JP2665620B2 - How to prevent the contrast at the shoulder of the characteristic curve from decreasing - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material. More specifically, the present invention relates to a silver halide color photographic light-sensitive material. The present invention relates to a silver halide color photographic material having excellent storage stability.

(Prior Art) At present, color photography generally used in the market uses a photosensitive material obtained by combining silver halide as a photosensitive element and a color coupler as a dye-forming element. When the photosensitive material is exposed to an image and then processed with a developing solution containing an aromatic primary amine compound as a developing agent, only the exposed silver halide particles are reduced to metallic silver by the developing agent. The oxidized form of the developing agent and the coupler develop a color by a coupling reaction, and a dye image corresponding to the exposure pattern is formed. Further, a stable color image can be obtained by removing metallic silver generated by development and undeveloped silver halide by bleaching and fixing processes, respectively. At this time, if couplers that emit yellow, magenta, and cyan are used, that is, natural colors can be reproduced by a subtractive color method using these as three primary colors.

The color image forming system based on such a principle is the most popular system today, but much improvement research is still ongoing.

First of all, shortening of access time is mentioned. Taking the color print market as an example, the demand for finishing a large number of prints in a short delivery time has raised the importance of speeding up the processing time, and silver halide emulsions with a high development speed, couplers with a high coupling activity, There have been many reports on processing agents that can be developed. As one example, WO 87-04534 discloses a method of processing a color photographic light-sensitive material using a silver halide emulsion having a high silver chloride content with a color developing solution substantially free of sulfite ions and benzyl alcohol. It has been disclosed.

Second, there is an improvement in the storability of the recorded image.
It is needless to say that maintaining the initial state for a long period of time when the obtained dye image is stored in a light place or a dark place is particularly important for a hard copy material such as a color print. Therefore, much research has been conducted on the improvement of the image storability.

The stability of the resulting color print image can be evaluated by both the fastness of the formed dye and the stability of the white background. Regarding the former, couplers that form fast dyes, color image stabilizers and dispersion media for stabilizing the formed dyes, and the like have been developed. As for the latter, couplers that hardly decompose to form a colored substance and stabilizers for remaining couplers have been developed.

However, new problems have arisen with the development of the rapid processing technology as described above. That is, as a result of shortening the processing time or reducing the replenishing amount of the processing solution, the developing agent tends to remain on the processed photosensitive material, and the remaining developing agent reacts with the remaining coupler during long-term storage of the print. This is a problem of generating undesirable stains.

In order to solve such a problem, a technique for invalidating the remaining developing agent has been reported. For example, JP-A-63-15
Nos. 8545 and 64-86139 disclose novel compounds which react with residual aromatic primary amine developing agents to render them inactive.

However, in the course of our research, when the above compounds were applied to improve the image stability of a color light-sensitive material constituted by using a high silver chloride emulsion advantageous for rapid processing, serious defects occurred. It became clear. That is, when such a compound is used in combination with a light-sensitive material containing a high silver chloride emulsion, the contrast at the shoulder of the characteristic curve of photographic response is reduced when the product is stored for a long period of time. Turned out to be an obstacle in This was more remarkable in emulsions having a higher development rate and higher silver chloride content, and was more remarkable when exposure was performed at high illuminance for a short time.

For products that require efficient production of a large number of prints, such as color prints, it is extremely important that printing can be performed under almost the same conditions regardless of the storage state and storage period of the products. Therefore,
Fluctuations in photographic performance during storage of the product, which lead to a reduction in yield, can be said to be a fatal defect.

Furthermore, when applying a scanning exposure method using a laser or light-emitting diode, etc., which has recently been developed as a method of exposing these photosensitive materials, the above-mentioned defects are more and more serious because the effective exposure time is very short. It becomes a serious obstacle.

(Problems to be Solved by the Invention) As described above, improving the stability during storage of a product when a high silver chloride emulsion is used in combination with a compound that invalidates the residual active substance is a matter of high productivity. This is the most important technical issue in the development of a photosensitive material for color prints having a color curve and excellent preservation of the recorded curve.

Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material and a color image forming method which are excellent in rapid processing property, have small fluctuation in performance during storage of a product, and are excellent in storage property of a dye image.

(Means for Solving the Problems) The above object of the present invention has been effectively achieved by the following silver halide color photographic light-sensitive material and a color image forming method using the same.

A coupler which forms a dye by coupling with an oxidized form of an aromatic primary amine developing agent, and silver chlorobromide or silver chloride which contains substantially 90 mol% or more of silver chloride and substantially no silver iodide Silver halide emulsion comprising a compound represented by the following general formula (I), (II) and / or (III), and sensitizing the silver halide emulsion to gold. A method for preventing a decrease in contrast at a shoulder of a characteristic curve of a photographic response when the photosensitive material is stored, wherein R _{21 An} X is a general formula (II) In the general formulas (I) and (II), R ₂₁ and R ₂₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. X represents a group capable of reacting with the aromatic amine developer and leaving, and A represents a group capable of reacting with the aromatic amine developer to form a chemical bond. n represents 1 or 0. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group, and Y ₁ promotes the addition of an aromatic amine developer to the compound of the general formula (II). Represents a group.

Here, R ₂₁ and X, Y ₁ and R ₂₂ or B may be bonded to each other to form a cyclic structure.

Formula (III) R ₃₀ -Z In the formula, R ₃₀ represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group.

Next, the compounds represented by formulas (I), (II) and (III) will be described in more detail.

The compounds represented by the general formulas (I) and (II) have a secondary reaction rate constant k ₂ (80 ° C.) of 1.0 / mol · sec with p-anisidine measured by the method described in JP-A-63-158545. 1x
Compounds in the range of 10 ⁻⁵ / mol · sec are preferred. On the other hand, in the compound represented by the general formula (III), Z is Pearson's nucleophilicity “CH ₃ I value (RGPearson, et al., J. Am. Chem. Soc.,
90 , 319 (1968)) are preferably groups derived from 5 or more nucleophilic functional groups.

Among the compounds of the general formulas (I) to (III), it is preferable to use a compound of the formula (I) or (II) together with a compound of the formula (III).

Each group of the compounds represented by formulas (I), (II) and (III) will be described in more detail.

The aliphatic group represented by R ₂₁ , R ₂₂ , B and R ₃₀ is linear,
Represents a branched or cyclic alkyl group, alkenyl group or alkynyl group, and may be further substituted with a substituent. The aromatic group represented by R ₂₁ , R ₂₂ , B and R ₃₀ may be any of a carbocyclic aromatic group (eg, phenyl, naphthyl) and a heterocyclic aromatic group (eg, furyl, thienyl, pyrazolyl, pyridyl, indolyl). May be
It may be a single ring system or a condensed ring system (for example, benzofuryl, phenanthridinyl). Further, these aromatic rings may have a substituent.

The heterocyclic group represented by R ₂₁ , R ₂₂ , B and R ₃₀ is preferably a group having a 3- to 10-membered ring structure composed of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or a hydrogen atom, The hetero ring itself may be a saturated ring or an unsaturated ring, and may be further substituted with a substituent (eg, chromanyl, pyrrolidyl, pyrrolinyl, morpholinyl).

X in the general formula (I) represents a group which is released by reacting with an aromatic amine-based developer, represents an oxygen atom, a sulfur atom or a nitrogen atom, and binds to A via an oxygen atom, a sulfur atom or a nitrogen atom. Groups (for example, 2-pyridyloxy, 2-pyrimidyloxy, 4-pyrimidyloxy, 2- (1,2,3
-Triazine) oxy, 2-benzimidazolyl, 2-
Imidazolyl, 2-thiazolyl, 2-benzthiazolyl, 2-furyloxy, 2-thiophenyloxy, 4-
Pyridyloxy, 3-isoxazolyloxy, 3-pyrazolidinyloxy, 3-oxo-2-pyrazolonyl,
2-oxo-1-pyridinyl, 4-oxo-1-pyridinyl, 1-benzimidazolyl, 3-pyrazolyloxy, 3H-1,2,4-oxadiazoline-5-oxy, aryloxy, alkoxy, alkylthio, arylthio, substituted N-oxy) or a halogen atom is preferred.

A of the general formula (I) reacts with an aromatic amine-based developer,
Represents a group that forms a chemical bond, and contains a group having a low electron density atom, for example, It contains. When X is a halogen atom, n represents 0. Here, L is a single bond, an alkylene group, -O-, -S
−, (For example, carbonyl group, sulfonyl group, sulfinyl group, oxycarbonyl group, phosphonyl group, thiocarbonyl group, aluminocarbonyl group, silyloxy group, etc.).

Y ₁ has the same meaning as Y _{1 in} formula (II), and Y ₁ ′ has the same meaning as Y ₁ .

R 'and R "may be the same or different, .R respectively represent -L-R ₂₁ is a hydrogen atom, an aliphatic group (e.g. methyl, isobutyl, t- butyl, vinyl, benzyl, octadecyl, cyclohexyl), an aromatic Group (eg, phenyl, pyridyl, naphthyl), heterocyclic group (eg, piperidinyl, pyranyl, furanyl, chromanyl),
Represents an acyl group (eg, acetyl, benzoyl) and a sulfonyl group (eg, methanesulfonyl, benzenesulfonyl).

L ', L "and L are -O-, -S- and Represents L further represents a single bond.

Above all, A And -alkylene The divalent group represented by is preferred.

Among the compounds represented by the general formula (I), more preferable compounds are those represented by the general formulas (Ia), (Ib) and (Ic)
Or a secondary reaction rate constant k ₂ (80 ° C.) with p-anisidine of 1 × 10 ⁻¹ / mol · sec.
It is a compound that reacts in the range of 1 × 10 ⁻⁵ / mol · sec.

In the formula, R ₂₁ has the same meaning as R _{21 in} formula (I).
Link represents a single bond and -O-. Ar represents an aromatic group having the same meaning as defined for R ₂₁ , R ₂₂ and B. However, it is preferred that those released as a result of reaction with the aromatic amine-based developing agent are not groups useful as reducing agents for photography, such as hydroquinone derivatives and catechol derivatives. Ra, Rb and Rc may be the same or different and each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group having the same meaning as defined for R ₂₁ , R ₂₂ and B. Ra, Rb and Rc
Further includes an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an acyl group, an amide group, a sulfonamide group, a sulfonyl group, an alkoxycarbonyl group, and a sulfonyl group. Group, carboxyl group, hydroxy group,
Represents an acyloxy group, a ureido group, a urethane group, a carbamoyl group, and a sulfamoyl group. Where Ra and Rb
Alternatively, Rb and Rc may combine with each other to form a 5- to 7-membered heterocyclic ring, and the heterocyclic ring may be further substituted with a substituent, form a spiro ring, a bicyclo ring, or the like, or form an aromatic ring. It may be condensed. Z ₁ and a non-metallic atom group necessary for forming a 5- to 7-membered heterocyclic ring. This heterocyclic ring is further substituted with a substituent, forms a spiro ring, a bicyclo ring, or the like, or is condensed with an aromatic ring. It may be ringed.

Among the general formulas (Ia) to (Id), particularly the general formula (Ia)
-A) second-order rate constant k ₂ with p-anisidine in a)
(80 ° C) from 1 × 10 ^-1 / mol · sec to 1 × 10 ^-5 / mol · sec
When Ar is a carbocyclic aromatic group, it can be adjusted by a substituent. At this time, the sum of Hammett's σ values of the respective substituents is preferably 0.2 or more, more preferably 0.4 or more, even more preferably 0.6 or more, depending on the type of the group of R ₂₁ .

When the compounds represented by the general formulas (Ia) to (Id) are added during the production of a photosensitive material, the compounds preferably have 13 or more total carbon atoms. From the viewpoint of achieving the object of the present invention, it is not preferable that the compound of the present invention decomposes during development processing.

Y _{1 in the} general formula (II) is an oxygen atom, a sulfur atom, ＝ NR
₂₄ and Is preferred.

Here, R ₂₄ , R ₂₅ and R ₂₆ represent a hydrogen atom, an aliphatic group (eg, methyl, isopropyl, t-butyl, vinyl, benzyl, octadecyl, cyclohexyl), an aromatic group (eg, phenyl, pyridyl, naphthyl), a heterocyclic ring Groups (eg piperidyl, pyranyl, furanyl, chromanyl),
It represents an acyl group (eg, acetyl, benzoyl) or a sulfonyl group (eg, methanesulfonyl, benzenesulfonyl), and R ₂₅ and R ₂₀ may be bonded to each other to form a cyclic structure.

Among the compounds represented by the general formulas (I) and (II), a particularly preferred compound is the general formula (I). Among them, more preferred compounds are those represented by the general formula (Ia) or the general formula (Ic).
Compounds represented by -a) are preferred.

Z in the general formula (III) represents a nucleophilic group or a group which is decomposed in a light-sensitive material to release a nucleophilic group. For example, a nucleophilic group in which an atom directly bonded to an oxidized form of an aromatic amine developer is an oxygen atom, a sulfur atom, or a nitrogen atom (for example, an amine compound, an azide compound, a hydrazine compound,
Mercapto compounds, sulfide compounds, sulfinic acid compounds, cyano compounds, thiocyano compounds, thiosulfate compounds, seleno compounds, halide compounds, carboxy compounds, hydroxamic acid compounds, active methylene compounds, phenol compounds, nitrogen heterocyclic compounds, etc.) are known. ing.

A more preferred compound among the compounds of the general formula (III) can be represented by the following general formula (III-a).

General formula (III-a) Wherein M is an atom or group forming an inorganic (eg, Li, Na, K, Ca, Mg, etc.) or organic (eg, triethylamine, methylamine, ammonia, etc.) salt; And a hydrogen atom.

Here, R _15a and R _16a may be the same or different and each represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. R _15a and R _16a may combine with each other to form a 5- to 7-membered ring. R _17a , R _18a , R _20a and R _21a may be the same or different, and each is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group,
Represents a sulfonyl group, a ureido group and a urethane group.
However, at least one of R _17a and R _18a , and R _20a
And at least one of R _21a is a hydrogen atom. R _19a
And R _22a represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. R _19a further represents an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Here, at least two groups of R _17a , R _18a and R _19a may be bonded to each other to form a 5- to 7-membered ring, and at least two groups of R _20a , R ₂₁ and R _22a May combine with each other to form a 5- to 7-membered ring. R _23a represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R _24a represents a hydrogen atom, an aliphatic group, an aromatic group,
Represents a halogen atom, an acyloxy group or a sulfonyl group. R _25a represents a hydrogen atom or a hydrolyzable group.

R _10a , R _11a , R _12a , R _13a and R _14a may be the same or different and each represents a hydrogen atom, an aliphatic group (eg, methyl, isopropyl, t-butyl, vinyl, benzyl, octadecyl, cyclohexyl), aromatic Groups (eg, phenyl, pyridyl, naphthyl), heterocyclic groups (eg, piperidyl, pyranyl, furanyl, chromanyl), halogen atoms (eg, chloro, bromo), —SR _25a , —O
R _26a , Acyl groups (eg, acetyl, benzoyl), alkoxycarbonyl groups (eg, methoxycarbonyl, butoxycarbonyl, cyclohexylcarbonyl, octyloxycarbonyl), aryloxycarbonyl groups (eg,
Phenyloxycarbonyl, naphthyloxycarbonyl), sulfonyl group (eg, methanesulfonyl, benzenesulfonyl), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide), sulfamoyl group, ureido group, urethane group, carbamoyl group,
Sulfo group, carboxyl group, nitro group, cyano group, alkoxalyl group (for example, methoxalyl, isobutoxalyl, octyl oxalyl, benzoyl oxalyl),
Aryloxalyl groups (eg, phenoxalyl, naphthoxalyl), sulfonyloxy groups (eg, methanesulfonyloxy, benzenesulfonyloxy), And a formyl group. Here, R _25a and R _27a may be the same or different and each represent a hydrogen atom, an aliphatic group,
Represents an aromatic group, an acyl group and a sulfonyl group. R _28a
And R _29a may be the same or different and each represent a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group or an aryloxy group.

Of these, Hammet of benzene substituent with respect to -SO ₂ M group
The sum of the σ values of t is preferably 0.5 or more from the viewpoint of the effect of the present invention.

The representative examples of these compounds are shown below, but the compounds used in the present invention are not limited thereto.

(I a-7) (n ) C 18 H 37 I (I a-8) (n) C 18 H 37 Br _{(II a-3) CH 2} = CH-SO 2 -C 18 H 37 (n) (IIIa-30) NaN ₃ These compounds are described in JP-A-62-143048 and JP-A-63-115855.
Nos. 63-115866 and 63-158545, European Patent Publication No.
The compound can be synthesized by the method described in 255722 or a method analogous thereto.

The preferred compounds of the present invention are described in the above patents and
Compounds specifically exemplified in the specifications of 283338 and 62-229145 are also included.

Of the compounds represented by the general formulas (I), (II) and (III), those having a low molecular weight or those which easily dissolve in water may be added to the processing solution and incorporated into the photosensitive material during the development process. Good. Preferably, it is a method of adding to the hydrophilic colloid layer in the photosensitive material at the stage of producing the photosensitive material.

The compounds represented by the general formulas (I), (II) and (III) of the present invention are preferably soluble in a high-boiling organic solvent, and preferably 1 × 10 ^-2 to 10 × 10 ⁻² per mol of the coupler used in the present invention. Moles, more preferably 3 × 10 ^-2 to 5 moles. These compounds are preferably co-emulsified with the magenta coupler.

It is necessary that the silver halide emulsion of the present invention be substantially composed of silver chlorobromide or silver chloride containing 90 mol% or more of silver chloride without containing silver iodide. Substantially free of silver iodide means that the content is 0.5 mol% or less, preferably 0.1 mol% or less.
More preferably, it is not contained at all. Also, the silver chloride content needs to be 90 mol% or more,
It is preferably at least 95 mol%, more preferably at least 98 mol%. Further, an emulsion composed of pure silver chloride except that it contains a trace amount of polyvalent metal impurity ions is also preferable.

When the silver halide emulsion used in the present invention contains silver bromide, it can take various forms. That is,
A so-called solid solution in which silver bromide is uniformly distributed throughout the silver halide grains may be formed, or a phase containing silver bromide may be non-uniformly present in the grains. In such a case, the phase containing silver bromide can take various shapes. For example, phases having different silver bromide contents may be in the form of a core or a shell to form a so-called laminated structure, or a phase containing a large amount of silver bromide is separated into the inside of the grain or a part of the surface. A localized phase may be formed.

The silver halide emulsion of the present invention can contain polyvalent metal impurity ions alone or in combination for the purpose of obtaining high sensitivity and high contrast during grain formation. Examples thereof include salts or complex salts of Group VIII transition metal ions such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, and divalent metal ions such as copper, zinc, cadmium and lead. Can be mentioned.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average is taken) is from 0.1 μm to 2 μm. preferable.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%
In the following, a so-called monodispersed one of desirably 15% or less is preferable. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or by using a multi-layer coating.

The silver halide grains contained in photographic emulsions have a regular (regular, cubic, tetradecahedral or octahedral) shape.
r) Those having a crystal form, those having an irregular crystal form such as a sphere, a plate, or the like, or those having a composite form thereof can be used. Further, it may be composed of a mixture of those having various crystal forms. In the present invention, among these, 50% or more, preferably 70% or more of the particles having the regular crystal form,
More preferably, the content is 90% or more.

Silver chlorobromide or silver chloride emulsion used in the present invention, P.Gl
afkides Chimie et Phisique Photographique (Paul
Montel Publishing, 1967), Photographic Em by GFDuffin
ulsion Chemistry (Focal Press 1966), VLZ
Making and Coating Photographic Emulsion by elikman
(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 with a soluble halide salt includes any method such as a one-side mixing method, a double-mixing method, and a combination thereof. May be used. A method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which the silver ion concentration in a liquid phase in which silver halide is formed is kept 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 grain size close to monodispersion can be obtained.

The silver halide emulsion used in the present invention is subjected to chemical sensitization and spectral sensitization.

The silver halide emulsion of the present invention needs to be chemically sensitized using a gold compound. As the gold compound to be used, the oxidation number of gold may be monovalent or trivalent, and various kinds of gold compounds can be used. Typical examples are tetrachloroauric (III) acid, tetracyanoaurate (III) acid or tetrakis (thiocyanite) aurate (III) acid or an alkali metal salt thereof, bis (thiosulfato) aurate (I) acid salt, dimethyl chloride Complex ions or complex salts such as rhodanate gold (I) can be mentioned.

The amount of the gold compound added may vary widely depending on the case, but it is generally from 1 × 10 ^-7 to 1 / mol of silver halide.
X10 ^-2 mole half area, preferably from ^{1x10 -6} to 1x
It is in the range of 10 ^-3 mol, more preferably in the range of 2 x 10 ^-6 to 1 x 10 ^-4 mol.

The addition of these gold compounds is performed during the preparation of the silver halide emulsion, but is preferably performed until the completion of the chemical sensitization.

The silver halide emulsion of the present invention can be used in combination with so-called sulfur sensitization, selenium sensitization, reduction sensitization or noble metal sensitization, in addition to the chemical sensitization by the gold compound.

Compounds used for sulfur sensitization include thiosulfates, rhodanines, thioureas or thioamides (US Pat. Nos. 2,410,689, 3,501,313, 2,278,947,
No. 1,574,944, No. 2,728,668, No. 3,656,955
No. 4,001,025, 4,116,697, JP-A-55-45
No. 016), thioesters (JP-B-43)
-13485, 55-42374, compounds described in British Patent No. 1,190,678, etc.), polysulfur compounds (U.S. Patent Nos. 3,647,469, 3,656,955, 3,689,273,
JP-A-53-81230, JP-B-49-20533, 59-45134
And the like compounds described in No. 1).

As the compound used for selenium sensitization, JP-A-60-150046
And the like.

Compounds used for reduction sensitization include inorganic reducing agents such as SnCl ₂ and NaBH ₄ or amines, hydrazines, formamidine sulfinic acids, or silane compounds (U.S. Pat.Nos. 2,518,698, 2,743,182, 3,369,904,
No. 2,666,700, No. 2,419,973, No. 2,419,974
No. 2,419,975, No. 2,740,713, No. 2,521,92
No. 6, No. 2,487,850, No. 2,983,609, No. 2,983,6
No. 10, No. 2,694,637, No. 3,930,867, No. 3,904,
No. 415, British Patent No. 1,390,540, JP-A-50-127622,
And the aldehydes (compounds described in U.S. Pat. No. 2,604,397).

As the compound used for the noble metal sensitization, in addition to the gold compound which is a requirement of the present invention, a complex compound of a transition element of Group VIII of the periodic table such as platinum, iridium, and palladium (US Pat.
No. 2,399,083, No. 2,448,060, No. 3,503,749, No. 2,597,856, No. 2,597,915, No. 2,624,674,
Nos. 2,642,361 and British Patent No. 618,061).

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. Spectral sensitization can be performed by adding a dye that absorbs light in a wavelength range corresponding to the target spectral sensitivity-a spectral sensitizing dye. The spectral sensitizing dye used at this time is, for example, Heterocyclic by FM Harmer.
compounds-Cyanine dyes and related compounds (Joh
n Wiley & Sons [New York, London], 1964). Specific examples of compounds and spectral sensitization methods described in JP-A-62-215272, page 22, upper right column to page 38, are preferably used.

Various compounds or their precursors are added to the silver halide emulsion of the present invention for the purpose of preventing fogging during the production process of the light-sensitive material, storage or development of the product, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on pages 39 to 72 of JP-A-62-215272 described above are preferably used.

The color photographic light-sensitive material of the present invention can be constituted by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer on a support. In general, color printing paper is usually coated on a support in the order described above, but may be in a different order. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. In these light-sensitive emulsion layers, a silver halide emulsion having a sensitivity in each wavelength region and a dye having a complementary color with the light to be exposed, that is, yellow for blue, magenta for green, and cyan for red are formed. By incorporating a so-called color coupler, the color reproduction by the subtractive color method can be performed. However, the photosensitive layer and the color hue of the coupler may not have the above correspondence.

Cyan coupler preferably used in the present invention,
The magenta coupler and the yellow coupler are represented by the following formulas (C-I), (C-II), (M-I), (M-II) and (Y).

In the general formulas (CI) and (C-II), R ₁ , R ₂
And R ₄ represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group; R ₃ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group; ₃ may represent a non-metallic atomic group forming a 5- or 6-membered nitrogen-containing ring together with R ₂ . Y ₁ and Y _{2 each} represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent. n represents 0 or 1.

R ₅ in the general formula (C-II) is preferably an aliphatic group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentadecyl group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, Examples include a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group, a methoxymethyl group, and the like.

Preferred examples of the cyan coupler represented by the general formula (CI) or (C-II) are as follows.

In the general formula (CI), preferred R ₁ is an aryl group,
A heterocyclic group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, they are aryl groups substituted by a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

When R ₃ and R ₂ do not form a ring in formula (CI), R ₂ is preferably a substituted or unsubstituted alkyl group,
It is an aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R ₃ is preferably a hydrogen atom.

In formula (C-II), R ₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-II), preferred R ₅ has 2 to 15 carbon atoms.
And a methyl group having a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In the general formula (C-II), R ₅ is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

Preferred R ₅ in formula (C-II) is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred. Preferred Y ₁ and Y ₂ in the general formulas (CI) and (C-II) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In the general formula (MI), R ₇ and R ₃ represent an aryl group, R ₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y ₃ represents hydrogen. Represents an atom or a leaving group. The substituents permitted for the aryl group (preferably a phenyl group) for R ₇ and R ₃ are the same as the substituents permitted for the substituent R ₁ , and when there are two or more substituents, they are the same. But they may be different. R ₈
Is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Preferably, Y ₃ is of a type capable of releasing at any of a sulfur, oxygen or nitrogen atom, and for example, a sulfur atom releasing type as described in U.S. Pat.No. 4,351,897 and WO 88/04795 is particularly preferred. .

In the general formula (M-II), R ₁₀ represents a hydrogen atom or a substituent. Y ₄ represents a hydrogen atom or a leaving group, particularly preferably a halogen atom or an arylthio group. Za, Zb and
Zc represents methine, substituted methine, = N- or -NH-,
One of the -Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. When R ₁₀ or Y ₄ forms a dimer or more multimer, Za,
When Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is included.

Among the pyrazoloazole couplers represented by the general formula (M-II), the imidazo [1,2-b] pyrazole described in U.S. Pat. No. 4,500,630 is advantageous in terms of low yellow side absorption and light fastness of a coloring dye. Are preferred, US Pat.
The pyrazolo [1,5-b] [1,2,4] triazole described in 4,540,654 is particularly preferred.

In addition, a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2-, 3- or 6-position of the pyrazolotriazole ring to form a pyrazolotriazole coupler.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in 65246, JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A No. 226,849 and pyrazoloazole couplers having an alkoxy group or aryloxy group at the 6-position as described in EP-A-226,849 and EP 294,785. The use of zorotriazole couplers is preferred.

In the general formula (Y), R ₁₁ represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group, and R ₁₂ represents a hydrogen atom, a halogen atom or an alkoxy group. A is _{-NHCOR 13, -NHSO 2 -R 13,} -SO 2 NHR 13,
−COOR ₁₃ , Represents Here, R ₁₃ and R ₁₄ each represent an alkyl group, an aryl group or an acyl group. Y ₅ represents a leaving group. R ₁₂
And the substituents of R ₁₃ and R ₁₄ are the same as the substituents permitted for R ₁ and the leaving group Y ₅ is preferably of a type capable of leaving at either an oxygen atom or a nitrogen atom. Yes,
A nitrogen atom-elimination type is particularly preferred.

Formulas (C-I), (C-II), (M-I), and (M-
Specific examples of the couplers represented by II) and (Y) are listed below.

The couplers represented by the above general formulas (C-I) to (Y) are usually added in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 1.0 mol per mol of silver halide.
0.50.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with transfer. The alkali-soluble coupler can also be dispersed by a so-called Fisher dispersion method. After removing the low-boiling organic solvent from the coupler dispersion by a method such as distillation, noodle washing or ultrafiltration, it may be mixed with a photographic emulsion.

Inductivity (25 ° C) as a dispersion medium for such couplers
It is preferable to use a high-boiling organic solvent having a refractive index of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.7 and / or a water-insoluble polymer compound.

As the high boiling point organic solvent, preferably, the following general formula (A)
The high-boiling organic solvent represented by (E) is used.

General formula (B) W ₁ -COO-W ₂ Formula (E) W ₁ —O—W ₂ (wherein W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group; W ₄ is W ₁ , OW ₁ or SW
_And n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different. In the general formula (E), W ₁ and W ₂ represent a condensed ring. May be formed).

The high-boiling organic solvent that can be used in the present invention is a compound that is not miscible with water having a melting point of 100 ° C. or less and a boiling point of 140 ° C. or more other than the general formulas (A) to (E). Can be used. The high boiling point organic solvent preferably has a melting point of 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C.
And more preferably 170 ° C. or higher.

Details of these high-boiling organic solvents are described in
No. 215272, page 137, lower right column to page 144, upper right column.

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high boiling organic solvent, or dissolved in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, pages 12 to 30 of WO 88/00723
The homopolymers or copolymers described on the page are used, and the use of an acrylamide polymer is particularly preferred for stabilizing a color image.

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, hydroquinones as organic anti-fading agents for cyan, magenta and / or yellow images,
6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols,
Representative examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. No. Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent are described in the specifications of the following patents.

Hydroquinones are disclosed in U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
No. 728,659, No. 2,732,300, No. 2,735,765, No.
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No., U.S. Pat.Nos. 2,710,801 and 2,816,028,
6-Hydroxychromans, 5-hydroxycoumarins, and spirochromans are described in U.S. Pat.
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP-A-52-152225, Spiroindanes in U.S. Pat.No. 4,360,589, p-Alkoxyphenols in U.S. Pat. UK Patent 2,0
No. 66,975, JP-A-59-10539, JP-B-57-19765, and the like, hindered phenols are disclosed in U.S. Pat.
No., JP-A-52-72224, U.S. Pat.
No. 52-6623, gallic acid derivatives, methylenedioxybenzenes and aminophenols are described in U.S. Pat.
Nos. 3,457,079, 4,332,886 and JP-B-56-21144, hindered amines are disclosed in U.S. Pat.
No. 4,268,593, British Patent No. 1,326,889, No. 1,354,
No. 313, No. 1,410,846, JP-B-51-1420, JP-A-58
Nos. 1-114036, 59-53846 and 59-78344, metal complexes are disclosed in U.S. Pat.Nos. 4,050,938 and 4,241,155.
And British Patent No. 2,027,731 (A). These compounds can achieve the object by adding usually 5 to 100% by weight of the corresponding color coupler to the photosensitive layer after co-emulsification with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, those described in JP-A-46-2784) and cinnamate compounds (for example, US Pat.
3,705,805 and 3,707,395), butadiene compounds (described in U.S. Pat. No. 4,045,229),
Alternatively, benzooxide compounds (for example, US Pat.
3,406,070 and 3,677,672 and 4,271,307) can be used. UV-absorbing couplers (eg, α-naphthol-based cyan dye-forming couplers)
Alternatively, an ultraviolet absorbing polymer or the like may be used. These ultraviolet absorbers may be mordanted to a specific layer.

Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

The light-sensitive material prepared according to the present invention contains a water-soluble dye or a dye which becomes water-soluble by photographic processing as a filter dye in the hydrophilic colloid layer, or for various purposes such as prevention of irradiation or halation. You may. Such dyes include oxonol dyes, hexoxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in Arthur Wuice, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

As the support used in the present invention, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate, which is usually used for a photographic light-sensitive material, or a reflective support can be used. For the purposes of the present invention, the use of a reflective support is more preferred.

The term "reflective support" used in the present invention refers to a material which enhances reflectivity and sharpens a dye image formed in a silver halide emulsion layer. Examples include those coated with a hydrophobic resin dispersedly containing a light reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin dispersedly containing a light reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or combined with a reflective substance, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, Examples include a polyamide film, a polycarbonate film, a polystyrene film, and a vinyl chloride resin.

Other reflective supports include specular or secondary
A support having a seed diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above materials are preferred, and the metal surface is preferably roughened or diffusely reflective using metal powder. As the metal, aluminum, tin, silver, magnesium or an alloy thereof is used, and the surface may be the surface of a metal plate, a metal foil, or a metal thin layer obtained by rolling, vapor deposition, plating, or the like.
Above all, it is preferable to obtain a metal by vapor deposition on another substrate. It is preferable to provide a water-resistant resin, especially a thermoplastic resin layer, on the metal surface. An antistatic layer is preferably provided on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210346.
Nos. 63-24247, 63-24251 and 63-24255.

 These supports can be appropriately selected depending on the purpose of use.

As the light-reflective substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant.
It is preferable to use those treated with a to tetravalent alcohol.

The occupied area ratio (%) per defined unit area of the white pigment fine particles is most typically obtained by dividing the observed area into adjacent 6 μm × 6 μm unit areas and projecting the unit area. It can be obtained by measuring the occupied area ratio (%) (R _i ) of the fine particles. Variation coefficient of the occupied area ratio (%) is the ratio of the standard deviation s of R _i to the average value of R _i () s /
Can be obtained by The number (n) of the target unit areas is preferably 6 or more. Therefore the coefficient of variation s / Can be obtained by

In the present invention, the occupied area ratio of the pigment fine particles (%)
Is preferably 0.15 or less, particularly preferably 0.12 or less. 0.08
In the following cases, it can be said that the dispersibility of the particles is substantially “uniform”.

In order to form a color image using the color photographic light-sensitive material of the present invention, after imagewise exposure, a color developing process using a color developing solution containing an aromatic primary amine developing agent, developed silver and undeveloped halogen It is carried out by performing a bleach-fixing treatment for removing silver halide and a washing or stabilizing bath treatment.

Hereinafter, these processing solutions and processing steps will be described.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, representative examples of which are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotriene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-amino-3-methyl -N-ethyl-N-
[Β- (methanesulfonamido) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-amino -3-Methyl-N-ethyl-N-methoxyethylaniline D-10 4-Amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, particularly preferred is 4-amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamido) ethyl] -aniline (Exemplary compound D-6).

Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, p-toluenesulfonates and the like may be used. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g, per developer.

In the practice of the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol. Here, substantially not containing, preferably 2 ml / or less,
More preferably, the concentration of benzyl alcohol is 0.5 ml / or less, and most preferably, no benzyl alcohol is contained.

More preferably, the developer used in the present invention does not substantially contain sulfite ions. Sulfite ions have a function of dissolving silver halide and reacting with an oxidized form of the developing agent, and at the same time, function as a preservative of the developing agent to reduce the dye-forming efficiency. Such an effect is presumed to be one of the causes of the increase in the fluctuation of the photographic characteristics due to the continuous processing.
Here, substantially not containing, preferably 3.0 × 10 ^-3
It has a sulfite ion concentration of mol / or less, and most preferably contains no sulfite ion at all. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before preparing a working solution is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. this is,
This is because hydroxylamine itself has a silver developing activity at the same time as functioning as a preservative of the developer, and fluctuations in the concentration of hydroxylamine are considered to greatly affect photographic characteristics. The term "substantially free of hydroxylamine" as used herein means that the hydroxylamine concentration is preferably 5.0 × 10 ⁻³ mol / or less, and most preferably contains no hydroxylamine at all.

More preferably, the developer used in the present invention contains an organic preservative in place of the hydroxylamine and sulfite ions.

Here, the organic preservative refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy ketones, α-amino ketones,
Sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, and the like are particularly effective organic preservatives. These are disclosed in
−4235, 63−30845, 63−21647, 63−4465
No. 5, 63-53551, 63-43140, 63-56654,
63-58346, 63-43138, 63-146041, 63
-44657, 63-44656, U.S. Patent No. 3,615,503,
No. 2,494,903, JP-A-52-143020, JP-B-48-30496
No., etc.

Other preservatives include JP-A Nos. 57-44148 and 57-5.
Various metals described in 3749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. An aromatic polyhydroxy compound described in 3,746,544 or the like may be contained as necessary. In particular, addition of alkanolamines such as triethanolamine, dialkylhydroxylamine such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferred.

Among the above organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides are particularly preferred. For details, refer to Japanese Patent Application No. 62-255270.
Nos. 63-9713, 63-9714 and 63-11300.

It is more preferable to use the hydroxylamine derivative or the hydrazine derivative in combination with an amine in terms of improving the stability of the color developing solution, and further improving the stability during continuous processing.

Examples of the amines include cyclic amines described in JP-A-63-239447, amines described in JP-A-63-128340, and other amines disclosed in Japanese Patent Application No. 63-9713. 63
Amines as described in JP-11300.

In the present invention, 3.5 × 1 chloride ion in the color developer
The content is preferably 0 ^{-2 to} 1.5 × 10 ^-1 mol / mol. Particularly preferably, it is 4 × 10 ^-2 to 1 × 10 ^-1 mol /. When the chloride ion concentration is more than 1.5 × 10 ^-1 to 10 ^-1 mol / mol, it has a disadvantage of delaying the development, and is not preferable for achieving the object of the present invention of rapid and high maximum concentration. Further, if it is less than 3.5 × 10 ⁻² mol / mol, it is not preferable in preventing fog.

In the present invention, the bromine ion in the color developer is 3.0
The content is preferably from × 10 ⁻⁵ mol / to 1.0 × 10 ⁻³ mol /. More preferably, 5.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol /
It is. When the bromine ion concentration is higher than 1 × 10 ⁻³ mol / mol, the development is delayed, the maximum density and the sensitivity are lowered, and
If the amount is less than ^10-5 mol / m, fogging cannot be sufficiently prevented.

Here, chlorine ions and bromine ions may be directly added to the developer or may be eluted from the photosensitive material into the developer during the development processing.

When directly added to the color developer, examples of the chloride ion supply material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, with the preferred ones being preferred. Are sodium chloride and potassium chloride.

Further, it may be supplied from a fluorescent whitening agent added to the developer.

Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, potassium bromide, thallium bromide Among them, preferred are potassium bromide and sodium bromide.

When eluted from the light-sensitive material during the development processing, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from sources other than the emulsion.

The color developer used in the present invention is preferably pH 9
To 12, more preferably 9 to 11.0, and the color developer may further contain a compound of a known developer component.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt , Proline salts, trishydroxyaminomethane salts, lysine salts, and the like. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoate are soluble and have a high pH of 9.0 or more.
The H region has an excellent buffering ability, has the advantage of being inexpensive when added to a color developer without adverse effects on photographic performance (such as fogging), and it is particularly preferable to use these buffers.

Specific examples of these buffers include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraborate Potassium, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And the like. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer was 0.1 mol / mol.
It is preferably at least 0.1 mol / -0.4 mol / m.

In addition, various chelating agents may be used in the color developer as an inhibitor of precipitation of calcium or magnesium or for improving the stability of the color developer.
No. 26, No. 44-12380, No. 45-9019 and U.S. Pat.
No. 13,247, etc., thioether compounds
P-phenylenediamine compounds represented by JP-A Nos. 52-49829 and 50-15554; JP-A-50-137726;
-30074, quaternary ammonium salts described in JP-A-56-156826 and JP-A-52-43429, U.S. Pat.
No. 3, 3,128,182, 4,230,796, 3,253,919,
JP-B-41-11431, U.S. Pat.Nos. 2,482,546 and 2,596,
Nos. 926 and 3,582,346, amine compounds described in JP-B-37-16088, JP-B-42-25201, U.S. Pat.
No. 3, JP-B-41-11431, JP-B-42-23883, and U.S. Pat.No.3,532,501.Polyalkylene oxides, other 1-phenyl-3-pyrazolidones, imidazoles, etc. are added as necessary. be able to.

In the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiozolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer applicable to the present invention preferably contains a fluorescent whitening agent. 4,4 'as fluorescent whitening agent
-Diamino-2,2'-disulfostilbene compounds are preferred. The amount of addition is 0-5 g / preferably 0.1 g-4 /.

Further, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as needed.

The processing temperature of the color phenomenon liquid applicable to the present invention is 20 to 50.
° C, preferably 30 to 40 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. Although the replenishment amount is preferably small, it is suitably 20 to 600 ml, preferably 50 to 300 ml, per m ^{2 of} the light-sensitive material. More preferably 60ml-200ml,
Most preferably, it is 60 ml to 150 ml.

As the bleaching agent contained in the bleach-fixing solution of the present invention, various compounds can be used. In particular, organic complex salts containing iron (III) ions (for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid; Complex salts formed by aminopolyphosphonic acids, phosphonocarboxylic acids, organic phosphonic acids, and the like), organic acids such as citric acid, tartaric acid, and malic acid, persulfates, and hydrogen peroxide are preferably used.

Of these, organic complex salts containing iron (III) ions are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Iron (II
I) Useful aminopolycarboxylic acids, aminopolyphosphonic acids or organic polyphosphonic acids or salts thereof for forming organic complexes containing ions include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid,
Methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid and the like can be mentioned. These compounds can be used in the form of a sodium salt, a potassium salt, a lithium salt or an ammonium salt.
Among these compounds, iron (III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodiacetic acid and the like are preferable in terms of high bleaching power. These iron (III) complex salts may be used in the form of a complex salt or an iron (III) salt such as ferric sulfate, ferric chloride,
Using a salt such as ferric nitrate, ammonium ferric sulfate or ferric phosphate and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or phosphonocarboxylic acid to form an iron (III) complex salt in a solution It may be formed. At this time, the chelating agent may be used in excess of forming the iron (III) complex salt. The content of these compounds is 0.01 to 1.0 mol /,
Preferably it is 0.05-0.5 mol /.

Various compounds can be used as a bleaching accelerator in the bleach-fixing solution and / or its prebath. For example, mercapto compounds described in U.S. Pat. No. 3,893,858, German Patent 1,290,812, JP-A-53-95630, Research Disclosure No. 17129 (July 1978), No. 8506, JP-A-52-20832,
The thiourea compounds described in JP-A-53-32735 and U.S. Pat. No. 3,706,561, or halides such as iodide ions and bromide ions are preferred in terms of excellent bleaching power.

Other bleach-fixing solutions that can be used in the present invention include bromides such as potassium bromide, sodium bromide and ammonium bromide, chlorides such as potassium chloride, sodium chloride and ammonium chloride, and rehalogens such as ammonium iodide. An agent can be included. If necessary, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid,
One or more compounds having a pH buffering capacity, such as sodium citrate and tartaric acid, may be contained. Further, a corrosion inhibitor such as ammonium nitrate or guanidine can be added.

The fixing agent used in the bleach-fixing solution of the present invention includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, and ethylenebisthioglycolic acid. And thioether compounds such as 3,6-dithia-1,8-octanediol and water-soluble silver halide dissolving agents such as thioureas. These can be used alone or in combination of two or more. In addition, JP
A special bleach-fixing solution comprising a combination of a fixing agent described in -155354 and a large amount of a halide such as potassium iodide can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfate, is preferred. The content of these fixing agents is preferably 0.3 to 2.0 mol /,
More preferably, it is in the range of 0.5 to 1.0 mol /.

The pH of the bleach-fixing solution of the present invention is preferably from 3 to 10, more preferably from 5 to 9.

Further, the bleach-fixing solution of the present invention may contain other various types of fluorescent whitening agents, defoaming agents or surfactants, water-soluble polymers such as polyvinylpyrrolidone, organic solvents such as methanol, and the like.

Further, in the bleach-fixing solution of the present invention, as a preservative, sodium sulfite, potassium sulfite, sulfites such as ammonium sulfite, sodium bisulfite, potassium bisulfite,
It is preferable to contain a sulfite ion releasing compound such as bisulfite such as ammonium bisulfite, and metabisulfite such as sodium metabisulfite, potassium metabisulfite and ammonium metabisulfite. The preferred content of the compound used as a preservative is 0.02 to 0.5 mol / in terms of sulfite ion, more preferably 0.04 to 0.5 mol / mol.
~ 0.4 mol /.

As a preservative, sulfite is generally added,
In addition, ascorbic acid and carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

It is necessary that the bleach-fixing solution used in the image forming method of the present invention contains at least one compound selected from hydrazine compounds and substituted hydroxylamine compounds. As a result, stains generated when the color light-sensitive material of the present invention is stored after the development processing can be effectively suppressed.

The content of these compounds is 1 × 10 ^-3 to 2 × 10 ^-1 mol /, preferably 2 × 10 ^-3 to 1 × 10 ^-1 mol /. If the amount is less than the stipulation of the invention, the effect of preventing stain is small. On the other hand, when the amount is larger than the range of the present invention, desilvering failure occurs, which is not preferable in practical use.

In order to contain these compounds in the bleach-fix solution in the present invention, they may be added at the time of preparing a processing solution, may be contained in a replenisher, or may be contained in a pre-bath of the bleach-fix solution. It can be carried out by bringing it in with the processing.

The hydrazine compound used in the present invention is preferably represented by the following general formula (IV).

General formula (IV) In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ⁴ represents a hydrogen atom, a hydroxy group, a hydrazino group, an alkyl group, an aryl group, a heterocyclic group. Represents a group, an alkoxy group, an aryloxy group, a carbamoyl group or an amino group, X ¹ represents a divalent group, and n represents 0 or 1. However, when n = 0, R ⁴ represents an alkyl group, an aryl group or a heterocyclic group. R ³ and R ⁴ may together form a heterocycle.

The hydrazine analogs (hydrazines and hydrazides) represented by the general formula (IV) in the present invention are described in detail below.

R ¹ , R ² and R ³ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, a sulfopropyl group, a carboxybutyl group, a hydroxyethyl group, Cyclohexyl group,
A benzyl group, a phenethyl group or the like), a substituted or unsubstituted aryl group (preferably having 6 to 20 carbon atoms, such as a phenyl group, a 2,5-dimethoxyphenyl group, a 4-hydroxyphenyl group, a 2-carboxyphenyl group) or A substituted or unsubstituted heterocyclic group (preferably having 1 to 2 carbon atoms)
0, preferably a 5- to 6-membered ring containing at least one of oxygen, nitrogen, sulfur and the like as a hetero atom;
For example, a pyridin-4-yl group, an N-acetylpiveridin-4-yl group, etc.).

R ⁴ is a hydrogen atom, a hydroxy group, a substituted or unsubstituted hydrazino group (eg, hydrazino group, methylhydrazino group, phenylhydrazino group, etc.), a substituted or unsubstituted alkyl group (preferably having 1 to 20 carbon atoms, for example, A methyl group, an ethyl group, a sulfopropyl group, a carboxybutyl group, a hydroxyethyl group, a cyclohexyl group, a benzyl group, a t-butyl group, an n-octyl group, etc., a substituted or unsubstituted aryl group (preferably having 6 to 6 carbon atoms) 20, for example, a phenyl group, a 2,5-dimethoxyphenyl group, a 4-hydroxyphenyl group, a 2-carboxyphenyl group, a 4-sulfophenyl group and the like, a substituted or unsubstituted heterocyclic group (preferably having 1 to 20 carbon atoms) And preferably a 5- to 6-membered ring containing at least one of oxygen, nitrogen and sulfuric acid as a hetero atom. For example, a pyridin-4-yl group, an imidazolyl group or the like, a substituted or unsubstituted alkoxy group (preferably having 1 to 20 carbon atoms, for example, a methoxy group, an ethoxy group, a methoxyethoxy group, a benzyloxy group, a cyclohexyloxy group, an octyloxy group) Such),
A substituted or unsubstituted aryloxy group (preferably having 6 to 20 carbon atoms, such as a phenoxy group, a p-methoxyphenoxy group, a p-carboxyphenyl group, a p-sulfophenoxy group, etc.), a substituted or unsubstituted carbamoyl group (preferably 1-20 carbon atoms, for example, an unsubstituted carbamoyl group,
N, N-diethylcarbamoyl group, phenylcarbonyl group and the like, or substituted or unsubstituted amino group (preferably having 0 to 20 carbon atoms, for example, amino group, hydroxyamino group, methylamino group, hexylamino group, methoxyethylamino Group, carboxyethylamino group, sulfoethylamino group, N-phenylamino group, p-sulfophenylamino group).

Further substituents for R ¹ , R ² , R ³ and R ⁴ include a halogen atom (such as chlorine and bromine), a hydroxy group, a carboxy group, a sulfo group, an amino group, an alkoxy group, an amide group, a sulfonamide group, Carbamoyl group, sulfamoyl group,
Preferred are an alkyl group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a nitro group, a cyano group, a sulfonyl group, a sulfinyl group, and the like, which may be further substituted.

X ¹ is preferably a divalent organic residue, specifically, for example, -CO-, -SO-, and Represents n is 0 or 1. However, when n = 0, R ⁴ represents a group selected from a substituted or unsubstituted alkyl group, an aryl group and a heterocyclic group. R ¹ and R ² and
R ³ and R ⁴ may together form a heterocyclic group. n is 0
In at least one of R ^{1 to} R ⁴ is preferably a substituted or unsubstituted alkyl group, particularly R ¹ , R ² , R ³ and
Preferably, R ⁴ is a hydrogen atom or a substituted or unsubstituted alkyl group. (However, R ¹ , R ² , R ³ , and R ⁴ are not hydrogen atoms at the same time.) Particularly, R ¹ , R ² and
When R ³ is a hydrogen atom, R ⁴ is a substituted or unsubstituted alkyl group, when R ¹ and R ³ are a hydrogen atom, and R ² and R ⁴ are a substituted or unsubstituted alkyl group, Or R ¹
And R ² is a hydrogen atom, and R ³ and R ⁴ are preferably substituted or unsubstituted alkyl groups (in this case, R ³ and R ⁴ may form a heterocycle together). When n = 1, X ¹ is preferably —CO—, R ⁴ is preferably a substituted or unsubstituted amino group, and R ^{1 to} R ³ are preferably a hydrogen atom or a substituted or unsubstituted alkyl group.

 n is more preferably 0.

The alkyl group represented by R ^{1 to} R ⁴ preferably has 1 to 10 carbon atoms, and more preferably has 1 to 7 carbon atoms.
It is. Further, as a preferred substituent of the alkyl group,
Examples include hydroxyl, carboxylic, sulfonic and phosphonic groups. When there are two or more substituents, they may be the same or different.

The compound of the general formula (IV) may form a bis-form, a tris-form or a polymer linked by R ¹ , R ² , R ³ and R ⁴ .

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

(IV-1) (IV-2) CH ₃ NHNHCH ₃ (IV-3) (IV-4) (IV-5) (IV-7) (IV-8) HOOCCH ₂ NHNHCH ₂ COOH (IV-9) NH ₂ NHCH _{2 3} NHNH ₂ (IV-10) NH ₂ NHCH ₂ CH ₂ OH _{(IV-12) NH 2 NH-} (CH 2) 3 -SO 3 H (IV-13) NH 2 NH- (CH 2) 4 -SO 3 H (IV-14) NH 2 NH- (CH 2) 3 −COOH (IV-15) (IV-16) (IV-17) (IV-18) (IV-19) NH ₂ NHCH ₂ CH ₂ COONa (IV-20) NH ₂ NHCH ₂ COONa (IV-21) H ₂ NNHCH ₂ CH ₂ SO ₃ Na (IV-22) (IV-23) (IV-24) _{(IV-25) H2NNCH 2 CH} 7 SO 3 Na) 2 (IV-26) H 2 NNCH 2 CH 2 CH 2 SO 3 Na) 2 (IV-27) (IV-28) (IV-29) (IV-30) (IV-31) (IV-32) (IV-33) (IV-34) NH ₂ NHCONH ₂ (IV-35) (IV-36) NH ₂ NHCONHNH ₂ (IV-37) NH ₂ NHSO ₃ H (IV-38) NH ₂ NHSO ₂ NHNH ₂ (IV-39) CH ₃ NHNHSO ₂ NHNHCH ₃ (IV-40) NH ₂ NHCONH- _{(CH 2) 3 -NHCONHNH 2 (} IV-41) (IV-42) NH ₂ NHCOCONHNH ₂ (IV-43) (IV-44) (IV-45) (IV-46) NH ₂ COCONHNH ₂ (IV-47) (IV-48) (IV-49) (IV-50) (IV-51) (IV-52) (IV-53) (IV-54) (IV-55) (IV-56) (IV-57) (IV-58) (IV-59) (IV-60) (IV-61) (IV-62) (IV-63) NH ₂ NHCOOC ₂ H ₅ (IV-64) NH ₂ NHCOCH ₃ (IV-65) (IV-66) (IV-67) NH ₂ NHCH ₂ PO ₃ H ₂ (IV-68) (IV-69) (IV-70) (IV-71) (IV-72) _{(IV-73) (CH 3} ) 3 CCONHNH 2 (IV-74) (IV-75) (IV-76) (IV-77) (IV-78) (IV-79) _{(IV-80) HOCH 2 CH} 2 SO 2 NHNH 2 (IV-81) NaO 3 SCH 2 CH 2 CONHNH 2 (IV-82) H 2 NCONHCH 2 CH 2 SO 2 NHNH 2 (IV-83) (IV-84) 4 (IV-85) H ₂ NNHCH ₂ CH ₂ PO ₃ H ₂ (IV-86) The substituted hydroxyamine compound used in the present invention is preferably represented by the following general formula (V).

General formula (V) In the formula, R ¹ and R ² represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group.
R ₁ and R ₂ are not hydrogen atoms at the same time, and may be linked to each other to form a heterocycle together with the nitrogen atom. The ring structure of the hetero ring is a 5- to 6-membered ring,
It is composed of a hydrogen atom, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom and the like, and may be saturated or unsaturated.

R ¹ and R ² are preferably alkyl or alkenyl groups, and preferably have 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Examples of the nitrogen-containing hetero ring formed by linking R ₁ and R ₂ include a piperidyl group, a pyrrolidyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group, and a benzotriazole group.

Among the compounds represented by the general formula (V), a compound represented by the following general formula (Va) is particularly preferred in terms of preventing photographic fluctuation and preventing streaky fog.

General formula (Va) In the formula, L represents an alkylene group which may be substituted;
Is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be alkyl-substituted, an ammonium group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, or an alkyl-substituted group. R represents a hydrogen atom or an optionally substituted alkyl group;

 Hereinafter, the general formula (Va) will be described in detail.

In the formula, L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, methylene, ethylene, trimethylene,
Propylene is a preferred example. Examples of the substituent include a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, and an ammonium group which may be alkyl-substituted, and preferred examples thereof include a carboxy group, a sulfo group, a phosphono group, and a hydroxy group. . A is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be alkyl-substituted,
Ammonio group which may be substituted with alkyl (preferably 1 to 5 carbon atoms), carbamoyl group which may be substituted with alkyl (preferably 1 to 5 carbon atoms), and alkyl (preferably 1 to 5 carbon atoms) Represents a good sulfamoyl group,
Carboxy group, sulfo group, hydroxy group, phosphono group,
A preferred example is a carbamoyl group which may be alkyl-substituted. Preferred examples of -LA include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. Groups, carboxyethyl groups, sulfoethyl groups, sulfopropyl groups, phosphonomethyl groups, and phosphonoethyl groups can be mentioned as particularly preferred examples. R represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Examples of the substituent include a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be alkyl-substituted, an ammonium group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, and an alkyl group. Represents a sulfamoyl group which may be substituted. There may be two or more substituents. R represents a hydrogen atom, a carboxymethyl group,
Carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, hydroxyethyl group can be mentioned as preferred examples, hydrogen atom, carboxymethyl group, carboxyethyl group, sulfoethyl group, Preferred examples include a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group. L and R may combine to form a ring.

Specific examples of the compound of the general formula (V) in the present invention are shown below, but the present invention is not limited thereto.

The amount of the following compounds added to the color developer is 0.005
Mol / ~ 0.5 mol /, preferably 0.03 mol / ~
It is desirable to add so as to have a concentration of 0.1 mol /.

Compound example V-29 HO-NH-CH 2 CO 2 H V-30 HO-NH-CH 2 CH 2 CO 2 H V-36 HO-NH-CH ₂ CH ₂ SO ₃ H V-38 HO-NH- (CH ₂ ) ₃ SO ₃ H V-39 HO-NH- (CH ₂ ) ₄ SO ₃ H V-40 HO-NH-CH ₂ PO ₃ H ₂ V-42 HO-NH-CH 2 CH 2 PO 3 H 2 V-43 HO-NH-CH 2 CH 2 OH V-44 HO-NH- (CH 2) 3 OH V-45 HO-NH-CH 2 - PO ₂ H ₂ V-56 HONHCH ₂ CH (PO ₃ H ₂ ) ₂ The compound represented by the general formula (V) is obtained by subjecting commercially available hydroxyamines to an alkylation reaction (nucleophilic substitution reaction,
(Addition reaction, Mannich reaction). West German Patent No. 1159634, "Inorganica Chimica Act"
a), 93, (1984) 101-108, etc., and can be synthesized. Specific methods are described below.

Synthesis Example Synthesis of Exemplified Compound (17) 11.5 g of sodium hydroxide and sodium chloroethanesulfonate 9 were added to 200 ml of an aqueous solution of 20 g of hydroxylamine hydrochloride.
Add 6g, keep at 60 ℃ 40m of aqueous solution of 23g of sodium hydroxide
l was added slowly over 1 hour. 3 hours at 60 ° C
, The reaction mixture is concentrated under reduced pressure,
Heated to ° C. Filter the insolubles and add 500 ml of methanol to the filtrate.
Was added to obtain the desired product (exemplified compound (17)) as monosodium salt crystals. 41 g (yield 53%) Synthesis of Exemplified Compound (21) To a hydrochloric acid aqueous solution containing 7.2 g of hydroxyamine hydrochloride and 18.0 g of phosphorous acid was added 32.6 g of formalin, and the mixture was heated under reflux for 2 hours.
The resulting crystals were recrystallized from water and methanol to obtain 9.2 g (42%) of Exemplified Compound (11).

In the present invention, it is preferable that the color developer contains substantially no sulfite ion from the viewpoints of processing stability during continuous processing and preventing streaky pressure fog.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, representative examples of which are shown below, but are not limited thereto.

D-1 N, N-Diethyl-p-phenylenediamine D-2 2-Amino-5-diethylaminotoluene In the color image forming method of the present invention, washing and / or stabilizing treatment are performed after the bleach-fixing treatment.

The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (the type and amount of materials used such as couplers) and the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, etc. It can be set in a wide range depending on conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in Journal of the Society of Motion.
Picture of Television Engineers (Journal of the Society of Motion Picture and Tel
evision Engineers), Vol. 64, pp. 248-253 (May, 1955). The number of stages in the multistage countercurrent system is preferably 2 to 6.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced,
For example, 0.5 to 1 or less per 1 m ^{2 of the} photosensitive material is possible. However, an increase in the residence time of water in the tank causes a problem that bacteria proliferate and generated floating substances adhere to the photosensitive material. As a solution to such a problem, Japanese Patent Application Laid-Open
The method for reducing calcium and magnesium described in JP-A-288838 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based fungicides such as sodium chloride isocyanurate described in JP-A-61-120145, and benzotriazole described in JP-A-61-26761. Kinds, copper ions, and other "chemicals of fungicides and fungi" by Hiroshi Horiguchi (1986, Sankyo Publishing)
Disinfectants described in "Microbial disinfection, sterilization, and antifungal technology" edited by the Sanitary Technology Association (Industrial Technology Association, 1982), "Encyclopedia of Antifungal Agents", edited by the Japan Society of Antifungal and Antifungal Agents (1986), etc. It can also be used.

Further, a surfactant can be added to the washing water as a draining agent, or a chelating agent represented by EDTA can be added as a hardening agent.

It is possible to carry out the treatment with the stabilizing solution directly after the washing step or without the washing step. A compound having an image stabilizing function is added to the stabilizing solution. Examples of such a buffer include a aldehyde compound represented by formalin and a buffering agent for adjusting the film pH of a photosensitive material after processing to a value suitable for stabilizing a color image. In addition, the above-mentioned various bactericides and fungicides can be used for the purpose of preventing the growth of bacteria in the liquid and imparting fungicidal properties to the processed photosensitive material. Further, a surfactant, an optical brightener, and a hardener may be added.

In the image forming method of the present invention, when the photosensitive material is directly subjected to the stabilizing treatment without going through the washing step, the method disclosed in
Known methods described in JP-A-57-8543, JP-A-58-14834, JP-A-60-220345 and the like can all be used.

In addition, it is also a preferable embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

The preferred pH of the washing step or the stabilizing step is 4 to 10, more preferably 5 to 8.

The preferable processing temperature of the washing step or the stabilization step can be variously changed depending on the use and characteristics of the photographic material, but is usually 15 to 45 ° C, preferably 20 to 40 ° C.

The preferable treatment time of the washing step or the stabilization step can be arbitrarily set, but a shorter treatment time is preferable from the viewpoint of shortening the treatment time. Specifically, it is preferably about 15 seconds to 1 minute and 45 seconds.

The smaller the preferable amount of replenishment to the washing tank or the stabilizing bath tank, the more preferable from the viewpoints of reduction of running cost, reduction of waste liquid amount, and ease of handling. Specifically, 0.5 to 5 of the amount brought in from the previous bath per unit area of photosensitive material
It is 0 times, preferably 3 to 40 times. Or photosensitive material 1
It is 1 or less per m ² , preferably 0.5 or less. Also,
Replenishment may be performed continuously or intermittently.

The liquid used in the washing step and / or the stabilizing step can be further used for the prebath. As an example of this, there can be mentioned a method in which an overflow of a washing / stabilizing bath in a multi-stage counter-current system flows into a bleach-fixing bath which is a preceding bath. According to such a method, it is possible to concentrate the bleach-fix replenisher and reduce the amount of waste liquid.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto.

Example 1 6.4 g of sodium chloride in a 3% aqueous solution of lime-processed gelatin
Was added, and 3.2 ml of N, N'-dimethylimidazolidin-2-thione (1% aqueous solution) was added. In this solution, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.08 mol of potassium bromide and 0.12 mol of sodium chloride were added and mixed at 52 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.8 mol of silver nitrate and an aqueous solution containing 0.32 mol of potassium bromide and 0.48 mol of sodium chloride were stirred vigorously for 52 hours.
C. and mixed. After keeping at 52 ° C. for 5 minutes, desalting and washing were performed, and 90.0 g of lime-processed gelatin was further added.
The obtained silver chlorobromide (cubic silver bromide having an average grain size of 0.46 μm, 40 mol%) emulsion was designated as Emulsion A.

Emulsion a was kept at 54 ° C., and spectral sensitizing dye (G) was added in an amount of 4 × 10 ^-4 mol per mol of silver halide.
On the other hand, triethylthiourea was added in an amount of 2.6
× 10 ^-5 mol per mole of silver halide and 2.6 × 10 ^-5 mol per mol of silver halide and 1.8 × 10 ^-5 mol per mole of chloroauric acid per mol of silver halide. After sensitization, emulsions A-1 and A-2 were obtained.

Next, sodium chloride was added to a 3% aqueous solution of lime-processed gelatin.
3.3 g was added, and 1.6 ml of N, N'-dimethylimidazolidin-2-thione (1% aqueous solution) was added. In this solution, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.004 mol of potassium bromide and 0.196 mol of sodium chloride were added and mixed at 52 ° C. with vigorous stirring. Then, add silver nitrate
An aqueous solution containing 0.8 mol and an aqueous solution containing 0.016 mol of potassium bromide and 0.784 mol of sodium chloride were added and mixed at 52 ° C with vigorous stirring. After keeping at 52 ° C for 5 minutes,
After desalting and washing, 90.0 g of lime-processed gelatin was added. The obtained silver chlorobromide (cubic silver bromide having an average grain size of 0.48 μm, 2 mol%) emulsion was designated as Emulsion B.

Emulsion B was kept at 54 ° C, and after adding spectral sensitizing dye (G) at 4 × 10 ^-4 mol per mol of silver halide, the mixture was divided into two.
One uses triethylthiourea at a rate of 1.
8 × 10 ^-5 mol was added, and on the other hand, 1.8 × 10 ^-5 mol of triethylthiourea per mol of silver halide and 1.4 × 10 ^-5 mol of chloroauric acid were added per mol of silver halide for spectral sensitization and After chemical sensitization, emulsions B-1 and B-2 were obtained, respectively.

Next, 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and N, N'-dimethylimidazolidin-2-
3.2 ml of thione (1% aqueous solution) was added. An aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride were added and mixed at 52 ° C. with vigorous stirring. Subsequently, while vigorously stirring an aqueous solution containing 0.8 mol of silver nitrate and an aqueous solution containing 0.8 mol of sodium chloride,
Added and mixed at 2 ° C. After keeping at 52 ° C. for 5 minutes, desalting and washing were performed, and 90.0 g of lime-processed gelatin was further added. Silver chloride obtained (cube with average grain size of 0.47μ)
The emulsion was designated as emulsion C.

Emulsion C was kept at 54 ° C., and 4 × 10 ^-4 mol of a spectral sensitizing dye (G) was added per 1 mol of silver halide.
After adding 2 mol% of silver bromide fine particles (grain size 0.05 μ) to the first emulsion, triethylthiourea was added at 1.6 × 10 ^-5 mol per mol of silver halide. And chloroauric acid in an amount of 1.4 mol per mole of silver halide.
× 10 ^-5 mol, and triethylthiourea was added to the third emulsion in an amount of 1.6 mol / mol of silver halide without adding fine silver bromide particles.
× 10 ^-5 mol, and the fourth emulsion was further subjected to spectral sensitization and chemical sensitization by adding 1.4 × 10 ^-5 mol of chloroauric acid per mol of silver halide. , C-
2, C-3 and C-4.

 Table 1 shows the characteristics of these emulsions.

Next, 25.0 g of the magenta coupler (a), 18.75 and 2.5 g of the color image stabilizer (b) were dissolved in 50.0 ml of ethyl acetate and 50.0 g of the solvent (d), and the resulting solution was dissolved in 10% dodecylbenzenesulfonic acid. It was emulsified and dispersed in 400 ml of a 10% aqueous gelatin solution containing 20 ml of sodium. The obtained emulsified dispersion was designated as coupler dispersion M-1.

The coupler dispersion M-1 is a compound of the present invention (Ia-3
1) An emulsified dispersion which was different only by adding 3.75 g and 2.5 g of (IIIa-1) was prepared, and this was mixed with coupler dispersion M-
And 2.

The silver halide emulsion obtained above and the above-mentioned coupler dispersion were mixed to prepare a coating solution having the composition shown in Table 2, and the layer constitution shown in Table 2 was formed on a paper support laminated on both sides with polyethylene. Were applied together with the protective layer to prepare 16 types of photosensitive materials shown in Table 3. As the gelatin hardener for each layer,
1-oxy-3,5-dichloro-s-triazine sodium salt was used.

The following tests were performed using the 16 types of photosensitive materials thus obtained.

Pass each sample through an optical wedge and green filter
After exposure at 250 CMS for 2 seconds, color development was performed using the following processing steps and processing solutions.

Next, in order to examine the change in photographic properties when the exposure illuminance changed, the same processing was performed with the exposure changed to 250 CMS for 0.01 second.

Further, in order to examine the change in photographic performance when the photosensitive material was stored for a long period of time, a coated sample was prepared and, as a forced test, stored at 40 ° C. for 2 weeks and then subjected to the same treatment for two types of exposure time.

Measure the reflection density of the processed sample created in this way,
A so-called characteristic curve was obtained. The sensitivity was defined as the reciprocal of the exposure amount giving a density 0.5 higher than the fog density, and expressed as a relative value with the sensitivity of 1 second exposure immediately after the sample 101 was prepared as 100.

The color density corresponding to the exposure increased by 0.6 in logE was determined from the exposure for which the sensitivity was determined, and shoulder gradation was determined.

Further, in order to examine the generation of stain when the color-developed sample was stored for a long period of time, the change in white background after storage for two weeks at 60 ° C.-70% RH was measured as a forced test.

 Table 4 shows the results.

Processing process Temperature Time Color development 35 ° C 45 seconds Bleaching and fixing 35 ° C 45 seconds Rinse 30-35 ° C 20 seconds Rinse 30-35 ° C 20 seconds Rinse 30-35 ° C 20 seconds Rinse 30-35 ° C 30 seconds Dry 70- 80 ° C for 60 seconds (Rinse → 3 tank countercurrent method) The composition of each processing solution is as follows.

Color developer Water 800 ml Ethylenediamine-N, N, N'N'-tetramethylphosphonic acid 1.5 g Triethylenediamine (1,4 diazabicyclo [2,2,2] octane) 5.0 g Sodium chloride 1.4 g Potassium carbonate 25.0 g N-ethyl -N- (β-methanesulfonicamidoethyl)-
3-methyl-4- aminoaniline sulfate 5.0 g N, N-diethylhydroxylamine 4.2 g Optical brightener (UVITEX CK Ciba-Geigy) 2.0 g Add water 1000 ml pH (25 ° C) 10.10 Bleaching fixer Water 400 ml Thio Ammonium sulfate (70%) 100 ml Sodium sulfite 18.0 g Iron (III) ethylenediaminetetraacetate 55.0 g Disodium ethylenediaminetetraacetate 3.0 g Ammonium bromide 40.0 g Glacial acetic acid 8.0 g Add water 1000 ml pH (25 ° C) 5.50 Rinse solution Ion Exchange water (calcium and magnesium are each 3ppm or less) As is evident from the results, by applying the stain inhibitor of the present invention, the stain generated after processing the photosensitive material can be effectively prevented. On the other hand, rapid development becomes possible by increasing the silver chloride content. However, if only the sulfur sensitization is applied, the storage stability of the product when the stain inhibitor of the present invention is applied, especially when exposed to high-intensity light, is high. The softening of the partial gradation is remarkably difficult to put to practical use. For the first time, the combination of a high silver chloride emulsion with gold sensitization makes it possible to achieve both the prevention of stain after processing and the stability during storage of a product with a light-sensitive material capable of rapid processing.

Example 2 The sample 116 prepared in Example 1 was subjected to a process different from that of Example 1 except that the composition of the bleach-fixing solution used in the development process was changed as shown in Table 5, and then processed in the same manner as in Example 1. The occurrence of stain after the treatment was examined.

 The results are shown in Table 6.

As is evident from the results, by adding a hydrazine compound or a substituted hydroxylamine compound to the bleach-fix solution, the stain generated when the processed photographic material is stored can be further reduced. However, when the amount exceeds the range specified in the present invention, poor desilvering occurs, which is not preferable.

Example 3 In the same manner as in Example 1, blue-sensitive, green-sensitive and red-sensitive halide emulsions as shown in Table 7 were prepared. However, the size of the silver halide grains was changed by changing the addition time of the reaction solution and the temperature during the reaction. When preparing silver halide grains, potassium hexacyanoferrate (II) trihydrate was used in an amount of 2.1 mg for a blue-sensitive emulsion, and 8.4 mg for a green-sensitive and red-sensitive emulsion.
In addition, potassium hexachloroiridate (IV) was added in an amount of 24.2 μg to the emulsion for blue sensitivity, and 96.6 μg in the emulsions for green and red sensitivity. Further, for spectral sensitization to a target wavelength region, the spectral sensitizing dye (B) is added to the blue-sensitive emulsion in an amount of 3 × 10 ^-4 mol per mol of silver halide, and the spectral sensitizing dye (B) is added to the green-sensitive emulsion. G) and (G ') were 4 × 10 ^-4 mol and 8 × 10 ^-5 mol, respectively, per mol of silver halide. For red-sensitive emulsions, the spectral sensitizing dye (R) was 5 ×, per mol of silver halide. 10 ^-5 mol, each used in place of the spectral sensitizing dye (G) in Example 1. 4. Further, 1 × 10 ⁻³ mol of compound (S) was added to 1 mol of silver halide to the red-sensitive emulsion.

The emulsions thus obtained were coated in multiple layers with combinations of compositions, layer constitutions, emulsions and coupler dispersions shown in Tables 8 and 9 to prepare 16 types of color light-sensitive materials. Preparation of the coating solution for each layer was performed as follows.

First layer coating solution 19.1 g of yellow coupler (e), color image stabilizer (f) 4.4
27.2 ml of ethyl acetate and 7.9 ml of the solvent (h) were added to and dissolved in 0.7 g of (g) and (g), and this solution was emulsified and dispersed in 200 ml of a 10% aqueous gelatin solution containing 8.0 ml of 10% sodium dodecylbenzenesulfonate. The emulsified dispersion thus obtained was designated as coupler dispersion Y-1.

The coupler dispersion Y-1 is a compound of the present invention (Ia-3
1) An emulsified dispersion which was different only by adding 0.70 g and 0.47 g of (IIIa-1) was prepared, and this was used as a coupler dispersion Y-
And 2.

The coupler dispersion thus obtained and the blue-sensitive silver halide emulsion shown in Table 7 were mixed and dissolved, and the amount of gelatin and the like were adjusted so that the composition shown in Table 8 was obtained. Was prepared.

Next, a dispersion of the cyan coupler was prepared in the same manner so as to have the composition shown in Table 8. Those containing no compound of the present invention were designated as coupler dispersion C-1 and those containing the compound of the present invention were designated as C-2.

Then, coating solutions for the second to seventh layers were prepared in the same manner. However, the emulsified dispersion used for the fifth layer coating solution is
After emulsification and dispersion, the pressure was reduced at 40 ° C., and ethyl acetate was distilled off before use.

As the gelatin hardener for each layer, the same compound as used in Example 1 was used.

1: 1 mixture with (molar ratio) 4: 2: 4 mixture (weight ratio) 2: 4: 4 mixture by weight of each 2: 4: 4 mixture (weight ratio) Color image stabilizer (O) 1: 1 mixture (weight ratio) Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

Also, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol and 2 × 10 mol, respectively, per mol of silver halide. ×
10 ^-4 mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

The following tests were performed using the 16 types of photosensitive materials thus prepared.

Each sample was exposed to 250 CMS for 1 second through an optical wedge and filters of three colors of blue, green and red, and then subjected to color development using the following processing steps and processing solutions.

Next, the photographic property variation when the exposure illuminance was changed, the photographic property variation when the photosensitive material was stored for a long time, and the generation of stain when the processed sample was stored were tested in the same manner as in Example 1.

However, the measurement of the reflection density in the sensitometry and the measurement of the stain density after the processing were performed for three types of cyan density, magenta density and yellow density.

Table 10 shows the results. However, the sensitivities shown in the table are represented by relative values with respect to the blue-sensitive layer, the green-sensitive layer, and the red-sensitive layer, with the value of sample 310 being 100.

The composition of each processing solution is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g 40 g ammonium bromide Add 1000 ml pH ( 25 ° C) 6.0 Rinse solution (same for tank solution and replenisher) Deionized water (3ppm for calcium and magnesium respectively)
In this continuous processing, the amount of processing liquid brought in when the photosensitive material moves from the color developing bath to the bleach-fixing bath is 60 ml / m ^2.
Therefore, in an equilibrium state during continuous processing, processing was performed by adding 8.1 × 10 ⁻³ mol / N, N-bis (carboxymethyl) hydrazine as a hydrazine compound according to the present invention to a bleach-fixing solution. Equivalent to.

As is evident from the results, even in the multilayer color light-sensitive material, the softening of the shoulder gradation of high illuminance exposure during storage caused by combining the high silver chloride emulsion and the stain inhibitor of the present invention was achieved by using a gold compound. Sensitization can be effectively prevented. Furthermore, the presence of the hydrazine compound of the present invention in the bleach-fix solution reduces the generation of stain to a lower level.

Example 4 3.3 g of sodium chloride in a 3% aqueous solution of lime-processed gelatin
Was added, and 3.2 ml of N, N'-dimethylimidazoline-2-thione (1% aqueous solution) was added. In this solution, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride and 15.0 μg of rhodium trichloride were added and mixed at 56 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.78 mol of silver nitrate and an aqueous solution containing 0.78 mol of sodium chloride and 4.2 mg of hexacyanoiron (III) potassium trihydrate were added and mixed at 56 ° C. with vigorous stirring. Five minutes after the addition of the aqueous silver nitrate solution and the aqueous alkali halide solution was completed, an aqueous solution containing 0.02 mol of silver nitrate and a potassium bromide solution were further added.
An aqueous solution containing 015 mol, 0.005 mol of sodium chloride and 0.8 mg of potassium hexachloroiridate (IV) was added and mixed at 40 ° C. with vigorous stirring. Thereafter, desalting and washing were performed, and 90.0 g of lime-processed gelatin was further added. Silver chloride obtained (cube with average particle size 0.52μ)
The emulsion was designated as emulsion D.

Emulsion D was kept at 54 ° C., and spectral sensitizing dye (R ′) was added at 2 × 10 ⁻⁴ mol per mol of silver halide, and then triethylthiourea was added at 1.4 × 10 ⁻⁵ mol per mol of silver halide. ,
The second emulsion was further added with 1.2 × 10 ^-5 mol of chloroauric acid per mol of silver halide and subjected to spectral sensitization and chemical sensitization to obtain emulsions D-1R and D-2R, respectively.

These emulsions were prepared by changing the spectral sensitizing dye to (IR1) and changing the amount of addition to 4.5 × 10 ^-5 mol per mol of silver halide to prepare emulsions D-1IR1 and D-2IR1. .

In addition, these emulsions contain a spectral sensitizing dye (IR2)
Then, emulsions were prepared by changing the amount of addition to 0.5 × 10 ⁻⁵ mol per mol of silver halide, and were referred to as emulsions D-1IR2 and D-2IR2.

When the spectral sensitizing dyes (IR1) and (IR2) were used, the compound (S) was added in an amount of 1.8 × 10 ^-3 mol per mol of silver halide.

These emulsions were used as silver halide in the light-sensitive material having the layer constitution shown in Table 8 of Example 3 and were combined as shown in Table 11 to prepare four types of light-sensitive materials of Samples 401 to 404.

Spectral sensitizing dye (R ') 1: 1 mixture (molar ratio) of spectral sensitizing dye (IR1) Spectral sensitizing dye (IR2) Further, 8.0 × 10 ^-4 mol of 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the yellow, magenta and cyan coloring emulsion layers per mol of silver halide.

The following dyes were added to the emulsion layer to prevent irradiation.

Next, the semiconductor laser AlGaInP (oscillation wavelength, about 670n
m), semiconductor laser GaAlAs (oscillation wavelength, about 750 nm), Gi
Using an AlAs (oscillation wavelength, about 810 nm), the laser light is rotated by a rotating polyhedron to assemble a device that can sequentially scan and expose on color photographic paper that moves in the direction perpendicular to the scanning direction. The photosensitive material was exposed.
For the exposure amount, the exposure time and light emission amount of the semiconductor laser were electrically controlled.

The exposure pattern for each sample was a wedge-shaped pattern in which the exposure amount continuously changed in the length direction of the sample, and was a sensitometric pattern of three colors of yellow, magenta, and cyan.

The exposed photographic material was subjected to the same processing steps and color development as in Example 3 using a processing solution.

For these photosensitive materials, the same test as in Example 3 was carried out for the purpose of examining the change in photographic properties when the sample was stored and the degree of stain generated after processing. The results are shown in Table 12.

As is clear from the results, according to the present invention, in a photosensitive material for laser scanning exposure having a spectral sensitivity in the infrared region and an image forming method using the same, the stability when the sample is stored and the stain after processing are improved. It can be seen that there is a remarkable effect of achieving a balance with the reduction of.

(Effects of the Invention) As described above, by using the embodiment of the present invention, rapid processing is possible, the generation of stains when storing prints after processing is small, and the product can be used for a long time. It is possible to provide an excellent photosensitive material which has little change in photographic properties upon storage, especially softening of shoulder gradation in high illuminance exposure. In addition, by combining the processing solution of the present invention with the photosensitive material of the present invention, it is possible to realize a color image forming method in which the generation of stain is further suppressed.

Claims (1)

(57) [Claims] 1. A coupler which forms a dye by coupling with an oxidized form of an aromatic primary amine developing agent, and a salt smell containing 90 mol% or more of silver chloride containing substantially no silver iodide. In a silver halide color photographic light-sensitive material containing a silver halide emulsion comprising silver halide or silver chloride and a compound represented by the following general formula (I), (II) and / or (III), the silver halide emulsion A method for preventing a decrease in contrast at a shoulder portion of a characteristic curve of a photographic response when the photosensitive material is stored, characterized by sensitizing the photosensitive material with gold. General formula (I) R _{21 An} x General formula (II) In the general formulas (I) and (II), R ₂₁ and R ₂₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. X represents a group capable of reacting with the aromatic amine developer and leaving, and A represents a group capable of reacting with the aromatic amine developer to form a chemical bond. n represents 1 or 0. B is a hydrogen atom, an aliphatic group,
Y ₁ represents an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group, and Y ₁ represents a group which promotes addition of an aromatic amine developer to the compound of the general formula (II). Here, R ₂₁ and X, Y ₁ and R ₂₂ or B may be bonded to each other to form a cyclic structure. Formula (III) R ₃₀ -Z In the formula, R ₃₀ represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group.