JP2547587B2 - Color reversal image formation method - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a color reversal image with improved inter-image effect and improved color reproducibility.

[Conventional technology]

Color development of a silver halide color photographic material causes a reaction between an oxidized aromatic primary amine color developing agent and a coupler to produce indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and similar dyes. It is known that a color image is formed.

The dyes produced from these couplers are not ideal spectral absorption spectra.Magenta and cyan dyes, in particular, have broad absorption spectra and secondary absorption in the short wavelength region, and It is not preferable in color reproduction.

In particular, secondary absorption in the short wavelength region tends to cause a decrease in saturation. As a means for improving this, it can be improved to some extent by expressing an inter-image effect.

For a general explanation of the inter-image effect, see, eg, Hanson et al., “Journal of the Optical Society of America.
he Optical Society of America ”, Vol. 42, pp. 663-669, and A. Thiels,“ Zuite Toshiyu Rift Fuyuru Vuitssenshiya Futritsie Huotographie Huotofusijk. Unit Huotohiemi (Zeitschrift fr Wissenschaftliche P
hotographie, Photophysique und Photo-chemie), 4th
7, pages 106-118 and 246-255.

JP-A-62-136649 describes a dye-forming coupler, a first silver halide emulsion layer spectrally sensitized to a certain spectral region, and a first dye image-forming unit. A color reversal light-sensitive material containing a second silver halide emulsion layer containing an inter-image effect generating means for forming a compound which is spectrally sensitized in a different spectral region and does not substantially contribute to color sensitization during color development. It is disclosed that the inter-image effect is improved by.

Further, JP-A-54-118245 contains a DIR compound which couples with an oxidation product of a color developing agent to release a development inhibitor and produces a substantially colorless reaction product. A method of providing a silver halide emulsion layer that does not substantially contribute to improve color reproducibility and sharpness is disclosed.

However, in order to reduce fluctuations in photographic performance due to development conditions of color reversal light-sensitive materials, if the pH of color development is 11.0 or higher and / or the color development time is sufficiently long, the inter-image effect will be developed during color development. Even if the inhibitor is released, the development inhibition is hardly effective, and as a result, the interimage effect is hardly exhibited.

(Object of the Invention) An object of the present invention is to provide a color reversal light-sensitive material exhibiting a large inter-image effect in a preferable spectral region and improving color reproducibility.

(Structure of the Invention) An object of the present invention is to provide a method of black and white development of a silver halide color light-sensitive material and then color development to form a color reversal image, wherein the color light-sensitive material is combined with an image dye-forming coupler. A sensitized silver halide emulsion layer and a means for imparting an inter-image effect during black-and-white development in combination with a spectrally sensitized silver halide emulsion layer, the emulsion layer being substantially It was achieved by a method of forming a color reversal image which is characterized in that it does not form image dyes.

 Hereinafter, the present invention will be described in detail.

The following methods can be given as examples of means for imparting an inter-image effect during black and white development.

1-1, silver iodobromide emulsion or silver chloroiodobromide emulsion having a silver iodide content of 2.5 mol% or more, and the silver iodide content of the first silver halide emulsion is At least 2.0 mol% higher.

1-2 Compounds represented by the following general formula [I] disclosed in JP-A-62-103639 1-3 Compounds represented by the following general formulas [II] and [III] 1-4 U.S. Pat. No. 3,536,487 Disclosed diffusible 4-thiazoline-2-thione compound or Japanese Patent Publication No. 48-
N-Substituted 4-thiazoline-2 disclosed in 34169
-Thion Compounds Means for the first silver halide emulsion layer and / or its adjacent non-photosensitive layer to magnify the inter-image effect from the second silver halide emulsion layer.

2-1 Containing grain-fogged silver halide emulsion disclosed in U.S. Pat. No. 4,082,553 2-2 Containing grain-fogged silver halide emulsion disclosed in U.S. Pat. No. 4,626,498 2-3 Compounds represented by the following general formula [I] disclosed in JP-A-62-103639 2-4 Compounds represented by the following general formulas [II] and [III] 2-5 Disclosed in U.S. Pat. No. 3,536,487 Diffusible 4-thiazoline-2-thione compound, Japanese Patent Publication No. 48-3416
N-Substituted 4-thiazoline-2-thione compounds disclosed in No. 9 2-6 Research Discloser
Closure), No. 131, Colloidal silver described on page 13116 The present invention is required to include at least one selected from 1-1 to 1-4 as a means for exhibiting an interimage effect in black and white development. If necessary, a means selected from 2-1 to 2-6 can be further used in combination.

The spectral sensitization area of the silver halide emulsion layer combined with the means for producing the inter-image effect may be substantially the same as the spectral sensitization area of the silver halide emulsion layer containing some dye-forming coupler, but different. It may be attached.

That the emulsion layer containing the compound imparting the inter-image effect of the present invention does not substantially form an image dye means that the maximum color density is less than 0.3, particularly preferably less than 0.2.

General formula [I] A- (Time) _t- X General formula [II] General formula (III) In the general formula [I], A means a redox mother nucleus, and represents an atomic group that allows Time _t X to be released only by being oxidized during photographic development processing, and Time is a sulfur atom, Represents a timing group linked to A by a nitrogen atom or an oxygen atom, t is an integer of 0 or 1, and X is
Means a development inhibitor.

The compound of the general formula [I] used in the present invention will be described below.

First, A of the general formula [I] will be described in more detail.
Examples of the redox nucleus represented by A include hydroquinone, catechol, p-aminophenol, o-aminophenol, 1,2-naphthalene diol, 1,4-naphthalene diol, 1,6-naphthalene diol, 1,2 -Aminonaphthol, 1,4-aminonaphthol, 1,6-aminonaphthol and the like. At this time, the amino group has 1 to 1 carbon atoms.
It is preferably substituted with 25 sulfonyl groups or an acyl group having 1 to 25 carbon atoms. Examples of the sulfonyl group include a substituted or unsubstituted aliphatic sulfonyl group and an aromatic sulfonyl group. Examples of the acyl group include a substituted or unsubstituted aliphatic acyl group and aromatic acyl group. The hydroxyl group or amino group forming the redox mother nucleus of A may be protected by a protecting group that can be deprotected during development processing. Examples of protecting groups include those having 1 to 25 carbon atoms.
Wherein, for example, an acyl group, an alkoxycarbonyl group,
Carbamoyl group, JP-A-59-197,037, JP-A-5-197,037
The protecting groups described in 9-201,057 are mentioned. Further, this protecting group may be combined with a substituent of A described below, if possible, to form a 5-, 6-, or 7-membered ring.

The redox mother nucleus represented by A may be substituted with an appropriate substituent as long as the redox function is not lost. Examples of these substituents are those having 25 or less carbon atoms, such as an alkyl group, an aryl group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, an amino group,
Amido group, sulfonamide group, alkoxycarbonylamino group, ureido group, carbamoyl group, alkoxycarbonyl group, sulfamoyl group, sulfonyl group, cyano group, halogen atom, acyl group, carboxyl group, sulfo group, nitro group, heterocyclic residue , Or Time _t X. These substituents may be further substituted with the above-mentioned substituents. If possible, these substituents may be bonded to each other to form a saturated or unsaturated carbocycle or a saturated or unsaturated heterocycle.

Preferred examples of A include hydroquinone, catechol, p-aminophenol, o-aminophenol, 1,
4-naphthalenediol, 1,4-aminonaphthol and the like. A is more preferably hydroquinone,
Examples include catechol, p-aminophenol and o-aminophenol. A is most preferably hydroquinone.

Preferred specific examples of A in the general formula [I] are shown below. In addition, (*) in each structural formula shows the position where Time _t X is bonded.

 Time_tX is an acid represented by A in the general formula [I]
The redox nucleus undergoes a cross-oxidation reaction during development to form an oxidant.
For the first time Time_tA group released as X
You.

 Time is connected to A by sulfur, nitrogen, or oxygen atom
It is a timing group to be entangled and released during development Time
_tAfter one or more stages of reaction from X, X
Groups that release For example, Time
U.S. Pat.Nos. 4,248,962 and 4,409,323; British Patent No.
No. 2,096,783, U.S. Pat.No. 4,146,396, Publication No. 51-14
No. 6,828, published No. 57-56,837
There are things. Time is listed in these
It may be a combination of two or more selected from the existing ones.

The timing group represented by Time in the general formula [I] is particularly preferably represented by the following general formula. Where * represents the site where the redox nucleus is bound,
** indicates the site where PUG binds. The Time may be a combination of two or more of the following.

General formula (T-1) Where Z ₁ is -O -, - S -, - S-CH 2 -, Or Represents Here, R _{31 is a} hydrogen atom, an aliphatic hydrocarbon group, an aromatic group or a heterocyclic group.

X ₁ is a hydrogen atom, an aliphatic hydrocarbon group, an aromatic group, a heterocyclic group, -OR ₃₂ , -SR ₃₂ , Cyano group, halogen atom (eg fluorine, chlorine, bromine,
Iodine) or nitro group. R ₃₂ and R ₃₃ may be the same or different and each represents the group described for R ₃₁ . X ₂
Represents the group described for R ₃₁ .

q represents an integer of 1 to 4. When q is 2 or more, X ₁
The substituents represented by may be the same or different. q
When is 2 or more, X _1's may be connected to each other to form a ring.

 p represents 0, 1 or 2. r represents 0 or 1.

The group represented by formula (T-1) is described in, for example, British Patent No. 4,248,962.

General formula (T-2) In the formula, Z ₁ , X ₁ , X ₂ , q, and r are represented by the general formula (T-
It has the same meaning as defined in 1).

General formula (T-3) In the formula, Z ₂ is -S-, Represents m is an integer of 1 to 4, preferably 1, 2 or 2. Regarding R _31, X ₂ , and r, the general formula (T−
It has the same meaning as defined in 1).

General formula (T-4) In the formula, Z ₃ is —O—, —S— or Represents Here, R ₃₆ represents an aliphatic group, an aromatic group, an acyl group, a sulfonyl group or a heterocyclic group. R ₃₄ and R ₃₅ have the same meaning as R ₃₁ defined in formula (T-1). X ₁
And q have the same meaning as defined in formula (T-1).

The group represented by formula (T-4) is a timing group described in, for example, US Pat. No. 4,409,323.

General formula (T-5) In the formula, Z ₃ , X ₁ , R ₃₄ , R ₃₅ , and q are the general formula (T-4).
Has the same meaning as defined in.

General formula (T-6) In the formula, X ₃ is composed of at least one atom selected from carbon, nitrogen, oxygen or sulfur and has 5 to 7 members.
Is an atomic group necessary for forming a heterocyclic ring of a member. This heterocycle may be further condensed with a benzene ring or a 5- to 7-membered heterocycle. Preferred heterocycles include, for example, pyrrole, pyrazole, imidazole, triazole, furan, oxazole, thiophene, thiazole, pyridine, pyridazine, pyrimidine, pyrazine, azepine, oxepin, indole, benzofuran and quinoline. R ₃₄ , R ₃₅ , Z ₃ , X ₁ and q are represented by the general formula (T
It has the same meaning as defined in -4). General formula (T
-6) is a group represented by, for example, British Patent No. 2,096,783.
It is a timing group described in No.

General formula (T-7) In the formula, X ₅ is an atomic group which is composed of at least one atom selected from carbon, nitrogen, oxygen and sulfur and is necessary for forming a 5- to 7-membered heterocycle. X ₆ and
X ₇ is Or -N =. Here, R ₃₇ represents a hydrogen atom, an aliphatic group, or an aromatic group. This heterocycle may be further condensed with a benzene ring or a 5- to 7-membered heterocycle. Preferred heterocycles include, for example, pyrrole, imidazole, triazole, furan, oxazole, oxadiazole, thiophene, thiazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, azepine, oxepin and isoquinoline. R ₃₄ , R ₃₅ , Z ₃ , X ₁ and q have the same meanings as defined in formula (T-4).

General formula (T-8) In the formula, X ₁₀ is at least one atom selected from carbon, nitrogen, oxygen or sulfur
It is an atomic group necessary for forming a 7-membered heterocycle. X ₈ and
X ₉ is Or Is. This heterocycle is further a benzene ring or 5 to 7 members.
Membered heterocycles may be condensed. Preferred heterocycles include, in addition to those described in formula (T-6), pyrrolidine, piperidine, benzotriazole and the like.

Z ₁ , X ₁ , X ₂ , n, q, and r have the same meaning as defined in formula (T-1).

General formula (T-9) In the formula, X ₁₁ has the same meaning as X ₁₀ defined in formula (T-8). Z ₃ has the same meaning as defined in formula (T-4), and l represents 0 or 1. Examples of the preferable heterocycle for X ₁₁ include the following.

Here, X ₁ and q have the same meanings as defined in formula (T-1), and X ₁₂ represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, or a sulfamoyl group. Represents a heterocycle or a carbamoyl group.

General formula (T-10) In the formula, X ₁ and X ₂ are the general formula (T-1), and Z ₃ is the general formula (T
It has the same meaning as defined in -4). m has the same meaning as defined in formula (T-3), preferably 1
Or 2.

In the above general formulas (T-1) to (T-10), X ₁ ,
When X ₂ , R ₃₁ to R ₃₇ include an aliphatic group moiety, it preferably has 1 to 20 carbon atoms, and is saturated or unsaturated, substituted or unsubstituted, chain or cyclic, straight chain or branched. You can buy it. When X ₁ , X ₂ , R ₃₁ to R ₃₇ each contain an aromatic group moiety, it has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably a substituted or unsubstituted phenyl group. When X ₁ , X ₂ , R ₃₁ to R ₃₇ include a heterocyclic group moiety, a 5- or 6-membered heterocycle containing at least one nitrogen atom, oxygen atom, or sulfur atom as a hetero atom. Is. The heterocyclic group is preferably a pyridyl group, a furyl group, a thienyl group, a triazolyl group, an imidazolyl group, a pyrazolyl group, a thiadiazolyl group, an oxadiazolyl group or a pyrrolidinyl group.

Preferred timing groups are, for example, those shown below.

(32) * -S-CH ₂ -** X means a development inhibitor. Examples of the development inhibitor include a compound having a mercapto group bonded to the hetero ring or a hetero ring compound capable of forming imino silver. Examples of the compound having a mercapto group bonded to the heterocycle include, for example, substituted or non-substituted mercaptoazoles (for example, 1-phenyl-5-mercaptotetrazole, 1-propyl-5-mercaptotetrazole,
1-butyl-5-mercaptotetrazole, 2-methylthio-5-mercapto-1,3,4-thiadiazole, 3-
Methyl-4-phenyl-5-mercapto-1,2,4-triazole, 1- (4-ethylcarbamoylphenyl)-
2-mercaptoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-
Mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-phenyl-5-mercapto-1,3,4-
Oxadiazole, 1- {3- (3-methylureido)
Phenyl} -5-mercaptotetrazole, 1- (4-
Nitrophenyl) -5-mercaptotetrazole, 5-
(2-ethylhexanoylamino) -2-mercaptobenzimidazole, etc., and substituted or unsubstituted mercaptoazaindenes (for example, 6-methyl-4-mercapto-1,3,3a, 7-tetrazaindene, 4 , 6-Dimethyl-
2-mercapto-1,3,3a, 7-tetrazaindene etc.),
There are substituted or unsubstituted mercaptopyrimidines (for example, 2-mercaptopyrimidine, 2-mercapto-4-methyl-6-hydroxypyrimidine, etc.).

Heterocyclic compounds capable of forming imino silver include, for example, substituted or unsubstituted triazoles (eg, 1,2,
4-triazole, benzotriazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5
-Bromobenzotriazole, 5-n-butylbenzotriazole, 5,6-dimethylbenzotriazole and the like, and substituted or unsubstituted indazoles (eg, indazole, 5-nitroindazole, 3-nitroindazole, 3-chloro-5- Nitroindazole) and substituted or unsubstituted benzimidazoles (eg, 5-nitrobenzimidazole, 5,6-dichlorobenzimidazole and the like).

X is separated from Time of the general formula [I] and becomes a compound having a development inhibiting property, and then, it undergoes a certain chemical reaction with a developer component to substantially reduce the development inhibiting property. It may have no or a compound that is significantly reduced. Examples of the functional group that undergoes such a chemical reaction include an ester group, a carbonyl group, an imino group, an immonium group, a Michael addition accepting group, and an imide group. Examples of such a deactivating development inhibitor include, for example, 1- (3-phenoxycarbonylphenyl) -5-mercaptotetrazole, 1-
(4-Phenoxycarbonylphenyl) -5-mercaptotetrazole, 1- (3-maleimidophenyl)
-5-mercaptotetrazole, 5-phenoxycarbonylbenzotriazole, 5- (4-cyanophenoxycarbonyl) benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,3,4-thiadiazole, 5 -Nitro-3-phenoxycarbonylimidazole, 5- (2,3-dichloropropyloxycarbonyl) benzotriazole, 1- (4-benzoyloxyphenyl) -5-mercaptotetrazole, 5- (2-
Methanesulfonylethoxycarbonyl) -2-mercaptobenzothiazole, 5-cinnamoylaminobenzotriazole, 1- (3-vinylcarbonylphenyl)-
5-mercaptotetrazole, 5-succinimidomethylbenzotriazole, 2- {4-succinimidophenyl} -5-mercapto-1,3,4-oxadiazole,
6-phenoxycarbonyl-2-mercaptobenzoxazole and the like are mentioned.

In order to describe the content of the present invention more specifically, specific examples of the compound represented by the general formula [I] are shown below, but the compounds usable in the present invention are not limited thereto.

The compound represented by the general formula [I] can be generally synthesized by the following two methods. First, Time is just a bond (t =
In the case of 0), the first is in chloroform, 1,2-dichloroethane, carbon tetrachloride, tetrahydrofuran, without catalyst or in the presence of an acid catalyst such as p-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid. In addition, benzoquinone, orthoquinone, quinone monoimine and quinone diimine derivatives are reacted with a development inhibitor at a temperature between room temperature and 100 ° C. Second,
Acetone, tetrahydrofuran, potassium carbonate in an aprotic polar solvent such as dimethylformamide, sodium hydrogen carbonate, sodium hydride, benzoquinone substituted with chlorine, bromine or iodine in the presence of a base such as triethylamine, orthoquinone, quinone monoimine, In this method, a quinone derivative obtained by reacting a quinonediimine derivative with a development inhibitor at a temperature between -20 ° C and 100 ° C is reduced with a reducing agent such as diethylhydroxylamine or sodium hydrosulfite.

[Reference: Research Disclosure 18227 (1979); Liebi
gs Ann. Chem. 764.131 (1972)] Then, when X is released through Time (t = 1), it can be synthesized by a method substantially similar to the above. That is, Time-X is used instead of the above-mentioned development inhibitor (X), or Time having a group substitutable for X (for example, a halogen atom, a hydroxy group, or a precursor thereof) is first added to the redox nucleus. After the introduction, X is linked by a substitution reaction.

The compound represented by the general formula [I] may be added as an emulsifier obtained by dissolving in a high boiling point oil and stirring at high speed, or may be added by dissolving it in a water-soluble organic solvent such as alcohol or cellosolve. Further, it may be added in a gelatin solution and finely dispersed by stirring to be added.

In the general formula [II], R represents a linear or branched alkylene group, a linear or branched alkenyl group, a linear or branched aralkylene group, or an aryl group, and Z represents a polar substituent. Y is -S-, -O-, Or R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R
₁₀ represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, alkenyl group or aralkyl group. X'is -O-, Alternatively, -S- is represented, and R'represents a hydrogen atom or a substituted or unsubstituted alkyl group or alkenyl group, respectively. R ″ represents a hydrogen atom or a group capable of substituting it, M represents a hydrogen atom, an alkali metal atom, an ammonium group or a group capable of cleaving under alkaline conditions.
Or 1, and m represents 0, 1 or 2. However, when X'is -S-, m = 0 is not included. l is 4-
represents m.

In the general formula [III], R represents a linear or branched alkylene group, an alkenylene group, an aralkylene group, or an arylene group, and Z'represents a hydrogen atom or a polar substituent. Y'is -S-, Represents R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ or R
₁₈ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkenyl group, or an aralkyl group. n represents 0 or 1.

The general formulas [II] and [III] will be described in detail below.

In the general formula [II], R represents a linear or branched alkylene group, a linear or branched alkenylene group, a linear or branched aralkylene group, or an arylene group, and Z
Represents a polar substituent. Y is -S-, -O-, Or R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R
₁₀ represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, alkenyl group or aralkyl group. X'is -O-, Alternatively, -S- is represented, and R'represents a hydrogen atom or a substituted or unsubstituted alkyl group or alkenyl group, respectively. R "represents a hydrogen atom or a group capable of substituting it. M represents a hydrogen atom, an alkali metal atom, an ammonium mill group or a group capable of cleaving under alkaline conditions. N represents 0 or 1 and m represents 0. Represents 1 or 2. However, when X'is -S-, m = 0 is not included.
represents m.

More specifically, R is a linear or branched alkylene group (eg, methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene group,
Etc.), a linear or branched alkenylene group (for example, a vinylene group, a 1-methylvinylene group, etc.), a linear or branched aralkylene group (for example, a benzylidene group, etc.), an arylene group (for example, phenylene, naphthylene, Etc.).

The polar substituent represented by Z is, for example, a substituted or unsubstituted amino group (including a salt form, for example, amino group, hydrochloride of amino group, methylamino group, dimethylamino group, hydrochloric acid of dimethylamino group). Salt, dibutylamino group, dipropylamino group, N-dimethylaminoethyl-
N-methylamino group, etc.), quaternary ammonium mill group (eg, trimethine ammonium milk chloride group, dimethylbenzylammonium milk chloride group, etc.) alkoxy group (eg, methoxy group, ethoxy group, 2-hydroxyethoxy group, Etc.), an aryloxy group (eg a phenoxy group etc.), an alkylthio group (eg a methylthio group, a butylthio group etc.), an arylthio group (eg a
Phenylthio group, etc.), heterocyclic oxy group (eg, 2
-Pyridyloxy group, 2-imidazolyloxy group,
Etc.), heterocyclic thio group (for example, 2-benzthiazolylthio group, 4-pyrazolylthio group, etc.), sulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group,
p-toluenesulfonyl group, etc.), carbamoyl group (eg, unsubstituted carbamoyl group, methylcarbamoyl group,
Etc.), a sulfamoyl group (eg, an unsubstituted sulfamoyl group, a methylsulfamoyl group, etc.), a carbonamido group (eg, an acetamido group, a benzamido group, etc.),
A sulfonamide group (for example, a methanesulfonamide group,
Benzenesulfonamide group, etc.), acyloxy group (eg, acetyloxy group, benzoyloxy group, etc.),
Ureido group (eg, unsubstituted ureido group, methylureido group, ethylureido group, etc.), acyl group (eg,
Acetyl group, benzoyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), thioureido group (eg, unsubstituted thioureido group, methylthioureido group, etc.), sulfonyloxy group (eg, methane) Sulfonyloxy group, p-toluenesulfonyloxy group, etc.), heterocyclic group (for example, 1-morpholino group, 1-piperidino group, 2-pyridyl group, 4-pyridyl group, 2-thienyl group, 1-pyrazolyl group, 1-imidazolyl group, 2-imidazolyl group, 2-tetrahydrofuryl group, 2-tetrahydrothienyl group, etc.) and a hydroxy group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are hydrogen atoms, substituted or unsubstituted alkyl groups (for example, methyl group, ethyl group, propyl Group, 2-dimethylaminoethyl group, etc.), substituted or unsubstituted aryl group (eg, phenyl group, 2-methylphenyl group, etc.), substituted or unsubstituted alkenyl group (eg, propenyl group,
1-methylvinyl group, etc.), or a substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group,
Etc.).

R'is a hydrogen atom or a substituted or unsubstituted alkyl group (for example, methyl group, ethyl group, propyl group, 2-dimethylaminoethyl group, 2-hydroxyethyl group, 2-imidazolylethyl group, 2-dimethylaminopropyl group). ,
Etc.) and a substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.).

R represents a hydrogen atom or a group substitutable for it, and examples of the substitutable group include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), substituted or unsubstituted with 1 to 6 carbon atoms. Alkyl group (eg, methyl group, trifluoromethyl group, ethyl group, n-butyl group, etc.), substituted or unsubstituted aryl group having 6 to 12 carbon atoms (eg, phenyl group, 4-methylphenyl group, etc.), carbon number A substituted or unsubstituted alkoxy group having 1 to 6 (eg, methoxy group, ethoxy group, etc.), a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms (eg, phenoxy group,
4-methylphenyl group, etc., sulfonyl group having 1 to 12 carbon atoms (eg, methanesulfonyl group, p-toluenesulfonyl group, etc.), sulfonamide group having 1 to 12 carbon atoms (eg, methanesulfonamide group, p-toluenesulfonamide) Group, ethanesulfonamide group, etc.), sulfamoyl group having 1 to 12 carbon atoms (eg, diethylsulfamoyl group, phenylsulfamoyl group, etc.), carbamoyl group having 1 to 12 carbon atoms (eg, unsubstituted carbamoyl group, methyl Carbamoyl group, phenylcarbamoyl group, etc.), amide group having 2 to 12 carbon atoms (eg, acetamide group, benzamide group, etc.),
A ureido group having 1 to 12 carbon atoms (for example, an unsubstituted ureido group,
3-methylureido group, 3-phenylureido group, etc.),
Aryl or alkoxycarbonyl group having 2 to 12 carbon atoms (eg, methoxycarbonyl group, phenoxycarbonyl group, etc.), aryl or alkoxycarbonylamino group having 2 to 12 carbon atoms (eg, methoxycarbonylamino group,
And a cyano group.

M is a hydrogen atom, an alkali metal atom (eg, sodium atom, potassium atom, etc.), an ammoniumyl group (eg, trimethylammonium milk chloride group, dimethylbenzylammonium milk chloride group, etc.), or X under alkaline conditions. = H or a group that can be an alkali metal (eg, acetyl group, cyanoethyl group, methanesulfonylethyl group, etc.).

In the general formula [II], preferably R is a substituted or unsubstituted alkylene group and Y is _{R 2, R 3, R 6} , R 7 is a hydrogen atom, X 'is -NH- or -O
-, Z is a substituted or unsubstituted amino group or a salt thereof,
This is the case of a heterocyclic group.

Specific examples of the compound represented by the general formula [II] are shown below, but the invention is not limited thereto.

In the general formula [III], R represents a linear or branched alkylene group, an alkenyl group, an aralkylene group, or an arylene group, and Z'represents a hydrogen atom or a polar substituent. Y'is -S, Represents R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ or R
₁₈ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkenyl group, or an aralkyl group. M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group capable of cleaving under alkaline conditions. n represents 0 or 1.

More specifically, R is a linear or branched alkylene group (eg, methylene group, ethylene group, propylene group,
Butylene group, hexylene group, 1-methylethylene group,
Etc.), a linear or branched alkenylene group (eg, vinylene group, 1-methylvinylene group, etc.), a linear or branched aralkylene group (eg, benzylidene group, etc.), an arylene group (eg, phenylene, naphthylene, etc.) Etc.).

The polar substituent represented by Z ′ is, for example, a substituted or unsubstituted amino group (including a salt form, for example, an amino group, a hydrochloride of an amino group, a methylamino group, a dimethylamino group or a dimethylamino group). Hydrochloride, dibutylamino group, dipropylamino group, N-dimethylaminoethyl-
N-methylamino group, etc.), quaternary ammoniumyl group (eg, trimethylammonium milk chloride group, dimethylbenzylammonium milk chloride group, etc.), alkoxy group (eg, methoxy group, ethoxy group, 2-methoxyethoxy group, Etc.), an aryloxy group (eg a phenoxy group, etc.), an alkylthio group (eg a methylthio group,
Butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), heterocyclic oxy group (eg, 2-pyridyloxy group, 2-imidazolyloxy group, etc.), heterocyclic thio group (eg, 2-benzthia) Zolylthio group, 4
-Pyrazolylthio group, etc.), sulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (eg, unsubstituted carbamoyl group, methylcarbamoyl group, etc.), sulfamoyl group ( For example, an unsubstituted sulfamoyl group, a methylsulfamoyl group, etc.), a carbonamide group (for example,
Acetamide group, benzamide group, etc.), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), acyloxy group (eg, acetyloxy group, benzoyloxy group, etc.), ureido group (eg, none Substituted ureido group, methylureido group, ethylureido group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), thioureido group (eg, Unsubstituted thioureido group, methylthioureido group, etc.), sulfonyloxy group (for example, methanesulfonyloxy group, p-toluenesulfonyloxy group,
Etc.), a heterocyclic group (for example, 1-morpholino group, 1-piperidino group, 2-pyridyl group, 4-pyridyl group, 2-thienyl group, 1-pyrazolyl group, 2-imidazolyl group, 2
-Tetrahydrofuryl group, 2-tetrahydrothienyl group, etc.) and cyano group. Here, Z is a sulfonic acid group, a carboxylic acid group, a hydroxy group, and an alkoxycarbonyl group (for example, a methoxycarbonyl group,
Ethoxycarbonyl group, etc.).

R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ or R ₁₈ represents a hydrogen atom, a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, a propyl group). , 2-dimethylaminoethyl group, etc.), substituted or unsubstituted aryl group (eg, phenyl group, 2-methylphenyl group, etc.), substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group) , Etc.) or a substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, etc.).

Specific examples of the compound represented by the general formula [III] are shown below, but the compound of the present invention is not limited thereto.

The silver halide grain whose surface or inside is fogged in 2-1 or the like which is a means for expanding the interlayer effect is any one of silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide. In the case of silver halide containing iodide, the iodide content is preferably 20 mol% or less, more preferably 10 mol% or less. Further, these fogged silver halide grains may have internal structures having different halogen compositions inside the grains.

The average grain size of fogged silver halide grains that can be used in the present invention is not particularly limited, but when these fogged silver halide grains are added to a photosensitive silver halide emulsion layer or a non-photosensitive intermediate layer Is preferably smaller than the average size of the silver halide grains in the adjacent lowest sensitive layer. Specifically, it is preferably 0.7 μm or less, more preferably 0.5 μm or less, and further
Most preferably, it is 0.4 μm or less.

The grain shape of these fogged silver halide grains is not particularly limited, and may be regular grains or irregular grains. Further, these fogged silver halide grains may be polydisperse, but monodisperse grains are preferred.

Here, the monodispersed silver halide emulsion (non-tabular grains) means that the total weight or 95% or more of the silver halide grains contained therein is within ± 40% of the average grain size, more preferably ± 30%. Are defined as

The amount of these fogged silver halide grains can be arbitrarily changed according to the degree required in the present invention, but when used in a light-sensitive silver halide emulsion layer, the amount of the light-sensitive silver halide grains To the ratio of the amount of silver, or when used in the non-photosensitive intermediate layer, to the ratio of the amount of silver with the minimum silver halide grains adjacent to the non-photosensitive intermediate layer,
0.05 to 50 mol% is preferable, 0.1 to 25 mol% is more preferable, and 0.5 to 20 mol% is the most preferable.

The light-sensitive material to which the present invention is applied may be, for example, a color reversal film (inner type or outer type), color reversal paper, or the like.

The color reversal light-sensitive material referred to in the present invention is "The Theory of the Photograph Process" edited by TH James, edited by TH James.
ic Process), 4th Edition, p. 336, Macmillan
an) As described in the company publication (1977), the development processing step is the first development in which black and white development is performed, and the silver halide not developed in the first development is exposed to light or activated by a chemical method to develop. It is a color photographic light-sensitive material that is subjected to a treatment including a step of enabling, a color development in the presence of a coupler, a bleaching step of returning developed silver to silver halide, and a defined step of dissolving and removing it, and a silver halide agent used is , Refers to those that are negative.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention,
Any silver halide such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. Preferred silver halides are silver iodobromide or silver iodochlorobromide containing up to about 30 mol% silver iodide. Particularly preferred is silver iodobromide containing from about 0.5 mol% to about 10 mol% silver iodide.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may be a so-called Regular particle having a regular crystal such as a tetradecahedron, an irregular crystal form such as a sphere, a crystal defect such as a twin plane, or a composite form thereof. But it's okay. Also, a mixture of particles having various crystal forms may be used.

The grain size of the silver halide may be fine grains of about 0.1 μm or less, or large grains having a projected area diameter of about 10 μm, and may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. Good.

The silver halide photographic emulsion which can be used in the present invention can be produced by a known method, for example, Research Disclosure (hereinafter abbreviated as RD), Volume 176, No.
17643 (December 1978), pp. 22-23, "I. Emulsion production (Emuls
ion Preparation and Types) ”and ibid., 187, No.1
8716 (November 1979), p.648 can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphkides, published by Paul Montel (P.Glafkides,
Chimie et Physique Photograhpique Paul Montel, 196
7), Duffin “Photographic Emulsion Chemistry”, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry)
(Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Forcal Press (VLZelikman et.
al, Making and Coating Photographic Emulsion, Focal
Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, a one-sided mixing method, a simultaneous mixing method,
Any combination of them may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg 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 substantially uniform grain size can be obtained.

Known silver halide solvents (eg, ammonia,
Rodankari or U.S. Pat.No. 3,271,157, JP-A-51-1
Physical ripening in the presence of thioethers and thione compounds described in JP-A-2360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717 or JP-A-54-155828. Can also be performed. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size distribution can be obtained.

The silver halide emulsion consisting of the above-mentioned regular grains,
Obtained by controlling pAg and pH during particle formation.
For details, see, for example, Photographic Science and Emg.
ineering, Vol. 6, pp. 159-165 (1962);
Journal of Pho
tographic Science), 12, 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

The monodisperse emulsion is a silver halide grain having an average grain diameter of more than about 0.1 micron and at least 95
Emulsions are typically such that the weight percentage is within ± 40% of the average grain diameter. Have an average particle diameter of 0.25 to 2 microns and at least 95% by weight or (particle number) of at least
An emulsion in which 95% of silver halide grains are within the range of average grain diameter ± 20% can be used in the present invention. A method for producing such an emulsion is described in U.S. Patent Nos. 3,574,628 and 3,655,394.
And British Patent 1,413,748. Further, JP-A-48-8600, JP-A-51-39027, JP-A-51-83097,
53-137133, 54-48521, 54-99419, 58
Monodisperse emulsions such as those described in -37635 and 58-49938 can also be preferably used in the present invention.

Tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering, Gutoff, Photographic Science and Engineering,
Volume 14, Pages 248-257 (1970); U.S. Pat. No. 4,434,226.
No. 4,414,310, 4,433,048, 4,439,520, and British Patent No. 2,112,157. When tabular grains are used,
It has advantages such as increased covering power and increased color sensitization efficiency by the sensitizing dye.
It is described in detail in No. 4,226.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent No. 1,027,146.
U.S. Pat. Nos. 3,505,068, 4,444,877 and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be joined by an epitaxial junction, or may be joined to a compound other than silver halide, such as, for example, rhodan silver or lead oxide. These emulsion grains are described in U.S. Patent Nos. 4,094,684 and 4,142,900.
No. 4,459,353, British Patent No. 2,038,792, British Patent No. 4,349,622, No. 4,395,478, No. 433,501, No. 4,46.
3,087, 3,656,962, 3,852,067, JP 59-1
No. 62540 is disclosed.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be present together.

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

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

The emulsion used in the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is RD, No. 17643 (December 1978).
No. 18716 (November) and No. 18716 (November 1979), and the relevant places are summarized in the table below.

Known photographic soluble additives that can be used in the present invention are also described in the above two RDs, and the points described in the table below are shown.

Various Lar couplers can be used in the present invention, specific examples of which are described in the patents described in the above-mentioned RD, No. 17643, VII-C to G. As the dye-forming coupler, a coupler that gives the three primary colors (that is, yellow, magenta, and cyan) of the subtractive color method by color development is important. In addition to the couplers described in the patents of RD, No. 17643, VII-C and D, the following can be preferably used in the present invention.

Representative examples of the yellow coupler that can be used in the present invention include a hydrophobic acylacetamide-based coupler having a ballast group. An example is U.S. Pat.
Nos. 407,210, 2,875,057 and 3,265,506. In the present invention, the use of a two-equivalent yellow coupler is preferred, and U.S. Pat.
No. 3,447,928, Nos. 3,933,501 and 4,022,620, etc., and oxygen atom-elimination type yellow couplers or JP-B-58-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, and RD18053 (April 1979) , UK Patent No. 1,
No. 425,020, West German Application Publication No. 2,219,917, No. 2,261,36
Representative examples thereof include nitrogen atom-releasing yellow couplers described in No. 1, No. 2,329,587 and No. 2,433,812. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Magenta couplers that can be used in the present invention include hydrophobic, indazolone-based or cyanoacetyl-based, preferably 5-pyrazolone- and pyrazoloazole-based couplers having a ballast group. 5-pyrazolone-based couplers are preferably couplers in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. Representative examples thereof are described in U.S. Pat.
No. 311,082, No. 2,343,703, No. 2,600,788, No Withstand
Nos. 2,908,573, 3,062,653, 3,152,896, and 3,936,015. 2 equivalents of 5
-As a leaving group for a pyrazolone coupler, U.S. Pat.
Particularly preferred are nitrogen atom leaving groups described in 310,619 or arylthio groups described in US Pat. No. 4,351,897. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density. U.S. Patent No.
Pyrazolobenzimidazoles described in 3,016,432, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in US Pat. No. 3,725,067, Research Disclosure No. 24220 (1984 June) and JP-A-60
Examples include pyrazolotetrazoles described in -33552 and Research Disclosure No. 24230 (June 984) and pyrazolopyrazoles described in JP-A-60-43659. The imidazo [1,2-b] pyrazoles described in U.S. Pat.No.4,500,630 are preferred in view of low yellow side absorption and light fastness of the coloring dye, and EP 11
Parazolo [1,5-b] [1,2,4] triazoles described in 9,860A are particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol-based and phenol-based couplers, and the naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.
Representative examples are the oxygen atom-elimination type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Specific examples of phenolic couplers are described in U.S. Patent Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,826 and the like.

A cyan coupler which is fast against humidity and temperature is preferably used in the present invention, and typical examples thereof include a phenol system having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in U.S. Pat. No. 3,772,002. Cyan coupler, U.S. Pat.Nos. 2,772,162, 3,758,308,
No. 4,126,396, No. 4,334,011, No. 4,327,173
, German Patent Publication No. 3,329,729 and European Patent No. 121,3
2,5-diacylamino-substituted phenol-based couplers described in U.S. Pat.No. 65 and U.S. Pat.Nos. 3,446,622 and 4,3.
33,999, No. 4,451,559, No. 4,427,767 and the like, and phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position.

In order to correct unnecessary absorption of various color-developing systems, it is preferable to mask a color negative photosensitive material for photographing with a colored coupler. Typical examples are yellow colored magenta couplers described in U.S. Pat.No. 4,163,670 and Japanese Patent Publication No. 57-39413, or magenta colored cyan couplers described in U.S. Pat. Can be mentioned. Other colored couplers are described in Research Disclosure, No. 17643, Item VII-G.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are disclosed in U.S. Pat.No. 4,366,237 and British Patent 2,125,570.
No. 96,5 for a specific example of a magenta coupler.
No. 70 and West German Publication No. 3,234,533 have yellow,
Specific examples of magenta or cyan couplers are described.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

A coupler which releases a photographically useful residue upon coupling is also preferably used in the present invention. DIR couplers that release development inhibitors are RD, No.17643, VII-
The couplers of the patents listed in Section F are useful.

Preferred in combination with the present invention is disclosed in
Developer inactivated type represented by 151944; U.S. Pat. No. 4,248,
962 and a timing type represented by JP-A-57-154234; a reaction type represented by Japanese Patent Application No. 59-39653,
Particularly preferred are JP-A-57-151944 and JP-A-58-2179.
No. 32, Japanese Patent Application No. 59-75474, No. 59-82214, No. 59-8221
Developer inactivated DI described in No. 4, No. 59-90438, etc.
R couplers and reactive DIR couplers described in Japanese Patent Application No. 59-39653.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples thereof include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, a high-boiling point organic solvent having a boiling point of 175 ° C. or higher and a low-boiling point so-called auxiliary solvent are dissolved in a single liquid or a mixed liquid of both, and then water or gelatin is added in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. Examples of high boiling organic solvents are U.S. Pat.No. 2,322,027
No. etc. The dispersion may be accompanied by a phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing or ultrafiltration before use for coating.

The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

The light-sensitive material produced by using the present invention, as a color antifoggant or a color mixing inhibitor, is a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a non-absorption coupler, a sulfonamide phenol. You may contain a derivative etc.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans spirochromans, p-alkoxyphenols,
Hindered phenols such as 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. A representative example is given. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

The present invention is also applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. These layer arrangements can be arbitrarily selected as needed. The preferred order of the layer arrangement is red sensitivity, green sensitivity, blue sensitivity or blue sensitivity, red sensitivity, and green sensitivity from the support side. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. Usually, a cyan-forming coupler is contained in the red-sensitive emulsion layer, a magenta-forming coupler is contained in the green-sensitive emulsion layer, and a yellow-forming coupler is contained in the blue-sensitive emulsion layer, but different combinations can be used depending on circumstances.

In addition to the silver halide emulsion layer, the light-sensitive material of the present invention is preferably provided with an auxiliary layer such as a protective layer, an intermediate layer, a filter, an anti-halation agent and a back layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are a flexible support such as plastic film, paper, cloth or the like usually used for photographic light-sensitive materials or glass, ceramics,
It is applied to a rigid support such as metal. What is useful as a flexible support is a film made of a cellulose derivative (sulfuric acid nitrate, cellulose acetate, cellulose acetate butyrate, etc.) or a synthetic polymer (polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.), a variator layer or α. -Paper coated or laminated with an olefin polymer (for example, polyethylene, polypropylene, ethylene / butene copolymer) or the like. The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports is generally subbed to improve adhesion with photographic emulsion layers and the like.

The color developer used for the development processing of the light-sensitive material of the present invention,
It is preferably an alkaline aqueous solution whose main sentence is an aromatic primary amine-based color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N, N-diethylaniline. Methyl-4-amino-N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Methoxyethylaniline and their sulphates, hydrochlorides or p-toluenesulphonates. Two or more of these compounds can be used in combination depending on the purpose.

Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, bromide salts, iodide salts,
It is common to include a development inhibitor such as benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Fogging agent such as sodium boron hydride, 1
An auxiliary developing agent such as -phenyl-3-pyrazolidone,
Various chelating agents represented by viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid. , Hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine -Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

When the reversal process is performed, color development is usually performed after black-and-white development. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The color developing solution of the present invention preferably has a pH of 11 to 12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed,
Generally less than 3 per square meter of photosensitive material,
It is also possible to reduce the bromide ion concentration in the replenisher to 500 ml or less. When the replenishment amount is reduced, it is preferable to prevent the evaporation of liquid and air oxidation by reducing the contact area of the treatment tank with air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but it is possible to process at a lower pH for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specification; U.S. Pat. No. 3,893,858, West German Patent 1,290,812,
95,630, Research Disclosure No. 17,129 (July 1978) and the like, compounds having a mercapto group or a disulfide bond; thiazolidine derivatives described in JP-A-50-140,129; U.S. Pat. A thiourea derivative described in JP-A-58-16235; a polyoxyethylene compound described in West German Patent No. 2,748,430; a polyamine compound described in JP-B-45-8836; a bromide ion and the like. Can be used. Among them, a compound having a mercapto group or a disulphide group is preferable from the viewpoint of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858,
The compounds described in West German Patent No. 1,290,812 and JP-A No. 53-95,630 are preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but the use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler), the purpose, and the rinsing water temperature.
It can be set in a wide range depending on the number of washing tanks (the number of stages), a replenishment system such as countercurrent and forward flow, and various other conditions. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the photographic light-sensitive material of the present invention, as a solution to such a problem, the method of reducing both calcium ion and magnesium ion to 3 ppm or less described in Japanese Patent Application No. 61-131632 can be used very effectively. . Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" It is also possible to use the bactericides described in “Microbial Sterilization, Sterilization, and Antifungal Technologies” edited by the Society of Hygiene and Technology, and “Encyclopedia of Antibacterial and Antifungal Agents” edited by the Society for Nonbacterial and Antifungal Society.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but in general, at 15-45 ° C for 20 seconds-10 minutes, preferably at 25-40 ° C.
A range of 30 seconds-5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such a stabilizing process, the method disclosed in
Methods such as multistage countercurrent stabilization treatment, low replenishment, and ion exchange treatment described in Nos. 57-8,543, 58-14,834, and 60-220,345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat.Nos. 3,342,597, 3,342,599, Schiff base type compounds described in Research Disclosure 14,850 and 15,159, aldol compounds described in 13,924, and U.S. Pat. And urethane compounds described in JP-A-53-135,628.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-type light-sensitive materials for the purpose of promoting color development, if necessary.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A Nos. 56-64,339, 57-144,547, and 58.
-115,438 etc. are described.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, the processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 226,770 or US Pat. No. 3,674,499 may be performed.

Example 1 A multilayer color light-sensitive material having the following composition was prepared on a triacetate film base to prepare Sample 101.
And

1st layer: Anti-halation layer Black colloidal silver 0.25 g / m ² UV absorber U-1 0.04 g / m ² UV absorber U-2 0.1 g / m ² UV absorber U-3 0.1 g / m ² High boiling point Organic solvent O-1 Gelatin layer containing 0.1 CC / m ² (dry film thickness 2 μ) Second layer; Intermediate layer Compound H-1 0.05 g / m ² High boiling organic solvent O-2 Gelatin containing 0.05 CC / m ² Layer (dry film thickness 1 μ) Third layer; Intermediate layer Compound H-1 0.05 g / m ² Gelatin layer containing high boiling point organic medium O-2 0.05 CC / m ² (Dry film thickness 1 μ) Fourth layer; 1 Red-sensitive emulsion layer Monodisperse silver iodobromide emulsion ... Silver amount ... 0.5 g / m ² (iodine content 4 mol%, average grain size 0.3 μs / = 0.
15) Sensitizing dye S-1 1.4 mg / m ² Sensitizing dye S-2 0.06 mg / m ² Coupler C-1 0.30 g / m ² Gelatin layer containing high boiling organic solvent O-2 0.12 CC / m ² ( Dry film thickness 1 μ) Fifth layer; second red-sensitive emulsion layer Sensitizing dye S-1 1.6 mg / m ² and sensitizing dye S-2 0.06 mg
Polydisperse silver iodobromide emulsion containing / m ² ... silver amount ... 0.8 g / m ² (iodine content 2.5 mol%, average grain size 0.55 μ s / =
0.27) Dye D-1 0.02 g / m ² Coupler C-1 0.70 g / m ² High boiling point organic solvent O-2 Gelatin layer containing 0.28 CC / m ² (dry film thickness 2.5 μm) 6th layer; intermediate layer Compound H-1 0.1 g / m ² Dye D-2 0.02 g / m ² High boiling organic solvent O-2 Gelatin layer containing 0.1 CC / m ² (dry film thickness 1 μm) 7th layer; 1st green sensitive emulsion layer Sensitizing dye S-3 (3.3 mg / m ² ) and sensitizing dye S-4 (1.5 m
g / m ² ) containing monodisperse silver iodobromide emulsion ... Silver amount ... 0.7 g / m ² (iodine content 3 mol%, average grain size 0.3 μs / = 0.
15) Dye D-3 0.02 g / m ² Coupler C-3 0.40 g / m ² High boiling point organic solvent O-2 0.24 CC / m ² Gelatin layer (dry film thickness 1 μm) 8th layer; 2nd green feeling Emulsion layer Sensitizing dye S-3 (1.3 mg / m ² ) and sensitizing dye S-4 (0.05
mg / m ²⁾ tabular silver iodobromide emulsion C silver containing ... 0.8 g / m ² (iodine content 2.5 mole%, 50% of the projected area diameter / thickness ratio is 5 or more particles all particles, The average particle thickness is 0.13
μ) Coupler C-4 0.40 g / m ² Coupler C-8 0.40 g / m ² Gelatin layer containing high boiling point organic solvent O-2 0.48 CC / m ² (dry film thickness 2.5 μ) 9th layer; intermediate layer Dye D-4 0.01 g / m ² compound H-1 0.05 g / m ² high-boiling point organic solvent O-2 0.1 gelatin layer containing CC / m ² (dry film thickness 1 μm) 10th layer; intermediate layer compound H-1 0.05 g / m ² Gelatin layer containing high boiling point organic solvent O-2 0.1 CC / m ² (dry film thickness 1 μm) 11th layer; Yellow filter layer Yellow colloidal silver 0.1 g / m ² Compound H-1 0.02 g / m ² Compound H-2 0.03 g / m ² Gelatin layer containing high boiling organic solvent O-2 0.04 CC / m ² (dry film thickness 1 μm) 12th layer; 1st blue-sensitive emulsion layer Sensitizing dye S-5 (1.0 mg silver iodobromide emulsion containing / m ² )
0.7 g / m ² (iodine content 2.5 mol%, average particle size 0.4 μ s / =
0.30) Coupler C-5 0.5 g / m ² High boiling organic solvent O-2 Gelatin layer containing 0.1 CC / m ² (dry film thickness 1.5 μ) 13th layer; 2nd blue-sensitive emulsion layer Sensitizing dye S-5 (1.7 mg / m ² ) tabular silver iodobromide emulsion C silver amount ... 1.1 g / m ² (iodine content 2.5 mol%, grains having a diameter / thickness ratio of 5 or more are 50% of the projected area of all grains) %, The average thickness of the particles is 0.13
μ) Dye D-5 0.02 g / m ² coupler C-6 0.6 g / m ² coupler C-7 0.6 g / m ² High boiling organic solvent O-2 0.24 CC / m ² gelatin layer (dry film thickness 3 μ ) 14th layer; 1st protective layer UV absorber U-1 0.02 g / m ² UV absorber U-2 0.03 g / m ² UV absorber U-3 0.03 g / m ² UV absorber U-4 0.29 g / m ² High boiling organic solvent O-1 Gelatin layer containing 0.28CC / m ² (dry film thickness 1μ) 15th layer; 2nd protective layer Gelatin layer containing polymethylmethacrylate particles (average particle size 1.5μ) (dry) Thickness 0.8 μ) Non-photosensitive fine grain silver iodobromide emulsion 0.1 g / m ² yellow colloidal silver 0.005 g / m ^{2 In} each layer, in addition to the above composition, gelatin hardener H-3,
And surfactant was added.

 The compounds used to make the samples are shown below.

The development processing was performed as follows.

Processing process Process temperature Temperature 1st development 6 minutes 38 ℃ Water wash 2 minutes 〃 Reversal 2 minutes 38 ℃ Color development 6 minutes 〃 Adjustment 2 minutes 〃 Bleach 6 minutes 〃 Soaking 4 minutes 〃 Water wash 4 minutes 〃 Stabilization 1 minute Normal temperature Drying solution Use the following composition.

First developer Water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid 5 Sodium sulphate 2 g Sodium sulfite 30 g Potassium hydroquinone monosulphonate 20 g Potassium carbonate 33 g 1-Phenyl-4-methyl-4 -Hydroxymethyl-3-pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2 mg Water was added 1000 ml Inversion solution Water 700 ml Nitro-N, N, N-trimethylenephosphonic acid-5 nato Lithium salt 3 g Stannous chloride (dihydrate) 1 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to 1000 ml Color developer water 700 ml Nitro-N, N, N- Trimethylenephosphonic acid-5 sodium salt 2 g Sodium sulfite 7 g Sodium triphosphate (12-hydrate) 36 g Potassium bromide 1 g Potassium iodide 90 mg Sodium hydroxide 3 g Citrazic acid 1.5 g N -Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / sulfate 11 g 3,6-dithiaoctane-1,8-diol 1 g Water was added to 1000 ml (pH 11.6) Conditioned water Water 700 ml Sodium sulfite 12 g Sodium ethylenediamine tetraacetate (dihydrate) 8
g Thioglycerin 0.4 ml Water was added 1000 ml Bleaching solution Water 800 ml Sodium ethylenediaminetetraacetate (dihydrate) 2
g Ethylenediaminetetraacetate Ammonium iron (III) (dihydrate) 120 g Potassium bromide 100 g Ammonium nitrate 10 g Water added 1000 ml Fixer water 800 ml Ammonium thiosulfate 80.0 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water In addition, 1000 ml Stabilized water 800 ml Formalin (37% by weight) 5.0 ml Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.5 ml Add water to 1000 ml. Similar results were obtained when treated with a washing solution.

Water-washing solution Ethylenediaminetetraacetic acid disodium salt 0.4 g Water was added and 1000 ml of sodium hydroxide was added to pH 7.0. Then, a silver bromide cubic emulsion with an average grain size of 0.15μ was prepared by the controlled double jet method. Fog under low pAg with complex salts. The emulsion thus prepared is designated as emulsion A, and emulsion B is obtained by shelling silver bromide on the surface of emulsion A at a thickness of 250 Å. Emulsion B was not chemically sensitized.

(Compounds described in US Pat. No. 3,536,487) C-9 (Compound described in JP-A-62-136649) Preparation of Sample 102 In the second layer of Sample 101, the same emulsion as the seventh layer (silver amount 0.2 g /
Sample 102 was prepared in exactly the same manner as Sample 101 except that m ² ) and the sensitizing dye were added.

Preparation of Sample 103 In the 10th layer of Sample 101, the same emulsion as the 4th layer (silver amount 0.2 g /
Sample 103 was prepared in exactly the same manner as Sample 101, except that m ² ) and the sensitizing dye were added.

Preparation of Samples 104 and 105 I-2 was applied to the second layer of Sample 102 and the 10th layer of Sample 103, respectively.
Samples 104 and 105 were prepared in exactly the same manner as Samples 102 and 103, respectively, except that 5 mol% was added to the silver halide emulsion.

Preparation of Samples 106 to 107 Samples 106 to 107 were prepared except that Compounds II-1 and III-45 were added to the second layer of Sample 102 at 1 mol% based on the silver halide emulsion.
Samples 106 to 107 were prepared in exactly the same manner as 102.

Preparation of Samples 108-109 Samples except that Compounds II-5 and III-33 were added to the 10th layer of Sample 103 at 1 mol% based on the silver halide emulsion.
Samples 108 to 109 were prepared in exactly the same manner as 103.

Preparation of Sample 110 Sample 110 was prepared in exactly the same manner as Sample 102, except that the silver iodide content of the second silver halide emulsion layer of Sample 102 was changed from 3 mol% to 6 mol%.

Preparation of Samples 111 to 112 Samples 111 to 1 were prepared in exactly the same manner as Samples 104 and 107, except that Emulsion A (silver amount 0.05 g / m ² ) was added to the fourth layer of Samples 104 and 107.
12 were produced.

Preparation of Samples 113 to 116 Emulsion B (silver content 0.05%) was added to the fourth layer of Samples 102, 104, 106 and 107.
Samples 113 to 116 were prepared in exactly the same manner as Samples 102, 104, 106 and 107 except that g / m ² ) was added.

Preparation of Samples 117 to 119 Samples 102, 104 and 107 were prepared by adding Compound III-50 to the fourth layer in an amount of 0.5 mol% based on the silver halide emulsion.
Samples 117 to 119 were prepared in the same manner as 104 and 107.

Preparation of Sample 120 Sample 120 was prepared in exactly the same manner as Sample 102 except that Compound A was added to the second layer of Sample 102 in an amount of 0.5 mol% based on the silver halide emulsion.

Preparation of Samples 121 to 123 Emulsion A (silver content) was added to the seventh and twelfth layers of Samples 103, 105 and 109.
Samples 121 to 123 were prepared in exactly the same manner as Samples 103, 105 and 109 except that 0.05 g / m ² ) was added.

Preparation of Samples 124 to 126 Emulsion B (silver content) was added to the seventh and twelfth layers of Samples 103, 105 and 109.
Samples 124 to 126 were produced in exactly the same manner as Samples 103, 105 and 109 except that 0.05 g / m ² ) was added.

Preparation of Samples 127 to 129 Compounds III-33 were added to the seventh and twelfth layers of Samples 103, 105 and 109.
Samples 127 to 129 were prepared in exactly the same manner as Samples 103, 105 and 109 except that was added to the silver halide emulsion in an amount of 1 mol%.

Preparation of Sample 130 In the 10th layer of Sample 102, the same emulsion as the 4th layer (silver amount 0.2 g /
Sample 130 was prepared in exactly the same manner as Sample 102, except that m ² ) and the sensitizing dye were added.

Preparation of Sample 131 5 mol% of Compound I-2 was added to the second layer and the 10th layer of Sample 130 in relation to the silver halide emulsion, and emulsion B (silver B) was added to the 4th, 7th and 12th layers. 0.05 g / m ² ) and Sample 131 was prepared in exactly the same manner as Sample 130 except that Compound III-33 was added in an amount of 1 mol% based on the silver halide emulsion.

Preparation of Sample 132 Emulsion A (silver content 0.0%) was added to the fourth, seventh and twelfth layers of Sample 130.
5 g / m ² ) was added, and Sample 132 was prepared in exactly the same manner as Sample 130 except that Compound A was added to the second and tenth layers in an amount of 1 mol% based on the silver halide emulsion.

Preparation of Samples 133 and 134 Sample 102, except that an emulsified dispersion of C-6 was added to the second layer of Sample 102 and the second and tenth layers of Sample 130, respectively, in an amount of 1 mol% based on the silver halide emulsion. Sample just like 130
133 and 134 were produced.

These samples 101 to 133 were divided into four equal parts, and each of them was subjected to red wedge exposure, green wedge exposure, blue wedge exposure, and white wedge exposure (red + green + blue light). The red exposure amount during white exposure is the same as the red exposure amount, the green exposure amount during white exposure is the same as the green exposure amount, and the blue exposure amount during white exposure is the same as the blue exposure amount during white exposure. Were equivalent.

These exposed samples were subjected to color reversal processing as follows.

Compare red light exposure cyan and white light exposure cyan,
An exposure amount difference ΔlogE (R) at a density of 1.0 was obtained. Similarly, ΔlogE (G) and Δlog (B) were obtained.

It can be said that the larger the value of ΔlogE (R), ΔlogE (G), and ΔlogE (B), the greater the inter-image effect.

 The results are shown in Tables 1 and 2.

From the results in Tables 1 and 2, it is clear that the present invention exhibits a greater interimage effect than the comparative example.

Similarly, when the samples 101 to 134 were treated with the following treatment steps and treatment liquid compositions, the present invention exhibited a greater inter-image effect than the comparative example. Processing time Temperature First development 6 minutes 38 ℃ First water wash 45 seconds 38 ℃ Reverse 45 seconds 38 ℃ Color development 6 minutes 38 ℃ Bleach 2 minutes 38 ℃ Bleach fix 4 minutes 38 ℃ Second water wash (1) 1 minute 38 ° C Second water washing (2) 1 minute 38 ° C Stable 1 minute 25 ° C The composition of each treatment solution was as follows.

First developer nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g sodium sulfite 30 g hydroquinone monopotassium sulfonate 20 g potassium carbonate 33 g 1-phenyl-4-methyl-4-hydroxy Methyl-3-pyrazolidone 2.0 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2.0 mg Water was added to 1000 ml pH 9.6 pH was adjusted with hydrochloric acid or potassium hydroxide. First washing liquid Mother liquor Ethylenediaminetetramethylenephosphonic acid 2.0 g Disodium phosphate 5.0 g Water was added to 1000 ml pH 7.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Inversion solution Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 3.0 g Stannous chloride dihydrate 1.0 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 14 ml Add water 1000 ml pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Color developer Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g Sodium sulfite 7.0 g Trisodium phosphate-12-hydrate 36 g Potassium bromide 1.0 g Potassium iodide 90 mg Sodium hydroxide 3.0 g Citrazinic acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 11 g 3,6-dithiaoctane-1,8-diol 1.0 g Water added 1000 ml pH 11.80 pH was adjusted with hydrochloric acid or potassium hydroxide.

Bleach-fixing solution Ethylenediaminetetraacetic acid ・ Fe () ・ Ammonium ・ dihydrate 50 g Ethylenediaminetetraacetic acid ・ sodium dihydrate 5.0 g Ammonium thiosulfate 80 g Sodium sulfite 12.0 g Water is added 1000 ml pH 6.60 pH is hydrochloric acid Alternatively, it was adjusted with aqueous ammonia.

Second washing water Tap water is passed through a mixed bed column filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400). Water was added to control the calcium and magnesium ion concentration to 3 mg / or less, and then 20 mg / sodium diisocyanurate dichloride and 1.5 g / sodium sulfate were added. The pH of this solution is in the range 6.5-7.5.

Stabilizer Formalin (37%) 5.0 ml Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.5 ml Add water to 1000 ml without adjusting pH

Claims (2)

(57) [Claims] 1. A method for forming a color reversal image by black-and-white development and then color development of a silver halide color light-sensitive material, wherein the color light-sensitive material is combined with an image dye-forming coupler to spectrally sensitize a halogenated material. A silver emulsion layer and a means for imparting an inter-image effect during black and white development, in combination with a spectrally sensitized silver halide emulsion layer, the emulsion layer substantially forming the image dye. A method of forming a color reversal image, which is characterized by not performing. 2. The method for forming a color reversal image according to claim 1, wherein color development is performed using a color developing solution having a pH of 11.0 or higher.