JPS62254147A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the aging stability of a coating liq. when a silver chloride color photographic material contg. silver halide particles having >=80mol% silver chloride content is produced, by forming a silver halide emulsion layer contg. a specified compound and a specified solvent for a coupler. CONSTITUTION:A silver halide emulsion layer contg. at least one kind of com pound represented by formula I and a solvent for a coupler represented by formula II is formed. In the formula I, A is a bivalent aromatic residue and each of R1-R4 is H, hydroxy, lower alkyl or the like. In the formula II, each of R5-R7 is alkyl, cycloalkyl, alkenyl or aryl. The compound represented by the formula I may be disodium 4,4'-bis[4,6-di(benzothiazolyl-2-thio)pyrimidin-2- ylamino]-stilbene-2,2'-disulfonate. A concrete example of the compound represented by the formula II is represented by formula II-1.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic material having a silver halide emulsion layer containing silver halide grains consisting essentially of silver chloride. The present invention relates to a silver halide color photographic light-sensitive material having improved stability over time of an emulsion coating solution.

[Background of the invention]

Usually, in the method of forming dye images using silver halide color photographic light-sensitive materials, after imagewise exposure, oxidized p-
A dye image is formed by reacting a phenylenediamine color developing agent with a dye image forming coupler. In this method, a subtractive color reproduction method is usually applied, and cyan, magenta, and yellow dye images corresponding to red, green, and blue are formed on respective photosensitive layers. In recent years, in the formation of such dye images, high-temperature development and omission of processing steps have become common in order to shorten the development processing time. In particular, in order to shorten the development processing time by high-temperature development processing, it is extremely important to increase the development speed in color development. The development speed in color development is influenced by three aspects. One is a silver halide color photographic light-sensitive material, and the other is a color developer.

In the former case, the shape, size and composition of the grains of the light-sensitive silver halide emulsion used have a great influence on the development speed, while in the latter case, the development speed is easily affected by the conditions of the color developer, especially the type of development inhibitor. It has been found that silver chloride grains, in particular, exhibit significantly higher development rates under certain conditions.

For this reason, silver chloride color photographic materials (hereinafter referred to as silver chloride color photographic materials) having a silver halide emulsion layer containing silver halide grains consisting essentially of silver chloride have a conventional salt odor. Since the processing speed can be much faster than photosensitive materials using silver oxide, it has been attracting attention in recent years for its short processing time, miniaturization of automatic processors, reduction of developer replenisher, and reduction of pollution and load. Since minilabs and the like have great advantages, various studies have been made to put them into practical use, and are expressed in various documents, patents, etc. However, when producing a silver halide color photographic light-sensitive material containing silver halide grains consisting essentially of silver chloride, after preparing a coating solution containing the silver halide emulsion, It has been found that there is a drawback that the emulsion sensitivity tends to fluctuate over time during continuous coating. According to the inventors' study regarding this phenomenon,
It was assumed that the main cause of the sensitivity variation was caused by desorption of the sensitizing dye used in preparing the emulsion when it was left in the coating solution state over time.

On the other hand, geometrical methods have been proposed in the past as a means of improving the stability of coating liquids over time;
When the exemplified stilbene compounds described in No. 35461 are used, the stability is significantly improved in the case of silver chlorobromide, but the effect is ineffective when used in emulsions containing silver halide grains consisting essentially of silver chloride. Although it was approved, it was found that it was not sufficient.

It is especially important to maintain the stability of the coating solution over time, especially when using color paint, −
In the case of par, it is not only necessary to maintain uniformity within the lot;
This is an extremely important technology in that it allows the user to always print under constant conditions, as it also improves uniformity between lofts.

In view of the above, there is a strong demand for developing an emulsion preparation technique with excellent stability over time of a coating solution in order to produce a silver chloride color light-sensitive material with excellent high-temperature and rapid processability.

-5= [Object of the present invention] The present invention has been made in view of the above circumstances, and an object of the present invention is to obtain a silver chloride grain containing silver halide grains having a silver chloride composition of 80 mol% or more. An object of the present invention is to provide a silver halide color photographic material in which the stability of a coating solution over time is improved in the production of a color photographic material.

[Structure of the invention]

The object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing silver halide grains having a silver chloride composition of 80 mol% or more on a support. The emulsion layer contains at least one compound represented by the following general formula (1,),
A silver halide color photographic light-sensitive material characterized by containing a coupler solvent represented by the following general formula (n) is achieved by the silver halide color photographic light-sensitive material of the general formula (I), where A represents a divalent aromatic residue.

R1r R2+ R3 and R2 may be the same or different, and each represents a hydrogen atom, a hydroxy group, a lower alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic group, an alkylthio group, a heterocyclylthio group, an arylthio group, It represents an amino group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a heterocyclylamino group, a substituted or unsubstituted acylylamino group, an aryl group, or a mercapto group.

General formula (II) OR.

R,,0-P=0 ■ OR.

In the formula, RII + Ra r and R7 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group.

[Specific structure of the invention]

Hereinafter, the configuration of the present invention will be explained in more detail.

The light-sensitive silver halide emulsion used in the silver halide color photographic light-sensitive material of the present invention is silver halide grains containing silver chloride in an amount of 80 mol% or more, preferably silver chloride content of 95 mol% or more, Particularly preferred is 100 mol%. This silver halide emulsion can contain silver bromide and/or silver iodide as a silver halide composition in addition to silver chloride, but the silver bromide content is not more than 5 mol %, preferably 5 mol %.
When silver iodide is present, it is usually 1 mol% or less, preferably 0.5 mol% or less, and most preferably 0%. Such silver halide grains having a silver chloride composition of 80 mol% or more according to the present invention account for 80% by weight of all the silver halide grains in the silver halide emulsion layer containing the silver halide grains. % or more, more preferably 100%.

The silver halide color photographic light-sensitive material of the present invention can be composed of two or more light-sensitive silver halide emulsion layers. At least one of these two or more photosensitive silver halide emulsion layers must be a silver halide emulsion layer containing silver halide grains consisting essentially of silver chloride. There are no particular restrictions on the composition of silver halide in other photosensitive silver halide emulsion layers, but at least
It is preferable to contain silver chlorobromide grains or silver chloroiodide grains containing mol % of silver chloride. The amounts of silver bromide and silver iodide in the silver halide color photographic light-sensitive material of the present invention are preferably about mol% or less, more preferably about 10 mol% or less, based on the total silver halide emulsion. It is.

These silver halides may be produced by the ammonia method, neutral method, acidic method, etc., or by simultaneous mixing method, forward mixing method, back mixing method, conversion method, etc. It may be something that has been done.

The crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure in which the inside and outside are different. Further, the silver halide may be a surface latent image type that forms a latent image mainly on the surface, or an internal latent image type that forms a latent image mainly inside the grain.

In addition, the silver halide emulsion of the present invention includes salts of noble metals such as ruthenium, rhodium, palladium, iridium, platinum, and gold (for example, ammonium chloroparadate, potassium chloroparadate, potassium chloroparadite, potassium chloroaurate, etc.). Noble metal sensitization with active gelatin, sulfur sensitization with unstable sulfur (e.g. sodium thiosulfate, etc.), selenium sensitization with selenium compounds, stannous salts,
Reduction sensitization using polyamines, thiourea dioxide, etc. and low pAg can be performed.

Furthermore, stabilizers such as triazoles, imidazoles, azaindenes, benzothiazolium compounds, zinc compounds, cadmium compounds, and mercaptans are used in these silver halide emulsions to the extent that they do not impair the effects of the present invention. be able to.

Furthermore, it is necessary to optically sensitize these silver halide emulsions using various sensitizing dyes in order to impart photosensitivity in a desired wavelength range. Preferred sensitizing dyes include, for example, U.S. Pat.
No. 072,908, No. 2,739,149, No. 2
．． No. 213,995, No. 2,493,748, No. 2,519,001, West German Patent No. 929,080
The cyanine dyes, merocyanine dyes, or complex cyanine dyes described in the specifications of British Patent No. 505,979 can be used alone or in a mixture of two or more. It is particularly preferred that the sensitizing dye useful in combination with the compound represented by ) is a red sensitizing dye.

General formula (III) In the formula, R and R8 each represent an alkyl group, a hydroxyl group, an alkoxy group, an acetoxy group, or an aryl group, and each of the alkyl group, alkoxy group, acetoxy group, and aryl group may have a substituent. good.

However, at least one of R and R8 represents an alkyl group containing a sulfo group or a carboxyl group. Ro and Rlo
represents an alkyl group.

2 represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic nucleus together with the nitrogen atom.

Next, typical examples of the dye represented by the general formula (III) are shown below.

(P-8) (P-15) The compound of general formula (I) used in the present invention is represented by the following formula.

General formula (I) In the formula, -person- represents a divalent aromatic residue, and these are -
503M group [where M represents a hydrogen atom or a cation (eg, sodium, potassium) that provides water solubility. ] may be included.

-A- is usefully selected from, for example, -A, -t or -A2-. However, R,, R2, R, or R4
When does not contain a -8o8M group, -Am is -A+-
selected from the group of

-A, -: Here, M represents a hydrogen atom or a cation that provides water solubility.

-A2-: RI + R2+ R3 and R4 are each a hydrogen atom, a hydroxy group, a lower alkyl group (preferably 1 to 8 carbon atoms; for example, a methyl group, an ethyl group, an n-propyl group,
n-butyl group, etc.), alkoxy group (carbon number: 1
~8 is good. (e.g. methoxy group, ethoxy group, propoxy group, butoxy group, etc.), aryloxy group (e.g. phenoxy group, naphthoxy group, 0-)roxy group, p-sulfophenoxy group, etc.), halogen atom (e.g. chlorine atom, bromine atom, etc.) , heterocyclic nucleus (e.g., morpholinyl group, piperidyl group, etc.), alkylthio group (e.g., methylthio group, ethylthio group, etc.), heterocyclylthio group (e.g., benzothiazolylthio group, benzimidazolylthio group, phenyltetrazolylthio group, etc.), Arylthio groups (e.g. phenylthio group, tolylthio group), amine group, alkylamino group or substituted alkylamino group (e.g. methylamino group, ethylamino group, propylamine group, dimethylamine group, diethylamino group, dodecylamino group, cyclohexylamino group) group, β-hydroxyethylamino group, di(β-hydroxyethyl)amino group, β-sulfoethylamino group), arylamino group, or substituted arylamino group (e.g. anilino group,
-sulfoanilino group, m-sulfoanilino group, p-sulfoanilino group, 0-toluidino group, m-)luidino group,
p-) Luidino group, 0-carboxyanilino group, m-carboxyanilino group, p-carboxyanilino group, o-
Chloroanilino group, m-chloroanilino group, p-chloroanilino group, p-aminoanilino group, 0-anisidino group, m-anisidino group, p-anisidino group, o-acetaminoanilino group, hydroxyanilino group, disulfophenyl amino group, naphthylamino group, sulfonaphthylamino group, etc.), heterocyclylamino group (e.g., 2-benzothiazolyl amino group, 2-pyridylamino group, etc.)
, a substituted or unsubstituted aralkylamino group (eg, benzylamino group, 0-anisylamino group, m-anisylamino group, p-anisylamino group, etc.), an aryl group (eg, phenyl group, etc.), and a mercapto group.

RI r RQ r R & + R4 may be the same or different from each other. When -A- is selected from the group -A2-, at least one of Rt * Rt + Rs r R4 has one or more sulfo groups (which may be free acid groups or may form salts). It is necessary to have one.

Next, specific examples of compounds included in general formula (I) used in the present invention will be given. However, the present invention is not limited only to these compounds.

(I-1) 4,4'-bis[4,6-di(benzothiazolyl-2-thio)pyrimidin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt (I-2) 4, 4'-bis[4,6-di(benzothiazolyl-2-amino)pyrimidin-2-ylaminocostilbene-212'-1 disodium sulfonate ((-3)4.4'-bis[4,6- di(naphthyl-2)
-oxy)pyrimidin-2-ylaminocostilbene-
2,2'-disulfonic acid disodium salt (I-4) 4,4'-bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylaminocopibenzyl-2,2/-disulfonic acid Disodium 2l- (I-5) 4,4'-bis(4,6-dianilinopyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (i-6) 4,4'- Bis[4-chloro-6-(2
-naphthyloxy)pyrimidin-2-ylaminocobiphenyl-2,2'-disulfonic acid disodium salt (I-7) 4,4'-bis[4,6-di(1-phenyltetrazolyl-5thio) ) Pyrimidin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt (I-8) 4,4'-bis[4,6-di(benzimidazolyl-2-thio)pyrimidin-2-ylamino Costilbene-2,2'-disulfonic acid disodium salt (I-9) 4.4'-bis(4,6-diphenoxypyrimidin-2-ylamino)stilbene-2°2/-disulfonic acid disodium salt ( I-10) 4,4t-bis(4,6-cyphenylthiopyrimidin-2-ylamino)stilbene-2゜2
'-Disulfonic acid sodium salt (I-11) 4,4'-bis(4,6-dimercabutopyrimicin-2-ylamino)biphenyl-2゜27
-Disulfonic acid sodium salt Among these specific examples, (I-1), (I-2)
, (I-3), (I-4), (I-5), (I-7)
is preferred.

Said tetramethine merocyanine dyes are advantageously used in concentrations of from about 2.times.10@-6 moles to 1.times.10""3 moles per mole of silver halide therein.

The tetramethine merocyanine dye can be directly dispersed into the emulsion. In addition, these are suitable solvents,
For example, it can be dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and added to the emulsion in the form of a solution.

Ultrasonic waves can also be used for dissolution. The method for adding this tetramethine merocyanine dye is as described in US Pat. No. 3,469,987, etc., in which the dye is dissolved in a volatile organic solvent and the solution is dispersed in a hydrophilic colloid. , a method of adding this dispersion to an emulsion, as described in Japanese Patent Publication No. 46-24185, etc., involves dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding this dispersion to an emulsion. Method: As described in U.S. Pat. No. 3,822,135, the dye is dissolved in a surfactant and the solution is added to the emulsion; As described in JP-A-51-74624, A method in which a dye is dissolved using a red-shifting compound and the solution is added to an emulsion; as described in JP-A-50-80826, a dye is dissolved in an acid substantially free of water, and the solution is added to an emulsion. A method such as adding it into an emulsion is used.

Other additions to emulsions include U.S. Patent No. 2,912,34
No. 3, No. 3,342,605, No. 2,996,2
Methods described in specifications such as No. 87 and No. 3,429,835 can also be used. Further, the tetramethine merocyanine dye may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but can of course also be dispersed during the preparation of the silver halide emulsion.

The compound of general formula (II) used in the present invention is advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion.

The ratio (weight ratio) of the tetramethine merocyanine dye of general formula (I) to the compound represented by general formula (II) is the dye represented by general formula (I)/-compound represented by general formula n) = 1 A range of /2 to 1/20 is advantageously used;
In particular, a range of 115 to 1/10 is advantageously used.

The compound represented by the general formula (II) used in the present invention can be directly dispersed in an emulsion, or can be dispersed in a suitable solvent (for example, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof. It can also be dissolved in and added to the emulsion.

The dye image-forming coupler used in the present invention is not particularly limited, and various couplers can be used, but the compounds described in the following patents are representative examples.

Yellow dye image-forming couplers include 4-equivalent or 2-equivalent couplers of the acylacetamide type and benzoylmethane type, which are described, for example, in U.S. Pat. No. 2,778.
, No. 658, No. 2,875,057, No. 2.90
No. 8,573, No. 2,908.513, No. 3, 2
No. 27,155, No. 3,227,550, No. 3,
No. 253,924, No. 3.265,506, No. 3
, 277.155, 3.341,331, 3,369.895, 3,384,657, 3,408,194, 3.415,652 ,
Same No. 3,447,928, Same No. 3,551,155, Same No. 3,582,322, Same No. 3,725,072
German Patent No. 1.547,868, German Patent No. 2,05
No. 7,941, No. 2,162,899, No. 2.1
No. 63.812, No. 2.213.461, No. 2,
No. 219,917, No. 2,261,361, No. 2
, No. 263,875, Japanese Patent Publication No. 49-13576, Japanese Patent Publication No. 48-29432, No. 48-66834, No. 49
-10736, 49-122335, 50-2
No. 8834, No. 50-132926, No. 55-144
No. 240 and No. 56-87041.

Examples of magenta dye image-forming couplers include 4-equivalent or 2-equivalent magenta dye image-forming couplers of the 5-pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indashilon type, and cy-anoacetyl type; For example, U.S. Patent No.
．． No. 600,788, No. 3.061,432, No. 3.062,653, No. 3,127,269, No. 3,311,476, No. 3.152,896,
Same No. 3,419,391, Same No. 3,519,429, Same No. 3.558,318, Same No. 3.684,514
No. 3.705゜896, No. 3.888,68
No. 0, No. 3.907,571, No. 3.928,0
No. 44, No. 3.930,861, No. 3,930,
No. 816, No. 3.933.500, JP-A-49-2
No. 9639, No. 49-111631, No. 49-129
No. 538, No. 51-112341, No. 52-5892
No. 2, No. 55-62454, No. 55-118034, No. 56-38643, No. 56-135841, Special Publication No. 46-60479, No. 52-34937, No. 5
No. 5-29421, No. 55-35696, British Patent No. 1.247,493, Belgian Patent No. 792,525
No. 2,156,111.

The cyan dye image-forming coupler may be a 4-equivalent or 2-equivalent cyan dye image-forming coupler of phenol type or naphthol type.
, No. 369,929, No. 2,423,730, No. 2.434.272, No. 2,474,293, No. 2,698,794, No. 2,7o6,6g4 ,
Same No. 2.772,162, Same No. 2.801.171, Same No. 2,895,826, Same No. 2.908,573
No. 3,034,892, No. 3,046,12
No. 9, No. 3,227,550, No. 3,253,2
No. 94, No. 3.311,476, No. 3.386,
No. 301, No. 3,419,390, No. 3.458
, No. 315, No. 3.476゜563, No. 3.51
No. 6,831, No. 3.560,212, No. -3
, No. 582,322, No. 3,583,971, No. 3,591,383, No. 3,619,196, No. 3.632,347, No. 3.652,286 ,
Same No. 3,737,326, Same No. 3,758.308, Same No. 3,779゜768, Same No. 3,839,044
No. 2,163°811, West German Patent No. 2.2
No. 07,468, Special Publication No. 39-27563, No. 45-
No. 28836, JP-A-47-37425, JP-A No. 50-1
No. 0135, No. 50-25228, No. 50-1120
No. 38, No. 50-117422, No. 50-13044
No. 1, No. 53-109630, No. 55-32071, No. 55-163537, No. 56-1938, No. 5
No. 6-13643, No. 56-29235, No. 56-6
No. 5134, No. 56-104333, and Research Disclosure.
sure) 1976, 14853, etc.

Particularly in the present invention, it is useful to use the cyan coupler described above.

As mentioned above, the present inventors have conducted intensive research on the stability over time of a coating solution of a silver halide emulsion containing silver halide grains consisting essentially of silver chloride, and have surprisingly found that The present invention has been accomplished by discovering the fact that when a coupler dispersion emulsified and dispersed with a compound represented by the following general formula (II) is used in combination with an emulsion using a compound, sensitivity fluctuations are significantly reduced. It's arrived.

General formula (n) a In the formula, R6, Ro and R7 each represent an alkyl group, an alkenyl group, an aryl group, or a cycloalkyl group.

The alkyl groups represented by R3, Ro and R7 include, for example, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group. group, heptadecyl group, octadecyl group,
Nonadecyl group, etc. Examples of the alkenyl group include allyl group, aryl group includes phenyl group and tolyl group, and cycloalkyl group includes cyclohexyl group.

These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents. Preferably R3, R6 and R7 are alkyl groups, such as 2-ethylhexyl group, n-octyl group, 3.5.
5-) Limethylhexyl group, n-nonyl group, n-decyl group, 5ec-decyl group, 5ec-dodecyl group, t-octyl group, and the like.

=(g)-(II-1)([-2)(I
I-3) (II-4) (n
-5) (II-6) (II
-7) 2H5 0-CH2CH(CH2), CH3 CH2CH(CH2), CH8 2H1l (II-8) 1 (n-9)(
n −10) (II −
11) (II-12) (
II-13) (II-14)
(II-15) (II-16)
(II-17) (n-18)
(II-19) The general formula (n
The high boiling point organic solvent represented by ) can be added in any amount as long as it is 10% by weight or more based on the coupler, but it is preferably added in a weighted amount of % to 300%.
It can be used in a range of % by weight, particularly preferably in a range of 30% by weight to 200% by weight.

Further, it is also possible to use it in combination with other types of high boiling point organic solvents as long as the effects of the present invention are not impaired.

Methods for emulsifying and dispersing couplers using these compounds are described in known literature and patents, such as U.S. Patent No. 2,322.
, No. 027 may be used.

In the present invention, it is advantageous to use gelatin as the hydrophilic colloid for dispersing silver halide, but other hydrophilic colloids can also be used.

Examples of preferred hydrophilic colloids include gelatin such as alkali-treated gelatin or acid-treated gelatin, which is most commonly used; however, a portion of this gelatin may be substituted with derivative gelatin such as phthalated gelatin, phenylcarbamoyl gelatin, albumin, agar, Gum arabic, alginic acid, partially hydrolyzed cellulose derivative, partially hydrolyzed polyvinyl acetate,
Boria-34 = Acrylamide, polyvinyl alcohol, polyvinylpyrrolidone and copolymers of these vinyl compounds may be mentioned.

The silver halide color photographic material of the present invention may contain various known photographic additives. Examples of such agents include ultraviolet absorbers (such as benzophenone compounds and benzotriazole compounds), dye image stabilizers (such as phenolic compounds, bisphenol compounds, hydroxychroman compounds, bispirochroman compounds, and hydantoin compounds). compounds, dialkoxyhenzene compounds, etc.), stain inhibitors (e.g., hydroquinone derivatives, etc.), surfactants (e.g., sodium alkylnaphthalene sulfonate, sodium alkylbenzene sulfonate, sodium alkyl succinate sulfonate, polyalkylene glycol, etc.) ),
Water-soluble anti-irradiation dyes (e.g. azo compounds, styryl compounds, triphenylmethane compounds, oxonol compounds, anthraquinone compounds, etc.),
Hardeners (e.g. halogen 4-) IJ azine compounds, hinyl sulfone compounds, acryloyl compounds, ethyleneimino compounds, N-methylol compounds, epoxy compounds, water-soluble aluminum salts, etc.), film property improvers (e.g. Examples include glycerin, aliphatic polyhydric alcohols, polymer dispersions (latex), solid/liquid paraffin, and colloidal silica), optical brighteners (e.g. diaminostilbene compounds), and various oil-soluble paints. be able to.

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

The support for the silver halide color photographic light-sensitive material of the present invention includes supports such as paper, glass, cellulose acetate, cellulose nitrate, polyester, polyamide, and polystyrene, or, for example, paper and polyolefin (
For example, a laminate of two or more substrates, such as a laminate with polyethylene, polypropylene, etc., can be used as appropriate depending on the purpose.

In order to improve the adhesion to the silver halide emulsion layer, this support is generally subjected to various surface treatments, such as roughening the surface mechanically or with a suitable organic solvent, electron impact treatment, or It is also possible to use a material that has been subjected to surface treatment such as flame treatment, or undercoating treatment to provide a subbing layer.

The silver chloride color photographic light-sensitive material of the present invention includes all kinds of silver halide color photographic light-sensitive materials such as color negative films, color positive films, color reversal films, and color papers, but is particularly preferably used for color papers.

As the color developing agent used in the color developing solution for color development processing of the silver halide color photographic light-sensitive material of the present invention, aromatic primary amine compounds, particularly p-phenylenediamine compounds, are representative. As a preferable example, N
, N-diethyl-p-phenylenediamine hydrochloride, N-
:r-f/l/-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride,
2-amino-5-(N-'f-f-N-)"decylamino)-)luene, N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-N-(2-methoxyethyl)
-N-ethyl-3-methylaniline-p-toluenesulfonate, N,N-diethyl-3-methyl-4-aminoaniline, N-ethyl-N-(β-hydroxyethyl)
-3-methyl-4-aminoaniline and the like can be mentioned. These color developing agents may be used alone or in combination of two or more.
species or species and other black and white developing agents such as hydroquinone, 1-phenyl-3-pyrazolidone, N-methyl-
It may also be used in combination with p-aminophenols. This color developing agent may be included in the silver chloride color photographic light-sensitive material of the present invention. In this case, the amount of the color developing agent added is usually in the range of 0.2 mol to 2 mol, preferably 0.4 mol to 0.7 mol, per 1 mol of silver halide contained in the color photographic light-sensitive material. is within the range of

In addition to the above-mentioned color developing solution, the color developing solution includes, for example, alkaline agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, tribasic sodium phosphate, potassium carbonate, potassium hydrogen carbonate, and N,N-diethylhydroxylamine. , preservatives such as sodium sulfite, potassium sulfite, and glucose, organic solvents such as methanol, ethanol, phthanol, benzyl alcohol, ethylene glycol, and diethylene glycol, development regulators and optical brighteners such as citrazic acid and polyethylene glycol, and heavy metal ions. Various photographic additives known in the photographic field, such as hiding agents and development accelerators, can be contained as necessary.

The color photographic light-sensitive material of the present invention is developed with a color developing solution that does not contain any water-soluble bromide or contains a very small amount of water-soluble bromide. When an excessive amount of water-soluble bromide is contained, the development speed of the color photographic light-sensitive material is drastically reduced, making it impossible to achieve the object of the present invention. The bromide ion concentration in the color developer is calculated in terms of potassium bromide.
1 part is usually about 0.12 or less, preferably 0.051
i' is F.

Development control agents (capri control) contained in the color developing solution include chlorides such as sodium chloride and potassium chloride, or chlorides such as adenine and guanine as disclosed in Japanese Patent Application Laid-Open No. 58-953.
A compound described in Japanese Patent No. 45 that has an acid dissociation constant of 1O-8 or less and a solubility product with silver ions of IQ-10 or less is used.

The pH of the color developing solution used in the present invention is generally 9.0 to 9.0.
12.0, preferably between 9.5 and 11.0.

The color photographic material of the present invention is color developed by a conventionally known method. That is, the imagewise exposed silver chloride color photographic material is color developed with the color developing solution of the present invention to form a dye image and a silver image. Thereafter, in order to leave only the dye image, a negative-positive method can be used in which the silver salt is oxidized to silver salt in a bleaching bath, and then the remaining silver halide and other silver salts are dissolved and removed in a fixing bath. Also,
A negative silver image is developed by developing with a developer containing a black and white developing agent, and then subjected to at least one full exposure or capri processing with a suitable capri agent, followed by color development, bleaching and fixing processing. Color reversal methods can be used to form images.

The bleaching and fixing treatments performed to leave a dye image may be performed in separate steps, but from the standpoint of rapid processing, it is preferable to perform the bleaching treatment and the fixing treatment at the same time.

The bleaching agent used for individual bleaching treatment is iron (m
), cobalt (III), chromium (Vl), copper (II)
Compounds of polyvalent metals such as, peracids, quinones, nitroso compounds, etc. can be used. Specifically, ferricyanide, dichromate, iron(III) or cobal)
Organic acid salts of (1'II), such as aminopolycarboxylic acid salts such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and 1,3-diamino-2-propatoltetraacetic acid, or organic acids such as citric acid, tartaric acid, and malic acid. Complex salts; persulfates, permanganates; nitrosophenols, etc. can be used.

Examples of fixing agents include thiosulfates (e.g., ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, etc.), thiocyanates (e.g., ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, etc.), 3.6 -Thioether compounds such as 1,8-octanediol can be mentioned.

The processing temperature for various processing steps such as color development, bleach-fixing, washing with water (or stabilization as an alternative to water washing), and drying of the color photographic material of the present invention is set at 30'C from the viewpoint of rapid processing. It is preferable to carry out the above process.

[Specific embodiments of the invention]

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 A monodisperse silver chloride emulsion having an average grain size of about 0.4 μm was prepared by a neutral method and a simultaneous mixing method. This silver chloride emulsion -42= was chemically sensitized at 45°C using 4.2 x 10-' mol of thiosulfate per mol of silver chloride, and then treated with the illustrative red-sensitive sensitizing dye described in the text. 2.0 x 10-4 mol of P-1 per mol of silver chloride and 5 x 10-3 mol of the compound according to the present invention (exemplified compound 1) as shown in Table 1 were added, and 4-hydroxy- as a stabilizer was added. 6-Methyl/l/-1,3,3a, 7-chitrazaindene (S
TB-1) was added in an amount of 1xlo-2 mol per mol of silver chloride.

On the other hand, a cyan coupler having the following structure is a compound according to the present invention (compound of general formula (II)) as shown in Table 1.
Comparative compounds were dissolved in a high-boiling organic solvent, emulsified and dispersed in an aqueous gelatin solution, and added to the silver chloride emulsion in an amount of 0.40 mol of cyan coupler per 1 mol of the above silver chloride emulsion. To this emulsion was further added 8×10 −4 moles of an anti-irradiation dye having the structure shown below per mole of silver chloride. Using the coating solution containing the silver halide emulsion thus obtained, the coating solution was heated to 40° C. (forced deterioration condition) to check the stability of the coating solution over time.
Immediately after preparation of the coating solution, after 3 hours of aging, and after 6 hours of aging, coating solutions were prepared and simultaneously coated in two layers together with a gelatin protective film onto a support of polyethylene laminate paper. This coating has silver chloride of 0.29 y/rr? (in terms of silver), gelatin has a silver halide emulsion layer of 1.3! i'/silence, protective layer is 1. Of//d. In addition, in the protective layer, 0.0309 2,4-dichloro-
6-Hydroxy-8-) riazine sodium salt was added as a hardening agent, and the resulting color photographic light-sensitive material was stored at 40° C. and 80% relative humidity for a period of time to harden it to the desired film strength. Ta.

Cyan coupler (t)HIICll anti-irradiation dye The obtained sample was exposed to white light in stages and then processed in the following processing steps.

Processing process Temperature Time (1) Color development 35℃ Seconds (2) Bleach fixing 35℃ Leap seconds (3) Stability 30~
34℃ 2 minutes (4) Drying 60~
90°C - The composition of the treatment liquid used in each step is as follows.

Color developing solution (per 11) Bleach fixing solution = 46- Stabilizing solution for conditioning Measurement of reflection density of each sample using a photoelectric densitometer (PDA-60 model manufactured by Konishiroku Photo Industry Co., Ltd.) Then, the sensitivity was determined, and the relative sensitivity of each sample was determined when the sensitivity immediately after preparing the coating solution was set as 100. The results are shown in Table 1.

From the results shown in Table 1, when the compound represented by the general formula (I) according to the present invention is added and the coupler solvent of the present invention is used in combination, the coating liquid has excellent stability over time and the sensitivity is substantially reduced. It can be seen that this is not seen.

On the other hand, when the compound represented by the general formula (I) is not contained or when a coupler solvent other than the one according to the present invention is used, a significant decrease in sensitivity occurs, and in practice, the comparative compound (1
)...Dioctyl phthalate comparison compound (2)...
N,N diethyl laurylamide comparison compound (3)...
Diethyl glycol dibutyl ether comparative compound (4)...dicyclohexyl phthalate (
*) 0.72 of I-1 was added per mole of silver halide.

Example 2 An experiment similar to Example 1 was conducted except that the red-sensitive sensitizing dye and cyan coupler were replaced with the compounds shown below.

The results are shown in Table 2.

Red-sensitive sensitizing dyes Exemplary sensitizing dyes P-5, P-9 Cyan coupler From Table 2, the coating solution using the compound of general formula (I) and the coupler solvent of general formula 〇 according to the present invention is as follows: It can be seen that the stability over time is excellent and the effects of the present invention can be reproduced even if the red-sensitive sensitizing dye and cyan coupler are changed.

On the other hand, in the case of a coating liquid that does not use the compound according to the present invention or a coating liquid that is used alone, the stability over time is as shown in Example 3. A silver halide color photographic material of the present invention was prepared by coating in the following order from the support side. Note that the amounts added below are per 1 m' unless otherwise specified.

Layer 1: Gelatin (1,2F) and silver chloride (silver equivalent: 0.
282) containing a blue-sensitive silver chloride emulsion layer [average grain size of silver chloride 0.55μ; chemical sensitizer sodium thiosulfate 5.
2 Xl0-'/1 mole of silver halide; Blue sensitizing dye (BSD-1) 5.5X10-' mole/1 mole of silver halide; Stabilizer (STB-1) lX10-2 mole/
1 mole of silver halide] and 0.75 mole of silver halide in this emulsion layer.
f yellow coupler (Y-1) and 0.015F 2
．． 0,42 dioctyl phthalate (DOP') dissolved in 5-di-t-octylhydroquinone (HQ-1)
Contains.

Layer 2: Gelatin (0,68f/2) and the above 2.5-G were mixed with monooctylhydroquinone (HQ-1'') (0,
06r) dissolved in dioctyl phthalate (DOP) (
0.1Of).

Layer 3: Gelatin (1,25f), green-sensitive silver chloride emulsion (0,29f, average grain size of silver chloride 0.4ttm: chemical sensitizer sodium thiosulfate 0.8 X 10-5 mol/silver halide 1 mol; green sensitizing dye (GSD-1)
2.0X10-4 mol/silver halide 1 mol, stabilizer (
STB-1) lXl0-2 mol/silver halide 1 mol), this layer is magenta coupler (Ml) (o, 5f)
and 2,5-di-t-octylhydroquinone (HQ-1
) (0,015f) dissolved in dioctyl phthalate) (DOP) (0,01y).

Layer 4: Gelatin (1,28f), 2,5-di-t-
Octylhydroquinone (HQ-1) (o, os t
) and an ultraviolet absorber (IJV-1) (0,1) dissolved in dioctyl phthalate (DOP) (0,35f
).

Layer 5: Gelatin (1,4f), silver chloride (0 in terms of silver)
．． 21f) [average grain size of silver chloride 0.32 μm; chemical sensitizer sodium thiosulfate 1. OX 10-” mol/1 mol of silver halide; Red sensitizing dye (P-11) 8.0×10-S mol/1 mol of silver halide; Compound (I- 4) 5XIO-3 mol/silver halide 1 mol; cyan coupler (C-1) 0.25F, 2.5-di-t-octylhydroquinone (HQ-1) (0,0
A layer containing a coupler solvent (exemplary compound n-70,10f) according to the present invention in which 22) is dissolved and an anti-irradiation dye (AID-2) (0,011).

Layer 6: Gelatin (1, Of ), UV-1 (0,2 f
) containing DOP (0,2f) dissolved therein.

Layer 7: Gelatin (1,Of), polyvinylpyrrolidone (0,005f) and 0.089 Example-1 with BSD-1 Green sensitizing dye (GSD-1) Ultraviolet absorber (UV-1) Yellow coupler ( Y-1) 56-magenta coupler (M-1) C72 cyan coupler (C-1) A Anti-irradiation dye (AID-1) Anti-irradiation dye (AID-2) In preparing this sample Immediately after preparing the coating solution for forming the red-sensitive emulsion layer of Layer 5, the coating solution was applied after 5 hours at 36°C and 10 hours at 36°C to obtain three types of multilayer color light-sensitive materials.

Using this sample, the same exposure and processing as in Example 1 was carried out to obtain sensitometric data, and the sensitivity of the red-sensitive emulsion layer was found to be It was found that there was no substantial difference in the results, and that the characteristic effects of the combination of the compounds of the present invention could be reproduced, and therefore, an excellent silver chloride color light-sensitive material without loss of color balance could be produced.

Applicant Roku Konishi Photo Industry Co., Ltd. Procedural amendment writing method) % formula % 2. Name of the invention Silver halide color photographic light-sensitive material 3. Person making the amendment Relationship to the case Patent applicant address 1-chome Nishi-Shinjuku, Shinjuku-ku, Tokyo No. 26-2, 1 Sakura-cho, Hino-shi, Tokyo 191 Konishiroku Photo Industry Co., Ltd. (Tel: 0425-83-152)
1) 5. Full text of the specification subject to amendment 6. Contents of amendment

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing silver halide grains having a silver chloride composition of 80 mol% or more on a support,
A silver halide color photographic light-sensitive material, wherein the silver halide emulsion layer contains at least one compound represented by the following general formula (I) and a coupler solvent represented by the following general formula (II). General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼ A represents a divalent aromatic residue. R_1, R_2, R_3 and R_4 may be the same or different, and each represents a hydrogen atom, a hydroxy group, a lower alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic group, an alkylthio group, a heterocyclylthio group, an arylthio group. group, amino group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group,
It represents a heterocyclylamino group, a substituted or unsubstituted aralkylamino group, an aryl group, or a mercapto group. General Formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R_5, R_6 and R_7 each independently represent an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group.