JPH0621942B2 - Image forming method - Google Patents

Description

TECHNICAL FIELD The present invention relates to an image forming method with improved image sharpness and / or graininess without impairing storage stability.

(Prior Art) Generally, the image quality of a silver halide photographic light-sensitive material is determined by its sharpness and graininess.

The image sharpness of the photographic light-sensitive material is deteriorated due to light scattering and refraction in the silver halide emulsion layer, reflection at the interface, and the like, and in particular, the degree of deterioration increases as the thickness of the light-sensitive layer increases. In particular, in a color light-sensitive material, in order to record by dividing the three primary colors of light, a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer, the emulsion layer is divided into at least three types and coated in layers. But it will be thicker. Therefore, the sharpness of the lowermost emulsion layer is significantly deteriorated.

Various methods are known for improving this deteriorated image sharpness. It is known to add a dye to absorb the scattered light in order to reduce the effect of the scattered light. This method also involves a decrease in sensitivity because it absorbs originally necessary light. Especially for color photographic light-sensitive materials, a method using a so-called DIR-coupler is known. This is a technique in which a development inhibitor is released from a coupler along with the formation of a color image during color development of a color light-sensitive material, and an edge effect is produced due to a difference in the concentration of the development inhibitor to improve sharpness. This method is applicable only to color photosensitive materials such as color negatives and color papers because it is effective only during color development, but the main effect of image formation is black and white development. It cannot be expected to be used for black-and-white photosensitive materials that do not use development.

DIR-hydroquinone, which releases a development inhibitor upon development, is known as a technology that utilizes the edge effect at the time of development and can be applied to many color light-sensitive materials and especially black-and-white light-sensitive materials without color development processing ( US-336
4022, US-3379529, JP-A-50-624.
35, JP-A-50-133833, JP-A-51-519
41, JP-A-50-119631, and JP-A-52-578.
28). Since DIR-hydroquinone has an effect not only in color development but also in black and white development, it can be applied to a wide range of silver halide light-sensitive materials.

However, the present inventors have found that when DIR-hydroquinone is mixed and coated with a conventionally used emulsion, it is decomposed with the lapse of time after adjustment of the coating solution to cause an adverse effect, and the prepared light-sensitive material is preserved. If you try to use the product after storing it for a long time, it has the problems of increased fog and decreased sensitivity. Furthermore, this problem has a large effect on the image in the light-sensitive material that is processed including the black and white development process. Found.

On the other hand, in JP-A-53-20324, a scavenger of an oxidized product of a developing agent or a compound which releases a development inhibitor by a reaction with the oxidized product is added to a non-photosensitive layer adjacent to a silver halide emulsion layer. By the color image forming method of developing the photosensitive material using a specific aromatic primary amine developing agent,
Although it is described that color fog and color mixing are improved and high image density and sensitivity are obtained, the above-mentioned storability is not mentioned at all.

(Object of the Invention) An object of the present invention is to provide an image forming method excellent in sharpness and / or graininess without deteriorating storage stability.

(Constitution of the Invention) An object of the present invention is to provide at least one silver halide photosensitive layer and at least one hydrophilic colloid layer containing substantially no silver halide on a support, and further to provide the following general formula (I):
A method of forming an image, which comprises subjecting a silver halide photographic light-sensitive material containing at least one layer of the compound represented by the above-mentioned to a photographic layer containing substantially no silver halide, a process including a black and white developing step.

General formula (I) A- (Time) _t -X In the formula, A means a redox mother nucleus, and is first oxidized by black and white development. Represents the atomic group that makes it possible for the
Represents a timing group linked to A by a sulfur element, a nitrogen atom, an oxygen atom or a selenium atom, t is an integer of 0 or 1, and X represents a development inhibitor.

The processing including the black-and-white development step of the present invention means black-and-white development using a silver image itself in the black-and-white development step as an image, or color reversal processing for forming a dye image by so-called color development after the black-and-white development step. In the present invention, the phrase "substantially free of silver halide" means that the coated silver amount is about 0.1 g / dm ² or less.

Hereinafter, the compound of the general formula (I) used in the present invention will be described.

First, A of the general formula (I) will be described in more detail. A
Examples of the redox mother nucleus represented by the formula:
-Aminonaphthol, 1,4-aminonaphthol, 1,6-aminonaphthol and the like can be mentioned. At this time, the amino group is preferably substituted with a sulfonyl group having 1 to 25 carbon atoms or an acyl group having 1 to 25 carbon atoms.
Examples of the sulfonyl group include a substituted or unsubstituted aliphatic sulfonyl group and an aromatic sulfonyl group. Examples of the acyl group include a substituted or unsubstituted aliphatic acyl group and aromatic acyl group. The hydroxyl group or amino group forming the redox mother nucleus of A may be protected by a protecting group that can be deprotected during development processing. Examples of the protecting group are those having 1 to 25 carbon atoms, such as an acyl group,
Examples thereof include an alkoxycarbonyl group, a carbamoyl group, and a protecting group described in JP-A-59-197037 and JP-A-59-201057. Further, this protecting group is bonded to the substituent of A described below by combining 5,
A 6- or 7-membered ring may be formed.

The redox mother nucleus represented by A may be substituted at a suitable position with a suitable substituent. Examples of these substituents are those having 25 or less carbon atoms, such as an alkyl group, an aryl group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, an amino group, an amide group, a sulfonamide group, and an alkoxycarbonylamino group. , Ureido group, carbamoyl group, alkoxycarbonyl group, sulfamoyl group, sulfonyl group, cyano group, halogen atom,
Acyl group, carboxyl group, sulfo group, nitro group, heterocyclic residue, or And so on. These substituents may be further substituted with the above-mentioned substituents. Further, these substituents may be bonded to each other to form a saturated or unsaturated carbocycle or a saturated or unsaturated heterocycle.

Preferred examples of A include hydroquinone, catechol, p-aminophenol, o-aminophenol,
1,4-naphthalenediol, 1,4-aminonaphthol and the like can be mentioned. More preferable examples of A include hydroquinone, catechol, p-aminophenol and o-aminophenol. Most preferably, A is hydroquinone.

Preferred specific examples of A in the general formula (I) are shown below. In addition, (*) in each structural formula Combine.

(1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) (26) (27) (28) (29) Is the first time when the oxidized ring nucleus represented by A in the general formula (I) undergoes a cross-oxidation reaction during development and becomes an oxidant. Is a group released as.

Time is a timing group linked to A by a sulfur atom, a nitrogen atom, an oxygen atom or a selenium atom, and is released during development. To a group capable of being released to X through a reaction of one step or more steps. The time is, for example, US Pat. Nos. 4,248,962 and 4,409,323.
No., British Patent No. 2,096,783, US Patent No. 4,
No. 146, 396, Kokai Sho 51-146, 828,
Examples include those described in JP-A-57-56,837. Time may be a combination of two or more selected from those described in these.

X means a development inhibitor. Examples of development inhibitors include:
Examples thereof include a compound having a mercapto group bonded to a hetero ring or a hetero ring compound capable of producing imino silver. Examples of compounds having a mercapto group bonded to the heterocycle include, for example, substituted or unsubstituted mercaptoazoles (e.g., 1-phenyl-5-mercaptotetrazole, 1-propyl-5-mercaptotetrazole, 1-
Butyl-5-mercaptotetrazole, 2-methylthio-5-mercapto-1,3,4-thiadiazole, 3-
Methyl-4-phenyl-5-mercapto-1,2,4-
Triazole, 1- (4-ethylcarbamoylphenyl) -2-mercaptoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-phenyl-
5-mercapto-1,3,4-oxadiazole, 1-
{3- (3-Methylureido) phenyl} -5-mercaptotetrazole, 1- (4-nitrophenyl) -5-
Mercaptotetrazole, 5- (2-ethylhexanoylamino) -2-mercaptobenzimidazole, etc., and substituted or unsubstituted mercaptoazaindenes (eg, 6-methyl-4-mercapto-1,3,3)
a, 7-tetrazaindene, 4,6-dimethyl-2-mercapto-1,3,3a, 7-tetrazaindene, etc.) or a substituted or unsubstituted mercaptopyrimidine (for example, 2-mercaptopyrimidine, 2-mercapto) −
4-methyl-6-hydroxypyrimidine) and the like.

Examples of the heterocyclic compound capable of forming imino silver include substituted or unsubstituted triazoles (for example, 1,
2,4-triazole, benzotriazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-bromobenzotriazole, 5-n-butylbenzotriazole, 5,6-dimethylbenzotriazole, etc.), substituted or unsubstituted Indazoles (eg, indazole, 5-nitroindazole, 3-nitroindazole, 3-chloro-5-nitroindazole, etc.), and substituted or unsubstituted benzimidazoles (eg, 5-nitrobenzimidazole, 5,6-dichlorobenzimidazole) Etc.) and so on.

Further, X is a compound which has a development inhibitory property after it is removed from the general formula (I) Time, and then it causes a certain chemical reaction with the developer component to have a substantial development inhibitory property. It may be a compound that is not used, or is converted to a significantly reduced compound. Examples of the functional group that undergoes such a chemical reaction include an ester group, a carbonyl group, an imino group, an immonium group, a Michael addition accepting group, and an imide group. Examples of such a deactivating development inhibitor include, for example, 1- (3-phenoxycarbonylphenyl) -5-mercaptotetrazole and 1- (4
-Phenoxycarbonylphenyl) -5-mercaptotetrazole, 1- (3-maleimidophenyl) -5
-Mercaptotetrazole, 5-phenoxycarbonylbenzotriazole, 5- (4-cyanophenoxycarbonyl) benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,3,4-thiadiazole, 5-nitro -3-phenoxycarbonylimidazole, 5- (2,3-dichloropropyloxycarbonyl) benzotriazole, 1- (4-benzoyloxyphenyl) -5-mercaptotetrazole, 5- (2
-Methanesulfonylethoxycarbonyl) -2-mercaptobenzothiazole, 5-cinnamoylaminobenzotriazole, 1- (3-vinylcarbonylphenyl)
-5-mercaptotetrazole, 5-succinimidomethylbenzotriazole, 2- {4-succinimidophenyl} -5-mercapto-1,3,4-oxadiazole, 6-phenoxycarbonyl-2-mercaptobenzoxazole, etc. Can be given.

In order to more specifically arrange the contents of the present invention, specific examples of the compound represented by the general formula (I) are shown below, but the compounds usable in the present invention are not limited thereto.

(I-1) (I-2) (I-3) (I-4) (I-5) (I-6) (I-7) (I-8) (I-9) (I-10) (I-11) (I-12) (I-13) (I-14) (I-15) (I-16) (I-17) (I-18) (I-19) (I-20) (I-21) (I-22) (I-23) (I-24) (I-25) (I-26) (I-27) (I-28) (I-29) (I-30) (I-31) (I-32) (I-33) (I-34) (I-35) (I-36) (I-37) (I-38) (I-39) (I-40) (I-41) (I-42) (I-43) (I-44) (I-45) (I-46) (I-47) (I-48) (I-49) (I-50) (I-51) (I-52) (I-53) (I-54) (I-55) (I-56) (I-57) (I-58) (I-59) (I-60) (I-61) The compound represented by the general formula [I] can be generally synthesized by the following two methods. First, Time is just a bond (t =
In the case of 0), the first is in chloroform, 1,2-dichloroethane, carbon tetrachloride, tetrahydrofuran, without catalyst or in the presence of an acid catalyst such as p-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid. In addition, benzoquinone, orthoquinone, quinone monoimine and quinone diimine derivatives are reacted with a development inhibitor at a temperature between room temperature and 100 ° C. Second
Is a benzoquinone substituted with chlorine, bromine or iodine in the presence of a base such as potassium carbonate, sodium hydrogen carbonate, sodium hydride or triethylamine in an aprotic polar solvent such as acetone, tetrahydrofuran or dimethylformamide, orthoquinone or quinone mono. Imine,
Add quinone diimine derivative and development inhibitor from -20 ° C to 10
In this method, the quinone compound obtained by reacting at 0 ° C. is reduced with a reducing agent such as diethylhydroxylamine or sodium hydrosulfite. [Reference: Resear
ch Disclosure 18227 (1979); Liebige An
n.Chem.764, 131 (1972)] Then, also in the case of the type (t = 1) in which X is released via Time, it can be synthesized by a method substantially similar to the above. That is, use Time-X instead of the above development inhibitor (X),
Alternatively, it is a method in which Time having a substitutable group for X (for example, a halogen atom, a hydroxy group, or a precursor thereof) is first introduced into the redox nucleus, and then X is linked by a substitution reaction.

The amount of the compound represented by the general formula (I) used in the present invention is
In the color reversal light-sensitive material, it is 10 ^-7 mol / m ² to 10 ^-3 mol / m ² , preferably 10 ^-6 mol / m ² to 10 ^-4 mol / m ^2.
In the case of a black-and-white negative light-sensitive material or an X-ray light-sensitive material, 10 ⁻⁷ to 10 ⁻¹ mol, preferably 10 ⁻⁶ to 10 ⁻² mol, and more preferably 5 × 10 5 mol per mol of silver.
^-6 mol to 5 × 10 ^-3 mol.

The compounds represented by the general formula of the present invention may be used alone or in combination of two or more kinds.

The compound represented by the general formula may be added as an emulsion obtained by dissolving in a high-boiling point oil and stirring at high speed, or dissolved in a water-soluble organic solvent such as alcohol or cellosolve in a gelatin solution and finely dispersed by stirring. You may add it.
Furthermore, Japanese Examined Patent Publication Nos. 51-39853 and 58-352.
The dispersion method using polymer latex described in No. 14 may be used.

Specific examples of the high boiling point organic solvent suitable for dissolving DIR-hydroquinone used in the light-sensitive material of the present invention include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, etc.). , Phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2
-Ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p) -Hydroxybenzoate, etc.), amides (diethyldodecane amide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (Dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivative (N, N-dibutyl-2-butoxy-5-tert-) Kuchiruanirin etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene), and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C or higher and about 16 ° C.
An organic solvent at 0 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

Particularly preferred are phosphoric acid esters such as tri-2-ethylhexyl phosphate and tridodecyl phosphate, and amides such as diethyl dodecane amide.

The amount of oil used is 1/10 to 20 times, preferably 1/5 to 10 times the weight ratio of DIR-hydroquinone.

The hydrophilic colloid layer containing substantially no silver halide adjacent to the silver halide emulsion layer of the present invention is, for example, a layer containing gelatin or a hydrophilic polymer as a binder, and is a coupler, a color mixing inhibitor, a browning inhibitor. And the like, and may further contain various chemicals such as dyes, development inhibitors, stabilizers, development accelerators, pH regulators and film quality improvers. It can be provided at any position in the light-sensitive material emulsion layer.

Next, the processing including the black and white development step used in the present invention will be described.

The black-and-white development process is a process of reducing silver halide grains forming a latent image by exposure to form a silver image,
In this case, it is different from the process of forming a dye image by coupling an oxidative coupler with a phenylenediamine derivative, which is used in so-called color development.

The black and white development step used for image formation of the present invention contains at least one developer represented by the following general formula (II) and / or general formula (III). These developers may be salts of inorganic acids or organic acids.

General formula (II) R ¹ to R ⁴ may be the same or different, and are a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a sulfo group or a salt thereof, a carboxyl group, or Represents X'is a hydroxyl group, Or represents a hydrogen atom. However, when X ′ is a hydrogen atom, R ¹ or R ⁴ is a hydroxyl group or Is.

R ⁵ and R ⁶ may be the same or different and each represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group or a sulfonyl group. X ′ or R ¹ to R ⁶ may have a substituent, if possible, and may form a ring.

The general formula (I) will be described in more detail.

The aliphatic group represented by R ¹ to R ⁴ has 1 to 12 carbon atoms.
And an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a hexyl group, and a cyclohexyl group. As an alkenyl group, an allyl group,
Examples include butenyl group. Examples of the alkynyl group include a propargyl group and a pentynyl group. Examples of the aralkyl group include a benzyl group, a 1,1-dimethylbenzyl group, a phenethyl group and the like.

The aromatic group represented by R ¹ to R ⁴ has 6 to 12 carbon atoms.
And examples thereof include a phenyl group, a p-tolyl group, and a naphthyl group.

The halogen atom of R ¹ to R ⁴ is chlorine, bromine, fluorine or iodine.

Examples of the aliphatic group and aromatic group of R ⁵ to R ⁶ include those described for R ¹ to R ⁴ .

The acyl group represented by R ⁵ to R ⁶ has 1 to 10 carbon atoms.
And examples thereof include an acetyl group or a benzoyl group.

The sulfonyl group of R ⁵ to R ⁶ has 1 to 1 carbon atoms
No. 0, and examples thereof include a methanesulfonyl group, a benzenesulfonyl group, and a toluenesulfonyl group.

Examples of the substituents of X'and R ¹ to R ⁶ include cyano group, alkoxy group, aryloxy group, carbamoyl group, alkylthio group and arylthio group in addition to those described for R ¹ and R ⁵ .

When a ring is formed in X'and R ¹ to R ⁶ , they are each independently or R ¹ and R ² , R ² and X ', X'and R ³ or R ³ and R ⁴ are bonded to each other to have 5 to 8 members. And a ring containing a carbon ring or a ring containing oxygen or nitrogen.

R ¹ to R ⁴ are preferably a hydrogen atom, an alkyl group,
An aryl group, a halogen atom, a hydroxyl group, or a sulfo group (or a salt thereof), more preferably a hydrogen atom, an alkyl group, a halogen atom, or a sulfo group (or a salt thereof), and most preferably a hydrogen atom or a sulfo group. A group (or a salt thereof).

X ′ is preferably a hydroxyl group or And more preferably a hydroxyl group, —NH ₂ , —
NHCH _3, or a -NHC ₂ H _5, and most preferably a hydroxyl group or a -NHCH _3.

Specific examples of the general formula (II) are shown below, but the invention is not limited thereto.

(II-1) (II-2) (II-3) (II-4) (II-5) (II-6) (II-7) (II-8) (II-9) (II-10) (II-11) (II-12) (II-13) (II-14) (II-15) (II-16) (II-17) (II-18) (II-19) (II-20) (II-21) (II-22) (II-23) (II-24) (II-25) (II-26) (II-27) (II-28) (II-29) (II-30) (II-31) (II-32) (II-33) (II-34) (II-35) (II-36) (II-37) (II-38) (II-39) (II-40) General formula (III) In the formula, R ²¹ is an aryl group, and R ²² to R ²⁵ may be the same or different and each represents a hydrogen atom, an aliphatic group, or an aromatic group.

R ²¹ to R ²⁵ may have a substituent or may form a ring, and the general formula (I) will be described in more detail.

The aryl group of R ²¹ has 6 to 10 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

Examples of the aliphatic group and aromatic group of R ²² to R ²⁵ include those described as the aliphatic group and aromatic group of R ¹ of the general formula (I).

The substituents of R ²¹ to R ²⁵ include R ^{1 of the} general formula (I).
The substituents mentioned above may be mentioned.

R ²¹ to R ²⁵ may form a ring, either alone or in R ²² and R ²³ , R ²² and R ²⁴ , R
Examples thereof include those in which ²⁴ and R ²⁵ or R ²⁵ and R ²¹ are combined to form a 5-membered to 8-membered carbon ring or a ring containing oxygen or nitrogen.

R ²¹ is preferably phenyl group, p-tolyl group, m-
It is a tolyl group or a p-methoxyphenyl group, more preferably a phenyl group, a p-tolyl group or an m-tolyl group, and most preferably a phenyl group.

R ²² and R ²³ are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group or a hydroxymethyl group, and most preferably R ²² is a methyl group and R ^23.
Is a hydroxymethyl group.

R ²⁴ and R ²⁵ are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom.

Specific examples of the general formula (II) are shown below, but the invention is not limited thereto.

(III-1) (III-2) (III-3) (III-4) (III-5) (III-6) (III-7) (III-8) (III-9) (III-10) (III-11) (III-12) (III-13) (III-14) These developing agents may be used alone or in combination of two or more and added to the developing solution, or may be contained in the photosensitive material.

When these developing agents are added to the developer, they can be represented by the general formula (II)
The compound represented by 0.3 to 80 g /, preferably 0.5 to 60 g /, more preferably 0.8 to 40 g /
The amount of the compound represented by the general formula (III) is 0.02 to 10 g /, preferably 0.05 to 8 g.
/, More preferably in the range of 0.075 to 6 g /.

Next, the silver halide grains used in the present invention will be described.

The silver halide grains used in the present invention are silver bromide, silver iodide,
It may be any of silver iodobromide, silver chlorobromide, silver chloroiodobromide, and silver chloride, but silver bromide and silver iodobromide are preferable, and a silver iodide content of 0 to 30 is particularly preferable. It is preferably silver iodobromide having a mol%.

These silver halide grains may be so-called Regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having irregular crystal shapes such as spheres and tabular grains. Those having crystal defects such as grain twin planes or a composite form thereof may be used. Also, a mixture of particles having various crystal forms may be used.

The grain size of these silver halides may be fine grains of about 0.1 micron or less or large grains having a projected area diameter of up to about 10 microns, a monodisperse emulsion having a narrow distribution, or a wide distribution. It may be a polydisperse emulsion.

The silver halide photographic emulsion used in the present invention can be produced by a known method, for example, Research Disclosure, 17
Volume 6, NO.17643 (December 1978), 22-2
Page 3, "1. Emulsion Preparalion and Type
s) ”and Vol. 187, No. 18716 (1979, 1)
January), page 648.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by P.Glafkides, Chimi.
e et Physique Photographique Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press, Inc. (G.
F. Duffin, Photographic Emulsion Chemistry (Focal Pre
ss, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Forcal Press (VL Zelikman et al, Makin.
g and Coating Photographic Emulsoion, Focal Press,
1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Further, tabular grains are described in, for example, British Patent No. 1,335,92.
5, US Pat. Nos. 3,672,900 and 3,65
0,757, 4,242,445, JP-A-55.
-142329, 55-158124, 58-
113927, 58-113928, 58-1
It can be produced by referring to the methods described in Nos. 11934 and 58-111936.

Known silver halide solvents (for example, ammonia, rhodancal or U.S. Pat. No. 3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-53-144319, JP-A-53-144319, SHO 54-100717
Physical aging in the presence of thioethers and thione compounds described in JP-A No. 54-155828. By this method also, a silver halide emulsion having a regular crystal form and a nearly uniform grain size distribution can be obtained.

The silver halide emulsion composed of the above-mentioned regular grains can be obtained by controlling pAg and pH during grain formation. For details, see, for example, Photographic Science.
And Engineering (Photographic science and
Engineering) Volume 6, 159-165 (1962);
Journal of Photographic Science (Jou
enal of Photographic Science), Volume 12, 242-2
51 (1964), U.S. Pat. No. 3,655,934 and British Patent No. 1,413,748.

The monodisperse emulsion comprises silver halide grains having an average grain diameter of greater than about 0.1 micron, at least 9
Emulsions such that 5% by weight are within ± 40% of the average grain diameter are typical. The average grain diameter is 0.25 to 2 microns and at least 95% by weight or (number of grains) at least 95% of the silver halide grains have an average grain diameter of ± 2.
Emulsions such as those in the 0% range can be used in the present invention. Such an emulsion method is described in US Pat. No. 3,574,62.
No. 8, 3,655,394 and British Patent No. 1,
No. 413,748. In addition, JP-A-48-
No. 8600, No. 51-39027, No. 51-8309
No. 7, No. 53-137133, No. 54-48521
No. 54-99419, No. 58-37635, No. 58-49938 and the like can also be preferably used in the present invention.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent 1,027,1
46, U.S. Pat. Nos. 3,505,068 and 4,44
No. 4,877 and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halides such as silver rhodanide and lead oxide. These emulsion grains are described in U.S. Pat. Nos. 4,094,684, 4,142,900, 4,459,353 and British Patent 2,038,792.
U.S. Pat. Nos. 4,349,622 and 4,395.
No. 478, No. 4,433, 501, No. 4,463, 0
No. 87, No. 3,656,962, No. 3,852,06
No. 7, JP-A-59-162540 and the like.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist.

These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

In order to remove the soluble silver salt from the emulsion before and after physical ripening, Nudel water washing, flocculation precipitation method, ultrafiltration method or the like is used.

The emulsion used in the present invention is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643 (December 1978) and No. 1 mentioned above.
8716 (November 1979), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures (RD), and the locations described in the table below are shown.

Various color couplers can be used in the present invention. Here, the color coupler means a compound capable of reacting with an oxidized product of an aromatic primary amine developing agent to form a dye. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds, and open or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Disclosure (RD) 17643 (197).
December 1988) Item VII-D and Ibid. 18717 (1979)
(November, 2014).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. Two-equivalent color couplers substituted with a leaving group are preferable to four-equivalent color couplers having a coupling active position of hydrogen atom. A coupler in which a color-forming dye has an appropriate diffusibility, a non-coloring coupler or a DIR coupler which releases a development inhibitor along with a capping reaction, a coupler which releases a development accelerator, and a compound which undergoes a redox reaction with an oxidized product of a developing agent. A coupler that emits can also be used.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is US Pat. No. 2,40.
No. 7,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,447,928 are preferred.
No. 3,933,501 and No. 4,022.
No. 620 and other yellow couplers of oxygen atom elimination type or Japanese Patent Publication No. 58-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, R
D18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application Publication No. 2,219,917,
Typical examples thereof include nitrogen atom releasing yellow couplers described in Nos. 2,261,361, 2,329,587 and 2,433,812. The α-bivaloylacetanilide type coupler is excellent in the fastness of the color forming dye, especially the fastness to light, while
-The benzoylacetanilide type coupler provides a high color density.

Examples of magenta couplers that can be used in the present invention include oil-protection-type, indazolone-type or cyanoacetyl-type, preferably 5-pyrazolone-type and pyrazoloazole-type couplers such as pyrazolotriazoles. The 5-pyrazolone type coupler is a coupler in which the 3-position is substituted with an arylamino group or an acylamino group,
It is preferable from the viewpoint of hue and color density of the color forming dye, and typical examples thereof are U.S. Patent Nos. 2,311,082 and 2,3.
43,703, 2,600,788, 2,
908,573, 3,062,653, 3,152,896, and 3,936,015. A 2-equivalent 5-pyrazolone-based coupler is preferred because it provides high color density and high sensitivity with a small amount of coated silver, and it is preferred as a leaving group in US Pat.
The nitrogen atom leaving group described in 619 or the arylthio group described in US Pat. No. 4,351,897 is particularly preferable. The ballast group described in EP 73,636 also has the effect of increasing the color density for 5-pyrazolone type couplers. As the pyrazoloazole-based coupler, pyrazolobenzimidazoles described in US Pat. No. 3,369,897, preferably US Pat.
Pyrazolo [5,1-c] described in No. 725,067
[1,2,4] triazoles, RD24220 (19
And the pyrazolopyrazoles described in RD24230 (June 1984). European Patent No. 119,741 in terms of low yellow sub-absorption of color forming dye and light fastness
Are preferred, and the pyrazolo [1,5-b] [1,2,4] triazoles described in EP 119,860 are particularly preferred.

Cyan couplers usable in the present invention include oil-protection type naphthol type and phenol type couplers, and the naphthol type couplers described in US Pat. No. 2,474,293, preferably US Pat. No. 4,05.
No. 2,212, No. 4,146,396, No. 4,2
Representative examples thereof include oxygen atom desorption type two-equivalent naphthol couplers described in Nos. 28,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Pat. No. 2,369,929 and No. 2,369,929.
801,171, 2,772,162, 2,895,826 and the like. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, of which typical examples are US Pat.
No. 72,002, a phenol cyan coupler described in U.S. Pat. Nos. 2,772,162 and 3,75.
No. 8,308, No. 4,126,396, No. 4,3
34,011, 4,327,173, West German Patent Publication 3,329,729, and Japanese Patent Application No. 58-426.
2,5-diacylamino-substituted phenol-based couplers described in U.S. Pat.
No. 2, No. 4,333, 999, No. 4,451, 5
59 and No. 4,427,767, and the like, and phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position.

These color couplers may form a dimer or higher polymer. Typical examples of polymerized couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

Further, a color forming dye diffusion type coupler can be used in combination to improve the graininess. Such a coupler is disclosed in US Pat.
66,237 and British Patent 2,125,570, specific examples of magenta couplers, and European Patent 96,237.
873 and West German Patent Publication (OLS) 3,324,5
33), specific examples of yellow, magenta and cyan are described.

The silver halide recording material of the present invention includes a black and white photographic light-sensitive material, color reversal, color reversal paper, and the like. Containing and forming a color image in the light-sensitive material at the time of processing, it is extremely useful in an external reversal color light-sensitive material.

Of the silver halide recording materials of the present invention, the silver halide color reversal light-sensitive material has at least one red-sensitive, green-sensitive and blue-sensitive emulsion layer, but the order of these light-sensitive layers is not particularly limited. Instead, it is set according to the purpose.

Further, as described later, a dye-forming coupler is used in the silver halide color reversal light-sensitive material of the present invention. Usually, a cyan dye-forming coupler is used in the red-sensitive layer and a magenta dye-forming coupler is used in the green-sensitive layer. Although a yellow dye-forming coupler is used in the blue-sensitive layer, different combinations may be used depending on the purpose.

To process the color reversal light-sensitive material of the present invention, black and white development (first development) → stop → washing → reversal → washing → color development → stop →
Washing → Conditioning bath → Washing → Bleaching → Washing → Fixing → Washing → Stable →
Dry steps are used. This step is further pre-bath,
A pre-hardening bath, an intermediate bath or the like may be provided. Further, washing with water after stop, reversal, color development, conditioning bath or bleaching may be omitted. The reversal may be performed by a fogging bath or re-exposure. It can also be omitted by adding a fogging agent to the color developing bath. Furthermore, the conditioning bath can be omitted.

In the black-and-white developer used in the present invention, if necessary, a preservative (for example, sulfite, bisulfite, etc.), a buffer (for example, carbonate, boric acid, borate, alkanolamine),
Alkaline agents (eg hydroxides, carbonates), solubilizers (eg polyethylene glycols, their esters), pH adjusters (eg organic acids such as acetic acid), sensitizers (eg quaternary ammonium) Salt), a development accelerator, a surfactant, a color tone agent, a defoaming agent, a film hardener, a viscosity imparting agent and the like.

The first developing solution used in the present invention needs to contain a compound which acts as a silver halide solvent, and the sulfite salt added as the preservative usually plays the role. As the sulfite and silver halide solvent capable of other uses, specifically _{KSCN, NaSCN, K 2 SO 3} , Na 2 SO 3, K 2 S 2 O 5, Na 2 S 2
O, etc. _{5, K 2 S 2 O 3} , Na 2 S 2 O 3 can be mentioned.

Further, a development accelerator is used for imparting a development accelerating action. Particularly, a compound represented by the following formula (A) described in JP-A-57-63580 is used alone or in combination of two or more kinds, May be used in combination with the above silver halide solvent.

General formula (A) If the amount of these silver halide solvents used is too small, the progress of development is slowed, and if the amount is too large, fogging occurs in the silver halide emulsion, and therefore, there is a preferable amount used by itself. Can be easily done by those skilled in the art.

For example, SCN ⁻ is preferably 0.005 to 0.02 mol, particularly 0.01 to 0.015 mol, and SO ₂ ²⁻ is 0.05 to 1 mol, particularly 0.1 to 0.1 mol, per developer. 0.5
It is preferably molar.

When the compound of the general formula (A) is used by adding it to the black and white developing solution used in the present invention, the addition amount is preferably the developing solution 1
It is 5 × 10 ^-6 mol to 5 × 10 ^-1 mol, and more preferably 1 × 10 ^-4 mol to 2 × 10 ^-1 mol.

The pH value of the developer thus adjusted is selected to an extent sufficient to give the desired density and contrast, but it is preferably in the range of about 8.5 to about 11.5.

To perform a sensitization process using such a first developing solution,
The time may be extended up to about 3 times the standard processing.
At this time, if the processing temperature is raised, the extension time for the sensitization processing can be shortened.

The fogging bath used for processing the light-sensitive material of the present invention may contain a known fogging agent. That is, stannous ion-organic phosphoric acid complex salt (US Pat. No. 3,617,2)
82), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-32616), stannous ion-aminopolycarboxylic acid complex salt (UK Patent No. 1,20).
Stannous ion complex salt borohydride compounds (US Pat. No. 2,984,567), heterocyclic amine borane compounds (GB Pat. No. 1,01).
1,000), and the like, and the like. The pH of the fogging bath (reversal bath) is wide ranging from the acidic side to the alkaline side.
The range is preferably 2.5 to 10, particularly preferably 3 to 9.

The color developer used in the present invention has a composition of a general color developer containing an aromatic primary amine developing agent. Preferred examples of aromatic primary amine color developing agents are the following p-phenylenediamine derivatives. N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5- (N-ethyl-
N-laurylamino) toluene, 4- [N-ethyl-N
-(Β-Hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline, N-ethyl-N- (β-methanesulfoamidoethyl) -3 -Methyl-4-aminoaniline, N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide, N, N-dimethyl-p-
Phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline described in U.S. Pat. Nos. 3,656,950 and 3,698,525. Amino-3-methyl-N-ethyl-
N-β-ethoxyethylaniline and 4-amino-3
-Methyl-N-ethyl-N-β-butoxyethylaniline and salts thereof (for example, sulfate, hydrochloride, sulfite, p
-Toluenesulfonate, etc.) is a preferred representative example.

When the photographic light-sensitive material of the present invention is a black-and-white silver halide photographic light-sensitive material, Research Disclosure Vol.
17643, pp. 28-29, Vol. 187, No. 1871
It can be developed by the method described in page 6, 651, left column, right column.

When the photographic light-sensitive material of the present invention is a color light-sensitive material, color reversal film, color reversal paper and the like can be mentioned, but it is preferably used for color reversal film.

When the photographic light-sensitive material of the present invention is a black-and-white light-sensitive material, specifically, a black-and-white negative light-sensitive material, an X-ray light-sensitive material, a printing light-sensitive material
Black-and-white photographic paper and the like can be mentioned, but preferably black-and-white negative photosensitive materials are used.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.
It is not limited to these.

(Example 1) Sample 101 was prepared by forming a silver halide light-sensitive material having various compositions as follows on a triacetate film base.
And

First layer Gelatin layer Gelatin layer containing 0.75 g / m ² of gelatin Second layer Emulsion layer Silver iodobromide emulsion 1.0 g / m ² Iodine content 4 mol% Average grain size 0.5 μ Sensitizing dye S -1 1.0 mg / m ² S-2 1.0 mg / m ² Gelatin 2.0 g / m ² 3rd layer Protective layer Gelatin 0.9 g / m ² containing gelatin layer In addition to the above composition in each layer Gelatin hardener H-3 and surfactant were added.

In Sample 101, the first gelatin layer was made of compound NO.I.
-51, 10 g, oil (N, N-diethyllaurylamide) 50 g, ethyl acetate 50 g, a solution prepared by heating and dissolving 10 g of a surfactant were replaced by coating by adding 1000 g of an aqueous gelatin solution and an emulsion prepared by stirring with a mixer. And a sample 102 was prepared.

A compound 103 was prepared by changing the compound NO.I-51 of the sample 102 to the compound NO.I-52.

A compound 104 was prepared by changing the compound NO.I-51 of the sample 102 to the compound NO.I-53.

In Sample 101, Sample 102 in the second emulsion layer
Sample 105 was prepared in place of adding the emulsion of the compound used in 1. and coating.

A compound 106 was prepared by changing the compound NO.I-51 of the sample 105 to the compound NO.I-52.

The sample No. I-51 of the sample 105 was changed to the compound No. I-53 to prepare the sample 107.

The obtained sample was exposed through a pattern for measuring the sharpness and then subjected to the development processing described later to obtain a silver image.

The processing steps used here are as follows.

Processing time Temperature Development 5 minutes 20 ° C Stop (1.5% acetic acid aqueous solution) 1 minute 20 ° C Fixing 10 minutes 20 ° C Wash 10 minutes 20 ° C Dry developer water 750ml Metol (II-28 sulfate) 3g Anhydrous sodium sulfite 45 g Hydroquinone (II-1) 12 g Sodium carbonate monohydrate 80 g Sodium bromide 2 g Water was added to 1000 ml Fixer water 600 ml Sodium thiosulfate 15 g Glacial acetic acid 13.4 ml Boric acid 7.5 g Powdered potassium maliban 15 g Water was added to 1000 ml S -1 S-2 The density of the obtained silver image was measured with a microdensitometer, and the sharpness was measured with an MTF value.

The results obtained are shown in Table 1.

(Storability test) The coated sample was stored under the following conditions.

1) 45 ° C 30% for 3 days 2) 45 ° C 80% for 3 days 3) Refrigerator 5 ° C for 3 days After exposing a sample stored for 3 days through a wedge whose exposure light amount continuously changes, the above-mentioned development treatment is performed. I got a silver image.
The density of the obtained silver image was measured, the sensitivity was determined from the density Dmin of the portion with the lowest light intensity and the light intensity at which the density was Dmin + 0.2, and the comparison with the Dmin and the sensitivity under the condition (3) was determined.

As shown in Table 1, it is clear that the present invention achieves the sharpness improving effect of DIR-hydroquinone without any adverse effects such as an increase in Dmin during storage and a decrease in sensitivity.

(Example 2) Sample 20 was prepared by coating each layer having the following composition on a triacetate film base to prepare a multilayer color light-sensitive material.
It was set to 1.

1st layer; anti-halation layer Black colloidal silver 0.25 g / m ² UV absorber U-1 0.04 g / m ² UV absorber U-2 0.1 g / m ² UV absorber U-3 0.1 g / m ² high boiling point organic solvent-1 0.1 CC / m ² gelatin layer containing 2.3 g / m ² gelatin Second layer; intermediate layer compound H-1 0.05 g / m ² high boiling point organic solvent-2 0.05 CC / m ² gelatin 0.75 g / m ² gelatin layer a third layer comprising; first red-sensitive emulsion layer silver iodobromide emulsion silver ...... 0.5g / m ² (iodine content 4 mole%, mean grain size 0 .3Myu) sensitizing dye S-3 1.2mg / m ² sensitizing dye S-4 0.3mg / m ² coupler C-1 0.2g / m ² coupler ^C-2 0.05g / m 2 high-boiling organic the solvent -2 0.03 cc / m ² gelatin 0.7 g / m containing ² layers fourth layer: second red-sensitive emulsion layer silver iodobromide emulsion ...... silver ...... 0.8 g / m ² (yaw Content 2.5 mole%, average particle size 0.5 [mu]) Sensitizing dye S-3 1.0mg / m ² Sensitizing dye S-4 0.25mg / m ² Coupler C-1 0.55g / m ² Coupler C -2 0.14 g / m ² high-boiling organic solvent -2 0.08CC / m ² gelatin 1.40 g / m containing ² layers fifth layer; intermediate layer compound H-1 0.1g / m ² high-boiling organic solvent -2 0.1cc / m ² gelatin 1.2g / m ² containing gelatin layer 6th layer; 1st green emulsion layer Silver iodobromide emulsion Silver amount ...... 0.7g / m ² (iodine content 3 mol% , Average particle size 0.3 μ) Sensitizing dye S-5 0.6 mg / m ² Sensitizing dye S-6 1.2 mg / m ² Coupler C-3 0.35 g / m ² High boiling organic solvent-2. Layer containing 0.05 CC / m ² gelatin 1.20 g / m ² 7th layer; second green emulsion layer Silver iodobromide emulsion Silver amount ... 0.7 g / m ² (iodine content 2.5 mol%, average grain Size 0 8 micron) Sensitizing dye S-5 0.4mg / m ² Sensitizing dye S-6 0.8mg / m ² Coupler C-4 0.25g / m ² High-boiling organic solvent -2 0.04 cc / m ² Gelatin 1 layer eighth layer comprising a .0g / m ^2; the intermediate layer compound gelatin layer ninth layer containing H-1 0.05g / m ² high-boiling organic solvent -2 0.1 g / m ² gelatin 0.47 g / m ² Yellow filter layer yellow colloidal silver 0.1 g / m ² compound H-1 0.02 g / m ² compound H-2 0.03 g / m ² high boiling organic solvent-2 0.04 CCm ² gelatin 0.96 g / m ² Gelatin layer containing 10th layer; first blue-sensitive emulsion layer Silver iodobromide emulsion Silver amount: 0.6 g / m ² (iodine content 2.5 mol%, average grain size 0.7 μ) Sensitizing dye S- layer 11th layer containing 7 0.9 mg / m ² coupler C-5 0.5g / m ² high-boiling organic solvent -2 0.05 cc / m ² gelatin 0.8 g / m ^2; 2 blue-sensitive emulsion layer Silver iodobromide emulsion silver ...... 1.1g / m ² (iodine content 2.5 mole%, average particle size 1.2 microns) Sensitizing dye S-7 0.4mg / m ² Coupler C -5 1.2 g / m ² high boiling organic solvent-2 0.12 CC / m ² gelatin 1.70 g / m ² containing layer 12th layer; 1st protective layer UV absorber U-1 0.02 g / m ² Ultraviolet absorber U-2 0.03 g / m ² Ultraviolet absorber U-3 0.03 g / m ² Ultraviolet absorber U-4 0.29 g / m ² High boiling organic solvent-1 0.28 CC / m ² Gelatin 0 Gelatin layer containing 0.9 g / m ² 13th layer; 2nd protective layer Surface-fogged fine grain silver iodobromide emulsion Silver amount ... 0.1 g / m ² (iodine content 1 mol%, average grain size 0. 06Myu) polymethyl methacrylate particles (average particle size 1.5 microns) above the gelatin layer each containing 0.2 g / m ² gelatin 0.9 g / m ² In addition to the compositions, gelatin hardener H-3, and a surface active agent was added. The compounds used to make the samples are shown below.

C-1 C-2 C-3 C-4 C-5 U-1 U-2 U-3 U-4 H-1 H-2 H-3 -1 -2 S-3 S-4 S-5 S-6 S-7 The obtained sample was exposed at a light source of 4800 ° K to an exposure surface illuminance of 1
It was exposed to white light through a pattern for measuring the sharpness at 000 lux and then subjected to the development processing described later to obtain a color image.

The processing steps and processing solutions used here are as follows.

Treatment process Time Temperature First development 6 minutes 38 ° C Water wash 2 minutes 〃 Inversion 2 minutes 〃 Color development 6 minutes 〃 Adjustment 2 minutes 〃 Bleach 6 minutes 〃 Fixation 4 minutes 38 ° C Water washing 4 minutes 〃 Stable 1 minute 〃 Drying The following liquid composition is used. First developer water 700 ml sodium tetrapolyphosphate 2 g sodium sulfite 20 g hydroquinone potassium monosulfonate (II-7) 30 g sodium carbonate (monohydrate) 30 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone (III-3) 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Water was added 100.0 ml (pH 10.1) Inversion solution water 700 ml Nitro-N, N , N-trimethylene phosphonic acid ・ 6Na salt 3 g Stannous chloride (dihydric acid) 1 g p-Aminophenol 0.1 g Hydroxyl tonaulim 8 g Glacial acetic acid 15 ml Water was added 1000 ml Color developer water 700 ml Sodium tetrapolyphosphate 2 g Sulfite Sodium 7g Tribasic sodium phosphate (12-hydrate) 36g Potassium bromide Um 1 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3 g Citrazinic acid 1.5 g N-Ethyl-N- (β-methanesulphonamidoethyl) -3-methyl-4-aminoaniline / sulfate 11 g Ethylenediamine 3g Water is added 1000ml Adjusted water 700ml Sodium sulfite 12g Ethylenediamine, sodium tetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Water is added 1000ml Bleached water 800g Ethylenediaminetetraacetic acid sodium (2water) Salt) 2.0 g Ammonium (dihydrate) 120.0 g Potassium bromide 100.0 g Water added 1000 ml Fixer water 800 ml Ammonium thiosulfate 80.0 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water added 1000 ml Stability water 800ml Formalin (37% by weight) 5.0 ml Fuji Drywell 5.0 ml Water was added to 1000 ml The sharpness of the images of these treated samples was measured.

Table 2 shows MTF at 10 and 20 frequencies per mm.
Showed the value.

In Sample 201, the second intermediate layer was used as Example 1, Sample NO.
Sample 2 was prepared in exactly the same manner as Sample 201, except that the emulsion of compound NO.I-51 used in 102 was added and applied.
I got 02.

In sample 202, compound NO.I-51 was replaced with compound NO.I-
Sample 52 was obtained in place of 52.

In sample NO.202, compound NO.I-51 was converted to compound N.
Sample 204 was obtained in place of O.I-53.

In Sample 201, the first red-sensitive emulsion layer of the third layer was used in Example 1,
A sample was prepared in exactly the same way as the sample 201 except that the emulsion of the compound NO.I-51 used in the sample 102 was added and applied.
Sample 205 was obtained.

In Sample 205, the compound NO.I-51 was replaced with NO.I-52.
To obtain a sample 206.

After the sample was placed under the same storage conditions as in Example 1, the sample was exposed through a wedge in which the exposure light amount was continuously changed, and then the above-described developing process was performed in Example 2 to obtain a color image.

The density of the obtained color image was measured through a red filter.

ΔDmax = (maximum concentration of refrigerated product) − (maximum concentration of sample stored under conditions 1 or 2) ΔS _0.5 = {sensitivity of refrigerated product concentration 0.5 (logE)} − {sample stored under conditions 1 or 2 The sensitivity (logE) at the density of 0.5 is smaller than both ΔDmax and ΔS _0.5 shown in Table 2.

It can be seen from Table 2 that the samples using the present invention can improve the sharpness without an increase in Dmin and a decrease in sensitivity during storage.

Example 3 (1) Preparation of Photosensitive Silver Halide Emulsion Potassium bromide and potassium iodide and silver nitrate were added to an aqueous solution of gelatin with vigorous stirring to form a plate-shaped silver iodobromide having an average particle diameter of 1 μ ( AgI = 4 mol%) was prepared. Then, it was washed with water by a usual precipitation method, and then chemically sensitized by a gold / sulfur sensitization method using chloroauric acid and sodium thiosulfate to obtain a photosensitive silver iodobromide emulsion A.

(2) Preparation of Emulsion Compound NO.I-54, 12 g, oil (N, N-diethyllaurylamide) 50 g, ethyl acetate 50 g, and surfactant 10 g were dissolved by heating to prepare a gelatin aqueous solution 100.
An emulsion (A) was obtained by stirring with 0 g of the mixture with a mixer.

(3) Preparation of coating sample As shown in Table 3, compound I-54 as an emulsion (A) was added to each layer of the following formulation on a triacetyl cellulose support, and the coating was sequentially applied from the support side to prepare samples 301 to 301. 307
It was created. However, samples 301 to 307 have a chemical concentration of 0.3.
Was used.

Emulsion A was added to the emulsion layer so that the coated silver amount was 3 g / m ² .

Additives other than the emulsion emulsion and the surface protective layer of the emulsion layer are as follows.

1st layer (gelatin layer) Binder: gelatin 0.7 g / m ² Coating aid: N-oleoyl-N-methyl taeline sodium salt 0.2 mg / m ² 2nd layer (emulsion layer) Binder: gelatin increase Sensitizer: Coating aid: sodium dodecylbenzene sulfonate 0.1 mg / m ² poly-p-styrene sulfonate potassium salt 1 mg / m ² 3rd layer (surface protection layer) Binder: gelatin 0.7 g / m ² coating aid : N-oleoyl-N-methyltaurine sodium salt 0.2 mg / m ² matting agent: polymethylmethacrylate fine particles (average particle size 3 μ) 0.13 mg / m ² (4) sensitometry These samples were prepared at 25 ° C. 7 after application at 65% RH temperature and humidity
Stored for days. Each sample was developed with the following developer at 20 ℃.
It was developed for a minute, fixed, washed with water and dried to measure the MTF.

Processing time Temperature Development 7 minutes 20 ° C. Stop (2.5% acetic acid) 30 seconds 20 ° C. Fixing 10 minutes 20 ° C. Water wash 5 minutes 20 ° C. Dry developer Metol (II-28 sulfate) 2 g Sodium sulfite 100 g Hydroquinone (II) -1) 5 g borax.10H ₂ O 2 g Water was added 1 Fixer Ammonium thiosulfate 240.0 g Sodium sulfite (anhydrous) 15.0 g Acetic acid (28%) 48 ml Sodium metaborate 15 g Kalimiban 15 g Water was added 1.0 MTF Measurement of MTF was measured with an aperture of 400 × 2 μ ² .
The evaluation was quantified by the spatial frequency at which the MTF value was 0.5. For MTF, T.E.T.J.Ames (T.
H. James) The Theory of the Photographic
Process) (1977. Macmillan) 592-6
It is described on page 18.

(5) Preservation test The coated samples 301 to 307 were stored under the storage conditions shown in (4) and then stored under the following conditions.

1) 45 ° C. 30% for 3 days 2) 45 ° C. 80% for 3 days 3) Refrigerator 5 ° C. for 3 days Got
The density of the obtained silver image was measured, and the sensitivity was determined from the density Dmin of the portion with the lowest light intensity and the light intensity at which the density was Dmin + 0.2, and the comparison with the Dmin and the sensitivity under the condition 3) was determined.

As is clear from Table 4, the samples using the present invention can improve the sharpness without an increase in Dmin and a decrease in sensitivity during storage.

The sample of the present invention also had a slight improvement in graininess.

Example 4 A sample was prepared in the same manner as in Example 3 except that Compound I-54 was dissolved in methanol and the addition amount was adjusted to directly add to the gelatin layer instead of the emulsion as in Example 3. As a result of evaluation, the sample using the present invention was able to improve the sharpness without an increase in Dmin and a decrease in sensitivity during storage.

(Example 5) Ethyl acrylate as the following dispersant After stirring and emulsifying with, potassium persulfate was added as a polymerization initiator to prepare polyethyl acrylate latex having a dispersed particle diameter of 0.02 to 0.08 μm.

On the other hand, compound I-54 was dissolved in ethyl acetate and roughly dispersed in an aqueous gelatin solution, and then mixed with the above-mentioned polyethyl acrylate latex and stirred to fill and disperse compound I-54 in the latex to prepare a latex dispersion (A ) Got. A sample was prepared and evaluated in the same manner as in Example 3, except that the compound I-54 was added as the latex dispersion (A) in Example 3 instead of the emulsion to the gelatin layer. The sample using the present invention was able to improve the sharpness without an increase in Dmin and a decrease in sensitivity during storage.

(Example 6) The sharpness and granularity were the same as in Example 3 except that the emulsion A was changed to the emulsion (B) having the following formulation and the addition amount of the emulsion was changed as shown in Table 5. When the storability was examined, it was as shown in Table 6.

Preparation of Emulsion Compound NO.I-51 10 g N, N-diethyllaurylamide 50 g Ethyl acetate 50 g Surfactant 10 g A solution obtained by heating and stirring was stirred with a gelatin aqueous solution 1000 g with a mixer to obtain an emulsion (B).

As is clear from Table 6, the samples using the present invention can improve the sharpness without an increase in Dmin and a decrease in sensitivity during storage.

Example 7 (1) Preparation of Photosensitive Silver Halide Emulsion Plate-shaped twinned grains of silver iodobromide (3.5 mol% of silver iodide) were prepared by the double jet method in the presence of ammonia and potassium thiocyanate. Formed. The average particle size is 0.78 as the average (sphere equivalent diameter) of the diameters of spheres having the same volume as each particle.
μm. Emulsion B was obtained by chemically sensitizing the grains with chloroaurate and sodium thiosulfate.

(2) Preparation of Emulsion Compound NO.I-4 10 g Oil (N, N-diethyllaurylamide) 50 g Ethyl acetate 50 g Surfactant 10 g A solution prepared by heating and dissolving the mixture was stirred with a gelatin aqueous solution 1000 g with a mixer ( C) got. Emulsion (C) except that the compound NO.I-4 is changed to NO.I-55 in the emulsion (C)
An emulsion (D) was prepared exactly as in.

(3) Preparation of coating sample On the polyethylene terephthalate support, as shown in Table 7, emulsions (C) and (D) were compound NO.I-4 and NO.I-5.
5 was added to each layer of the following formulation, and sequentially applied from the support side to prepare samples 701 to 705.

Emulsion B was added to the emulsion layer so that the coated silver amount was 2.0 g / m ² .

The emulsion of the emulsion layer, additives other than the emulsion, and the surface protective layer are as follows.

First layer (gelatin layer) Binder: gelatin 0.7 g / m ² Coating aid: N-oleoyl-N-methyl taurine sodium salt 0.2 mg / m ² Second layer (emulsion layer) After chemical sensitization , An antifoggant 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added,
The sensitizing dye (I) having the following structural formula was added in an amount of 200 mg per mol of silver halide grains to perform orne sensitization.

(I) Further, dodecylbenzene sulfonate as a coating aid and a thickener polypotassium-p-vinylbenzene sulfonate were added to prepare a basic formulation for the emulsion layer. At this time, the weight ratio of silver / gelatin was 1.35.

Third layer (surface protection layer) Contains polymethylmethacrylate fine particles, saponin, sodium polystyrene sulfonate, etc. in addition to gelatin 7
A wt% gelatin aqueous solution was prepared and used as a basic formulation.

(4) Sensitometry After applying these samples at a temperature and humidity of 25 ° C. and 65% RH, 7
Stored for days. Each sample was developed with the following developing solution.
Processing was carried out by an automatic processor at 25 ° C. for 25 seconds, and MTF was measured in the same manner as in Example 3.

(5) Preservation test After the coating samples 701 to 705 were stored under the storage conditions shown in (4), they were further stored under the conditions of 1) to 3) shown in (5) of Example 3. The same evaluation as in Example 3 was performed.

As is clear from Table 8, the samples using the present invention were able to improve the sharpness without an increase in Dmin and a decrease in sensitivity during storage.

As the automatic developing machine, "Fuji X Ray Processor FPM4000" manufactured by Fuji Photo Film Co., Ltd. was used. The developer and fixer had the following compositions.

(Developer) 1-phenyl-3-pyrazolidone (III-1) 1.5 g Hydroquinone (II-1) 30 g 5-Nitroindazole 0.25 g Potassium bromide 3.0 g Anhydrous sodium sulfite 50 g Potassium hydroxide 30 g Boric acid 10 g Glutar Aldehyde 5 g Water was added to adjust the total amount to 1 (pH) was adjusted to 10.20. (Fixer) Ammonium thiosulfate 200.0 g Sodium sulfite (anhydrous) 20.0 g Boric acid 8.0 g Ethylenediaminetetraacetic acid disodium 0.1 g Aluminum sulfate 15.0 g Sulfuric acid 22.0 g Glacial acetic acid 1.0 Water was added (pH). Adjust to 4.20.)

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-58-160954 (JP, A) JP-A-59-131937 (JP, A) JP-B 61-20855 (JP, B2) JP-B 53- 39137 (JP, B2)

Claims (1)

[Claims] 1. A silver halide photosensitive layer and at least one hydrophilic colloid layer containing substantially no silver halide are provided on a support, and at least one of compounds represented by the following general formula (I) is further provided. An image forming method, which comprises subjecting a silver halide photographic light-sensitive material containing one of the above-mentioned photographic layers containing substantially no silver halide to a process including a black and white developing step. In the general formula (I) A- (Time) _t -X, A means a redox mother nucleus, and-(Time) _t -X can be released only by being oxidized during the black and white development process. Represents an atom group to be trained. Time represents a timing group linked to A by a sulfur atom, a nitrogen atom, an oxygen atom or a selenium atom. t is 0 or 1
Is an integer. X means a development inhibitor.