming layer, an intermediate layer,
Particularly preferred are magenta dye image-forming layers, interlayers, cyan dye image-forming layers, interlayers, and protective layers.

As the binder (or protective colloid) used in the silver halide photographic material of the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugars, etc. Hydrophilic colloids such as derivatives, cellulose derivatives, synthetic hydrophilic polymeric substances such as single or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. Ru. It is desirable to add a hardening agent to the processing solution so that the photosensitive material can be hardened to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add a hardening agent to the processing solution.

In the present invention, in order to harden the silver halide emulsion layer, it is preferable to use a chlorotriazine hardener represented by the following general formula [HDAI or CHDB].

General formula [HDAI In the formula, Rd+ is a chlorine atom, hydroxy group, alkyl group, alkoxy group, alkylthio group, -0M group (here, M is a monovalent metal atom), -NR'R'' group ( Here, R' and Rn are each a hydrogen atom, an alkyl group,
aryl group) or -N HCOR'' group (where Rh is a hydrogen atom, an alkyl group, or an aryl group), and Rd2 has the same meaning as the above Rd+ except for the chlorine atom.

General formula [HDB] In the formula, Rd3 and Rd4 are respectively a chlorine atom and a hydro4
; cy group, alkyl group, alkoxy group or 10Mm (
Here, M represents a monovalent metal atom. Q and Q' each represent a linking group representing -0-1-8- or -N]-1-, and L represents an alkylene group or an arylene group. p and q each represent O or 1.

Next, describe typical examples of preferred hardeners represented by the general formulas [HDAI and [HDB].

To add a hardener represented by the general formula "HDAI General formula [HDB] to the silver halide emulsion layer or other constituent layers, add water or water to the silver halide emulsion layer or other constituent layers. It is sufficient to dissolve it in a solution miscible with tS (for example, methanol, ethanol, etc.) and add it to the coating solution for the above-mentioned constituent layer. The addition method may be either a batch method or an in-line method. The timing of addition is not particularly limited, but it is preferably added immediately before coating.

These hardeners are used in an amount of 0.5 to 10 per gram of coated gelatin.
0 mg, preferably 2.0 to 50 ma.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic material of the present invention.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

The silver halide photographic material of the present invention can contain an image stabilizer that prevents deterioration of the dye image.

Examples of image stabilizers include hydroquinone derivatives, gallic derivatives, phenol derivatives and their bis forms, hydroxycoumarans and their spiro forms, hydroxychroman and their spiro forms, piperidine derivatives, aromatic amine compounds, penzodioxane derivatives, and benzodi-quaternary derivatives. Preferred are sole derivatives, silicon atom-containing compounds, thioether compounds, and the like. As a specific example, 1,410 for British patents,
No. 846, special nN No. 1984-134326, No. 52-3
No. 5633, No. 52-147434, No. 52-15
No. 0630, No. 54-145530, No. 55-6
No. 321, No. 55-21004, No. 55-12414
No. 1, No. 59-3432, No. 59-5246, No. 5
No. 9-10539, Special Publication No. 48-31625, No. 49
-20973, 49-20974, 50-23
No. 813, No. 52-27534, U.S. Patent No. 2,36
No. 0,290, No. 2,418.613, No. 2,675
, 314, No. 2,701,197, No. 2.704.
No. 713, No. 2,710,801, No. 2,728.6
No. 59, No. 2,732,300, No. 2.735.76
No. 5, No. 2.816,028, No. 3.069.26
No. 2, No. 3.336.135, No. 3,432,30
No. 0, No. 3.457.079, No. 3.573.050
No. 3.574.627, No. 3.698.909, No. 3.7001455, No. 3.764.337,
3,935,016, 3,982.944, 4,013,701, 4,113,495,
4,120,723, 4,155.765, 4,159,910, 4,254,216, 4
, No. 268,593, No. 4,279.990, No. 4
．． No. 332.886, No. 4.360.589, No. 332.886, No. 4.360.589, No.
4,430.425, and 4,452,884.

In order to prevent fogging caused by discharge caused by frictional charging of the photosensitive material in the hydrophilic colloid layers such as the protective layer and intermediate layer of the silver halide photographic light-sensitive material of the present invention, and to prevent image deterioration due to UV light. It may also contain an ultraviolet absorber.

The silver halide photographic material of the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

The silver halide emulsion layer of the silver halide photosensitive material of the present invention,
And/or a matting agent can be added to other hydrophilic colloid layers for the purpose of reducing the gloss of the photosensitive material, increasing the ease of writing, preventing the photosensitive materials from sticking together, etc.

A lubricant can be added to the silver halide photographic material of the present invention in order to reduce sliding friction.

The silver halide photographic light-sensitive material of the present invention may contain an antistatic agent for the purpose of preventing static electricity. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
Other hydrophilic colloid layers may contain various additives for the purpose of improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and sensitizing). Surfactants are used.

The silver halide photographic light-sensitive material of the present invention has a photographic emulsion layer, and other layers include a flexible reflective support such as baryta paper, paper laminated with α-olephne polymer, synthetic paper, cellulose acetate, cellulose nitrate, polystyrene, etc. , polyvinyl chloride, polyethylene terephthalate, polycarbonate], films made of semi-synthetic or synthetic polymers such as polyamide, and rigid bodies such as glass, metal, and ceramics.

The silver halide light-sensitive material of the present invention can be produced by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, and then directly or (adhesiveness, antistatic property, dimensional stability of the support surface). , one or more subbing layers) to improve abrasion resistance, hardness, antihalation properties, friction properties, and/or other properties.

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays, or the like.

The exposure time is 1 millisecond to 1 millisecond, which is normally used in printers.
Not only can exposure times be 0 seconds, but also exposures shorter than 1 millisecond, such as 100 microseconds or more using a cathode ray tube or xenon flash lamp.
Exposures of 1 millisecond can be used, or exposures longer than 10 seconds are possible.

The exposure may be performed continuously or intermittently.

There are no particular limitations on the processing method for the silver halide photographic material of the present invention, and any processing method can be applied. For example, typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and/or stabilization treatment if necessary; bleaching and fixing are performed separately after color development; A method of washing with water and/or stabilizing; or pre-hardening, neutralization, color development, stop-fixing,
Washing with water, bleaching, fixing, washing with water, post hardening, washing with water in this order, color development, washing with water, supplementary color development, stopping, bleaching, fixing,
Processing may be performed using any of the following methods, including washing with water and stabilization in that order, or halogenation bleaching of the developed silver produced by color development, and then color development again to increase the amount of dye produced. .

The color developing solution used in the processing of the silver halide emulsion according to the present invention is an alkaline aqueous solution containing a color developing agent and preferably having a pH of 8 or more, more preferably 9 to 12. This aromatic primary amine developing agent as a color developing agent is a compound having a primary amine group on an aromatic ring and having the ability to develop exposed silver halide.
Furthermore, a precursor for forming such a compound may be added as necessary.

The color developing agent mentioned above is typically p-phenylenediamine type, and the following are preferred examples.

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesul Bonamidoethylaniline, 3
-methoxy-4-amino-N-ethylene-N-β-hydroxyethylaniline, 3-methoxy-4-amino-N
-Ethyl-N-β-methoxyethylaniline, 3-aledamide, 4-amino-N, N-dimethylaniline, N
-ethyl-N-β-[β-(β-methoxyethoxy)-1-xy]ethyl-3-methyl-4-aminoaniline,
N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline and salts thereof such as sulfates, salts, sulfites, p-toluenesulfonates, etc. .

Furthermore, for example, JP-A-48-64932, JP-A-50-1
31526, September 51-95849 and Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951).
The ones described above are also listed as representative ones.

The amount of these aromatic primary amino compounds used depends on where the activity of the developer is set, but it is preferable to increase the amount used in order to increase the activity. Use ■
It is used in a range from 0.0002 mol/P to 0.7/l. Furthermore, two or more compounds can be used in appropriate combination for the purpose. For example, 3-methyl-4-amino-N,N-diedylaniline and 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-
Combinations of ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, etc. can be freely used in combination depending on the purpose.

The color developer used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites,
Alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol,
Water softeners, thickeners, river edge promoters, etc. can also be optionally included.

Here, it is preferable that benzyl alcohol is not added to the color developing solution.

In other words, benzyl alcohol has a pollution load value of BO
D and COD are high, and benzyl alcohol has low hydrophilicity, so diethyl glycol and triethylene glycol are required as solvents, but glycols also have BOD.

Since the COD is high, the processing liquid that is discarded due to overflow poses a problem of environmental pollution. In addition, it has low solubility in benzyl alcohol developer solution and requires a long time to prepare a developer or a replenisher, which poses a problem in terms of work. Also,
If the amount of replenishment is large, the number of times the replenisher must be prepared increases, which also adds to the workload.

Therefore, environmental pollution and operational problems are eliminated by substantially not containing benzyl alcohol in the color developer, which is very preferable.

Examples of additives other than the above added to the color developing solution include bromides such as potassium bromide and ammonium bromide;
Alkali iodide, nitrobenzimidazole, metocab 1
- Compounds for rapid processing solutions such as benzimidazole, 5-methyl-benzotriazole, 1-phenyl-5-mercaptotetrazole, etc., as well as sudein inhibitors, sludge inhibitors, preservatives, interlayer effect promoters, chelating agents, etc. There is.

In addition, the color developing solution used in the present invention may optionally contain antioxidants such as dimethylhydroxylamine, diethylhydroxylamine, tetronic acid, tetronimide,
-anilinoethanol, dihydroxyace], aromatic secondary alcohol, hydroxamic acid, pentose or hexose, pyrogallol-1,3-dimethyl ether, etc. may be contained.

Various 4:rate agents can be used as metal ion sequestering agents in the color developing solution used in the present invention.

For example, ethylenediaminetetraacetic acid as the chelating agent,
Amine polycarboxylic acids such as diethylenetriaminopentaacetic acid, organic phosphonic acids such as 1-hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acids such as aminotri(meblenphosphonic acid) or ethylenediaminedetralinic acid, citric acid Alternatively, examples thereof include quaternary dicarboxylic acids such as gluconic acid, phosphonocarboxylic acids such as 2-phosphobutane-1,2°4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

Color development time is generally preferably 20 seconds to 60 seconds, more preferably 30 seconds to 50 seconds.
P! It is surrounded.

Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is. Representative examples of the above aminopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acid di]-lilotriacetic acidiminodiacetic acid ethyl etherdiaminete1-ethyl acetateethylenediaminetetrapropionic acidendylenediaminetetraacetic acid disodium saltdiethylene1-liaminebentaacetic acid bentana]-lium salt nitrilotriacetate sodium The salt bleach solution may contain various additives along with the bleaching agent described above. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. The bleach-fix solution may further contain a halogen compound such as potassium bromide. As in the case of the above-mentioned bleaching solution, various other additives such as DH buffers, optical brighteners, antifoaming agents, surfactants, preservatives, cleaning agents, stabilizers, and organic Melt! S or the like may be added or contained.

Examples of silver halide fixing agents include sodium thiosulfate, ammonium diosulfate, potassium thiocyanate, sodium thiocyanate, thiourea, thioether, etc., which react with silver halide and are used in ordinary fixing processes. Mention may be made of compounds that form water-soluble silver salts.

A coloring image of the silver halide color photographic light-sensitive material of the present invention,
The processing temperature of bleach-fixing (or bleaching, fixing), and various processing steps such as washing with water, stabilization, and drying, which are carried out as necessary, is preferably 30''C or higher from the viewpoint of rapid processing.

The silver halide color photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58
-14834, 58-105145, 58-1
No. 34634, Japanese Patent Application No. 58-18631, Japanese Patent Application No. 58-2709 and Japanese Patent Application No. 59-89288, etc., may be used.

[Specific Effects of the Invention] The silver halide photographic material of the present invention configured as described above enables rapid processing, has fairly good image storage stability, and has excellent resistance to BF contamination and pH
We were able to provide excellent characteristics with improved resistance to fluctuations.

[Specific Examples of the Invention] Hereinafter, the present invention will be specifically explained using Examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of silver halide emulsions) Twenty-two types of silver chloride emulsions and silver chlorobromide emulsions shown in Table 1 were prepared by a neutral method and a simultaneous mixing method.

[5D-1] [5D-2] S Oy HN (C2H,) 3 [5D-3] C21(s
C2 to1s comparative compound-
1 Comparative Compound-2 Next, on a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare silver halide color photographic light-sensitive material samples Nos. 1 to 44. .

Layer 1...1.2g/12 gelatin, 0.32(1/
Blue-sensitive silver halide emulsion No. T12 (in terms of silver, the same applies hereinafter).

21.0,80i:l/,2 yellow coupler (Y-1
).

Layer 2: Intermediate layer consisting of 0.70 g/12 gelatin.

Layer 3...1.25 (1/1' gelatin, 0.30C
I/i' green-sensitive silver halide emulsion No. 22.0.30
(0,52 dissolved in 1/n' dioctyl phthalate
Layer containing 0/1' magenta coupler (M-1).

Layer 4: Intermediate layer consisting of gelatin of 1.20 (1/i').

Layer 5: Gelatin of 1.2H/v2, 0.300/V
Red-sensitive silver halide emulsion shown in Table 1 of l', 0.20
0 dissolved in the high boiling point organic solvent shown in Table 1 of 0/n2,
A layer containing 9 mmol/12 of the cyan coupler shown in Table 1.

Layer 6...1.00 (1/i' gelatin and 0.20
0,30(
]/l' A layer containing the following ultraviolet absorber (UV-1>).

Layer 7: A layer containing 0.50 (1/n2) gelatin.

As a hardening agent, 1-I D-2 was added to layers 2.4 and 7 in an amount of 0.017 (l) per 10 gelatin, respectively.

(Y-1) (M-1) ρt (cc-i) (UV-1) The obtained sample was subjected to wedge exposure using a sensitometer KS-7 model (manufactured by Konishiroku Photo Industry Co., Ltd.), and then subjected to the following steps. After processing according to the color development process, the maximum density of the red-sensitive emulsion layer was measured using an optical densitometer (Model PDA-65, manufactured by Konishi Roku Photo Industry Co., Ltd.).

[Processing ■Culm 1 Temperature Time Visual color development image 34.7±0.3℃ 45 seconds bleach-fixing 347±0.5℃ 50 seconds stabilization 30
~34℃ Dry for 90 seconds 60~80℃
60 seconds [Color developer - 8] Pure water
800 yen l ~ reethanolamine
8ON, N-Diedylhydroxylamine
5g potassium chloride 2ON-
Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4= Aminoaniline sulfate 5g Sodium Tellila polyphosphate 2g Potassium carbonate
30g potassium sulfite
0.2 (] Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1 (1) Add pure water to bring the total amount to 12 and adjust to 11!10.2.

[Bleach-fix solution-A] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 (1 ethylenediaminetetraacetic acid R3 (1) ammonium thiosulfate (70% solution) 100d ammonium sulfite (40% solution) 27.5d potassium carbonate or glacial acetic acid Adjust the pi to 15.7 and add water to bring the total amount to 12.

[Stabilizing liquid] 5-chloro-2-medyru 4 = isothiazolin-3-one 1g 1-hydroxyethylidene-1°1-diphosbosonic acid 2g Add water and 1! Doji, pl-1 with sulfuric acid or potassium hydroxide to 7
．． Adjust to 0.

Next, a B F'de human resistance test and p
A H fluctuation tolerance test was conducted.

[BF contamination resistance test The above color developer [A] per IN, the above bleach-fix solution [A]
A color developing solution [B] was prepared in which 0.4 d of each of the following were added.

Using this color developing solution [B], processing was carried out according to the color development process described above, and sensitometric measurement of the red-sensitive emulsion layer was performed.

The results are shown in Table-2. In the table, Δγb is defined as the gradation γ (0) when processed with color developer [A] without bleach-fix solution and color developer [B] with bleach-fix solution, as shown in the following formula. The γ value in the case of processing with γ (0, 11) is a value indicating a fluctuation between γ (0, 11), and the smaller this value is, the better the resistance to BFF entry is.

Δγb=1γ(0)-γ(0,4) 1 Note that γ, which represents gradation, is the reciprocal of the difference in the logarithm of each exposure amount required to obtain densities of 0.8 and 1.8. The thicker the numerical value expressed as the product of the above density difference, the higher the contrast.
A color developing solution [C] was prepared. Using this color developing solution [C], processing was carried out according to the color development process described above, and the red-sensitive emulsion layer was subjected to sensimetry measurement.

The results are shown in Table-2. In the table, Δγp is expressed by the following formula: gradation γ (10,2> and p date '10.6 This is a value indicating that the gradation level γ (10, 6) is in the middle of variation when processed with the color developer [C].

Δγp=lγ(10,2)−γ(10,6) 1 On the other hand,
The bright and dark fading properties of the dye images were examined for the samples after each of the above treatments using the methods described below.

<Bright fading> Xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.)
The image was exposed to light for 300 hours, and the residual rate (%) of the dye image at an initial density of 1.0 was determined.

<Dark fading> Stored at 85℃ and 60% relative humidity for 20 days, with an initial concentration of 1.
．． The residual rate (%) of the dye image at 0 was determined.

The results are shown in Table-2.

As is clear from Table 2, test FA1.5 and 9.13
uses a silver halide emulsion with a low silver chloride content of 30 mol %, so the suitability for rapid development is greatly inferior, and a sufficient maximum density cannot be obtained with a development time of 45 seconds.

In addition, samples 1 to 8 and 4 using comparative cyan couplers
All of Nos. 4 and 4 have very poor light fading properties and cannot be put to practical use even if they have rapid development suitability.

On the other hand, Samples 10 to 1 using the silver halide emulsion of the present invention, the cyan coupler of the present invention, and the high boiling point organic solvent of the present invention
2 has a high maximum density with 45 seconds of development processing and excellent rapid development suitability, and also has good light fading and light fading properties, is completely free of bleach-fix solution, and has a DHtJ < standard. If the development process is carried out using an ideal color developing solution that does not deviate from the standard value, it will have good photographic performance, but if the bleach-fixing solution is slightly mixed in or the color development is performed with I)H deviating from the standard value. It can be seen that the gamma value fluctuates greatly when processed with an image carrier.

In contrast, Samples 14 to 16 of the present invention, which use the silver halide emulsion of the present invention, the cyan coupler of the present invention, and the high-boiling point organic solvent of the present invention, and contain the compound represented by the general formula [S] of the present invention. , J9-35 and 37-42, the BF contamination resistance and ρ)-1 variation resistance are greatly improved without impairing rapid development suitability, and they also exhibit good bright color fading resistance and bright color fading resistance. I understand. Looking more closely,
Samples 16 and 28 using pure silver chloride as silver halide
It can be seen that Samples 15 and 24 containing a slight amount of silver bromide have improved resistance to BF contamination and 1) I-1 fluctuation resistance. In addition, samples 24-28 and 37-42 using a gold compound as a sensitizer are samples 15.19°22.23.16 and 29-35 not using a gold compound.
It was observed that the resistance to BF contamination and the resistance to I)H fluctuation were improved.

In addition, Sample 17 using Comparative Compounds 1 and 2 outside the present invention
Although slight improvements in BF loading resistance and IIH fluctuation resistance were observed for 1 day and 1 day, the effects could not be said to be sufficient.

Moreover, even if the cyan coupler of the present invention is used, the test FINo.
, 36.43 is found to be inferior in light fading and light fading properties.

As described above, using a high silver chloride emulsion, the cyan coupler of the present invention containing the compound of the present invention represented by the general formula [S] and represented by the general formula [I], and the high boiling point organic solvent of the present invention. It can be seen that only when using this method, a silver halide photographic material that is suitable for rapid processing, which is the object of the present invention, has excellent processing variability, and has good dye image storage stability can be obtained.

Example-2 In sample N017 of Example-1, 8-2, S-6,5-1 instead of compound S-1 represented by general formula [S]
4, 5-19, 5-21, 5-28, 5-33, 5-3
Samples similar to Sample No. 37 were prepared except that Samples No. 6 and 5-41 were used, and the same evaluation as in Example-1 was performed. As a result, the effects of the present invention were obtained almost the same as in Example-1. .

Procedural amendment (voluntary) August 1, 1985 field

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having photographic constituent layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. , the red-sensitive silver halide emulsion layer contains silver halide grains having a silver chloride content of 90 mol % or more, and further contains a compound represented by the following general formula [S], and
A silver halide photographic material comprising a cyan dye-forming coupler represented by the following general formula [I] dispersed using a high boiling point organic solvent having a dielectric constant of 6.0 or less. General formula [S] ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Q is 1,3,4-oxadiazole ring, 1,3
, 4-thiadiazole ring or 1,3,5-triazine ring. M represents a hydrogen atom, an alkali metal atom, or an ammonium group. ) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents an alkyl group having 2 to 6 carbon atoms. R_2 represents a ballast group. Z is a hydrogen atom or oxidation of a color developing agent. (represents a group that can be separated by reaction with a body)