JP2822105B2 - Color reversal image forming method - Google Patents

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 which can be preferably applied 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, and for copying a photographic print, a printed matter, a picture or the like. In the color reversal image forming method, a black-and-white developing process, a reversing process, a color developing 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 a silver halide in an exposed portion by an image exposure process. (2) The silver halide in the exposed area is developed by black-and-white development to form a silver image. (3) A latent image is formed on the silver halide remaining in the unexposed area by the reversal process. Inversion processing includes light fogging processing and chemical fogging processing using a fogging agent. (4) The unexposed portions of the silver halide are color-developed by color development to form a color image. (5) The silver image is removed by a desilvering process.

In order to obtain a good color reversal image by the above method, it is necessary to improve black-and-white development processing. A typical composition of a black-and-white developer includes a developing agent (eg, 3-pyrazolidones, hydroquinones) and a preservative (eg, sulfite, bisulfite) as main components, and an alkali agent (eg, Carbonates), accelerators (eg, thioether compounds) and antifoggants (eg, potassium bromide). Usually, 0.5 to 1 g (0.0042 mol / L to 0.0084 mol / L), and at most 2 g (0.0168 mol / L) of potassium bromide as an antifoggant in 1 L of a black-and-white developer. Formulation examples including degrees are known.

[0004]

When INVENTION Problems to be Solved] bromide is added 0.025 to 0.1 mole / liter Black White developer, the maximum color density Ru obtain high good color reversal image. When a black and white developer containing a relatively high concentration of bromide is used as described above, the replenishment amount of the black and white developer can be reduced. However, as a result of advanced inventors have GaKen Research, when using the above black-and-white developer, it was found that the color reproducibility is degraded.

An object of the present invention is to provide a color reversal image forming method which has high maximum color density and excellent color reproducibility. Another object of the present invention is to reduce the replenishment amount of a black-and-white developer without deteriorating color reproducibility.

[0006]

The object of the present invention has been achieved by the following color reversal image forming method.

The present invention provides an image exposure method 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. Processing, containing 0.025 to 0.1 mol / l of bromide
Black-and-white development processing using the processing solution, the inversion process, a method of forming a color reversal image on the photographic material by a color development process and a desilvering process, compounds photographic material having the following formula (I A) or (Ib) the providing color reversal image forming method, comprising the early days free.

[0008]

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[0009]

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Wherein R ¹² is an alkyl, alkenyl, alkynyl, aryl or heterocyclic group; M is —CO—, —SO ₂ —, —N (R ¹⁵ ) CO
—, —OCO— or —N (R ¹⁵ ) SO ₂ —;
¹⁴ and R ¹⁵ are each a hydrogen atom, is an alkyl group or an aryl group; R ²¹ is a hydrogen atom or hydroquinone nucleus substituents; A and A 'is a group which can be removed by a hydrogen atom or an alkali L is a divalent group that forms a 5- or more-membered heterocyclic ring condensed with the hydroquinone nucleus; Time is a group that releases X after leaving the oxidized hydroquinone; X is a development inhibitor And t is 0 or an integer greater than or equal to 1.

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

[0012] In (1) above formula (I A), 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.

[0013] In (2) the formula (I A), 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 ) CO— or —OCO—.

[0015] In (4) the formula (I A) and (Ib), A and A 'are hydrogen atoms.

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

[0017]

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[0018]

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[0019]

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[0020]

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

[0022]

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In the formula, L ² represents 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 combination thereof; and R ²¹ , A, A ′, Time, X and t have the same definition as in the formula (Ib). .

[0024] (7) the photographic material contains the above formula (I A) or a compound having a (Ib) 0.001 mmol / m ² to 0.2 mmol / m ^2.

(8) The bromide contained in the processing solution of the black-and-white development processing is potassium bromide or sodium bromide.

(9) The processing solution of the black-and-white development processing contains 0.03 to 0.08 mol / l of bromide.

[0027]

As described above, when 0.025 to 0.1 mol / l of bromide is added to a black-and-white developer, a good color reversal image having a high maximum color density is obtained, and the replenishment amount of the black-white developer is reduced. However, the color reproducibility deteriorates. Specifically, the degradation of color reproducibility
Inter-image effect (caused by the difference in color image between multi-color exposure and single-color exposure, contributing to improved image sharpness and color reproducibility. Journal of the Optical Society
Of America, Vol. 42, No. 9, pages 663-669 (1
976)).

According to the study of the present inventor, the above formula (I A )
Alternatively, by adding a specific hydroquinone compound having (Ib) to a photographic material, deterioration of color reproducibility can be prevented without impairing the excellent action of bromide. Therefore, according to the method of the present invention, a color reversal image having a high maximum color density and excellent color reproducibility can be formed. Further, in the method of the present invention, the replenishment amount of the black and white developer can be reduced without deteriorating color reproducibility. These effects are obtained for the first time by combining a bromide and a hydroquinone compound, and cannot be expected from the respective effects.

[Detailed Description of the Invention] The color reversal image forming method of the present invention employs a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a halide containing a cyan coupler on a support. Having a silver emulsion layer and further having the formula (I)
A ) a color photographic material containing a compound having ( A ) or (Ib) is image-exposed; the photographic material is subjected to black-and-white development using a processing solution containing 0.025 to 0.1 mol / l of bromide; A color reversal process; a color development process of the photographic material; and a desilvering process of the photographic material to form a color reversal image on the photographic material.

[0030] In color reversal image forming method of the present invention include compounds photographic material has the formula (I A) or (Ib). It will be described in more detail for the compounds having the formula (I A) or (Ib).

[0031]

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[0032]

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[0033] formula (I A), 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 include methyl, ethyl, isopropyl, t-butyl, nonyl, 1-hexylnonyl, decyl, pentadecyl, hexadecyl, 3- (2,5-di-t-pentylphenoxy) propyl, cyclohexyl and benzyl. Can be mentioned.

[0035] It should be noted that, in the formula (I A), 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. Among the examples of the above 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 the aryl group include phenyl, naphthyl, 3,5-bis (octadecanamido) phenyl, 3-dodecanamidophenyl, 2-
Hexadecane sulfonamidophenyl, 3-hexadecane sulfonamidophenyl and 4-dodecyloxyphenyl can be mentioned.

The heterocyclic group represented by R ¹² has 5 to 20 members
It preferably has 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 Morpholinyl can be mentioned.

[0040] In the formula (I A), M is, -CO -, -
SO ₂ —, —N (R ¹⁵ ) CO—, —OCO— or —N
(R ¹⁵ ) SO ₂ —. M represents -SO _2- , -N (R
¹⁵⁾ CO -, - OCO- or -N (R ¹⁵⁾ SO ₂ - is preferably. -N (R ¹⁵⁾ CO- or -OC
More preferably, it is 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 those described above for R ¹²
Are the same as the examples of the alkyl group and the aryl group represented by. R ¹⁵ is preferably a hydrogen atom.

R ²¹ in the formula (Ib) is a hydrogen atom or a substituent of a hydroquinone nucleus, respectively.

[0043] formula R ²¹ in (I b) are water atom, Hammett substituent constants (sigma _p) is 0.3 or less substituents, A
Sil group, alkoxycarbonyl group, carbamoyl group,
It is preferably a rufamoyl group, a sulfonyl group or a heterocyclic group . The Hammett's substituent constant (σ _p ) is 0.
Examples of the three or less substituents 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, a ureido group, a urethane group, a sulfamoylamino group, and a halogen atom. , A hydroxy group and-(Time) _t- X. Each group may further have a substituent. Examples of the substituent of R ²¹ 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 include phenoxy and naphthoxy.

The alkylthio group has 1 to 30 carbon atoms.
It is preferred that 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 include phenylthio, naphthylthio and 2
-Butyloxy-5-t-octylphenylthio.

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

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

The ureido group preferably has 1 to 30 carbon atoms. Examples of ureido groups include 3-methylureido, 3-dodecylureide 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 the sulfamoylamino group include 3-methylsulfamoylamino and 3-phenylsulfamoylamino.

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

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

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 the alkoxycarbonyl group include methoxycarbonyl, octyloxycarbonyl, phenoxycarbonyl, octadecyloxycarbonyl, and methoxyethoxycarbonyl.

The carbamoyl group preferably has 1 to 30 carbon atoms. Examples of carbamoyl groups include carbamoyl, N-propylcarbamoyl, N-hexadecylcarbamoyl, N- {3- (2,4-di-tert-pentylphenoxy)} propylcarbamoyl and N-
Phenylcarbamoyl can be mentioned.

The sulfamoyl group has 0 to 30 carbon atoms.
It is preferred that Examples of the sulfamoyl group include sulfamoyl and dibutylsulfamoyl.

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

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

[0062] formula (I A) and (Ib), A and A 'is a group which can be removed by a hydrogen atom or an alkali. Examples of groups that can be removed by an alkali include a group that can be hydrolyzed (eg, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imidoyl group, an oxalyl group, a sulfonyl group), and a reverse Michael reaction. Precursor group (U.S. Pat.
No. 29), a precursor group utilizing the anion generated by the ring cleavage reaction as an intramolecular nucleophilic group (described in US Pat. No. 4,310,612), and the cleavage reaction is carried out by electron transfer of the anion via a conjugated system. Precursor groups (US Pat. Nos. 3,674,478 and 393)
No. 2480 and No. 3993661),
A precursor group (described in US Pat. No. 4,335,200) that causes a cleavage reaction by electron transfer of an anion reacted after ring cleavage, and a precursor group utilizing an imidomethyl group (US Pat. Nos. 4,363,865 and 44106)
No. 18, each specification). Generally A
And A ′ are preferably hydrogen atoms.

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

Examples of preferred heterocyclic rings formed by L are shown below.

[0065]

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[0066]

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[0067]

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[0068]

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

[0070] formula (I A) and (Ib), -
(Time) _t- X is a group having a function of releasing the development inhibitor after the hydroquinone nucleus is oxidized by the oxidized developing agent during development to become a quinone. Specifically, Time
Is a group that releases X after leaving from 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 control function, and may be a group which becomes a coupler which reacts with another oxidized developing agent molecule to release X or a redox group. When t is 0, it means that X is directly bonded to the hydroquinone nucleus. When t is 2 or more, it means a combination of a plurality of Times (which may be different).

An example in which Time is a group having a timing adjusting function will be described below.

(1) Group utilizing cleavage reaction of hemiacetal (US Pat. No. 4,146,396, JP-A-60-249148)
(2) A group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction (described in US Pat. No. 4,248,962) (3) Electron transfer reaction along a conjugated system (US Pat. Nos. 4,409,323 and 4)
(Described in each specification of No. 421845) (4) Group utilizing cleavage reaction by hydrolysis of ester (described in Japanese Patent Publication No. 2626315) (5) Group utilizing cleavage reaction of imino ketal (described in US Pat. No. 4,460,073) )

Other groups having a timing adjusting function are described in British Patent Specification No. 2097833 and JP-A Nos. 51-146828 and 57-56837. As Time, two or more of these groups may be used in combination.

Time can function as a phenol coupler or a 5-pyrazolone coupler. When Time is a phenolic coupler, it binds to the hydroquinone nucleus at an oxygen atom excluding the hydrogen atom of the hydroxyl group.
When Time is a 5-pyrazolone type coupler,
Hydroxypyrazole (tautomer of 5-pyrazolone) binds to the hydroquinone nucleus at an oxygen atom obtained by removing a hydrogen atom from a hydroxyl group. These dissociate from the hydroquinone nucleus and then function as couplers, react with the oxidized developing agent, and release X bonded to the coupling position.

Preferred examples when Time is a coupler are shown below.

[0076]

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[0077]

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Wherein V ¹ and V ² are substituents;
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 may be different from each other, and a plurality of V ⁷ may form a ring; V ⁸ is -C
V ⁹ is a non-metallic atomic group forming a 5- to 8-membered ring together with -V ⁸ -NC = C-; V ¹⁰ is O-, -SO _2- , an oxygen atom or a substituted imino group; Is a hydrogen atom or a substituent; * is the point of attachment to the hydroquinone nucleus; and ** is the point of attachment to X.

A preferred example when Time is an oxidation-reduction group is represented by the following formula (R-1).

(R-1) *-P- (X = Y) _m -QA

Wherein P and Q are each an oxygen atom or an imino group (which may have a substituent);
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 from which alkali can be removed;
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); Is the binding position to

The oxidation-reduction group represented by the formula (R-1) includes
A group represented by the following formula (R-2) or (R-3) is more preferred.

[0083]

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In the formula, R ⁶⁴ is a substituent (examples of the substituent are the same as the examples of R ^{21 in} the formula (Ib)); q is an integer of 0 to 3; when a plurality of R ⁶⁴ may be different from each other, if more than one R ⁶⁴ is a substituent of the adjacent carbon atoms may form a ring; *
Is the point of attachment to the hydroquinone nucleus; and *
* Is the bonding position 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 a compound represented by the following formula (X-2)
And a heterocyclic compound capable of producing imino silver represented by

[0086]

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In the formula, Z ¹ is a nonmetallic atomic group forming a monocyclic or condensed-ring heterocyclic ring (which may have a substituent); Z ² is a monocyclic or condensed-ring heterocyclic ring together with a nitrogen atom. Is a non-metallic atomic group forming a heterocyclic ring (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 hetero ring is preferably a 5- to 8-membered ring, more preferably a 5- 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, bentazaindene, tria Zindene) and azines (eg, pyrimidine, triazine, pyrazine, pyridazine).

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, bentazaindene) and tetrazole.

Examples of the substituent of the development inhibitor represented by the formulas (X-1) and (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.

[0092] In the Examples of the substituent, 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 s} , they may combine 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 (Example: 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-nitrobenzotriazole, 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).

X is a group represented by the formulas (I A ) and (Ib)
After departure from Time and once becoming a compound with a development inhibitory function, it further reacts with the developer component and changes to a compound that has substantially no development inhibitory function or a compound with a significantly reduced development inhibitory function (Deactivated type development inhibitor). Examples of functional groups that undergo the above reaction include ester groups, carbonyl groups, imino groups, immonium groups, Michael addition accepting groups, and imide groups.

Regarding the development inhibitor residue of the deactivated development inhibitor, see US Pat. No. 4,477,563 and JP-A-60-218644, JP-A-60-221750, and JP-A-60-221750.
It is described in each of JP-A Nos. 0-233650 and 61-11743.

As the deactivated development inhibitor, a compound having an ester group is preferred. Examples of the deactivated development inhibitor include 1- (3-phenoxycarbonylphenyl) -5-
Mercaptotetrazole, 1- (4-phenoxycarbonylphenyl) -5-mercaptotetrazole, 1-
(3-maleimidophenyl) -5-mercaptotetrazole, 5-phenoxycarbonylbenzotriazole, 5- (4-cyanophenoxycarbonyl) benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,3,4 -Thiadiazole, 5-
Nitro-3-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)
And -5-mercapto-1,3,4-thiadiazole and 5-butoxycarbonylmethoxycarbonylbenzotriazole.

X is preferably a mercaptoazole or a benzotriazole. As mercaptoazoles, mercaptotriazoles, 5-mercapto-1,3,4-thiadiazoles and 5-mercapto-1,3,4-oxadiazoles are more preferred. As X, 5-mercapto-1,3,4-thiadiazoles are particularly preferred.

[0099] formula (I A) and (Ib), t is preferably 0, 1 or 2, more preferably 0 or 1.

In the formula (IA), M is —N (R ¹⁵ ) C
It is preferably O- or -OCO- . Also, 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, or a combination thereof. R ²⁸ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Hydrogen atoms are 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 preferred.

[0103]

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Wherein L ² has the above definition. R ²¹ ,
A, A ', Time, X and t have the same definition as in formula (Ib).

[0105] When a M is -CO- in formula (I A), a compound represented by the following formula (IC) or (ID) are especially preferred.

[0106]

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[0107]

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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 may be different from each other; and A, A', Time, X and t Is the formula (I
It has the same definition as A ).

[0109] Examples of the R ³⁴ and R ³⁵ are the same as the examples of R ¹² of formula (I A). Each group may further have a substituent. In the formula (IC), R ³⁴ preferably has 5 to 30 carbon atoms, and n ′ is preferably an integer of 2 to 5. In the formula (ID), R ³⁵ preferably has 5 to 30 carbon atoms.

[0110] Specific examples of the compound represented by the formula (I A) or (Ib) below.

[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0186]

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[0191]

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[0193]

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[0197]

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[0199]

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[0200]

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[0201]

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[0202]

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[0203]

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[0205]

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[0206]

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[0207]

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[0208]

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[0209]

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[0210]

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[0211]

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[0212]

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[0213]

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The above compounds can be easily synthesized according to the following synthesis examples. [Synthesis Example 1]

[0215]

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1) Synthesis of 1-A Acetonitrile 4 was added to 50 g of 2,5-dimethoxyaniline.
After adding 00 ml and pyridine 26 ml, and further adding phenyl chloroformate 46 g dropwise, the mixture was stirred at room temperature for 3 hours. After completion of the reaction, an aqueous hydrochloric acid solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate, washed with water, dried, and concentrated to give the compound (1-
A) 50 g were obtained. 2) Synthesis of 1-B 300 ml of acetonitrile was added to 25 g of compound (1-A).
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) Synthesis of 1-C 250 ml of 47% hydrobromic acid was added to 16 g of compound (1-B).
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 a compound (1-C). 4) Synthesis of 1-D 50 g of ethanol was added to 1.5 g of the compound (1-C).
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 the completion of the reaction, the precipitated crystals were separated by filtration and dried, to give compound (1-D)
1.3 g were obtained

5) Synthesis of Ia-12 To 1.3 g of the compound (1-D), 150 ml of ethyl acetate, 0.6 g of 2-mercapto-5-methylthio-1,3,4-thiadiazole, 0.6 g of p-toluenesulfonic acid. 0.1 g of monohydrate was added, and the mixture was stirred at 50 ° C. for 1 hour. After the completion of the reaction, the precipitated insolubles were removed by filtration, and the dew solution was concentrated. The residue was crystallized from acetonitrile, separated by filtration, and dried to obtain 0.9 g of compound (Ia-12). (Melting point: 131.1-
133.2 ° C.) [Synthesis Example 2]

[0219]

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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 obtained by adding 20 ml of methylmalonyl chloride to 50 ml of acetonitrile was added dropwise. 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 from a mixed solvent of ethyl acetate and n-hexane to obtain 31 g of a compound (2-A). 2) Synthesis of 2-B 50 ml of methanol was added to 5.0 g of the compound (2-A), and 3.8 g of a 28% methanol solution of sodium methoxide was further added. After stirring at room temperature for 10 minutes, 4.9 g of 2-dodecyl bromide was added dropwise. 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) Synthesis of 2-C To 1.8 g of the compound (2-B), 30 ml of a 5% aqueous sodium hydroxide solution and 10 ml of methanol were added, and 70 to 75 ° C.
For 2.5 hours. After cooling, the reaction mixture was poured into an aqueous hydrochloric acid solution, and the precipitated crystals were separated by filtration, washed with water, and dried to obtain 1.7 g of a compound (2-C).

4) Synthesis of 2-D To 3.0 g of the compound (2-C) was added 15 ml of phosphorus oxychloride, and the mixture was heated under reflux for 1 hour. After cooling, 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 were obtained. 5) Synthesis of 2-E Compound (2-D) 2.5 g was added to isopropyl alcohol 3
After 0 ml and 10 ml of water were added, and 5 ml of concentrated sulfuric acid were further added, the mixture was heated under reflux for 8.5 hours. After cooling, 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 a compound (2-E). 6) Synthesis of 2-F To 3.5 g of compound (2-E) was added isopropyl alcohol 1
10 ml, a solution obtained by adding 10 ml of water to 0.3 g of sodium hydroxide was added, and 1.0 g of 10% palladium carbon was further added.
Was added, and the mixture was stirred for 7.5 hours under the conditions of 20 kg / cm ^{2 of} hydrogen and 80 to 85 ° C. After cooling, the catalyst was removed by filtration and the filtrate was concentrated. Pour water into the residue, filter out the precipitated crystals,
After washing with water and drying, 2.7 g of compound (2-F) was obtained.

7) Synthesis of 2-G To a compound (2-F) (2.6 g), 47% hydrobromic acid (40 ml) was added.
Was added and 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) Synthesis of 2-H To 2.0 g of compound (2-G) and 6.0 g of manganese dioxide, 150 ml of ethyl acetate was added, followed by stirring at room temperature for 1.5 hours. After filtering off the insolubles, the filtrate was concentrated to give the compound (2-
H) 1.9 g were obtained. 9) Synthesis of Ib-1 To 1.8 g of the compound (2-H) was added 50 ml of methylene chloride, 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 were separated by filtration, washed with acetonitrile,
After drying, 1.2 g of compound (Ib-1) was obtained. (Melting point:
111.3 to 111.9 ° C)

[0223] The above mentioned formula (I A) or a compound having a (Ib) may be added to any of silver halide emulsion layers or non-photosensitive layer. It can also be added to both layers. The added amount is 0.001 mmol / m ^{2 to} 0.2.
The amount is preferably mmol / m ² , more preferably from 0.005 mmol / m ^{2 to} 0.1 mmol / m ² .

In the method of the present invention, the black-and-white developer contains 0.025 to 0.1 mol / l of bromide. More preferably, the black-and-white developer contains 0.03 to 0.08 mol / l of bromide. The bromide is preferably an alkali metal bromide, particularly preferably potassium bromide or potassium bromide. Details of the black and white developer will be described later.

When bromide is used as described above, photographic characteristics tend to be slightly lowered and softened. To avoid this tendency, the average particle size should be 0.3 μm.
It is preferable to use silver halide grains of m or less in at least one silver halide emulsion layer. Details of the silver halide emulsion will be described later.

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

[Black-and-white developing treatment] 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 a condensed heterocyclic compound of a 1,2,3,4-tetrahydroquinoline ring and an indolene ring (described in U.S. Pat. No. 4,067,872) ). As the developing agent, two or more compounds may be used in combination. The amount of the developing agent used is 1 × 10 ^{-5 to} 1 mol per liter of the black-and-white developer. In the black-and-white developer, in addition to the developing agent, a preservative (eg, sulfite, bisulfite), a silver halide solvent, a buffer (eg, carbonate, boric acid, borate, alkanolamine), an alkali agent (Eg, hydroxides, carbonates), dissolution aids (eg, polyethylene glycols, esters thereof), pH adjusters (eg,
Organic acids such as acetic acid), sensitizers (eg, quaternary ammonium salts), development accelerators (eg, thioether compounds), surfactants, defoamers, hardeners, viscosity-imparting agents, antifoggants, A swelling inhibitor (eg, sodium sulfate, potassium sulfate), a chelating agent and the like can be added. The sulfite used as the preservative also functions as a silver halide solvent. Examples of silver halide solvents other than sulfites include:
Examples include potassium thiocyanate, sodium thiocyanate, potassium sulfite, sodium sulfite, potassium disulfite, sodium disulfite, potassium thiosulfate, sodium thiosulfate, and 2-methylimidazole. The amount of the silver halide solvent to be used is 0.005 to 0.5 as thiocyanate ion per liter of the black-and-white developer.
And preferably 0.01 to 0.01 mol.
More preferably, it is 5 mol. The sulfite ion is preferably used in an amount of 0.05 to 1 mol, more preferably 0.1 to 0.5 mol, per liter of the black-and-white developer. 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 ( Examples include 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole) and mercapto-substituted aromatic compounds (eg, thiosalicylic acid). Alkali metal salts of bromine are particularly preferred. Antifoggants may be added to the photographic material. In that case, the antifoggant elutes from the photographic material during black-and-white development and accumulates in the black-and-white developer. The amount of antifoggant used is black and white developer 1
It is preferably 0.001 to 0.1 mol per liter, and 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 compounds may be used in combination. The amount of the chelating agent used is preferably 0.1 g to 20 g per liter of the black and white developer,
g to 10 g is more preferable. The pH value of the black-and-white developer is preferably from 8.5 to 11.5, and more preferably from 9.0 to 10.5.
The replenishment amount of the black-and-white developer is preferably 50 ml to 500 ml per 1 m ² of the photographic material, and 50 ml to 33 ml.
More preferably, it is 0 ml. The processing time of the black and white development step is preferably 20 seconds to 3 minutes,
More preferably, the time is from 75 seconds to 75 seconds. The processing temperature is preferably 30 ° C. to 50 ° C., and 35 ° C. to 4 ° C.
More preferably, the temperature is 5 ° C. In black and white development processing,
After the black and white development step, a water washing step is performed. 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 amount of replenishment. The replenishment rate may be reduced to other treatment bath levels (in this case, called a rinsing bath).
The replenishing amount of the washing water is preferably 3 to 20 liters per 1 m ² of the photographic material. For rinsing bath,
The replenishing amount is preferably from 50 ml to 2 liters, more preferably from 100 ml to 500 ml, per m ² of the photographic material. An oxidizing agent, a chelating agent, if necessary,
Buffers, bactericides and the like can be added.

[Reversing Process] In the color image forming method of the present invention, a reversing process is performed after the black and white developing process. The reversal process comprises a chemical fogging step or a reversal exposure step. The reversal exposure step is more preferable. In the case of the chemical fogging step, a fogging agent such as a tin ion complex salt is used. By adding a fogging agent to a color developer described later, the reversal processing and the color development processing may be performed as the same step. In the case of the reversal exposure step, the entire surface of the photographic material is exposed.

[Color Developing Process] The color developing solution is usually an alkaline aqueous solution of an aromatic primary amine color developing agent. P as a developing agent
-A phenylenediamine compound is preferred. Examples of the p-phenylenediamine compound include 3-methyl-4-
Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates, p-toluenesulfonates, tetraphenylborates and p-
(T-octyl) benzenesulfonate can be mentioned. The developing agent was used in an amount of 1.
It is preferably used in an amount of 0 g to 15 g, more preferably 3.0 g to 8.0 g. In the color developer, in addition to a developing agent, a buffer (eg, an alkali metal carbonate, borate and phosphate), a preservative (eg, hydroxylamine, diethylhydroxylamine, triethanolamine, catechol- 3,5-disulfonate,
Sulfites, bisulfites), organic solvents (eg, diethylene glycol, triethylene glycol), dye-forming couplers, competitive couplers (eg, citrazic acid, J acid, H acid),
A nucleating agent (eg, sodium boron halide), an auxiliary developing agent (eg, 1-phenyl-3-pyrazolidone), a viscosity imparting agent, a development accelerator, an antifoggant, a chelating agent, and the like can be added. Examples of the antifoggant and the chelating agent are the same as the above-mentioned examples of the additive of the black-and-white developer. Examples of the development accelerator include benzyl alcohol, pyridinium compounds (described in JP-B-44-9503, and U.S. Pat. Nos. 2,648,604 and 3,171,247), cationic dyes (eg, phenosafranine), nitrates ( For example, thallium nitrate, potassium nitrate), polyethylene glycol and derivatives thereof
No. 9304, U.S. Pat. Nos. 2,533,990, 2,533,832, 2,577,127 and 295.
0970), 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 developer. The pH value of the color developer is preferably 9 or more, more preferably 9.5 to 12.0, and particularly preferably 10.0 to 11.5.
Replenishing amount of the color developing solution, the photographic material 1 m ² per 50ml
To 500 ml, preferably 50 ml to 1
More preferably, it is 00 ml. The processing temperature of the color development step is preferably 30 ° C to 50 ° C,
More preferably, the temperature is 31 ° C to 45 ° C.

[Desilvering treatment] The desilvering treatment comprises an adjusting step, a washing step, a bleaching step, a fixing step, a bleach-fixing step, a washing alternative stabilizing step and the like. As a method of replenishing the processing solution in each step, the replenishing solution of each bath can be individually replenished. When the bleach-fixing process is performed after the bleaching process, the overflow 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 the bleaching agent used in the bleaching step or the bleach-fixing step, iron (III) aminopolycarboxylate complex salts are typical. Examples of preferred bleaching agents include ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic acid diammonium salt, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, cyclohexanediaminetetraacetic acid disodium salt, iminodiacetic acid, and 1,3- Diaminopropanetetraacetic acid can be mentioned. The aminopolycarboxylic acid iron (III) complex salt may be formed by adding an iron (III) salt and an aminopolycarboxylic acid to the treatment liquid to form an iron (III) complex salt in the treatment liquid. Two or more aminopolycarboxylic acids may be used in combination. In addition, the aminopolycarboxylic acid may be used in an excessive amount (for forming an iron (III) complex salt).
In addition to the iron (III) complex salt, a metal ion complex salt of cobalt or copper other than iron 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
It is preferably from 1 mol to 1 mol, more preferably from 0.2 mol to 0.5 mol. Bleach pH
Is preferably from 4.0 to 8.0, and more preferably from 5.0 to 6.5. The amount of the bleach used per liter of the bleach-fix solution is 0.05 mol to 0.5 mol.
Mole, more preferably 0.1 mole to 0.3 mole. The pH of the bleach-fixing solution is preferably from 5 to 8, more preferably from 6 to 7.5. Bleaching accelerators can be added to the bleaching bath, bleach-fix bath or conditioning bath. Examples of the bleaching accelerator include a mercapto compound (JP-A-53-141623).
And US Pat. No. 3,938,858 and British Patent No. 1138842), compounds having disulfide bonds (described in JP-A-53-95630), thiazolidine derivatives (described in JP-B-53-9854), isothio Urea derivatives (JP-A-53-9492)
No. 7), thiourea derivatives (JP-B-45-850)
Nos. 6 and 49-26586), thioamide compounds (described in JP-A-49-42349), dithiocarbamates (described in JP-A-55-26506), and alkylmercapto compounds (eg, trithiophene) Glycerin, α, α′-thiodipropionic acid, δ-mercaptobutyric acid). The alkyl mercapto compound may have a substituent such as a hydroxyl group, a carboxyl group, a sulfonic acid group, and an amino group (which may further have a substituent such as an alkyl group or an acetoxyalkyl group). The amount of bleach accelerator used depends on the type of photographic material,
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, 10 ^{-5 to} 10 ^{-5 to} 10
^-1 mol is preferred, and 10 ^{-4 to} 5 × 10 ^{-2 is used.}
More preferably, it is used in molar. To the bleaching solution, in addition to the bleaching agent and the bleaching accelerator, a rehalogenating agent, an inorganic acid, an organic acid or a salt thereof having a pH buffering ability can be added. Examples of rehalogenating agents include bromides (eg, potassium bromide, sodium bromide, ammonium bromide) and chlorides (eg, potassium chloride, sodium chloride, ammonium chloride). Examples of acids or salts having a pH buffering capacity 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) and thiocyanates (eg, sodium thiocyanate, ammonium thiocyanate, potassium thiocyanate). Thioureas and thioethers. The amount of the fixing agent used per liter of the bleach-fix solution is preferably from 0.3 mol to 3 mol, and more preferably from 0.5 mol to 2 mol. The amount of the fixing agent used per liter of the fixing solution is 0.5
It is preferably from 1 to 4 mol, more preferably from 1 to 3 mol. The pH of the fixing solution is preferably from 6 to 10, and more preferably from 7 to 9. Known additives such as sulfites, bisulfites, buffers, chelating agents, and sulfinic acids may be further added to the fixing solution or the bleach-fixing solution. Further, an ammonium halide (eg, ammonium bromide) or an alkali metal salt of a 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 each component of the fixing solution or the bleach-fixing solution has a relatively high concentration. Considering the dilution by the overflow liquid, the amount of the discharged liquid can be reduced, and the load of the recovery process is reduced. The replenishment amount of the bleaching solution, the fixing solution and the bleach-fixing solution is 3 per m ² of the photographic material.
0 ml to 900 ml, preferably 50 ml
More preferably, the volume is from 150 to 150 ml.

In the desilvering treatment, a washing step or a washing alternative stabilizing step is finally performed. Known additives can be added to the washing water used in the washing step, if necessary.
Examples of additives include chelating agents (eg, inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid), fungicides, fungicides,
Hardening agents and surfactants can be mentioned. The washing step may use two or more tanks. Further, the washing water may be reduced by multi-stage countercurrent washing (for example, two to nine stages). The stabilizing solution used in the washing-substitute stabilizing step has an effect of stabilizing the dye image. Examples of stabilizing solutions include:
Examples thereof include a solution having a buffer capacity of pH 3 to 6, and a solution containing an aldehyde (eg, formaldehyde). If necessary, a chelating agent, a bactericide, a fungicide, a hardener, a surfactant, and the like can be added to the stabilizing solution. The water washing alternative stabilization step may use two or more tanks. The stabilizing solution may be saved by multi-stage countercurrent washing (eg, two to nine stages). The processing bath of each step as described above may be provided with 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, and the like, as necessary. .

Hereinafter, the color photographic material used in the present invention will be described. 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 generally sensitive to visible light, specifically, any one of 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 silver halide emulsion layer is generally arranged 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 layer and the coupler other than those described above, and the arrangement of the photoreceptive layer other than the above are also possible. Further, each emulsion layer may have a two-layer structure of a high-speed emulsion layer and a low-speed emulsion layer. In a general color photographic material, layers having various functions (eg, an antihalation layer, an intermediate layer, an ultraviolet absorbing layer, and a protective layer) are provided in addition to the silver halide emulsion layer.

Next, the silver halide emulsion will be described. Preferred silver halides include silver iodobromide, silver iodochloride and silver iodochlorobromide. The silver iodide contained in the silver halide is preferably at most 30 mol%. 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 are particularly preferred. The grain size of the silver halide may be fine grains of 0.2 μm or less or relatively large grains of about 10 μm. However, in the silver halide emulsion layer closest to the support, those having a small grain size (for example, 0.1 to 0.4 μm, preferably 0.1 to 0.3 μm in number average) are preferably used. Since the progress of development is delayed in the silver halide emulsion layer on the support side, 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 a diameter when a 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 monodispersed 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. Monodispersed silver halide emulsions are described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748. The silver halide grains are composed of regular crystals such as cubic, octahedral and tetrahedral. Those having an irregular crystal system such as spherical and flat, those having crystal defects such as twin planes,
Alternatively, any of these composite forms may be used. The tabular grains generally mean grains having an aspect ratio of 5 or more. For tabular grains, see Gatov, Photographic
Science and Engineering (Gutoff, Phot
ographic Science and Engineering), Vol. 14, 24
8-257 (1970), U.S. Patent No. 4,434,226
Nos. 4,441,310, 4,433,048, 44
No. 39,520 and British Patent 2,121,157. The crystal structure of the silver halide grains may be such that the inside and outside have different halogen compositions. Further, the particles may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining. Compounds other than silver halide, such as rodan silver and lead oxide, may be bonded. Further, a mixture of particles of various crystal forms may be used. The coating amount of the silver halide emulsion is preferably from 0.1 g / m ² to 1.5 g / m ^{2 in} terms of silver, and more preferably from 0.1 g / m ^{2 to} 1.0 g / m ^2. . A silver halide emulsion is usually subjected to physical ripening, chemical ripening and spectral sensitization during preparation. The method for preparing a silver halide emulsion is described in Research Disclosure Magazine No. 17643 (December 1978).
Mon) p. 22-23, "I. Emulsion preparation and t
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 uses 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 a double jet method in the reaction of the halogen salt, whereby the required regular crystal form can be obtained by keeping the pAg constant. (Monodispersed) silver halide emulsions having a suitable grain size distribution can be prepared, and examples of the silver halide solvent include ammonia, rodankari, rhodanammon, thioether compounds (US Pat.
No. 271157, No. 3574628, No. 370413
0, 4297439 and 4276374), tetrasubstituted thiourea compounds (JP-A-53-8).
2408 and 55-77737).
Thione compounds (JP-A-53-144319, JP-A-53-143319)
Nos. 82408 and 55-77737)
And amine compounds (described in JP-A-54-100717). The silver halide solvent is preferably used in an amount of 10 ^-5 mol 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 emulsions during precipitation of silver halide grains or during physical ripening.

For the purpose of improving the photographic characteristics of the color photographic material, a heavy metal can be added at the time of forming silver halide grains (preferably, silver halide grains sharing the low density side) or at the time of physical ripening. Examples of heavy metals include rhodium, cadmium, lead, thallium, iridium, copper,
Iron and zinc can be mentioned. Rhodium, cadmium, thallium and lead are preferred. Heavy metals may be added as metal salts. Two or more types of heavy metals may be used in combination. The amount of heavy metal used is 10
It is preferably from ^-10 mol to 10 ^-2 mol, and 10 ^-8
More preferably, the molar amount is from 10 to ³ mol. For the purpose of improving the photographic characteristics of the color photographic material, a phenol compound may be added to the silver halide emulsion layer. As the phenol compound, a hydroquinone compound is particularly preferred. The hydroquinone compound is disclosed in JP-A-55-4
Nos. 3521, 56-109344, 57-222
Nos. 37 and 60-172040 and U.S. Pat. No. 2,701,197. The phenol compound can be added to the photographic material as an aqueous alkaline solution. Further, it may be dissolved in a high boiling point oil and added to the photographic material as an emulsion. Phenol compound is 10
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 the coupler is not particularly limited. The yellow coupler is preferably a pivaloyl or benzoyl compound. For the yellow coupler, see JP-B-58-107.
39, and U.S. Pat.
73968, 40222620 and 4248961
No. 4314023, No. 4326024, No. 44
Nos. 01752 and 4511649, British Patent 1425
020, 1476760 and EP 2494
No. 73A is described in each specification. The magenta coupler is
5-Pyrazolone and pyrazoloazole compounds are preferred. The magenta coupler is disclosed in JP-A-55-1.
No. 18034, No. 60-33552, No. 60-357
No. 30, No. 60-43659, No. 60-185951
No. 61-72238, U.S. Pat.
Nos. 1432, 3725067 and 4310619
No. 4351897, No. 4500630, No. 45
40654, 4555630, European Patent 7363
6, International Publication W088 / 04795, and Research Disclosure Magazine No. 24220 (19)
June 1984) and 24230 (June 1984)
Month). Cyan couplers are preferably phenolic and naphthol compounds. The cyan coupler is described in JP-A-61-42658, and U.S. Pat. Nos. 2,369,929, 2,772,162 and 2,801.
No. 171, 2895826, 3446622,
No. 3758308, No. 3772002, No. 4052
No. 212, No. 4146396, No. 4228233,
Nos. 4254212, 4296199, 4296
No. 200, No. 4327173, No. 4333999,
Nos. 4334011, 4427767, 4451
No. 559, No. 4690889, No. 4775616,
German Patent Publication No. 3329729, European Patent 121365
No. A and No. 249453A are described in each specification.
Other couplers that can be added to photographic materials include colored couplers for correcting unnecessary absorption of coloring dyes (JP-B-57-39413, U.S. Pat.
04909, 4138258, 4163670
And British Patent 1146368 and Research Disclosure 17643 VII-G.
), A coupler which corrects 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 a dye precursor which reacts with a developing agent to form a dye as a leaving group (described in US Pat. No. 4,777,120), and a coupler having a color-forming dye having an appropriate diffusivity (US Pat. No. 43662)
No. 37, British Patent No. 2125570, West German Patent Publication 32
No. 34533 and EP 96570), polymerized dye-forming couplers (US Pat.
No. 451820, No. 4080211, No. 436728
Nos. 2, 409,320 and 4,576,910 and British Patent No. 2,210,173), and DIR couplers which release a development inhibitor upon coupling (JP-A-57-151944, JP-A-57-154234, and JP-A-57-154234). Nos. 60-184248, 63-37346 and 63-37350, U.S. Pat. Nos. 4,248,962 and 478,2012, and Research.
A coupler which releases a nucleating agent or a development accelerator in the form of an image during development (see JP-A-59-157538 and JP-A-5-157538).
Nos. 9-170840 and British Patent 20971
Nos. 40 and 2131188), competitive couplers (described in U.S. Pat. No. 4,130,427), multiequivalent couplers (described in U.S. Pat. Nos. 4,283,472 and 4,338).
No. 393 and No. 4310618), D
IR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing compound or DIR
Redox-releasing redox compounds (JP-A-60-185)
Nos. 950 and 62-24252), couplers that release dyes that recolor after release (EP 173)
Nos. 302A and 313308A).
Bleaching accelerator releasing couplers (JP-A-61-201247, and Research Disclosure 1144)
No. 9 and 24241), a ligand releasing coupler (described in U.S. Pat. No. 4,553,477) and a coupler releasing a leuco dye (described in JP-A-63-75747). The coupler used in the present invention is preferably added to a photographic material using a high boiling point 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 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, triethyl phosphate) Cyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (eg, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl) -P-hydroxybenzoate), amides (eg, N, N-diethyldodecaneamide, N, N-diethyllauramide, 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 a high boiling point solvent, the boiling point is 30 ° C. or higher, preferably 50 ° C. to 160 ° C.
May be used. Examples of co-solvents include
Examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

Other additives that can be used in photographic materials are described in Research Disclosure Nos. 17643 and 18716. The relevant sections are summarized below. ──────────────────────────────────── Additive RD17643 RD18716 ────────── ────────────────────────── Chemical sensitizer page 23 648 right column Sensitivity enhancer 648 right column Spectral sensitizer, supercolor Sensitizers page 23-24 page 648 right column-page 649 right column Brightener 24 antifoggants and stabilizers 24-25 page 649 right column Light absorbers, filter dyes 25-26 page 649 right column Page 650 right column and UV absorber Stain inhibitor 25 page right column 650 left column to right dye image stabilizer 25 hardener 26 page 651 left column Binder 26 page 651 left column plasticizer, lubricant Page 27, 650, right column Coating aids and surfactants Pages 26-27, page 650, right column Static inhibitor Page 27, page 650, right column In order to prevent deterioration, a compound which reacts with formaldehyde and is fixed may be added to the photographic material. Such compounds are described in U.S. Pat. Nos. 4,441,1987 and 44,355.
No. 03 is described in each specification. Hydroquinones that release development inhibiting compounds (described in JP-A-64-546 and U.S. Pat. Nos. 3,379,529 and 3,639,417) or naphthoquinones that release development inhibiting compounds (Research Disclosure, 1826)
No. 4 (June 1979)) may be added to the photographic material. Preservatives or fungicides may be added to the photographic materials. Examples of preservatives and fungicides include 1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5.
-Dimethylphenol, 2-phenoxyethanol and 2- (4-thiazolyl) benzimidazole. Preservatives and fungicides are described in JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941.

There is no particular limitation on the support used for the photographic material. For the support, see page 28 of Research Disclosure, 17643, and 64 of Research, No. 18716.
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 the 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 more preferably 12 μm or less. It is particularly preferred that there is.
Further, the film swelling speed (T _1/2 ) is preferably 30 seconds or less, and more preferably 20 seconds or less. The film swelling speed is defined as 90% of the maximum swelling film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds, and is defined as the time required to reach half the film thickness. . The film thickness can be measured using a serometer (swelling meter). A. Green et al. (A. Green
et al), Photographic Science and
Engineering (Photogr. Sci. Eng.), 19, 2
No. 9, pages 124 to 129. The membrane swelling rate is
It can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. Further, the swelling ratio is preferably from 150 to 400%.

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

[0241]

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

Example 1 The following first to twelfth layers were coated on a 220 μm thick paper support laminated on both sides with polyethylene to prepare a color photographic material. 15% by weight of anatase type titanium dioxide white was added as a white pigment and a trace amount of ultramarine blue as a bluing dye was added to the polyethylene on the first layer application side. The chromaticity of the support surface is (L *, a *, b
*) In color system, 89.0, -0.18, -0.
73.

(Composition of Each Layer) The components of each layer and the coating amount (g / m ² ) are shown below. However, the coating amount of silver halide is shown in terms of silver. 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 with (equivalent) (silver chloride 1 mol%, silver iodide 4 mol%, average grain size 0.3 μm, grain size distribution 10%, cubic, core iodine type core-shell structure) 0.06 Silver iodobromide spectrally sensitized with a red sensitizing dye (equivalent amounts of 1, 2, 3) (silver iodide 4 mol%, 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 (2-ethylhexyl) phthalate (a solution for couplers 0.02 Trinonyl phosphate (solvent for coupler) 0.02 Di (3-methylhexyl) phthalate (solvent for coupler) 0.02 Development accelerator 0.05 4th layer (highly sensitive red-sensitive layer) Red sensitization Silver iodobromide (silver iodide 6 mol%, average grain size 0.8 μm, grain size distribution 18%, tabular (aspect ratio = 8), core iodine spectrally sensitized with dyes (1, 2, 3) Degree 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 dispersing 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 (middle layer) Magenta colloidal silver 0.02 Gelatin 1.00 Color mixture inhibitor 1 0.04 Color mixture inhibitor 2 0.04 Tricresyl phosphate (Color mixture inhibitor) Solvent 0.08 dibutyl phthalate (solvent for color mixture inhibitor) 0.08 polyethyl acrylate latex (molecular weight 10,000 to 100,000) 0.10 6th layer (low-sensitivity green-sensitive layer) Spectral increase with green sensitizing dye 1 Felt silver chloroiodobromide (silver chloride 1 mol%, silver iodide 2.5 mol%, average grain size 0.28 μm, grain size distribution 6%, cubic, core iodine type core-shell structure) 0.03 green Silver iodobromide spectrally sensitized with sensitizing dye 1 (silver iodide 2.5 mol%, average grain size 0.45 μm, grain size distribution 10%, cubic) 0.05 gelatin 0.80 mazen Coupler 1 0.05 Magenta coupler 2 0.05 Anti-fading agent 4 0.10 Stain inhibitor 1 0.05 Stain inhibitor 2 0.05 Stain inhibitor 3 0.001 Stain inhibitor 4 0.01 Dispersion medium (coupler 0.05) Tricresyl phosphate (solvent for coupler) 0.075 Trioctyl phosphate (solvent for coupler) 0.075 7th layer (highly sensitive 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 iodine type) 0.10 Gelatin 0.80 Magenta coupler 1 0.05 Magenta coupler 2 0.05 Anti-fading agent 4 0.10 Stain inhibitor 3 0.001 Stain inhibitor 4 0.01 Dispersion medium (for coupler) 0.05 Licresyl phosphate (solvent for couplers) 0.075 Trioctyl phosphate (solvent for couplers) 0.075 Eighth layer (yellow filter layer) Yellow colloidal silver 0.14 Gelatin 1.00 Color mixture inhibitor 1 0.06 Tricle Zyl phosphate (solvent for color mixture inhibitor) 0.075 Dibutyl phthalate (solvent for color mixture inhibitor) 0.075 Polyethyl acrylate latex (molecular weight 10,000 to 100,000) 0.10 Ninth layer (low-sensitivity blue-sensitive layer) Blue increase Silver chloroiodobromide (2 mol% of silver chloride, 2.5 mol% of silver iodide, average grain size 0.38 μm, grain size distribution 8%, Cubic, core iodide type core-shell structure) 0.07 Silver iodobromide (2.5 mol% of silver iodide) spectrally sensitized with a blue sensitizing dye (1, 2 equivalents) 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 10th layer (highly sensitive blue-sensitive layer) Spectral sensitization with blue sensitizing dye (1, 2 each equivalent) Silver iodobromide felt (2.5 mol% silver iodide, average grain size 1.4 μm, grain size distribution 21%, tabular (aspect ratio = 14), core iodine type core-shell structure) 0.25 gelatin 1.00 Yellow coupler 1 0.20 Yellow coupler 2 0.20 Anti-fading agent 5 0.10 Stain inhibitor 3 0.002 Dispersion medium (for coupler) 0.15 Trinonyl Sulfate (solvent for coupler) 0.10 11th layer (ultraviolet absorbing layer) gelatin 1.50 ultraviolet absorbent 1 0.50 ultraviolet absorbent 2 0.50 dispersion medium (for ultraviolet 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 Twelfth layer (protective layer) Gelatin 0.90 1,2-bis (vinylsulfonylacetamide) ethane (hardening agent for gelatin) 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

In each layer, alkanol XC (manufactured by Du Pont) and sodium alkylbenzenesulfonate were used as emulsifying and dispersing agents, and succinic acid ester and Magfac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. Was. 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 materials are shown below.

[0246]

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[0250]

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[0255]

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[0256]

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[0259]

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[0260]

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[0261]

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[0262]

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[0263]

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[0264]

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[0268]

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[0269]

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[0271]

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[0272]

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[0276]

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[0277]

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[0278]

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[0279]

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Next, photographic materials (102) to (110) were prepared using various compounds as shown in Table 1 below.

[0281]

[Table 1] Table 1 Sample No. Compound Addition layer Addition amount (Mol / m ² ) １０１ 101 (Comparative Example) None None None 102 (Comparative Example) The following comparative compound Fifth layer 6 × 10 ⁻⁵ 103 (present invention) (Ia-12) Fifth layer 6 × 10 ⁻⁵ 104 (present invention) (Ia-19) Fifth layer 6 × 10 ^-5 105 (Invention) (Ib-5) Fifth layer 6 × 10 ^-5 106 (Comparative example) Comparative compound below Third and fourth layers 3 × 10 ^-5 107 (Invention) (Ia-12) 3 × 10 ⁻⁵ 108 (invention) (Ia-12) 3rd, 4th, 6th, 7th layer 3 × 10 ⁻⁵ 109 (invention) (Ia-19) 3rd, 4th and 4th layers 6,7-layer each 3 × 10 ^-5 1 0 (present invention) (Ib-5) the 3, 4, 6, 7 layer each 3 × 10 ^-5 ───────────────────────── ───────────

[0282]

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The photographic material obtained as described above was exposed to red light through a continuous wedge and developed as follows. Next, light of three colors (red light, green light, and blue light) is adjusted so that the sample exposed and developed by white light becomes gray, and each photographic material is exposed through a continuous wedge. did. In addition, the exposure amount of the red light at the time of red light exposure and the red light included in the white light were the same. Further, the black-and-white developing treatment was carried out by changing the concentration of bromide contained in the black-and-white developing solution as shown in Table 2 below. The density of the sample obtained as described above was measured, and the difference between the exposure amounts when the cyan density at the time of red light exposure and the white light exposure was 0.6, ΔlogE
(R) was determined as an interimage effect on the red-sensitive silver halide emulsion layer. In the same manner, the interimage effect on other silver halide emulsion layers, ΔlogE (G) and ΔlogE (B) were determined. Table 3 shows the results.

──────────────────────────────────── Processing time Time Temperature Mother liquor tank capacity Refill 量────────────────────────────────── Black and white development 75 seconds 38 ° C 8 liters 330 ml / m ² First rinse ( First bath) 45 seconds 33 ° C 5 liter None First water rinse (second 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 Washing 45 seconds 33 ° C. 5 liters 1000 ml / m ² Bleaching and fixing (first bath) 60 seconds 38 ° C. 7 liters None Bleaching and fixing (second bath) 60 seconds 38 ° C. 7 liters 220 ml / m ² Third washing (first bath) ) 45 seconds 33 ° C 5 liters None No. 3rd washing (second bath) 45 seconds 33 ° C 5 liters No No. Washing (Third bath) 45 sec 33 ° C. 5 liters 5000 ml / m ² Drying 45 sec 75 ℃ ───────────────────────────── ───────

[0285] The first and third rinsing steps are as follows:
Each was a countercurrent washing system. That is, in the first rinsing step, rinsing water was flowed into the second bath, and the overflow liquid was led to the first bath. In the third rinsing step, rinsing water was flowed into the third bath, the overflow was led to the second bath, and the overflow of the second bath was led to the first bath.

The composition of each processing solution is shown below.

──────────────────────────────────── Black and white developer mother liquor replenisher ───── ─────────────────────────────── Nitrilo-N, N, N-trimethylenephosphonic acid · 5 sodium salt 1.0 g 1.0 g diethylenetriaminepentaacetic acid / 5 sodium salt 3.0 g 3.0 g potassium sulfite 30.0 g 30.0 g potassium thiocyanate 1.2 g 1.2 g potassium carbonate 35.0 g 35.0 g potassium hydroquinone monosulfonate 25.0 g 25 1.0 g 1-phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g potassium bromide (see Table 2 below) Potassium iodide 5.0 mg None ────────── ──────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 ──────────────────── ────────────────────────────

[0288]

[Table 2] Table II Processing Bromide in black and white developer Concentration (mol / liter) A (Comparative Example) 0.010 B (present invention) 0.025 C (present invention) 0.040 D (present invention) 0.080 E (comparative example) 0.120 ────────────────── ──────────────────

──────────────────────────────────── Color developer mother liquor replenisher ─────ベ ン ジ ル Benzyl alcohol 15.0 ml 16.5 ml diethylene glycol 12.0 ml 13.0 ml 3,6- Dithia-1,8-octane-diol 0.20 g 0.22 g Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 0.5 g 0.5 g Diethylenetriaminepentaacetic acid / 5 sodium salt 2.0 g 2.0 g Sodium sulfite 2.0 g 2.22 g hydroxylamine sulfate 3.0 g 3.3 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-aminoaniline sulfate 5.0 g 6.5 g fluorescent brightening Agent (I-7) 0.0 g 1.1 g Potassium bromide 0.5 g 0.25 g Potassium iodide 1.0 mg None ─────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 10.25 10.35 ─────── ───────────────

──────────────────────────────────── Bleach-fixer mother liquor replenisher ─────エ チ レ ン Ethylenediaminetetraacetic acid disodium dihydrate 5.0 g 5.0 g Ethylenediaminetetraacetic acid Ammonium Fe (III) monohydrate 80.0 g 80.0 g Sodium sulfite 15.0 g 15.0 g Aqueous ammonium thiosulfate (700 ml / l) 160 ml 160 ml 2-mercapto-1,3,4-triazole 0.5 g 5g ──────────────────────────────────── Add water 1000ml 1000ml pH (with acetic acid or ammonia water) Adjustment) 6.50 6.50 ──────────────────

[0291]

[Table 3] Table 3 試 料 Sample number processing Maximum color density ( Dmax) Inter-image effect ΔlogE RGB GB GB Ｂ 101 A Comparative Example 2.l8 2.22 2.20 0.14 0.17 0.13 101 B Comparative Example 2.55 2.57 2.50 0.14 0.16 0.13 101 C Comparative Example 2.58 2.60 2.56 0.12 0.15 0.12 101 D Comparative Example 2.61 2.63 2.60 0.10 0.13 0.10 101 E Comparative Example 2.61 2.63 2.61 0.08 0.09 0.07 102 A Comparative example 2.18 2.23 2.19 0.14 0.17 0.13 102 B Comparative example 2.54 2.56 2.51 0.14 0.16 0.13 102 C Comparative example 2.57 2.60 2.57 0.12 0.15 0.12 102 D Comparative example 2.61 2.62 2.60 0.10 0.13 0.10 102 E Comparative example 2.61 2.62 2.60 0.08 0.09 0.07 103 A Comparative Example 2.l9 2.22 2.20 0.20 0.25 0.16 103 B Present invention 2.55 2.57 2.51 0.20 0.25 0.16 1 3C Present invention 2.58 2.62 2.58 0.19 0.23 0.15 103 D Present invention 2.62 2.64 2.61 0.18 0.22 0.14 103E Comparative example 2.62 2.64 2.61 0.13 0.14 0.11 ──────────────────── ────────────────

[0292]

[Table 4] Table 3 (continued) 試 料 Sample No. Treatment Max. Color density (Dmax) Inter-image effect ΔlogE RGB RGB B ─────────────────────────────────── １０４ 104 C Invention 2.59 2.61 2.57 0.20 0.23 0.15 105 C Invention 2.58 2.62 2.58 0.19 0.22 0.15 106 C Comparative Example 2.58 2.61 2.57 0.12 0.15 0.12 107 C Invention 2.59 2.62 2.59 0.20 0.24 0.15 108 C Invention 2.60 2.63 2.59 0.21 0.25 0.20 109 C Invention 2.59 2.62 2.58 0.22 0.26 0.21 110 C Invention 2.58 2.61 2.58 0.21 0.24 0.20 発 明───────

As shown in Table 3, the treatments B to D of the present invention having a higher bromide concentration than the comparison treatment A have improved maximum image density values. However, in the case of the processes B to D, the interimage effect is slightly reduced. In the comparative treatment E having an extremely high bromide concentration, the interimage effect is significantly reduced. Samples of the present invention comprising a compound of formula (I A) or (Ib) 103 to 105 and from 107 to 11
When 0 is used in the above processes B to D, it is possible to prevent a decrease in the interimage effect without lowering the maximum density value. Samples 102 and 106 containing the comparison compound
Then, such an effect cannot be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 7/00 G03C 5/50 G03C 7/305 G03C 7/407

Claims (3)

(57) [Claims] 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. Bromide
Solution containing 0.025 to 0.1 mol / L
Black-and-white development process are, reversal processing, a method of forming a color reversal image on the photographic material by a color development process and a desilvering process, over there containing compounds photographic material having the following formula (I A) or (Ib) And a color reversal image forming method. Embedded image Embedded image Wherein R ¹² is an alkyl, alkenyl, alkynyl, aryl or 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 ²¹ is a hydrogen atom or hydroquinone nucleus substituents; A and A 'is a group which can be removed by a hydrogen atom or an alkali; L forms a 5-membered or more hetero ring fused to the hydroquinone nucleus Time is a divalent group; 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. Wherein the above formula (I A), 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 with a hetero atom. Method. 3. In the above formula (I A ), M is —SO ₂
^{-, -N (R 15) CO} -, - OCO- or -N (R ¹⁵⁾ S
The image forming method according to claim 1, wherein O ₂ —.