JPH0534874A - Formation of color reversal image - Google Patents

Abstract

PURPOSE:To form color reversal images with high maximum coloring density a small variation in gradation and small unevenness of processing, to cause no problems of the lowering of coloring density, the variation in gradation and the unevenness of processing and to improve the sharpness the color reversal images. CONSTITUTION:Color reversal images are formed on photographic material with the processing of image exposure, monochrome development, reversal color development and desilverization by using color photographic material. The photographic material includes the specified hydroquinone compound and the processing solution for color development processing includes 0.005 to 0.1mol/l bromide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color reversal image forming method. In particular, the present invention relates to a positive color image forming method preferably applicable to color reversal paper.

[0002]

2. Description of the Related Art A color reversal image forming method is mainly used for printing a transparent positive image such as a color reversal film or a color positive film, or for copying a photographic print, a printed matter, a painting or the like. In the color reversal image forming method, a black and white development process, a reversal process, a color development process and a desilvering process are performed on an image-exposed color photographic material to form a positive color image on the photographic material. Specifically, a positive color image is formed as follows. (1) A latent image is formed on the silver halide in the exposed area by an image exposure process. (2) The silver halide in the exposed area is developed by a black and white development process to form a silver image. (3) A latent image is formed on the silver halide remaining in the unexposed area by the reversal process. The reversal treatment includes a light fogging treatment and a chemical fogging treatment using a fogging agent. (4) Color development is performed on the unexposed areas of silver halide to form a color image. (5) The silver image is removed by the desilvering process.

Generally, the image quality of a silver halide photographic material is determined by its sharpness and graininess. In the case of a reflection type photographic material, the image is not magnified and viewed, so the silver halide grains are sufficiently fine and the graininess does not pose a problem. Therefore, sharpness is particularly important. The sharpness of the photographic material is deteriorated by light scattering, refraction and reflection at the interface in the silver halide emulsion layer, and is further aggravated as the total thickness of the photosensitive layer is increased. A color photographic material requires at least three image forming layers, as well as a non-photosensitive intermediate layer and a protective layer for preventing color mixture, and the photosensitive layer as a whole has a considerable thickness. Various methods are known for improving the sharpness. For example, as a method of obtaining the edge effect at the time of development at the time of black and white development, D which releases the development inhibitor by the development
A method using an IR hydroquinone compound has been proposed. Regarding the DIR hydroquinone compound, U.S. Pat. Nos. 3,364,022 and 3,379,529, and JP-A Nos. 50-62435 and 50-133.
No. 8233, No. 50-119631, No. 51-519.
No. 41, No. 52-57828, No. 62-103639.
No. 62-251746.

[0004]

When the present inventors have used the above-mentioned DIR hydroquinone compounds in a color reversal image forming method, it has been found that these compounds have a detrimental effect on color development. This effect becomes greater as the processing is continuously performed (continuous processing), and as a result, a decrease in color density, a change in gradation and uneven processing occur. It was also found that this effect was greater when the temperature of the color developer was higher and the processing time was shorter.

The object of the present invention is to obtain a high color density,
An object of the present invention is to provide a color reversal image forming method in which gradation change and processing unevenness are less likely to occur. It is also an object of the present invention to improve the sharpness of a color reversal image without causing problems such as a decrease in color density, gradation change and processing unevenness.

[0006]

The objects of the present invention have been achieved by the following color reversal image forming method.

The present invention uses a color photographic material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler and a silver halide emulsion layer containing a cyan coupler on a support and imagewise exposed. A method of forming a color reversal image on a photographic material by processing, black-and-white development processing, reversal processing, color development processing and desilvering processing, wherein the photographic material is represented by the following formula (Ia) or (Ib)
A method for forming a color reversal image, which comprises a compound having the formula (1) and the processing solution for color development processing contains 0.005 to 0.1 mol / liter of bromide.

[Chemical 3]

[Chemical 4] In the formula, R ¹² is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; M is —CO
_{-, - SO 2 -, -} N (R 15) CO -, - OCO- or -N (R ¹⁵⁾ SO ₂ - is; R ¹⁴ and R ¹⁵ are each a hydrogen atom, is an alkyl group or an aryl group ;
R ¹¹ , R ¹³ and R ²¹ are each a hydrogen atom or a substituent of a hydroquinone nucleus; A and A ′ are a hydrogen atom or a group which can be removed by an alkali; L is 5 or more members condensed with a hydroquinone nucleus. Forming a heterocycle of 2
Is a valent group; Time is a group that releases X after being released from the hydroquinone oxidant; X is a development inhibitor; and t is 0 or an integer of 1 or more.

The color reversal image forming method of the present invention is preferably carried out in the following modes.

(1) In the above formula (Ia), M is -C.
When O- and R ¹² is an alkyl group, the alkyl group is an alkyl group having 2 or more carbon atoms in which a carbon atom adjacent to M is not substituted with a hetero atom.

(2) In the above formula (Ia), M is -S.
_{O 2 -, - N (R} 15) CO -, - OCO- or -N
(R ¹⁵ ) SO ₂ −.

(3) In the above formula (Ia), M is -N
(R ¹⁵⁾ is a CO- or -OCO-.

(4) In the above formula (Ia), R ¹¹ and R ¹³ are each a hydrogen atom or a substituent having a Hammett's substituent constant (σ _p ) of 0.3 or less.

(5) In the above formulas (Ia) and (Ib), A and A'are hydrogen atoms.

(6) In the above formula (Ib), the hetero ring formed by L has the following formulas (L-1) to (L-12).

[0015]

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8]

(5) The compound represented by the above formula (Ia) has the following formula (IA).

[Chemical 9] In the formula, M, R ¹² , R ¹⁴ , Time, X, A, A ′ and t have the same definitions as in formula (Ia).

(6) The compound represented by the above formula (Ib) has the following formula (IB).

[Chemical 10] In the formula, L ² is a divalent amino group, an ether bond, a thioether bond, an alkylene group, an imino bond, a sulfonyl group, a carbonyl group, an arylene group, a divalent heterocyclic group, or a group combining these; R ²¹ , A,
A ′, Time, X and t have the same definitions as in formula (Ib).

(7) The photographic material contains 0.001 mmol / m ^{2 to} 0.2 mmol / m ^{2 of the} compound having the above formula (Ia) or (Ib).

(8) The bromide contained in the processing solution for color development processing is potassium bromide or sodium bromide.

(9) The processing solution for color development processing contains bromide in an amount of 0.008 to 0.05 mol / liter.

[0021]

As described above, the DIR hydroquinone compound has an effect of improving the sharpness of the image. However, when the DIR hydroquinone compound is used in the color reversal image forming method, the color density is lowered and the gradation is changed in the color development. The problem of uneven processing occurs.

According to the research conducted by the present inventor, a specific hydroquinone compound having the above formula (Ia) or (Ib) was used as the DIR hydroquinone compound, and bromide was added in an amount of 0.005 to 0.005 in the processing solution for color development processing. By adding 0.1 mol / liter, it is possible to prevent problems such as lowering of color density, gradation change and uneven processing without impairing the action of the DIR hydroquinone compound. Therefore, according to the method of the present invention, it is possible to form a color reversal image having a high maximum color density and little gradation change or processing unevenness. Further, according to the method of the present invention, the sharpness of a color reversal image can be improved without causing problems such as a decrease in color density, a change in gradation and uneven processing. These effects were first obtained by combining the specific hydroquinone compound and bromide, and cannot be predicted from the respective actions.

DETAILED DESCRIPTION OF THE INVENTION The color reversal image forming method of the present invention comprises a support, a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a halogenation containing a cyan coupler. A color photographic material having a silver emulsion layer and further containing a compound having the formula (Ia) or (Ib) described above is imagewise exposed; the photographic material is subjected to black and white development processing; the photographic material is subjected to reversal processing; The material is color-developed using a processing solution containing bromide in an amount of 0.005 to 0.1 mol / liter; and decolorizing the photographic material to form a color reversal image on the photographic material.

In the color reversal image forming method of the present invention, the photographic material contains a compound having the formula (Ia) or (Ib). The compound having the following formula (Ia) or (Ib) will be described in more detail.

[0025]

[Chemical 11]

[0026]

[Chemical 12]

In the formula (Ia), R ¹² is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Each group may further have a substituent. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an amide group, a sulfonamide group, an alkoxycarbonylamino group, a ureido group, a carbamoyl group, an alkoxycarbonyl group, a sulfamoyl group, and a sulfonyl group. , A cyano group, a halogen atom, an acyl group, a hydroxyl group, a carboxyl group, a sulfo group, a nitro group and a heterocyclic group.

The alkyl group represented by R ¹² preferably has 1 to 30 carbon atoms, more preferably 2 to 25 carbon atoms, and particularly preferably 4 to 20 carbon atoms. Examples of alkyl groups are methyl, ethyl, isopropyl, t-butyl, nonyl, 1-hexylnonyl, decyl, pentadecyl, hexadecyl, 3- (2,5-di-t-pentylphenoxy) propyl, cyclohexyl and benzyl. Can be mentioned.

In the formula (Ia), M is -CO-
And when R ¹² is an alkyl group, the alkyl group is preferably an alkyl group having 2 or more carbon atoms in which a carbon atom adjacent to M is not substituted with a hetero atom. Of the examples of the alkyl group, groups other than methyl correspond to such an alkyl group.

The alkenyl group represented by R ¹² has 2 carbon atoms.
It is preferably from 30 to 30. Examples of alkenyl groups include vinyl, 1-butenyl, 1-octenyl, 2-phenylvinyl and 1-octadecenyl.

The alkynyl group represented by R ¹² has 2 carbon atoms.
It is preferably from 30 to 30. Examples of alkynyl groups include ethynyl, phenylethynyl and 1-octynyl.

The aryl group represented by R ¹² preferably has 6 to 30 carbon atoms. Examples of aryl groups are phenyl, naphthyl, 3,5-bis (octadecanamido) phenyl, 3-dodecanamidophenyl, 2-
Mention may be made of hexadecanesulfonamidophenyl, 3-hexadecanesulfonamidophenyl and 4-dodecyloxyphenyl.

The heterocyclic group represented by R ¹² has 5 to 20 members.
It is preferred to have a membered heterocycle. Examples of heteroatoms in the heterocycle include nitrogen, oxygen, sulfur and selenium. Examples of heterocyclic groups include 3-pyridyl, 4-pyridyl, 2-furyl, pyrrolo, 2-thiazolyl, 3-thiazolyl, 2-oxazolyl, 2-imidazolyl, triazolyl, tetrazolyl, benzotriazolyl, benzimidazolyl and Mention may be made of morpholinyl.

In the formula (Ia), M is --CO-- or-
_{SO 2 -, - N (R} 15) CO -, - OCO- or -N
(R ¹⁵ ) SO ₂ −. M _{is, -SO 2 -, - N (} R
¹⁵⁾ CO -, - OCO- or -N (R ¹⁵⁾ SO ₂ - is preferably. -N (R ¹⁵⁾ CO- or -OC
It is more preferably O-.

In the above definition of M, R ¹⁴ and R
¹⁵ is a hydrogen atom, an alkyl group or an aryl group, respectively. Examples of the alkyl group and the aryl group are the above R ¹²
The same as the examples of the alkyl group and aryl group represented by. R ¹⁵ is preferably a hydrogen atom.

R ¹¹ and R ¹³ in formula (Ia) and R ²¹ in formula (Ib) are each a hydrogen atom or a substituent of a hydroquinone nucleus.

Each of R ¹¹ and R ¹³ in the formula (Ia) is preferably a hydrogen atom or a substituent having a Hammett's substituent constant (σ _p ) of 0.3 or less. Examples of the substituent having a Hammett substituent constant (σ _p ) of 0.3 or less include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amide group, a sulfonamide group, and an ureido group. , Urethane group, sulfamoylamino group, halogen atom, hydroxy group and-(Time) _t -X. Each group may further have a substituent. Examples of the substituent of R ¹¹ and R ¹³ are the same as the examples of the substituent of R ¹² described above.

The alkyl group preferably has 1 to 30 carbon atoms. Examples of alkyl groups include methyl,
Mention may be made of ethyl, isopropyl, t-butyl, decyl, hexadecyl, t-octyl, cyclohexyl and benzyl.

The aryl group preferably has 6 to 30 carbon atoms. Examples of aryl groups include phenyl and naphthyl.

The alkoxy group preferably has 1 to 30 carbon atoms. Examples of alkoxy groups include methoxy, hexyloxy, hexadecyloxy, 2-dodecyloxy and benzyloxy.

The aryloxy group has 6 to 3 carbon atoms.
It is preferably 0. Examples of aryloxy groups may include phenoxy and naphthoxy.

The alkylthio group has 1 to 30 carbon atoms.
Is preferred. Examples of alkylthio groups include:
Mention may be made of methylthio, hexylthio, dodecylthio and benzylthio. The arylthio group preferably has 6 to 30 carbon atoms. Examples of arylthio groups are phenylthio, naphthylthio and 2
-Butyloxy-5-t-octylphenylthio may be mentioned.

The amide group preferably has 1 to 30 carbon atoms. Examples of amide groups include acetamide, butanamide, hexadecanamide and benzamide.

The number of carbon atoms of the sulfonamide group is 1 to 3
It is preferably 0. Examples of sulfonamide groups include methanesulfonamide, octanesulfonamide,
Hexadecane sulfonamide and benzene sulfonamide may be mentioned.

The ureido group preferably has 1 to 30 carbon atoms. Examples of ureido groups include 3-methylureido, 3-dodecylureido and 3-phenylureido.

The urethane group preferably has 2 to 30 carbon atoms. Examples of urethane groups include methoxycarbonylamino, decyloxycarbonylamino and phenoxycarbonylamino.

The sulfamoylamino group has 2 carbon atoms.
It is preferably from 30 to 30. Examples of sulfamoylamino groups include 3-methylsulfamoylamino and 3-phenylsulfamoylamino.

Examples of the above halogen atom include chlorine, bromine and fluorine.

Details of-(Time) _t -X will be described later.

Examples of R ²¹ in the formula (Ib) include, in addition to the examples of R ¹¹ and R ¹³ (hydrogen atom and Hammett's substituent constant (σ _p ) of 0.3 or less), an acyl group. Examples thereof include groups, alkoxycarbonyl groups, carbamoyl groups, sulfamoyl groups, sulfonyl groups and heterocyclic groups. Each group may further have a substituent.

The acyl group preferably has 1 to 30 carbon atoms. Examples of acyl groups include acetyl, octanoyl, benzoyl, chloroacetyl, 3-carboxypropionyl and octadecanoyl.

The alkoxycarbonyl group has 2 carbon atoms.
It is preferably from 30 to 30. Examples of alkoxycarbonyl groups include methoxycarbonyl, octyloxycarbonyl, phenoxycarbonyl, octadecyloxycarbonyl and methoxyethoxycarbonyl.

The carbamoyl group preferably has 1 to 30 carbon atoms. Examples of carbamoyl groups are carbamoyl, N-propylcarbamoyl, N-hexadecylcarbamoyl, N- {3- (2,4-di-tert-pentylphenoxy)} propylcarbamoyl and N-
Mention may be made of phenylcarbamoyl.

The sulfamoyl group has 0 to 30 carbon atoms.
Is preferred. Examples of sulfamoyl groups include sulfamoyl and dibutylsulfamoyl.

The sulfonyl group preferably has 1 to 30 carbon atoms. Examples of sulfonyl groups include methanesulfonyl, benzenesulfonyl and p-dodecylbenzenesulfonyl.

The above heterocyclic group preferably has a 5- to 20-membered heterocyclic ring. Examples of heteroatoms in the heterocycle include nitrogen, oxygen, sulfur and selenium. Examples of the heterocyclic group include 5-tetrazolyl, 2-benzoxazolyl, 2-thiazolyl, 2-imidazolyl, 2-pyridyl and morpholino.

In the formulas (Ia) and (Ib), A and A'are hydrogen atoms or groups which can be removed with an alkali. Examples of groups that can be removed with an alkali include groups that can be hydrolyzed (eg, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, imidoyl groups, oxalyl groups, sulfonyl groups), and reverse Michael reactions. Precursor group (US Patent No. 40090
29), a precursor group (described in U.S. Pat. No. 4,310,612) that utilizes an anion generated by a ring-cleavage reaction as an intramolecular nucleophilic group, and a cleavage reaction by electron transfer of the anion through a conjugated system. Precursor group to be raised (U.S. Pat.
2480 and 3993661 each specification description),
A precursor group (described in U.S. Pat. No. 4,335,200) that causes a cleavage reaction by electron transfer of an anion reacted after ring cleavage and a precursor group using an imidomethyl group (U.S. Pat. Nos. 4,363,865 and 44106).
No. 18, each description). Generally A
And A'is preferably a hydrogen atom.

In the formula (Ib), L is a divalent group forming a 5-membered or more heterocycle condensed with the hydroquinone nucleus. Examples of L include amide bond, divalent amino group, ether bond, thioether bond, imino bond, sulfonyl group, carbonyl group, alkylene group, alkenylene group and combinations of these groups. Each group may have a substituent. The heterocycle preferably has 5 to 7 members. However, when L contains an ether bond, the heterocycle preferably has 6 or more members.

Examples of preferred heterocycles formed by L are shown below.

[0060]

[Chemical 13]

[0061]

[Chemical 14]

[0062]

[Chemical 15]

[0063]

[Chemical 16]

(L-1), (L-2), (L-3),
(L-4), (L-6), (L-10) and (L-1
2) is particularly preferable.

In formulas (Ia) and (Ib),
(Time) _t- X is a group having a function of releasing a development inhibitor after the hydroquinone mother nucleus is oxidized by the oxidized form of the developing agent to become a quinone form during development. Specifically, Time
Is a group that releases X after leaving the oxidized form of hydroquinone, X is a development inhibitor, and t is 0 or an integer of 1 or more. Time may have a timing adjusting function, and may be a group that serves as a coupler that reacts with another molecule of an oxidized product of a developing agent to release X, or a redox group. When t is 0, it means that X is directly bonded to the hydroquinone mother nucleus. When t is 2 or more, it means a combination of multiple Times (which may be different).

An example in which Time is a group having a timing adjusting function is given below.

(1) Group utilizing cleavage reaction of hemiacetal (US Pat. No. 4,146,396, JP-A-60-24)
Nos. 9148 and 60-249149) (2) A group that causes a cleavage reaction by utilizing an intramolecular nucleophilic substitution reaction (described in US Pat. No. 4,248,962) (3) Electron transfer along a conjugated system Group that causes cleavage reaction by utilizing reaction (described in US Pat. Nos. 4,409,323 and 4,421,845) (4) Group that utilizes cleavage reaction by hydrolysis of ester (described in West German Laid-Open Patent No. 2626315) ( 5) Group utilizing cleavage reaction of imino ketal (described in US Pat. No. 4,546,073)

Other groups having a timing adjusting function are described in British Patent No. 2096783 and JP-A Nos. 51-146828 and 57-56837. As Time, a combination of two or more of these groups may be used.

Time can function as a phenol type coupler or a 5-pyrazolone type coupler. When Time is a phenol type coupler, it bonds with the hydroquinone nucleus at the oxygen atom excluding the hydrogen atom of the hydroxyl group.
If Time is a 5-pyrazolone type coupler,
It binds to a hydroquinone nucleus at an oxygen atom obtained by removing a hydrogen atom from a hydroxyl group of hydroxypyrazole (tautomer of 5-pyrazolone). These function as a coupler after they are released from the hydroquinone mother nucleus, react with the oxidized form of the developing agent, and release X bonded to the coupling position.

Preferred examples of the case where Time is a coupler are shown below.

[0071]

[Chemical 17]

[0072]

[Chemical 18]

Wherein V ¹ and V ² are substituents; V
³ , V ⁴ , V ⁵ and V ⁶ are each a nitrogen atom or a methine group (which may have a substituent); V ⁷ is a substituent; x is an integer of 0 to 4; When x is 2 or more, a plurality of V ^7's may be different from each other, or a plurality of V ⁷ 's may combine to form a ring; V ⁸ is -C
O -, - SO ₂ -, is an oxygen atom or a substituted imino group; V ⁹ is a non-metallic atomic group necessary for forming a 5-membered to 8-membered ring -V ⁸ -N-C = C- together; V ¹⁰ is A hydrogen atom or a substituent; * is a bonding position to the hydroquinone mother nucleus; and ** is a bonding position to X.

A preferred example when Time is a redox group is shown by the following formula (R-1).

(R-1) *-P- (X = Y) _m -Q-A

In the formula, P and Q are each an oxygen atom or an imino group (which may have a substituent); n
At least one of X and Y is a methine group having -X as a substituent, and the other X and Y are a methine group (which may have a substituent) or a nitrogen atom;
n is an integer of 1 to 3; when n is 2 or 3, a plurality of X and Y may be different from each other; A is a hydrogen atom or a group capable of alkali removal; P, X,
Any two substituents of Y, Q and A may combine to form a ring (for example, (X = Y) ₂ forms a benzene ring or a pyridine ring); and * represents a hydroquinone nucleus Is the binding position to.

As the redox group represented by the formula (R-1),
A group represented by the following formula (R-2) or (R-3) is more preferable.

[0078]

[Chemical 19] In the formula, R ⁶⁴ is a substituent (examples of the substituent are the same as the examples of R ^{21 in} formula (Ib)); q is an integer of 0 to 3;
when q is 2 or 3, a plurality of R ⁶⁴ may be different from each other, a plurality of R ⁶⁴ also may be a substituent to form a ring adjacent carbon atoms; Hydroquinone * Is the position of attachment to the mother nucleus; and ** is the position of attachment to X.

X is a development inhibitor. Preferred examples of X include a compound having a mercapto group bonded to a heterocycle represented by the following formula (X-1) and the following formula (X-2).
And a heterocyclic compound capable of producing imino silver.

[0080]

[Chemical 20]

In the formula, Z ¹ is a non-metallic atomic group forming a monocyclic or condensed ring heterocycle (which may have a substituent); Z ² is a monocyclic or condensed ring together with a nitrogen atom. It is a non-metal atomic group that forms a heterocycle (which may have a substituent); and * is a bonding position to Time.

Examples of the hetero atom of the hetero ring formed by Z ¹ and Z ² include nitrogen, oxygen, sulfur and selenium. The heterocycle is preferably a 5-membered to 8-membered ring, and more preferably a 5-membered or 6-membered ring.

Examples of the heterocycle represented by Z ¹ include azoles (eg, tetrazole, 1,2,4-triazole, 1,2,3-triazole, 1,3,4-thiadiazole, 1,3,3). 4-oxadiazole, 1,3-thiazole, 1,3-oxazole, imidazole, benzothiazole, benzoxazole, benzimidazole, pyrrole, pyrazole, indazole), azaindenes (eg, tetrazaindene, ventazaindene, tria) The indene) and azines (eg pyrimidine, triazine, pyrazine, pyridazine) can be mentioned.

Examples of the heterocycle represented by Z ² include triazoles (eg, 1,2,4-triazole, benzotriazole, 1,2,3-triazole), indazole, benzimidazole, azaindenes (eg, Tetrazaindene, Ventazaindene) and tetrazole.

Examples of the substituent of the development inhibitor represented by formula (X-1) and formula (X-2) include R ⁷⁷ — and R ⁷⁸ O.
^{-, R 77 S-, R 77} OCO-, R 77 OSO 2 -, a halogen atom, a cyano group, a nitro _{^{group, R 77 SO 2 -, R}} 78 CO
-, R ⁷⁸ COO-, R ⁷⁷ SO ₂ N (R ⁷⁸ )-, R ⁷⁸ N
(R ⁷⁹ ) SO ₂ −, R ⁷⁸ N (R ⁷⁹ ) CO −, R ⁷⁷ C (R
⁷⁸ ) = N−, R ⁷⁷ N (R ⁷⁸ ) −, R ⁷⁸ CON (R ⁷⁹ ).
-, R ⁷⁷ OCON (R ⁷⁸ )-, R ⁷⁸ N (R ⁷⁹ ) CON
(R ⁸⁰⁾ - and R ⁷⁷ SO ₂ O- and the like.

In the examples of the above substituents, R ⁷⁷ is an aliphatic group, an aromatic group or a heterocyclic group; and R ⁷⁸ , R
⁷⁹ and R ⁸⁰ are each an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. R ⁷⁷ , R ⁷⁸ , R ^{79 in} one molecule
And when there are two or more R ⁸⁰ , these may be linked to form a ring (eg, a benzene ring).

Examples of the development inhibitor represented by the formula (X-1) include mercaptoazoles (eg, 1-phenyl-5).
-Mercaptotetrazole, 1-propyl-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), mercaptoazaindenes (Eg, 6-methyl-4-mercapto-
1,3,3a, 7-tetraazaindene, 4,6-dimethyl-2-mercapto-1,3,3a, 7-tetraazaindene) and mercaptopyrimidines (eg, 2-mercaptopyrimidine, 2-mercapto-). 4-methyl-6
-Hydroxypyrimidine).

Examples of the development inhibitor represented by the formula (X-2) include triazoles (eg 1,2,4-triazole, benzotriazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5- Bromobenzotriazole, 5-n-butylbenzotriazole,
5,6-butylbenzotriazole), indazoles (eg, indazole, 5-nitroindazole, 3-nitroindazole, 3-chloro-5-nitroindazole) and benzimidazoles (eg, 5-nitrobenzimidazole, 5, 6-dichlorobenzimidazole).

Further, X is represented by the formulas (Ia) and (Ib).
After leaving Time, it became a compound with a development inhibitory function, and then it reacted with the developer components to have no development inhibitory function, or changed to a compound with a significantly reduced development inhibitory function. Those that do (deactivating development inhibitors) are also included. Examples of the functional group that undergoes the above reaction include an ester group, a carbonyl group, an imino group, an immonium group, a Michael addition accepting group and an imide group.

Regarding the development inhibitor residue of the deactivating development inhibitor, US Pat. No. 4,477,563 and JP-A Nos. 60-218644, 60-221750 and 6 are cited.
0-233650 and 61-11743.

As the deactivating development inhibitor, a compound having an ester group is preferable. Examples of the deactivating development inhibitor include 1- (3-phenoxycarbonylphenyl) -5-
Mercaptotetrazole, 1- (4-phenoxycarbonylphenyl) -5-mercaptotetrazole, 1-
(3-maleinimidophenyl) -5-mercaptotetrazole, 5-phenoxycarbonylbenzotriazole, 5- (4-cyanophenoxycarbonyl) benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,3,4 -Thiadiazole, 5-
Nitro-3-phenoxycarbonyl imidazole, 5
-(2,3-Dichloropropyloxycarbonyl) benzotriazole, 1- (4-benzoyloxyphenyl) -5-mercaptotetrazole, 5- (2-methanesulfonylethoxycarbonyl) -2-mercaptobenzothiazole, 5-cinnamoyl Aminobenzotriazole, 1- (3-vinylcarbonylphenyl) -5-mercaptotetrazole, 5-succinimidomethylbenzotriazole, 2- {4-succinimidophenyl}
-5-mercapto-1,3,4-oxadiazole, 6
-Phenoxycarbonyl-2-mercaptobenzoxazole, 2- (1-methoxycarbonylethylthio)-
5-mercapto-1,3,4-thiadiazole, 2-butoxycarbonylmethoxycarbonylmethylthio-5-
Mercapto, 1,3,4-thiadiazole, 2- (N-
Hexylcarbamoylmethoxycarbonylmethylthio)
Mention may be made of -5-mercapto-1,3,4-thiadiazole and 5-butoxycarbonylmethoxycarbonylbenzotriazole.

As X, mercaptoazoles and benztriazoles are preferable. As the mercaptoazoles, mercaptotriazoles, 5-mercapto-1,3,4-thiadiazoles and 5-mercapto-1,3,4-oxadiazoles are more preferable. As X, 5-mercapto-1,3,4-thiadiazoles are particularly preferable.

In formulas (Ia) and (Ib), t is preferably 0, 1 or 2, and more preferably 0 or 1.

As the compound represented by the formula (Ia), a compound represented by the following formula (IA) is particularly preferable.

[0095]

[Chemical 21]

In the formula, M, R ¹² , R ¹⁴ , Time, X, A,
A ′ and t have the same definitions as in formula (Ia). In the above formula (IA), M is -N (R ¹⁵⁾ CO- or -
It is preferably OCO-. R ¹⁵ is represented by the formula (Ia)
Has the same definition as Further, t is preferably 0 or 1.

In the formula (Ib), L is -N (R ²⁸ )-
CO-L ² - is preferably. L ² is a divalent amino group, an ether bond, a thioether bond, an alkylene group, an imino bond, a sulfonyl group, a carbonyl group, an arylene group, a divalent heterocyclic group, and a group in which these are combined. R ²⁸ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. A hydrogen atom is preferred.
R ²⁸ may have a substituent.

As the compound represented by the formula (Ib), a compound represented by the following formula (IB) is particularly preferable.

[0099]

[Chemical formula 22]

In the formula, L ² has the above definition. R ²¹ ,
A, A ′, Time, X and t have the same definitions as in formula (Ib).

When M in the formula (Ia) is —CO—, a compound represented by the following formula (IC) or (ID) is particularly preferable.

[0102]

[Chemical formula 23]

[Chemical formula 24]

Wherein R ³⁴ and R ³⁵ are substituents;
n ′ is an integer of 2 or more; m is an integer of 1 to 5; when m is 2 or more, a plurality of R ^35's may be different from each other; and A, A ′, Time, X and t. Is the formula (I
It has the same definition as in a).

The examples of R ³⁴ and R ³⁵ are the same as the examples of R ¹² of the formula (Ia). Each group may further have a substituent. In formula (IC), the carbon number of R ³⁴ is preferably 5 to 30, and n ′ is preferably an integer of 2 to 5. In formula (ID), the carbon number of R ³⁵ is preferably 5 to 30.

Specific examples of the compound represented by formula (Ia) or (Ib) are shown below.

[0106]

[Chemical 25]

[0107]

[Chemical formula 26]

[0108]

[Chemical 27]

[0109]

[Chemical 28]

[0110]

[Chemical 29]

[0111]

[Chemical 30]

[0112]

[Chemical 31]

[0113]

[Chemical 32]

[0114]

[Chemical 33]

[0115]

[Chemical 34]

[0116]

[Chemical 35]

[0117]

[Chemical 36]

[0118]

[Chemical 37]

[0119]

[Chemical 38]

[0120]

[Chemical Formula 39]

[0121]

[Chemical 40]

[0122]

[Chemical 41]

[0123]

[Chemical 42]

[0124]

[Chemical 43]

[0125]

[Chemical 44]

[0126]

[Chemical formula 45]

[0127]

[Chemical formula 46]

[0128]

[Chemical 47]

[0129]

[Chemical 48]

[0130]

[Chemical 49]

[0131]

[Chemical 50]

[0132]

[Chemical 51]

[0133]

[Chemical 52]

[0134]

[Chemical 53]

[0135]

[Chemical 54]

[0136]

[Chemical 55]

[0137]

[Chemical 56]

[0138]

[Chemical 57]

[0139]

[Chemical 58]

[0140]

[Chemical 59]

[0141]

[Chemical 60]

[0142]

[Chemical formula 61]

[0143]

[Chemical formula 62]

[0144]

[Chemical formula 63]

[0145]

[Chemical 64]

[0146]

[Chemical 65]

[0147]

[Chemical formula 66]

[0148]

[Chemical formula 67]

[0149]

[Chemical 68]

[0150]

[Chemical 69]

[0151]

[Chemical 70]

[0152]

[Chemical 71]

[0153]

[Chemical 72]

[0154]

[Chemical formula 73]

[0155]

[Chemical 74]

[0156]

[Chemical 75]

[0157]

[Chemical 76]

[0158]

[Chemical 77]

[0159]

[Chemical 78]

[0160]

[Chemical 79]

[0161]

[Chemical 80]

[0162]

[Chemical 81]

[0163]

[Chemical formula 82]

[0164]

[Chemical 83]

[0165]

[Chemical 84]

[0166]

[Chemical 85]

[0167]

[Chemical 86]

[0168]

[Chemical 87]

[0169]

[Chemical 88]

[0170]

[Chemical 89]

[0171]

[Chemical 90]

[0172]

[Chemical Formula 91]

[0173]

[Chemical Formula 92]

[0174]

[Chemical formula 93]

[0175]

[Chemical 94]

[0176]

[Chemical 95]

[0177]

[Chemical 96]

[0178]

[Chemical 97]

[0179]

[Chemical 98]

[0180]

[Chemical 99]

[0181]

[Chemical 100]

[0182]

[Chemical 101]

[0183]

[Chemical 102]

[0184]

[Chemical 103]

[0185]

[Chemical 104]

[0186]

[Chemical 105]

[0187]

[Chemical formula 106]

[0188]

[Chemical formula 107]

[0189]

[Chemical 108]

[0190]

[Chemical 109]

[0191]

[Chemical 110]

[0192]

[Chemical 111]

[0193]

[Chemical 112]

[0194]

[Chemical 113]

[0195]

[Chemical 114]

[0196]

[Chemical 115]

[0197]

[Chemical formula 116]

[0198]

[Chemical 117]

[0199]

[Chemical 118]

[0200]

[Chemical formula 119]

[0201]

[Chemical 120]

[0202]

[Chemical 121]

[0203]

[Chemical formula 122]

[0204]

[Chemical 123]

[0205]

[Chemical formula 124]

[0206]

[Chemical 125]

[0207]

[Chemical formula 126]

[0208]

[Chemical 127]

[0209]

[Chemical 128]

[0210]

[Chemical formula 129]

[0211]

[Chemical 130]

[0212]

[Chemical 131]

[0213]

[Chemical 132]

[0214]

[Chemical 133]

[0215]

[Chemical 134]

[0216]

[Chemical 135]

[0217]

[Chemical 136]

The above compounds can be easily synthesized according to the synthetic examples described below.

[Synthesis Example 1]

[Chemical 137]

1) Synthesis of 1-A 50 g of 2,5-dimethoxyaniline and 4 g of acetonitrile
00 ml and pyridine 26 ml were added, and phenyl chloroformate 46 g was further added dropwise, followed by stirring at room temperature for 3 hours. After completion of the reaction, aqueous hydrochloric acid solution was added to the reaction mixture, extracted with ethyl acetate, washed with water, dried and concentrated to give compound (1-
A) 50 g was obtained. 2) 25 g of 1-B synthetic compound (1-A), 300 ml of acetonitrile,
22 g of 1-hexadecylamine was added, and the mixture was heated under reflux for 5 hours. After completion of the reaction, an aqueous hydrochloric acid solution was added to the reaction mixture, and the precipitated crystals were separated by filtration, washed with acetonitrile and dried to obtain 35 g of compound (1-B). 3) 1-C synthetic compound (1-B) 16g to 47% hydrobromic acid 250ml
Was added and the mixture was heated under reflux for 2 hours. After completion of the reaction, water was added to the reaction mixture, and the precipitated crystals were separated by filtration, washed with acetonitrile and dried to obtain 11 g of compound (1-C). 4) 1-D synthetic compound (1-C) 1.5 g ethanol 50 ml, 2,
0.9 g of 3-dichloro-5,6-dicyano-1,4-benzoquinone was added, and the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, the precipitated crystals were filtered out and dried to give compound (1-D)
1.3 g of 5) Ia-12 synthetic compound (1-D) (1.3 g) was added to ethyl acetate (150 ml), 2-mercapto-5-methylthio-1,3,4-thiadiazole (0.6 g) and p-toluene. 0.1 g of sulfonic acid monohydrate was added, and the mixture was stirred at 50 ° C. for 1 hour. After completion of the reaction, the precipitated insoluble matter was filtered off, and the dew liquid was concentrated. The residue was crystallized from acetonitrile, filtered and dried to obtain 0.9 g of compound (Ia-12). (Melting point: 131.1-
133.2 ° C)

[Synthesis Example 2]

[Chemical 138]

1) Synthesis of 2-A 31 g of 2,5-dimethoxyaniline and 17 ml of pyridine
Was added to 350 ml of acetonitrile, and a solution of 20 ml of methylmalonyl chloride in 50 ml of acetonitrile was added dropwise thereto. After stirring at room temperature for 5 hours, water was added and the mixture was extracted with ethyl acetate, washed with water, dried, and concentrated. The residue was crystallized with a mixed solvent of ethyl acetate and n-hexane to obtain 31 g of compound (2-A). 2) To 5.0 g of the compound (2-A) of 2-B, 50 ml of methanol was added, and 3.8 g of 28% sodium methoxide methanol solution was added. After stirring at room temperature for 10 minutes, 4.9 g of 2-dodecyl bromide was added dropwise. The reaction mixture at 45 ° C.
After stirring for 3 hours and allowing to cool, the mixture was poured into water, and the precipitated crystals were separated by filtration, washed with water and dried. This is recrystallized with methanol,
1.9 g of compound (2-B) was obtained. 3) To 1.8 g of the synthetic compound (2-B) of 2-C, 30 ml of a 5% aqueous sodium hydroxide solution and 10 ml of methanol were added, and the mixture was heated at 70 to 75 ° C.
The mixture was stirred for 2.5 hours. After allowing to cool, the reaction mixture was poured into a hydrochloric acid aqueous solution, and the precipitated crystals were separated by filtration, washed with water, and dried to obtain 1.7 g of compound (2-C). 4) 15 ml of phosphorus oxychloride was added to 3.0 g of the synthetic compound (2-C) of 2-D, and the mixture was heated under reflux for 1 hour. After allowing to cool, the reaction mixture was gradually poured into water, and the precipitated crystals were separated by filtration, washed with water and dried. This was recrystallized from methanol to give compound (2-D)
2.0 g was obtained. 5) 2-E synthetic compound (2-D) 2.5 g to isopropyl alcohol 3
After adding 0 ml and 10 ml of water and further adding 5 ml of concentrated sulfuric acid, the mixture was heated under reflux for 8.5 hours. After allowing to cool, the reaction mixture was poured into water, and the precipitated crystals were separated by filtration, washed with water, and dried to obtain 2.0 g of compound (2-E). 6) Synthetic compound (2-E) of 2-F, 3.5 g of isopropyl alcohol 1
10 ml, a solution prepared by adding 10 ml of water to 0.3 g of sodium hydroxide was added, and 1.0 g of 10% palladium carbon was added.
After adding hydrogen, the mixture was stirred for 7.5 hours under the conditions of 20 Kg / cm ^{2 of} hydrogen and 80 to 85 ° C. After allowing to cool, the catalyst was filtered off and the filtrate was concentrated. Water was poured into the residue, and the precipitated crystals were filtered off,
It was washed with water and dried to obtain 2.7 g of compound (2-F). 7) 47 g of hydrobromic acid 47% to 2.6 g of the compound (2-F) of 2-G
Was added and the mixture was heated under reflux for 3.5 hours. After cooling, water was added and the mixture was extracted with ethyl acetate, washed with water, dried and concentrated. The residue was crystallized from acetonitrile to give compound (2-G) 2.
1 g was obtained. 8) To 2.0 g of the compound (2-G) of 2-H and 6.0 g of manganese dioxide, 150 ml of ethyl acetate was added, and the mixture was stirred at room temperature for 1.5 hours. The insoluble material was filtered off, the filtrate was concentrated, and the compound (2-
H) 1.9 g was obtained. 9) 50 g of methylene chloride was added to 1.8 g of the synthetic compound (2-H) of Ib-1, and 2-mercapto-5-methylthio-1,3,3 was added thereto.
After adding 0.9 g of 4-thiadiazole and 0.1 g of p-toluenesulfonic acid monohydrate, the mixture was stirred at room temperature for 1 hour. The precipitated crystals are separated by filtration and washed with acetonitrile,
It was dried to obtain 1.2 g of compound (Ib-1). (Melting point:
111.3-111.9 ° C)

The compound having the formula (Ia) or (Ib) described above may be added to either the silver halide emulsion layer or the non-photosensitive layer. It can also be added to both layers. The addition amount is 0.001 mmol / m ^{2 to} 0.2
It is preferably millimole / m ² , and more preferably 0.005 millimole / m ^{2 to} 0.1 millimole / m ² .

In the method of the present invention, the color developing solution contains bromide in an amount of 0.005 to 0.1 mol / liter. The color developer more preferably contains 0.008 to 0.05 mol / liter of bromide, and particularly preferably 0.01 to 0.03 mol / liter. The bromide is preferably an alkali metal bromide, with potassium bromide or potassium bromide being particularly preferred. Details of the color developing solution will be described later.

The present invention is particularly effective when the color developer contains a large amount of components of the prebath (eg, black-and-white developing agent, chemical fogging agent). For example, when 1 liter of color developer contains 3 ml or more, especially 5 ml or more of black-and-white developer, or when it contains 3 × 10 ^-4 mol or more, especially 5 × 10 ^-4 mol or more of dihydroxybenzenes per liter. In addition, a remarkable effect can be obtained.

Next, the main processing steps of the color image forming method of the present invention will be described in more detail.

[Black and White Development Processing] The black and white developing solution used in the present invention contains a developing agent. Examples of developing agents include dihydroxybenzenes (eg, hydroquinone, hydroquinone monosulfonate), 3-pyrazolidones (eg, 1-
Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone), aminophenols (eg, N-methyl-p-aminophenol), ascorbic acid and 1,2,3,4 -A fused heterocyclic compound of a tetrahydroquinoline ring and an indole ring (described in U.S. Pat. No. 4,067,872) can be mentioned. As the developing agent, two or more kinds of compounds may be used in combination. The amount of developing agent used is 1 × per liter of black and white developer.
It is 10 ^{−5 to} 1 mol. In black and white developers, in addition to developing agents, preservatives (eg, sulfite, bisulfite), silver halide solvents, buffers (eg, carbonate, boric acid, borate, alkanolamine), alkaline agents (Eg, hydroxides, carbonates), solubilizing agents (eg, polyethylene glycols, their esters), pH adjusters (eg, organic acids such as acetic acid),
Sensitizer (eg, quaternary ammonium salt), development accelerator (eg,
Thioether compound), surfactant, defoaming agent, hardener,
A viscosity imparting agent, an antifoggant, a swelling inhibitor (eg, sodium sulfate, potassium sulfate), a chelating agent and the like can be added. The sulfite used as the preservative is
It also acts as a silver halide solvent. Examples of silver halide solvents other than sulfite include potassium thiocyanate,
Mention may be made of sodium thiocyanate, potassium sulfite, sodium sulfite, potassium disulfite, sodium disulfite, potassium thiosulfate, sodium thiosulfate and 2-methylimidazole. The amount of the silver halide solvent used, as thiocyanate ion, is preferably 0.005 to 0.02 mol, and more preferably 0.01 to 0.015 mol, per liter of the black and white developer. The sulfite ion is preferably used in an amount of 0.05 to 1 mol per liter of black and white developer,
It is more preferable to use 0.1 to 0.5 mol.
Examples of the antifoggant include alkali metal salts of halogen (eg, potassium bromide, sodium bromide, potassium iodide), nitrogen-containing heterocyclic compounds (eg, benzotriazole, 6-nitrobenzimidazole, 5-nitro). Isoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, hydroxyazaindolizine), mercapto-substituted heterocyclic compound ( (Eg, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole)
And mercapto-substituted aromatic compounds (eg, thiosalicylic acid). Alkali metal salts of bromine are especially preferred. The antifoggant may be added to the photographic material. In that case, the antifoggant is eluted from the photographic material in the black-and-white developing process and accumulated in the black-and-white developing solution. The amount of antifoggant used is 0.00 per 1 liter of black and white developer.
The amount is preferably 1 to 0.1 mol, more preferably 0.01 to 0.05 mol. Examples of the chelating agent include aminopolycarboxylic acids (eg, ethylenediaminetetraacetic acid, hydroxyethyliminodiacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid) and phosphonic acids (eg, nitrilo-N). , N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenephosphonic acid, 1-hydroxyethylidene-1,1
-Diphosphonic acid). As the chelating agent, two or more kinds of compounds may be used in combination. The amount of chelating agent used is 0.1 g to 2 per liter of black and white developer.
It is preferably 0 g, more preferably 0.5 g to 10 g. The pH value of the black and white developer is 8.5.
Is preferably from 1 to 11.5, and from 9.0 to 10.
More preferably, it is 5. The replenishing amount of the black-and-white developing solution is preferably 50 ml to 500 ml, and more preferably 50 ml to 330 ml per 1 m ² of the photographic material. The processing time of the black and white development step is preferably 20 seconds to 3 minutes, and more preferably 25 seconds to 75 seconds. The treatment temperature is preferably 30 ° C to 50 ° C, more preferably 35 ° C to 45 ° C. In the black and white development process, a water washing process is performed after the black and white development process. In the water washing step, it is preferable to use a multi-stage countercurrent method with two or more tanks in order to reduce the replenishment amount. The replenishment rate may be reduced to the level of other treatment baths (in this case called the rinse bath). The replenishment amount of washing water is preferably 3 to 20 liters per 1 m ² of the photographic material. In the case of the rinse bath, the replenishing amount is preferably 50 ml to 2 liters per 1 m ² of the photographic material, and more preferably 100 ml to 500 ml. If necessary, an oxidizing agent, a chelating agent, a buffering agent, a bactericidal agent or the like can be added to the treatment liquid of the rinse bath.

[Reversal Processing] In the color image forming method of the present invention, the reversal processing is performed after the black and white development processing. The reversal process includes a chemical fogging process or a reversal exposure process. The reverse exposure step is preferred. In the case of chemical fogging process, a fogging agent such as tin ion complex salt is used. The reversal process and the color development process may be performed in the same step by adding a fogging agent to the color developing solution described later. In the case of the reversal exposure process, the photographic light-sensitive material is entirely exposed.

[Color Development Processing] The color developing solution is usually an alkaline aqueous solution of an aromatic primary amine type color developing agent. A p-phenylenediamine compound is preferable as the developing agent. Examples of p-phenylenediamine compounds include 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl- Four
-Amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochlorides, phosphates, p-toluenesulfonate,
Mention may be made of tetraphenyl borate and p- (t-octyl) benzene sulfonate. The developing agent is
It is preferable to use 1.0 g to 15 g, and more preferably 3.0 g to 8.0 g, per liter of color developing solution. In addition to developing agents, color developers include buffers (eg, alkali metal carbonates, borates and phosphates), preservatives (eg, hydroxylamine, diethylhydroxylamine, triethanolamine, catechol- 3,5-disulfonate, sulfite, bisulfite), organic solvent (eg, diethylene glycol, triethylene glycol), dye-forming coupler, competitive coupler (eg, citrazinic acid, J acid, H acid), nucleating agent (Eg, sodium boron halide), auxiliary developing agent (eg, 1-phenyl-3-pyrazolidone), viscosity imparting agent, development accelerator, antifoggant, chelating agent and the like can be added. Examples of the antifoggant and the chelating agent are the same as the examples of the additives of the black and white developing solution described above. Examples of the development accelerator include benzyl alcohol, pyridinium compounds (Japanese Patent Publication No. 44-9503, and U.S. Pat. No. 264860).
No. 4 and No. 3171247), cationic dyes (eg, phenosafranine), nitrates (eg, thallium nitrate, potassium nitrate), polyethylene glycol and its derivatives (JP-B-44-9304, and US Pat. No. 2,533,990). No. 2531832, No. 2
No. 57127 and No. 2950970), polythioethers and thioether compounds (described in US Pat. No. 3,012,242). Thioether compounds are particularly preferred. The thioether compound is preferably used in an amount of 0.1 to 10.0 g per liter of the color developing solution. The pH value of the color developing solution is preferably 9 or more, and 9.5 to 1
2.0 is more preferable, and 10.0 to 1
Particularly preferably, it is 1.5. The replenishing amount of the color developing solution is preferably 50 ml to 500 ml, and more preferably 50 ml to 100 ml per 1 m ² of the photographic material. Processing temperature of color development process is 30 ℃
To 50 ° C. is preferable, and 31 ° C. to 45 ° C. is more preferable.

[Desilvering Treatment] The desilvering treatment comprises a preparation step, a water washing step, a bleaching step, a fixing step, a bleach-fixing step, a water washing alternative stabilizing step and the like. As a method of replenishing the treatment liquid in each step, the replenisher in each bath can be individually replenished. When the bleach-fixing treatment is carried out after the bleaching treatment, the overflow solution of the bleaching bath may be introduced into the bleach-fixing bath, and the bleach-fixing bath may be supplemented with only the fixing solution.

As a bleaching agent used in the bleaching step or the bleach-fixing step, aminopolycarboxylic acid iron (III) complex salt is typical. Examples of preferred bleaching agents are ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic acid diammonium salt, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, cyclohexanediaminetetraacetic acid disodium salt, iminodiacetic acid and 1,3- Diaminopropane tetraacetic acid may be mentioned. The aminopolycarboxylic acid iron (III) complex salt may be formed by adding the iron (III) salt and the aminopolycarboxylic acid to the treatment liquid to form the iron (III) complex salt in the treatment liquid. Two or more kinds of aminopolycarboxylic acids may be used in combination. In addition, the aminopolycarboxylic acid may be used in an excessive amount (as long as the iron (III) complex salt is formed).
In addition to the iron (III) complex salt, a metal ion complex salt other than iron, such as cobalt or copper, may be added to the bleaching solution or the bleach-fixing solution. The amount of bleach used per liter of bleaching solution is 0.1
The amount is preferably 1 to 1 mol, more preferably 0.2 to 0.5 mol. PH of bleaching solution
Is preferably 4.0 to 8.0, and more preferably 5.0 to 6.5. The amount of the bleaching agent used per liter of the bleach-fixing solution is 0.05 mol to 0.5 mol.
It is preferably molar, and more preferably 0.1 to 0.3 mol. The pH of the bleach-fixing solution is preferably 5 to 8, and more preferably 6 to 7.5. Bleaching accelerators can be added to the bleaching bath, the bleach-fixing bath or the conditioning bath. Examples of bleaching accelerators include mercapto compounds (JP-A-53-141623).
JP-B No. 3893858 and U.S. Pat. No. 3,893,858 and British Patent No. 1138842), compounds having a disulfide bond (described in JP-A-53-95630), thiazolidine derivatives (described in JP-B-53-9854), and isothio. Urea derivative (JP-A-53-9492)
7), thiourea derivative (Japanese Patent Publication No. 45-850).
6 and 49-26586), thioamide compounds (described in JP-A-49-42349), dithiocarbamates (described in JP-A-55-26506) and alkylmercapto compounds (eg, trithio). Glycerin, α, α′-thiodipropionic acid, δ-mercaptobutyric acid) can be mentioned. The alkylmercapto compound may have a substituent such as a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group (which may further have a substituent such as an alkyl group and an acetoxyalkyl group). The amount of bleaching accelerator used depends on the type of photographic material,
It is determined in consideration of processing temperature and processing time. When a mercapto compound, a compound having a disulfide bond, a thiazolidine derivative or an isothiourea derivative is used as a bleaching accelerator, it is 10 ^{−5 to} 10 per liter of the processing solution.
^-1 mol is preferably used, and 10 ^{-4 to} 5 × 10 ^-2
More preferably, it is used in moles. In addition to the bleaching agent and the bleaching accelerator, a rehalogenating agent, an inorganic acid having a pH buffering ability, an organic acid or a salt thereof can be added to the bleaching solution. Examples of the rehalogenating agent include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) and chloride (eg, potassium chloride, sodium chloride, ammonium chloride). Examples of acids or salts having pH buffering ability include nitrates (eg, sodium nitrate, ammonium nitrate), boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, Mention may be made of citric acid, sodium citrate and tartaric acid.

Examples of the fixing agent used in the fixing step or the bleach-fixing step include thiosulfates (eg, sodium thiosulfate, ammonium thiosulfate), thiocyanates (eg, sodium thiocyanate, ammonium thiocyanate, potassium thiocyanate). , Thiourea and thioethers. The amount of the fixing agent used per liter of the bleach-fixing solution is preferably 0.3 mol to 3 mol, more preferably 0.5 mol to 2 mol. The amount of the fixing agent used per 1 liter of the fixer is 0.5
It is preferably from 4 to 4 mol, more preferably from 1 to 3 mol. The pH of the fixing solution is preferably 6 to 10, and more preferably 7 to 9. Known additives such as sulfites, bisulfites, buffers, chelating agents, and sulfinic acids may be added to the fixing solution or the bleach-fixing solution. Further, an ammonium halide (eg, ammonium bromide) or an alkali metal salt of halogen (eg, sodium bromide, sodium iodide) may be added to the fixing solution or the bleach-fixing solution. When the fixing solution or the bleach-fixing solution is diluted with the overflow solution of the bleaching bath, it is preferable that the respective components of the fixing solution or the bleach-fixing solution have relatively high concentrations. Considering the dilution with the overflow liquid, the amount of the discharged liquid can be reduced and the burden of the recovery process can be reduced. The replenishing amount of bleaching solution, fixing solution and bleach-fixing solution is 3 per 1 m ^{2 of} photographic material.
0 ml to 900 ml is preferred, 50 ml
It is more preferable that the volume is from 150 to 150 ml.

In the desilvering process, finally, a water washing process or a water washing alternative stabilizing process is carried out. If necessary, known additives can be added to the washing water used in the washing step.
Examples of additives include chelating agents (eg, inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid), bactericides, fungicides,
Mention may be made of hardeners and surfactants. The water washing step may use two or more tanks. Further, the washing water may be saved by multi-stage countercurrent washing (for example, 2 to 9 steps). The stabilizing solution used in the washing substitute stabilizing step has a function of stabilizing the dye image. Examples of stabilizing solutions include
Examples thereof include a liquid having a buffering capacity of pH 3 to 6 and a liquid containing an aldehyde (eg, formaldehyde). If necessary, a chelating agent, a bactericidal agent, a fungicide, a hardener, a surfactant and the like can be added to the stabilizing solution. Two or more tanks may be used in the washing and washing stabilizing process. The stabilizing liquid may be saved by multi-stage countercurrent water washing (for example, 2 to 9 stages). A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, a nitrogen stirring device, an air stirring device, etc. may be provided in the treatment bath of each step as described above, if necessary. .

The color photographic material used in the present invention will be described below. The color photographic material has a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler and a silver halide emulsion layer containing a cyan coupler on a support. The photosensitive wavelengths of the silver halide emulsion layers are different from each other. The emulsion layer is usually sensitive to visible light, specifically blue light, green light and red light. In conventional color photographic materials, the blue-sensitive silver halide emulsion layer contains a yellow coupler, the green-sensitive silver halide emulsion layer contains a magenta coupler, and the red-sensitive silver halide emulsion layer contains a cyan coupler. The arrangement of silver halide emulsion layers is generally in the order of a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer from the support side. Of course, the emulsion layer may have photosensitivity outside the visible region. Further, combinations of the photosensitivity of the emulsion layers and couplers other than the above, and arrangements of the photosensitive layers other than the above are also possible. Further, each emulsion layer may have a two-layer structure of a high sensitivity emulsion layer and a low sensitivity emulsion layer. In a normal color photographic material, layers having various functions (eg, antihalation layer, intermediate layer, ultraviolet absorbing layer, protective layer) are provided in addition to the silver halide emulsion layer.

The silver halide emulsion will be described below. Preferred silver halides include silver iodobromide, silver iodochloride and silver iodochlorobromide. The silver iodide contained in the silver halide is preferably 30 mol% or less. Silver iodobromide or silver iodochlorobromide containing 0.1 to 5.0 mol% (average) of silver iodide and 0 to 70.0 mol% (average) of silver chloride is particularly preferable. The grain size of silver halide may be 0.2 μm or less, or relatively large grains of about 10 μm. However, the silver halide emulsion layer closest to the support preferably has a small grain size (for example, 0.1 to 0.4 μm in number average, preferably 0.1 to 0.3 μm). Since the development of the silver halide emulsion layer on the support side is delayed, the reaction can be accelerated by using a silver halide emulsion having a small grain size. In the present specification, the grain size of silver halide is defined as the diameter when the projected image of the grain is converted into a circle having the same area. The silver halide emulsion preferably contains 70% by weight or more of a monodisperse emulsion having a silver halide grain size dispersion coefficient of 0.20 or less. It is particularly preferred that all silver halide emulsions used in the present invention are monodisperse emulsions having a dispersion coefficient of 0.20 or less. The monodisperse silver halide emulsions are described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 14,137,948. The silver halide grains are regular crystals such as cubes, octahedra and tetrahedra. Those having an irregular crystal system such as spheres, slabs, those having crystal defects such as twin planes,
Alternatively, any of these composite forms may be used. The tabular grain usually means a grain having an aspect ratio of 5 or more. For tabular grains, see Gatov, Photographic
Science and Engineering (Gutoff, Phot
ographic Science and Engineering), Volume 14, 24
8 to 257 (1970), U.S. Pat. No. 4,434,226.
No. 4414310, No. 4433048, No. 44
39520 and British Patent 2121157. The crystal structure of the silver halide grains may have different halogen compositions inside and outside. Further, the particles may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining. A compound other than silver halide such as silver rhodan and lead oxide may be bonded. Further, a mixture of particles having various crystal forms may be used. The coating amount of the silver halide emulsion is preferably 0.1 g / m ² to 1.5 g / m ^{2 in} terms of silver, and more preferably 0.1 g / m ^{2 to} 1.0 g / m ^2. . The silver halide emulsion is usually subjected to physical ripening, chemical ripening and spectral sensitization during preparation. The method of preparing a silver halide emulsion is described in Research Disclosure No. 17643 (December 1978).
Mon) 22 ~ 23, "I. Emulsion preparation and t
ypes ”. The silver halide emulsion can be prepared by a controlled double jet method or a method using a silver halide solvent at the time of grain formation. The controlled double jet method is a soluble silver salt and a soluble silver salt. This is a method in which the pAg in the liquid phase in which silver halide is formed is kept constant by using the simultaneous mixing method in the reaction of the halogen salt. It is possible to prepare a (monodisperse) silver halide emulsion having various grain size distributions.Examples of the above silver halide solvent include ammonia, rhodan potassium, rhodan ammonium, and thioether compounds (US Pat.
2711157, 3574628, and 370413.
No. 0, No. 4,297,439 and No. 4,276,374), and tetra-substituted thiourea compounds (JP-A-53-8).
2408 and 55-77737).
Thione compound (Japanese Patent Application Laid-Open Nos. 53-144319 and 53-43)
(No. 82408 and No. 55-77737)
And amine compounds (described in JP-A No. 54-100717). The silver halide solvent is preferably used in an amount of 10 ^{−5 to} 2.5 × 10 ⁻² mol per mol of silver halide. The silver halide solvent is particularly preferably added during the production of silver halide grain precipitates or during physical ripening in the production of silver halide emulsions.

For the purpose of improving the photographic characteristics of the color photographic material, a heavy metal can be added during grain formation or during physical ripening of silver halide grains (preferably silver halide grains sharing the low density side). Examples of heavy metals are rhodium, cadmium, lead, thallium, iridium, copper,
Mention may be made of iron and zinc. Rhodium, cadmium, thallium and lead are preferred. Heavy metals may be added as metal salts. You may use together two or more types of heavy metals. The amount of heavy metal used is 10 relative to silver halide.
^-10 mol to 10 ^-2 mol, preferably 10 ^-8
More preferably, it is from 10 to ³ mol. Phenolic compounds may be added to the silver halide emulsion layers for the purpose of improving the photographic properties of color photographic materials. As the phenol compound, a hydroquinone compound is particularly preferable. Regarding the hydroquinone compound, JP-A-55-4
No. 3521, No. 56-109344, No. 57-222.
37 and 60-172040, and U.S. Pat. No. 2,701,197. The phenolic compound can be added to the photographic material as an aqueous alkaline solution. Alternatively, it may be dissolved in a high boiling point oil and added to the photographic material as an emulsion. 10 phenolic compounds
It is preferable to use a coating amount of ^{-4 to} 1 g / m ² .

The photographic material used in the present invention contains a yellow coupler, a magenta coupler and a cyan coupler for forming a color image. Various compounds are already known for these couplers. In the present invention, the type of coupler is not particularly limited. The yellow coupler is preferably a pivaloyl-based or pyrazoloallol-based compound. For yellow couplers, Japanese Patent Publication No. 58-107
39, and US Pat. Nos. 3,933,501 and 39.
73968, 4022620, 4248961
No. 4314023, No. 4326024, No. 44
01752, 4511649 and British Patent 1425
020, 1476760 and European Patent 2494.
No. 73A is described in each specification. Magenta coupler
5-Pyrazolone and pyrazoloazole compounds are preferred. For the magenta coupler, see JP-A-55-1.
18034, 60-35552, 60-357.
No. 30, No. 60-43659, No. 60-185951
And 61-72238, U.S. Pat. No. 306
1432, 3725067 and 4310619.
No. 4351897, No. 4500630, No. 45
No. 40654, No. 4556630, and European Patent 7363.
6, International Publication W088 / 04795, each specification, and Research Disclosure No. 24220 (19)
June 1984) and No. 24230 (6 June 1984)
Month). The cyan coupler is preferably a phenol type compound or a naphthol type compound. Regarding cyan couplers, JP-A-61-42658 and US Pat. Nos. 2,369,929, 2,772,162 and 2801.
No. 171, No. 2895826, No. 3446622,
No. 3758308, No. 3772002, and No. 4052.
No. 212, No. 4146396, No. 4228233,
No. 4254212, No. 4296199, No. 4296
No. 200, No. 4327173, No. 4333999,
No. 4334011, No. 4427767, No. 4451
No. 559, No. 4690888, No. 4775616,
West German Patent Publication 3329729, European Patent 121365
No. A and No. 249453A are described in each specification.
As another coupler which can be added to a photographic material, a colored coupler for correcting unnecessary absorption of a coloring dye (Japanese Patent Publication No. 57-39413, U.S. Pat.
04909, 4138258, 4163670.
And British Patent No. 1146368, and Research Disclosure No. 17643 VII-G
Section), a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling (US Pat. No. 47.
No. 74181), a coupler having as a leaving group a dye precursor that reacts with a developing agent to form a dye (described in U.S. Pat. No. 4,777,120), and a coupler in which a colored dye has an appropriate diffusibility (U.S. Pat.
37, British Patent 2125570, West German Patent Publication 32
34533 and EP 96570), polymerized dye forming couplers (US Pat.
No. 451820, No. 4080211, No. 436728
No. 2, No. 4,409,320, No. 4,576,910 and British Patent No. 2,102,173), and a DIR coupler releasing a development inhibitor upon coupling (JP-A-57-151944, JP-A-57-154234, JP-A-57-154234). 60-184248, 63-37346 and 63-37350, U.S. Pat. Nos. 4,248,962 and 4782012, and Research.
(Disclosure magazine 17643, Item VII-F), couplers that release a nucleating agent or a development accelerator in an image during development (JP-A-59-157638 and JP-A-5-157638).
No. 9-170840 and British Patent 20971
40 and 2131188). Competitive couplers (US Pat. No. 4,130,427), multi-equivalent couplers (US Pat. Nos. 4,283,472 and 4,338).
No. 393 and No. 4310618 each description), D
IR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing compound or DIR
Redox-releasing redox compound (JP-A-60-185)
950 and 62-24252), a coupler that releases a dye that recolors after withdrawal (EP 173).
302A and 313308A each specification description),
Bleach accelerator releasing coupler (Japanese Patent Laid-Open No. 61-201247, and Research Disclosure 1144)
9 and 24241), a ligand releasing coupler (described in US Pat. No. 4,553,477), and a leuco dye releasing coupler (described in JP-A-63-75747). The coupler used in the present invention is preferably added to the photographic material using a high boiling solvent (preferably having a boiling point of 175 ° C. or higher).
Specifically, the coupler is dissolved in a high boiling point solvent, and the solution is emulsified in an aqueous liquid such as a silver halide emulsion. Examples of the high boiling point solvent include phthalic acid esters (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4
-Di-t-amylphenyl) phthalate, bis (2,4)
-Di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tri Cyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate), benzoates (eg, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl) -P-hydroxybenzoate), amides (eg, N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), Call acids (e.g., isostearyl alcohol), phenols (e.g., 2,4-di -tert-
Amylphenol), aliphatic carboxylic acid esters (eg, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg, N, N-dibutyl) -2-Butoxy-5
-Tert-octylaniline) and hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). As an auxiliary solvent for high boiling point solvents, the boiling point is 30 ° C or higher, preferably 50 ° C to 160 ° C.
You may use the organic solvent of. Examples of co-solvents include
Mention may be made of ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

Other additives usable in photographic materials are described in Research Disclosure Nos. 17643 and 18716. The relevant parts are summarized below. ──────────────────────────────────── Additive RD17643 RD18716 ─────────── ────────────────────────── Chemical sensitizer page 23 648 right column Sensitivity enhancer page 648 right column Spectral sensitizer, strong color Sensitizer, page 23-24, page 648, right column-page 649, right column Whitening agent, page 24, antifoggant and stabilizer, pages 24-25, page 649, right column-light absorber, filter dye, pages 25-26, page 649, right column Page 650 right column and ultraviolet absorber stain inhibitor page 25 right column page 650 left column to right column dye image stabilizer page 25 hardener 26 page 651 left column binder 26 page 651 left column plasticizer, lubricant Page 27, page 650, right column, coating aids and surfactants, pages 26-27, page 650, right column, antistatic agent Page 27 Page 650 Right column ──────────────────────────────────── In addition, In order to prevent deterioration, a compound which reacts with formaldehyde to be immobilized may be added to the photographic material. Such compounds are disclosed in US Pat. Nos. 4411987 and 44355.
No. 03 There is a description in each specification. Hydroquinones releasing a development inhibiting compound (described in JP-A-64-546 and U.S. Pat. Nos. 3,379,529 and 3639417) or naphthoquinones releasing a development inhibiting compound (Research Disclosure 1826).
No. 4 (described in June 1979) may be added to the photographic material. Preservatives or fungicides can also be added to the photographic materials. Examples of preservatives and fungicides are 1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5.
Mention may be made of dimethylphenol, 2-phenoxyethanol and 2- (4-thiazolyl) benzimidazole. Preservatives and antifungal agents are described in JP-A Nos. 63-257747, 62-272248 and 1-80941.

The support used for the photographic material is not particularly limited. Regarding the support, Research Disclosure No. 17643, page 28 and No. 18716, 64.
It is described in the right column on page 7 to the left column on page 648. In the color photographic material used in the present invention, the total thickness of all hydrophilic colloid layers on the side having the silver halide emulsion layer is preferably 28 μm or less, more preferably 20 μm or less, and 12 μm or less. It is particularly preferable that
The film swelling rate (T _1/2 ) is preferably 30 seconds or less, more preferably 20 seconds or less. The film swelling speed is defined as the time required to reach 90% of the maximum swelling film thickness reached when the film is treated with a color developer at 30 ° C. for 3 minutes and 15 seconds, and the saturation film thickness is reached. . The film thickness can be measured using a selometer (swelling meter). For the film swelling rate, see A. Green et al.
et al), Photographic Science and
Engineering (Photogr. Sci. Eng.), Volume 19, 2
No. 9, pp. 124-129. The film swelling rate is
It can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling ratio is preferably 150 to 400%.

The method of the present invention can be preferably applied to positive color image formation using a color reversal film for slides or televisions and a color reversal paper.

[0241]

EXAMPLES The present invention will be described below with reference to examples.

[Example 1] The following first to twelfth layers were multilayer-coated on a paper support having a thickness of 220 µm laminated on both sides with polyethylene to prepare a color photographic material. To the polyethylene coated on the first layer, 15% by weight of anatase type titanium dioxide white was added as a white pigment, and a slight amount of ultramarine blue was added as a bluing dye. The chromaticity of the surface of the support is (L *, a *, b *) color system, 89.
It was 0, -0.18, -0.73.

(Composition of each layer) The components of each layer and the coating amount (g / m ² ) are shown below. However, for silver halide, the coating amount in terms of silver is shown. First layer (gelatin layer) Gelatin 0.30 Second layer (antihalation layer) Black colloidal silver 0.07 Gelatin 0.50 Third layer (low sensitivity red sensitive layer) Red sensitizing dye (1, 2, 3 each) Silver chloroiodobromide spectrally sensitized (equal amount) (1 mol% silver chloride, 4 mol% silver iodide, average grain size 0.3 μm, grain size distribution 10%, cubic, core-iodine core-shell structure) 0.06 Silver iodobromide spectrally sensitized with a red sensitizing dye (equal amounts of 1, 2, and 3) (4 mol% silver iodide, average grain size 0.5 μm, grain size distribution 12%, cube) 0.07 Gelatin 1.00 Cyan coupler 1 0.14 Cyan coupler 2 0.07 Anti-fading agent 1 0.03 Anti-fading agent 2 0.03 Anti-fading agent 3 0.03 Dispersion medium (for coupler) 0.03 Di (2-Ethylhexyl) phthalate (solvent for coupler ) 0.02 Trinonyl phosphate (solvent for coupler) 0.02 Di (3-methylhexyl) phthalate (solvent for coupler) 0.02 Development accelerator 0.05 Fourth layer (high-sensitivity red-sensitive layer) Red sensitization Silver iodobromide spectrally sensitized with dyes (1, 2, 3) (6 mol% silver iodide, average grain size 0.8 μm, grain size distribution 18%, tabular (aspect ratio = 8), core iodide Degree type core-shell structure) 0.15 Gelatin 1.00 Cyan coupler 1 0.20 Cyan coupler 2 0.10 Anti-fading agent 1 0.05 Anti-fading agent 2 0.05 Anti-fading agent 3 0.05 Dispersion medium (for coupler) ) 0.03 Di (2-ethylhexyl) phthalate (solvent for coupler) 0.033 Trinonyl phosphate (solvent for coupler) 0.033 Di (3-methylhexyl) phthalate (coupler) Solvent) 0.033 Development accelerator 0.05 Fifth layer (intermediate layer) Magenta colloidal silver 0.02 Gelatin 1.00 Color mixing inhibitor 1 0.04 Color mixing inhibitor 2 0.04 Tricresyl phosphate (color mixing inhibitor) Solvent) 0.08 Dibutyl phthalate (solvent for color mixing inhibitor) 0.08 Polyethyl acrylate latex (Molecular weight 10,000-100,000) 0.10 6th layer (low sensitivity green sensitive layer) Spectral sensitization with green sensitizing dye 1 Sensed silver chloroiodobromide (silver chloride 1 mol%, silver iodide 2.5 mol%, average grain size 0.28 μm, grain size distribution 6%, cubic, core iodide type core-shell structure) 0.03 green Silver iodobromide spectrally sensitized with Sensitizing Dye 1 (2.5 mol% silver iodide, average grain size 0.45 μm, grain size distribution 10%, cubic) 0.05 gelatin 0.80 magenta Coupler 1 0.05 Magenta coupler 2 0.05 Anti-fading agent 4 0.10 Anti-staining agent 1 0.05 Anti-staining agent 2 0.05 Anti-staining agent 3 0.001 Anti-staining agent 4 0.01 Dispersion medium (coupler 0.05) Tricresyl phosphate (solvent for coupler) 0.075 Trioctyl phosphate (solvent for coupler) 0.075 7th layer (high-sensitivity green-sensitive layer) Iodine spectrally sensitized with green sensitizing dye 1 Silver bromide (3.5 mol% silver iodide, average grain size 0.8 μm, grain size distribution 21%, tabular (aspect ratio = 9), uniform iodide type) 0.10 gelatin 0.80 magenta coupler 1 0.05 Magenta coupler 2 0.05 Anti-fading agent 4 0.10 Anti-staining agent 3 0.001 Anti-staining agent 4 0.01 Dispersion medium (for coupler) 0.05 Ricresyl phosphate (solvent for coupler) 0.075 Trioctyl phosphate (solvent for coupler) 0.075 8th layer (yellow filter layer) Yellow colloidal silver 0.14 Gelatin 1.00 Color mixing inhibitor 1 0.06 Trickle Dil phosphate (solvent for color mixture) 0.075 Dibutyl phthalate (solvent for color mixture) 0.075 Polyethyl acrylate latex (Molecular weight 10,000-100,000) 0.10 9th layer (low sensitivity blue sensitive layer) Blue increase Silver chloroiodobromide spectrally sensitized with dyes (equal amounts of 1 and 2) (2 mol% silver chloride, 2.5 mol% silver iodide, average grain size 0.38 μm, grain size distribution 8%, Cube, core iodide type core-shell structure) 0.07 Silver iodobromide spectrally sensitized with a blue sensitizing dye (equal amounts of 1 and 2) (2.5 mol% of silver iodide, Uniform particle size 0.55 μm, particle size distribution 11%, cubic, core iodine type core shell structure) 0.10 gelatin 0.50 yellow coupler 1 0.10 yellow coupler 2 0.10 anti-fading agent 5 0.10 stain prevention Agent 3 0.001 Dispersion medium (for coupler) 0.05 Trinonyl phosphate (solvent for coupler) 0.05 Tenth layer (high-sensitivity blue sensitive layer) Spectral sensitization with blue sensitizing dye (equal amounts of 1 and 2) Sensed silver iodobromide (2.5 mol% silver iodide, average grain size 1.4 μm, grain size distribution 21%, tabular (aspect ratio = 14), core iodide core shell structure) 0.25 gelatin 1.00 Yellow coupler 1 0.20 Yellow coupler 2 0.20 Anti-fading agent 5 0.10 Anti-staining agent 3 0.002 Dispersion medium (for coupler) 0.15 Trinonyl Sulfate (solvent for coupler) 0.10 11th layer (UV absorbing layer) Gelatin 1.50 UV absorbing agent 1 0.50 UV absorbing agent 2 0.50 Dispersion medium (for UV absorbing agent) 0.15 di (2- Ethylhexyl) phthalate (solvent for UV absorber) 0.075 Trinonyl phosphate (solvent for UV absorber) 0.075 Dye 1 (for prevention of irradiation) 0.01 Dye 2 (for prevention of irradiation) 0.01 Dye 3 (For prevention of irradiation) 0.01 Dye 4 (for prevention of irradiation) 0.01 12th layer (protective layer) Gelatin 0.90 1,2-bis (vinylsulfonylacetamide) ethane (gelatin hardener) 0.085 4,6-Dichloro-2-hydroxy 1,3,5-triazine sodium salt (gelatin hardener) 0.085 non Light-sensitive silver halide (silver chlorobromide, silver bromide 3 mol%, average particle size 0.2 [mu] m) 0.02 modified Poval 0.05

Further, for each layer, alkanol XC (manufactured by Du Pont) and sodium alkylbenzenesulfonate were used as emulsifying dispersants, and succinate and Magfac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. I was there. The following stabilizers 1, 2 and 3 were used in the layer containing silver halide or colloidal silver. The photographic material thus prepared was designated as Sample No. 101.

The compounds used for preparing the photographic material are shown below.

[0246]

[Chemical 139]

[0247]

[Chemical 140]

[0248]

[Chemical 141]

[0249]

[Chemical 142]

[0250]

[Chemical 143]

[0251]

[Chemical 144]

[0252]

[Chemical 145]

[0253]

[Chemical 146]

[0254]

[Chemical 147]

[0255]

[Chemical 148]

[0256]

[Chemical 149]

[0257]

[Chemical 150]

[0258]

[Chemical 151]

[0259]

[Chemical 152]

[0260]

[Chemical 153]

[0261]

[Chemical 154]

[0262]

[Chemical 155]

[0263]

[Chemical 156]

[0264]

[Chemical 157]

[0265]

[Chemical 158]

[0266]

[Chemical 159]

[0267]

[Chemical 160]

[0268]

[Chemical 161]

[0269]

[Chemical 162]

[0270]

[Chemical formula 163]

[0271]

[Chemical 164]

[0272]

[Chemical 165]

[0273]

[Chemical 166]

[0274]

[Chemical 167]

[0275]

[Chemical 168]

[0276]

[Chemical 169]

[0277]

[Chemical 170]

[0278]

[Chemical 171]

[0279]

[Chemical 172]

The photographic material thus obtained was used for 3200
An image was formed on the photographic material by exposing through a sensitometric wedge at a K light source and then processing as follows using an automatic processor.

──────────────────────────────────── Treatment process time Temperature Mother liquor tank capacity Replenishment amount ── ────────────────────────────────── Black and white development 75 seconds 38 ℃ 8 liters 330ml / m ² First water washing ( 1st bath) 45 seconds 33 ° C 5 liters None 1st water washing (2nd bath) 45 seconds 33 ° C 5 liters 5000 ml / m ² Reverse exposure 15 seconds (100 lux) Color development 135 seconds 38 ° C 15 liters 500 ml / m ² 2 water washing 45 seconds 33 ℃ 5 liter 1000ml / m ² bleach-fixing (1st bath) 60 seconds 38 ℃ 7 liter none bleach-fixing (2nd bath) 60 seconds 38 ℃ 7 liter 220ml / m ² 3rd water washing (1st bath) ) 45 seconds 33 ° C 5 liters None 3rd water washing (second bath) 45 seconds 33 ° C 5 liters None 3rd Washing (Third bath) 45 sec 33 ° C. 5 liters 5000 ml / m ² Drying 45 sec 75 ℃ ───────────────────────────── ───────

[0282] The first and third washing steps are
Each was a countercurrent washing method. That is, in the first rinsing step, rinsing water was poured into the second bath, and the overflow liquid was led to the first bath. In the third washing step, washing water was poured into the third bath, the overflow solution was introduced into the second bath, and the overflow solution in the second bath was introduced into the first bath.

The composition of each processing solution is shown below.

[0284] ────────────────────────────────────   Black and white developer Mother solution Replenisher ────────────────────────────────────   Nitrilo-N, N, N-trimethylenephosphonic acid     ・ 5 sodium salt 1.0g 1.0g   Diethylenetriamine pentaacetic acid / 5 sodium salt 3.0g 3.0g   Potassium sulfite 30.0g 30.0g   Potassium thiocyanate 1.2g 1.2g   Potassium carbonate 35.0g 35.0g   Hydroquinone monosulfonate potassium 25.0 g 25.0 g   1-phenyl-4-hydroxymethyl-4-     Methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g   Without potassium bromide 0.5g   Potassium iodide 5.0 mg None ────────────────────────────────────   Add water 1000ml 1000ml   pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 ────────────────────────────────────

[0285] ────────────────────────────────────   Color developer Mother liquor Replenisher ────────────────────────────────────   Benzyl alcohol 15.0 ml 18.0 ml   Diethylene glycol 12.0 ml 14.0 ml   3,6-dithia-1,8-octane-diol 0.20 g 0.25 g   Nitrilo-N, N, N-trimethylenephosphonic acid     ・ 5 sodium salt 0.5g 0.5g   Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0g 2.0g   Sodium sulfite 2.0g 2.5g   Hydroxylamine sulfate 3.0 g 3.6 g   N-ethyl-N- (β-methanesulfonamidoethyl)-     3-Methyl-aminoaniline sulfate 5.0 g 8.0 g   Optical brightener (diaminostilbene type) 1.0 g 1.2 g   Potassium bromide (change according to experiment)   Potassium iodide 1.0 mg None ────────────────────────────────────   Add water 1000ml 1000ml   pH (adjusted with hydrochloric acid or potassium hydroxide) 10.25 10.40 ────────────────────────────────────

[0286] ────────────────────────────────────   Bleach-fix solution Mother liquor replenisher ────────────────────────────────────   Ethylenediaminetetraacetic acid / 2 sodium     ・ Dihydrate 5.0g 5.0g   Ethylenediaminetetraacetic acid / Fe (III)     Ammonium monohydrate 80.0g 80.0g   Sodium sulfite 15.0g 15.0g   Ammonium thiosulfate aqueous solution (700 ml / l) 160 ml 160 ml   2-mercapto-1,3,4-triazole 0.5 g 0.5 g ────────────────────────────────────   Add water 1000ml 1000ml   pH (adjusted with acetic acid or aqueous ammonia) 6.50 6.50 ────────────────────────────────────

Then, a comparative experiment was conducted by changing the amount of potassium bromide contained in the mother liquor of the color developing solution and the photographic material according to Table 1 below.

[0288]

[Table 1] Table 1 ──────────────────────────────────── Sample potassium bromide additive No. Mol / liter Compound addition layer Addition amount (mmol / liter) ───────────────────────────────────── 101 (Comparative example) 0.004 None None None 102 (Comparative example) 0.0025 1a-12 5th layer 0.08 103 (Comparative example) 0.004 1a-12 5th layer 0.08 104 (Invention) 0 0.008 1a-12 5th layer 0.08 105 (invention) 0.020 1a-12 5th layer 0.08 106 (invention) 0.080 1a-12 5th layer 0.08 107 (invention) 0.020 1a-12 5th layer 0.001 108 (invention) 0.020 1a-12 5th layer 0.01 109 (book) Invention) 0.020 1a-12 Fifth layer 0.04 110 (Invention) 0.020 1a-12 Fifth layer 0.20 111 (Invention) 0.020 1a-12 Fifth layer 0.08 112 ( The present invention) 0.020 1b-1 Third layer 0.08 113 (Comparative example) 0.020 Cpd-101 Fifth layer 0.08 114 (Comparative example) 0.020 Cpd-102 Fifth layer 0.08 ─ ───────────────────────────────────

The comparative compounds (Cpd-101) and (Cpd-102) used are shown below.

[0290]

[Chemical 173]

[0291]

[Chemical 174]

The results of the above comparative experiments are shown in Table 2 below.

[Table 2] Table 2 ──────────────────────────────────── Sample sharpness (10 cycles / min ) Photographic change number RG ΔDmax (G) ΔDmax (R) γ ₂ / γ _s (R) ΔDmax (B) ──────────────────────── ───────────── 101 0.42 0.47 −0.03 −0.05 0.99 +0.02 102 0.48 0.58 −0.35 −0.38 0 .68 +0.06 103 0.51 0.61 -0.27 -0.29 0.77 +0.03 104 0.54 0.63 -0.04 -0.05 0.97 +0.01 105 0. 55 0.64 -0.02 -0.02 0.99 +0.01 106 0.55 0.63 -0.01 -0.00 0.99 +0.00 107 0.47 0.51 -0.02 -0.01 1. 00 +0.00 108 0.51 0.59 -0.02-0.02 1.00 +0.01 109 0.54 0.61 -0.02-0.02 0.99 +0.01 110 0.56 0.63-0.06-0.07 0.98 +0.00 111 0.62 0.50 -0.01 -0.07 0.96 +0.01 112 0.62 0.63-0.02- 0.03 0.98 +0.01 113 113 0.42 0.48 -0.18 -0.23 0.81 +0.04 114 0.43 0.48 -0.21 -0.26 0.79 +0. 06 ────────────────────────────────────

In Table 2 above, "change in photographic property" indicates the difference between the sensitometry with the new solution and the sensitometry result after 2 weeks. That is, the photographic performance stability of the developer due to processing running is shown. “Dmax (G)” and “Dmax (R)” represent the amount of change in the values measured in the highest density part with the green and red filters, respectively, and the closer the value is to 0, the smaller the difference between days and the better. "Γ ₂ / γ _s
(R) "is the lowest photosensitive layer of the photographic material, the cyan color development of the red-sensitive layer is measured by a red filter, and the gradient (γ value) between densities of 0.5 to 1.5 is determined to obtain the value in 2 weeks. The change is shown as a ratio. The closer the value is to 1, the smaller the γ change, which is preferable. Further, "Dmax (B)" indicates the amount of change in the value measured in the lowest density portion with a blue filter, and the closer the value is to 0, the more preferable. On the other hand, as for the sharpness, after exposure through a sharpness measurement pattern, development processing is performed, and 10 lines /
The value which measured CTF of mm is shown. The larger this value, the higher the sharpness and the more preferable.

As is clear from the results shown in Table 2, the method of the present invention can improve the sharpness of the image without impairing the photographic performance stability of the developer. .

Example 2 The photographic material used in Example 1 was exposed in the same manner as in Example 1, and then processed as follows using an automatic processor to form an image on the photographic material.

[0296] ────────────────────────────────────   Treatment process time Temperature Mother liquor tank capacity Replenishment amount ────────────────────────────────────   Black and white development 40 seconds 38 ° C 1 liter 200ml   First water wash 40 seconds 20-30 ° C 1 liter Water: 15 liters or more   Color development (1) 40 seconds 38 ° C 1 liter 100ml   Color development (2) 40 seconds 38 ℃ 1 liter 100ml   Bleach 40 seconds 38 ℃ 1 liter 100ml   Bleach-fixing 40 seconds 38 ℃ 1 liter 100ml   Second water wash 40 seconds 20 ~ 30 ℃ 1 liter Water: 15 liters or more ────────────────────────────────────

The composition of each processing liquid is shown below.

[0298] ────────────────────────────────────   Black and white developer (common to mother liquor and replenisher) ────────────────────────────────────   800 ml of water (20-40 ° C)   Nitrilo-N, N, N-trimethylenephosphonic acid     ・ 5 sodium salt (40% by weight) 1.0 g   Potassium hydroxide (pure) 16.0 g   Potassium metabisulfite 21.0 g   3,6-dithia-1,8-octanediol 0.10 g   Potassium carbonate 14.0g   Sodium bicarbonate 12.0g   1-phenyl-4-hydroxymethyl-4-     Methyl-3-pyrazolidone 1.5 g   Hydroquinone 10.0g   1-phenyl-3-pyrazolidone 2.0 g   5-methylbenzotriazole 0.05 g   Sodium bromide 2.0g   Potassium iodide 0.008g ────────────────────────────────────   1000 ml with water   pH (25 ° C) 10.00 ± 0.05 ────────────────────────────────────

[0299] ────────────────────────────────────   Color developer replenisher ────────────────────────────────────   900 ml of water (20-40 degrees Celsius)   Diethylene glycol 15.0 ml   Benzyl alcohol 15.0 ml   Nitrilo-N, N, N-trimethylenephosphonic acid     ・ 5 sodium salt (40% by weight) 0.5g   2.50 g of sodium sulfite   26.0 g potassium carbonate   3.75 g of 3,6-dithia-1,8-octanediol   Hydroxylamine sulfate 2.60 g   N-ethyl-N- (β-methanesulfonamidoethyl)-     3-methyl-aminoaniline sulfate 7.0 g   Potassium bromide (change according to experiment) ────────────────────────────────────   1000 ml with water   pH (25 ° C, adjusted with potassium hydroxide) 11.10 ± 0.05 ────────────────────────────────────

[0300] ────────────────────────────────────   Color developer mother liquor ────────────────────────────────────   Color developer replenisher 800 ml   Acetic acid aqueous solution (color developer starter) 200 ml ────────────────────────────────────   pH (25 ° C) 10.20 ± 0.05 ────────────────────────────────────

[0301] ────────────────────────────────────   Bleach (common to mother liquor and replenisher) ────────────────────────────────────   Water (20-40 ℃) 700ml   Ammonia water (28%) 1.75 ml   Ammonium nitrate 15.0g   Ethylenediaminetetraacetic acid / Fe (III)     Ammonium dihydrate 130.0 g   Ethylene dian tetraacetic acid, disodium salt 3.0 g   Potassium bromide 100.0g ────────────────────────────────────   1000 ml with water   pH (25 ° C) 5.60 ± 0.10. ────────────────────────────────────

[0302] ────────────────────────────────────   Bleach-fixing solution (common to mother liquor and replenisher) ────────────────────────────────────   Water (20-40 ℃) 700ml   Ammonium thiosulfate aqueous solution (70%) 138.0 ml   Ethylenediamine tetraacetic acid ・ 2 sodium salt 2.0g   2-mercapto-5-aminothiazole 0.6 g   Sodium sulfite 14.0g   Ethylenediaminetetraacetic acid / Fe (III)     Ammonium dihydrate 70.0 g   Ammonia water (28%) 10.0 ml ────────────────────────────────────   1000 ml with water   pH (25 ° C) 7.20 ± 0.10. ────────────────────────────────────

Then, a comparative experiment was conducted in the same manner as in Example 1 except that the amount of potassium bromide contained in the mother liquor of the color developing solution and the photographic material were changed according to Table 3 below. However, the treatment amount was 1 day / m ² . The results are shown in Table 4.

[0304]

[Table 3] Table 3 ──────────────────────────────────── Sample potassium bromide additive No. Mol / liter Compound addition layer Addition amount (mmol / liter) ───────────────────────────────────── 201 (Comparative example) 0.004 None None None 202 (Comparative example) 0.004 1a-12 5th layer 0.07 203 (present invention) 0.008 1a-12 5th layer 0.07 204 (present invention) 0 .020 1a-12 5th layer 0.07 ─────────────────────────────────────

[0305]

[Table 4] Table 4 ──────────────────────────────────── Sample sharpness (10 cycles / min ) Photographic change number RG ΔDmax (G) ΔDmax (R) ──────────────────────────────────── -201 0.41 0.45 -0.08 -0.12 202 0.58 0.66 -0.45 -0.53 203 0.56 0.64 -0.13 -0.10 204 0.55 0.63 −0.08 −0.09 ─────────────────────────────────────

As is clear from the results shown in Table 4, the method of the present invention can improve the sharpness of the image without impairing the photographic performance stability of the developer. .

Claims (3)

[Claims] 1. An image exposure process using a color photographic material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler and a silver halide emulsion layer containing a cyan coupler on a support. A method of forming a color reversal image on a photographic material by black and white development processing, reversal processing, color development processing and desilvering processing, wherein the photographic material contains a compound having the following formula (Ia) or (Ib), The processing solution in the development process reduced bromide to 0.
A color reversal image forming method comprising 005 to 0.1 mol / liter. [Chemical 1] [Chemical 2] In the formula, R ¹² is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; M is —CO
_{-, - SO 2 -, -} N (R 15) CO -, - OCO- or -N (R ¹⁵⁾ SO ₂ - is; R ¹⁴ and R ¹⁵ are each a hydrogen atom, is an alkyl group or an aryl group ;
R ¹¹ , R ¹³ and R ²¹ are each a hydrogen atom or a substituent of a hydroquinone nucleus; A and A ′ are a hydrogen atom or a group which can be removed by an alkali; L is 5 or more members condensed with a hydroquinone nucleus. Forming a heterocycle of 2
Is a valent group; Time is a group that releases X after being released from the hydroquinone oxidant; X is a development inhibitor; and t is 0 or an integer of 1 or more. 2. In the above formula (Ia), M is —CO—
And when R ¹² is an alkyl group, the alkyl group is an alkyl group having 2 or more carbon atoms in which a carbon atom adjacent to M is not substituted by a hetero atom. Method. 3. In the above formula (Ia), M is —SO ₂
^{-, - N (R 15)} CO -, - OCO- or -N
The image forming method according to claim 1, wherein (R ¹⁵ ) SO ₂ −.