CN1346075A - Silver halide colour photosensitive material - Google Patents

Abstract

The present invention discloses a silver halide colour photosensitive photographic material, including at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer on the carrier, in which at least one layer of non-photosensitive layer contains incinerated silver halide emulsion, and said emulsion contains granules with previously-incinerated surface, and the non-photosensitive layer and/or other adjacent layer contain the compound capable of producin greaction with developing agent with oxidation form to release photographic useful group, and the incinerated emulsino can be devloped and formed into colour developing agent with oxidation form in the course of colour development, and the photographic useful compound can be released in the imagless mode by means of coupling reaction. Said invention material possesses excellent storage stability, and can stably and quickly release photographic useful group.

Description

Silver halide color photosensitive material

The present invention relates to a silver halide color photosensitive material which has high storage stability and is capable of stably and rapidly releasing a photographically useful group during color development.

Depending on the type of photographically useful groups released during color development, various effects may be obtained.

The photographically useful compounds necessary during development are typically added to the developer solution (i.e., the compounds are added to the replenisher solution to ensure the concentration necessary in flow equilibrium).

However, when a compound useful for photography is added to a developer or a replenisher, its effect is sometimes lost under the influence of long-term storage (storage or replenishment of the replenisher).

To prevent this, a photographically useful compound may be added to the photosensitive material in advance, and the effect thereof may be achieved during development. The advantage of this method is that the effect is only achieved in necessary locations, for example in the vicinity of a particular layer and its multiple layers of photosensitive material. However, if a photographically useful compound is added to a photosensitive material in an active form, the compound may decompose under the action of heat, moisture, or oxygen when the photosensitive material is stored before development. As a result, its effect cannot be achieved during development. In addition, the decomposition product sometimes causes unpreferable change in photographic properties to the photosensitive material. Therefore, this method is not applicable depending on the type of compound.

Japanese examined patent publication (hereinafter, referred to as JP-B-)4-73573 discloses a method for solving this problem. In this method, a photographically useful compound (e.g., a precursor of a photographically useful compound) is added to a photosensitive material in a substantially inactive form by blocking its reactive group, and the precursor functions as a reactive photographically useful compound in a developer.

This JP-B-4-73573 realizes both rapid release of the active photographically useful compound from the precursor during development and high storage stability of the photosensitive material. However, there is still a need to further improve the storage stability of photosensitive materials. In addition, the release of the active photographically useful compounds uses a reaction with hydroxylamine in a developer. This also produces a large variation in photographic properties due to the variation in hydroxylamine concentration.

Japanese patent application laid-open (hereinafter referred to as JP-A-)8-339058, which corresponds to current U.S. Pat. No.5,561,031, discloses ｃA color reversal photographic monomer in which ｃA non-photosensitive emulsion and ｃA bleach accelerator releasing compound capable of releasing ｃA bleach accelerator by reacting with an oxidized form of ｃA developer are added in ｃA single identical layer or in combined layers.

This is a very excellent process in which the bleach booster (photonically useful compound) is released in an imageless manner during color development. However, the non-photosensitive emulsion is chemically ashed in a reverse bath (ashing step) before color development. Therefore, this method cannot be applied to a color negative photosensitive material or a color photographic paper photosensitive material that does not use a reverse bath.

JP- ｃA-63-175850 discloses ｃA photosensitive material containing silver halide particles having ashing nuclei on the surface or subsurface thereof in ｃA silver halide emulsion. The photosensitive material also contains a bleach accelerator (photographic use compound) release coupler. The method is excellent in that high aging stability and good desilvering characteristics of the photosensitive material can be achieved. However, silver halide grains having an ashing nucleus on the surface or subsurface thereof coexist in one silver halide emulsion layer. Depending on the type of silver halide emulsion, this may sometimes adversely affect the aging stability of the photosensitive material.

Also, in this method, silver halide particles having ashing nuclei are present together in one silver halide emulsion layer, so that the bleach accelerator is released in an image-wise manner to some extent. Therefore, the amount of release and the like easily vary depending on the properties due to storage, release and the like of the coexisting silver halide emulsion.

JP- ｃA- 2-504 2 discloses ｃA color reversal material comprising ｃA surface-ashed silver halide emulsion and ｃA bleach accelerator releasing compound. Because the color reversal material needs to undergo black and white development before color development, the ashed silver halide emulsion forms developed silver during color development so that no oxidized form of the developer is formed. As a result, no photographically useful groups can be produced during development.

Accordingly, an object of the present invention is to provide a silver halide photosensitive material which has high storage stability and contains a compound capable of stably and rapidly releasing a photographically useful group during color development.

The above object of the present invention is achieved by the following silver halide photosensitive material. That is to say that the position of the first electrode,

(1) a silver halide color photosensitive material comprising at least one photosensitive silver halide emulsion layer and at least one nonphotosensitive layer on a support,

wherein at least one layer of the non-photosensitive layer comprises a pre-ashed silver halide emulsion comprising particles having a pre-ashed surface, and the non-photosensitive layer comprising the pre-ashed emulsion and/or a layer adjacent thereto comprises a compound capable of releasing a photographically useful group or a precursor thereof by a coupling reaction with an oxidized form of a developer; the pre-ashed emulsion is developed during color development to uniformly form an oxidized form of the color developer, while the photographically useful groups or precursors thereof are released imagewise by a coupling reaction.

(2) The silver halide color photosensitive material described in the above item (1), wherein the compound capable of releasing a photographically useful group or a precursor thereof forms substantially no image upon coupling reaction with an oxidized form of a developer.

(3) The silver halide color photosensitive material described in the above item (2), wherein the compound capable of releasing a photographically useful group or a precursor thereof is represented by the following formula (II):

COUP1-B1 (II) wherein COUP1 represents a color former group capable of liberating B1 by a coupling reaction with an oxidized form of a developer and also forming a water-soluble or alkali-soluble compound, and B1 represents a photographically useful group or a precursor thereof attached at the coupling position of COUP 1.

(4) The silver halide color photosensitive material described in the above item (3), wherein the compound represented by the formula (II) is a compound represented by the following formula (III):

COUP2-A-E-B2 (III) wherein COUP2 represents a color former group capable of coupling to an oxidized form of a developer; e represents an electrophilic moiety; a represents a linking group capable of releasing B2 by forming a ring through an intramolecular nucleophilic substitution reaction of a nitrogen atom, which is present in the coupling product between COUP2 and the oxidized form of the developer by the developer, and which directly links the coupling site with the nucleophilic moiety E; and B2 represents a photographically useful group or precursor thereof.

(5) The silver halide color photosensitive material described in any one of the above items (1) to (4), wherein the silver halide emulsion and the compound, which are previously ashed, are contained in the same layer.

(6) The silver halide color photosensitive material described in any one of the above items (1) to (5), wherein the non-photosensitive layer containing the previously ashed silver halide emulsion contains black colloidal silver.

(7) The silver halide color photosensitive material described in any one of the above items (1) to (5), wherein the layer adjacent to the non-photosensitive layer containing the previously ashed silver halide emulsion contains black colloidal silver.

(8) The silver halide color photosensitive material described in any one of the above items (1) to (7), wherein the photographically useful group is a bleaching accelerator.

(9) The silver halide color photosensitive material described in any one of the above items (1) to (7), wherein the photographically useful group is a development inhibitor.

(10) The silver halide color photosensitive material described in any one of the above items (1) to (9), wherein at least one of the photosensitive silver halide emulsions contained in the at least one photosensitive silver halide emulsion layer is an emulsion having a silver chloride content of at least 10 mol%.

(11) The silver halide color photosensitive material described in any one of the above items (1) to (10), wherein at least one of the previously ashed silver halide emulsions contained in the at least one nonphotosensitive layer is an emulsion having a silver chloride content of at least 10 mol%.

The present invention will be described in more detail below.

The compounds of the present invention capable of releasing a photouseful group or a precursor thereof by a coupling reaction with an oxidized form of a developer are described below.

The compound capable of releasing a photographically useful group or a precursor thereof by a coupling reaction with an oxidized form of a developer is preferably a compound represented by A-B.

A represents a coupler group, and preferable examples are as follows.

Examples of color former groups are yellow color former groups (e.g., open-chain ketone methylene coupler groups such as acyl acetanilides and malonodianilides), magenta color former groups (e.g., 5-pyrazolone, pyrazolotriazole, imidazopyrazole), cyan color former groups (e.g., phenol type coupler groups, naphthol type coupler groups, and imidazole type coupler groups described in european patent publication No. 249,453, pyrazolopyrimidine type coupler groups described in EP 304,001), and non-dye forming color former groups (e.g., imidaanone type and acetophenone type coupler groups). Heterocyclic coupler groups described in U.S. Pat. Nos. 4,315,070, 4,183,75 2,4,174,969, 3,961,959, and 4,171,223, and JP-A-5 2-82423 may also be used.

More preferred examples are the color former groups represented by the formulae (Cp-1), (Cp-2), (Cp-3), (Cp-4), (Cp-5), (Cp-6), (Cp-7), (Cp-8), (Cp-9), (Cp-10), and (Cp-11). These color formers are preferred because of their high color formation rate.

In the above formulae, the symbol derived from the coupling position^*Represents the position at which the color former is attached to B in formula A-B.

In the above formula, if R₅₁、R₅₂、R₅₃、R₅₄、R₅₅、R₅₆、R₅₇、R₅₈、R₅₉、R₆₀、R₆₁、R₆₂、R₆₃、R₆₄Or R₆₅Containing a non-diffusing group, then the non-diffusing groupIs selected so that the total carbon number is 8 to 40, preferably 10 to 30. In another case, the total number of carbons is preferably 15 or less.

R₅₁-R₆₅、Z₁、Z₂Specific details of j, d, e, and f will be described below. In the following description, R₄₁Represents an aliphatic group, an aromatic group, or a heterocyclic group. R₄₂Represents an aromatic group or a heterocyclic group. R₄₃、R₄₄And R₄₅Respectively represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.

R₅₁Represents and R₄₁The same groups. R₅₂And R₅₃Respectively represent with R₄₂The same groups. j represents 0 or 1. R₅₄Represents and R₄₁Same group, R₄₁CON(R₄₃) -group, R₄₁R₄₃N-radical, R₄₁SO₂N(R₄₃) -group, R₄₁S-group, R₄₃O-group, R₄₅N(R₄₃)CON(R₄₄) -a group, or R₄₁OCON(R₄₃) -a group. R₅₅Represents and R₄₁The same groups. R₅₆And R₅₇Respectively represent with R₄₃Same radicals, R₄₁S-group, R₄₃O-group, R₄₁CON(R₄₃) -a group, or R₄₁SO₂N(R₄₃) -a group. R₅₈Represents and R₄₁The same groups. R₅₉Represents and R₄₁Same radicals, R₄₁CON(R₄₃) -group, R₄₁OCON(R₄₃) -group, R₄₁SO₂N(R₄₃) -group, R₄₃R₄₄NCON(R₄₅) -group, R₄₁O-group, R₄₁S-group, halogen atom, or R₄₁R₄₃An N-group.

d represents 0 to 3. If d is complex, then multiple R₅₉Represent the same substituent or different substituents.

In addition, these R₅₉Can be used as covalent groups to be connected with each other to form a ring structure. Examples of such cyclic structures are pyridine rings and pyrrole rings.

R₆₀Represents and R₄₁The same groups. R₆₁Represents and R₄₁The same groups. R₆₂Represents and R₄₁Same radicals, R₄₁OCONH-group, R₄₁SO₂NH-group, R₄₃R₄₄NCON(R₄₅) -group, R₄₃R₄₄NSO₂N(R₄₅) -group, R₄₃O-group, R₄₁S-group, halogen atom, or R₄₁R₄₃An N-group. R₆₃Represents and R₄₁Same radicals, R₄₃CON(R₄₅) -group, R₄₃R₄₄NCO-group, R₄₁SO₂N(R₄₄) -group, R₄₃R₄₄NSO₂-group, R₄₁SO₂-group, R₄₃OCO-group, R₄₃O-SO₂A group, halogen atom, nitro group, cyano group, or R₄₃A CO-group.

e represents an integer of 0 to 4. If there are more than one R₆₂Or R₆₃They represent the same group or different groups.

R₆₄And R₆₅Each represents R₄₃R₄₄NCO-group, R₄₁CO-group, R₄₃R₄₄NSO₂-group, R₄₁OCO-group, R₄₁SO₂-a group, nitro, or cyano.

Z₁Represents a nitrogen atom or ═ C (R)₆₆) -a group (R)₆₆Represents a hydrogen atom or with R₆₃The same group). Z₂Represents a sulfur atom or an oxygen atom.

f represents 0 or 1.

In the above description, the aliphatic group is a saturated or unsaturated, chain or cyclic, straight or branched, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. Representative examples are methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, tert-pentyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,3, 3-tetramethylbutyl, decyl, dodecyl, hexadecyl, or octadecyl.

The aromatic group is 6 to 20 carbon atoms, preferably a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group.

The heterocyclic group is a substituted or unsubstituted heterocyclic group of 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, preferably 3 to 8 members, which contains a hetero atom selected from a nitrogen atom, an oxygen atom and a sulfur atom. Representative examples of such heterocyclic groups are 2-pyridyl, 2-furyl, 2-imidazolyl, 1-indolyl, 2, 4-dioxo-1, 3-imidazolin-5-yl, 2-benzoxazolyl, 1,2, 4-triazol-3-yl, and 4-pyrazolyl.

If any of these aliphatic hydrocarbon groups, aromatic groups, and heterocyclic groups has a substituent, representative examples are a halogen atom, R₄₇O-group, R₄₆S-group, R₄₇CON(R₄₈) -group, R₄₇N(R₄₈) CO-group, R₄₆OCON(R₄₇) -group, R₄₆SO₂N(R₄₇) -group, R₄₇R₄₈NSO₂-group, R₄₆SO₂-group, R₄₇OCO-group, R₄₇R₄₈NCON(R₄₉) -a group, with R₄₆Same radicals, R₄₆COO-group, R₄₇OSO₂-groups, cyano, and nitro. R₄₆Represents an aliphatic group, an aromatic group, or a heterocyclic group. R₄₇、R₄₈And R₄₉Each represents an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom. These aliphatic groups, aromatic groups and heterocyclic groups are the same as defined above.

Next, R will be described₅₁-R₆₅Preferred ranges for j, d, e and f.

R₅₁Preferably an aliphatic group or an aromatic group. R₅₂And R₅₅Each is preferably an aromatic group. R₅₃Aromatic or heterocyclic groups are preferred.

In the formula (Cp-3), R₅₄Preferably R is₄₁CONH-group or R₄₁R₄₃An N-group. R₅₆And R₅₇Are each preferably an aliphatic radical, an aromatic radical, R₄₁O-group, or R₄₁An S-group. R₅₈Preferably an aliphatic group or an aromatic group. In the formula (Cp-6), R₅₉Preferably a chlorine atom, an aliphatic group, or R₄₁CONH-group. d is preferably 1 or 2. R₆₀Preferably an aromatic group. In the formula (Cp-7), R₅₉Preferably R is₄₁CONH-group. d is preferably 1. R₆₁Preferably an aliphatic group or an aromatic group. In the formula (Cp-8), e is preferably 0 or 1. R₆₂Preferably R is₄₁OCONH-group, R₄₁CONH-group, or R₄₁SO₂An NH-group. The substitution position of these groups is preferably the (5) position of the naphthol ring. In the formula (Cp-9), R₆₃Preferably R is₄₁CONH-group, R₄₁SO₂NH-group, R₄₁R₄₃NSO₂-group, R₄₁SO₂-group, R₄₁R₄₃NCO-groups, nitro groups, or cyano groups, and e is preferably 1 or 2. In the formula (Cp-10), R₆₃Preferably is (R)₄₃)₂NCO-group, R₄₃OCO-group, or R₄₃CO-group, and e is preferably 1 or 2. In the formula (Cp-11), R₅₄Preferably an aliphatic group, an aromatic group, or R₄₁CONH-group, and f is preferably 1. Also, the color former group represented by A preferably has a non-diffusing group.

The photographically useful group represented by B or a precursor thereof is the same as explained for B1 and B2 in the following formulae (II) and (III).

Preferred examples of the compounds represented by A-B are development inhibitor-releasing couplers and bleach-accelerating agent-releasing couplers. However, the compound is not limited to these examples.

Examples of development inhibitor-releasing couplers are described in JP-A-6 2-34158, JP-A-63-37346, US-478201 2, JP-A-60-191241 and EP-252376.

Examples of bleach boosting agent releasing compounds are described in JP-A-60-191241, JP-A-64-31159, JP-A-1-185631, JP-A-7-15212 2, JP-A-8-339058 and JP-A-61-201247.

Examples of these compounds are shown below. However, the present invention is not limited to these examples.

The compound for releasing a photographically useful group represented by formula (II) will be described below:

COUP1-B1 (II) wherein COUP1 represents a color former group capable of liberating B1 by a coupling reaction with an oxidized form of a developer and also forming a water-soluble or alkali-soluble compound, and B1 represents a photographically useful group or a precursor thereof attached at the coupling position of COUP 1. )

The compound which releases a photographically useful group represented by formula (II) will be described below.

More specifically, the compound which releases a photographically useful group represented by formula (II) is represented by the following formula (IIa) or (IIb):

COUP1-(TIME)_m-PUG (IIa)

COUP1-(TIME)_iRED-PUG (IIb) in which COUP1 represents cleavage by coupling with an oxidized form of a developer (TIME)_mPUG or (TIME)_i-RED-PUG and forming a water-soluble or alkali-soluble compound, TIME representing a light-distributing (timing) group that cleaves PUG or RED-PUG after cleavage from COUP1 by a coupling reaction, RED representing a group that reacts with a developer in oxidized form after cleavage and cleavage of PUG by COUP1 or TIME, PUG representing a photographically useful group, m representing an integer from 0 to 2, and i representing 0 or 1. If m is 2, 2 TIMEs represent the same or different groups.

If COUP1 represents a yellow color-former group, examples of such color-former groups are pivaloyl N-acetylaniline type color-former groups, benzoyl N-acetylaniline type color-former groups, malonate diester type color-former groups, malonate diamide type color-former groups, dibenzoylmethane type color-former groups, benzothiazoleacetamide type color-former groups, malonate monoamide type color-former groups, benzoxazolethylacetamide type color-former groups, benzimidazolylethamide type color-former groups, quinazolin-4-one-2-yl N-acetanilide type color-former groups, and cycloalkanoylacetamide type color-former groups.

If COUP1 represents a magenta coupler group, examples of such coupler groups are a 5-pyrazolone-type coupler group, a pyrazolo [1, 5-a ] benzimidazole-type coupler group, a pyrazolo [1, 5-b ] [1, 2, 4] triazole-type coupler group, a pyrazolo [5, 1-c ] [1, 2, 4] triazole-type coupler group, an imidazo [1, 2-b ] pyrazole-type coupler group, a pyrrolo [1, 2-b ] [1, 2, 4] triazole-type coupler group, a pyrazolo [1, 5-b ] pyrazole-type coupler group, and a cyanoacetophenone-type coupler group.

If COUP1 represents a cyan coupler, examples of such coupler groups are phenol-type coupler groups, naphthol-type coupler groups, pyrrolo [1, 2-b ] [1, 2, 4] triazole-type coupler groups, pyrrolo [2, 1-c ] [1, 2, 4] triazole-type coupler groups, and 2, 4-diphenylimidazole-type coupler groups.

COUP1 may also be a color former group that leaves substantially no color image. Examples of this type of coupler group are indanone type and acetophenone type coupler groups.

Preferred examples of COUP1 are the color former groups represented by the following formulae (Cp '-1), (Cp' -2), (Cp '-3), (Cp' -4), (Cp '-5), (Cp' -6), (Cp '-7), (Cp' -8), (Cp '-9), (Cp' -10), (Cp '-11), and (Cp' -12). These color formers are preferred because of their high color formation rate.

In the above formula, the free bond derived from the coupling position represents the bonding position of the coupling cleavage group.

In the above formula, R'₅₁、R′₅₂、R′₅₃、R′₅₄、R′₅₅、R′₅₆、R′₅₇、R′₅₈、R′₅₉、R′₆₀、R′₆₁、R′₆₂、R′₆₃、R′₆₄、R′₆₅And R'₆₆The number of carbon atoms of (a) is preferably 10 or less, respectively.

The color former group represented by COUP1 preferably has at least one R selected from₇₁OCO-group, HOSO₂-group, HO-group, R₇₂NHCO-group, and R₇₂NHSO₂-a substituent of a group. That is to say, R ' of the formula (Cp ' -1) '₅₁And R'₅₂At least one of R ' of the formula (Cp ' -2) '₅₁、R′₅₂And R'₅₃At least one of R ' of the formula (Cp ' -3) '₅₄And R'₅₅R 'of at least one of the formulae (Cp' -4) and (Cp '-5)'₅₆And R'₅₇At least one of them, formula (A)R ' of Cp ' -6) '₅₈And R'₅₉At least one of R ' of the formula (Cp ' -7) '₅₉And R'₆₀At least one of R ' of the formula (Cp ' -8) '₆₁And R'₆₂At least one of the formulae (Cp ' -9) and (Cp ' -10) '₆₃And R 'of the formulae (Cp' -11) and (Cp '-12)'₆₄、R′₆₅And R'₆₆At least one of which has at least one R selected from₇₁OCO-group, HOSO₂-group, HO-group, R₇₂NHCO-group, and R₇₂NHSO₂-a substituent of a group. R₇₁Represents a hydrogen atom, an alkyl group having 6 or less carbon atoms (such as methyl, ethyl, propyl, isopropyl, butyl, and tert-butyl), or a phenyl group. R₇₂Represents R₇₁Group represented by R₇₄CO-group, R₇₄N(R₇₅) CO-group, R₇₃SO₂-a group, or R₇₄N(R₇₅)SO₂-a group. R₇₃Represents an alkyl group having 6 or less carbon atoms (such as methyl, ethyl, propyl, isopropyl, butyl, and tert-butyl), or a phenyl group. R₇₄And R₇₅Each represents R₇₁The group shown. These groups may also have a substituent.

R 'will be described in detail below'₅₁-R′₆₆A, b, d, e and f. In the following description, R'₄₁Represents an alkyl group, an aryl group or a heterocyclic group. R'₄₂Represents an aryl or heterocyclic group. R'₄₃、R′₄₄And R'₄₅Respectively represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

R′₅₁Represents and R'₄₁The same groups. a represents 0 or 1. R'₅₂And R'₅₃Respectively represent and R'₄₃The same groups. If R'₅₂R ' is not a hydrogen atom in formula (Cp ' -2) '₅₂And R'₅₁Can be combined with each other to form a 5-7 membered ring. b represents 0 or 1.

R′₅₄Represents and R'₄₁Are identical to each otherGroup R'₄₁CON(R′₄₃) -radical, R'₄₁SO₂N(R′₄₃) -radical, R'₄₁N(R′₄₃) -radical, R'₄₁S-radical, R'₄₃O-group, or R'₄₅N(R′₄₃)CON(R′₄₄) -a group. R'₅₅Represents and R'₄₁The same groups.

R′₅₆And R'₅₇Are each independently represented by R'₄₃Same radicals, R'₄₁S-radical, R'₄₃O-radical, R'₄₁CON(R′₄₃) -radical, R'₄₁OCON(R′₄₃) -a radical, or R'₄₁SO₂N(R′₄₃) -a group.

R′₅₈Represents and R'₄₃The same groups. R'₅₉Represents and R'₄₁Same radicals, R'₄₁CON(R′₄₃) -radical, R'₄₁OCON(R′₄₃) -radical, R'₄₁SO₂N(R′₄₃) -radical, R'₄₃N(R′₄₄)CON(R′₄₅) -radical, R'₄₁O-radical, R'₄₁S-group, halogen atom, or R'₄₁N(R′₄₃) -a group. d represents 0 to 3. If d is plural, then'₅₉Represent the same substituent or different substituents.

R′₆₀Represents and R'₄₃The same groups.

R′₆₁Represents and R'₄₃Same radicals, R'₄₃OSO₂-radical, R'₄₃N(R′₄₄)SO₂-radical, R'₄₃OCO-group, R'₄₃N(R′₄₄) CO-radical, cyano radical, R'₄₁SO₂(R′₄₃) CO-radical, R'₄₃CON(R′₄₄) CO-radical, R'₄₃N(R′₄₄)SO₂N(R′₄₅) CO-radical, R'₄₃N(R′₄₄)CON(R′₄₅) CO-radical, R'₄₃N(R′₄₄)SO₂N(R′₄₅)SO₂-a radical, or R'₄₃N(R′₄₄)CON(R′₄₅)SO₂-a group.

R′₆₂Represents and R'₄₁Same radicals, R'₄₁CONH-radical, R'₄₁OCONH-group, R'₄₁SO₂NH-group, R'₄₃N(R′₄₄) CONH-radical, R'₄₃N(R′₄₄)SO₂NH-group, R'₄₃O-radical, R'₄₁S-group, halogen atom, or R'₄₁N(R′₄₃) -a group. In the formula (Cp' -8), e represents an integer of 0 to 4. If e is 2 or greater, then a plurality of R'₆₂Represent the same substituent or different substituents.

R′₆₃Represents and R'₄₁Same radicals, R'₄₃CON(R′₄₄) -radical, R'₄₃N(R′₄₄) CO-radical, R'₄₁SO₂N(R′₄₃) -radical, R'₄₁N(R′₄₃)SO₂-radical, R'₄₁SO₂-radical, R'₄₃OCO-group, R'₄₃OSO₂-a group, a halogen atom, a nitro group, a cyano group, or R'₄₃A CO-group. In the formula (Cp' -9), e represents an integer of 0 to 4. If e is 2 or greater, then a plurality of R'₆₃Represent the same substituent or different substituents. In the formula (Cp' -10), f represents an integer of 0 to 3. If f is 2 or greater, then R'₆₃Represent the same substituent or different substituents.

R′₆₄、R′₆₅And R'₆₆Are each independently represented by R'₄₃Same radicals, R'₄₁S-radical, R'₄₃O-radical, R'₄₁CON(R′₄₃) -radical, R'₄₁SO₂N(R′₄₃) -radical, R'₄₁OCO-group, R'₄₁OSO₂-radical, R'₄₁SO₂-a group,R′₄₁N(R′₄₃) CO-radical, R'₄₁N(R′₄₃)SO₂-a group, nitro, or cyano.

In the above description, R'₄₁、R′₄₃、R′₄₄Or R'₄₅The aliphatic groups represented are saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted aliphatic groups of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Representative examples of such aliphatic groups are methyl, 1-propenyl, cyclopropyl, isopropyl, n-butyl, tert-butyl, isobutyl, tert-pentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-octyl, 1,3, 3-tetramethylbutyl, and n-decyl.

R′₄₁、R′₄₂、R′₄₃、R′₄₄Or R'₄₅The aryl group represented is an aryl group of 6 to 10 carbon atoms, and is preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.

R′₄₁、R′₄₂、R′₄₃、R′₄₄Or R'₄₅The heterocyclic group represented is a substituted or unsubstituted heterocyclic group of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, preferably 3 to 8-membered, which contains a hetero atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom. Representative examples of such heterocyclic groups are 2-pyridyl, 2-benzoxazolyl, 2-imidazolyl, 2-benzimidazolyl, 1-indolyl, 1,3, 4-thiadiazol-2-yl, 1,2, 4-triazol-2-yl, and 1-indolinyl.

If the above-mentioned aliphatic group, aromatic group, and heterocyclic group have a substituent, representative examples of the substituent are a halogen atom, R'₄₃O-radical, R'₄₁S-radical, R'₄₃CON(R′₄₄) -radical, R'₄₃N(R′₄₄) CO-radical, R'₄₁OCON(R′₄₃) -radical, R'₄₁SO₂N(R′₄₃) -radical, R'₄₃N(R′₄₄)SO₂-radical, R'₄₁SO₂-radical, R'₄₃OCO-group, R'₄₁SO₂O-group, and R'₄₁Same radicals, R'₄₃N(R′₄₄) -radical, R'₄₁CO₂-radical, R'₄₁OSO₂-a group, cyano, and nitro.

R 'will be described below'₅₁-R′₆₅Preferred ranges for a, b, d, e and f.

R′₅₁Preferably an aliphatic group or an aromatic group. a is most preferably 1. R'₅₂And R'₅₅Each is preferably an aromatic group. If b is 1, R'₅₃Preferably an aromatic group; if b is 0, R'₅₃Heterocyclic groups are preferred. R'₅₄Preferably is R'₄₁CON(R′₄₃) -group or R'₄₁N(R′₄₃) -a group. R'₅₆And R'₅₇Are each preferably aliphatic, aromatic, R'₄₁O-group or R'₄₁An S-group. R'₅₈Preferably an aliphatic group or an aromatic group.

In formula (Cp '-6), R'₅₉Preferably a chlorine atom, an aliphatic group, or R'₄₁CON(R′₄₃) -a group, and d is preferably 1 or 2. R'₆₀Preferably an aromatic group. In formula (Cp '-7), R'₅₉Preferably is R'₄₁CON(R′₄₃) -a group, and d is preferably 1.

R′₆₁Preferably is R'₄₃OSO₂-radical, R'₄₃N(R′₄₄)SO₂-radical, R'₄₃OCO-group, R'₄₃N(R′₄₁) CO-radical, cyano radical, R'₄₁SO₂N(R′₄₃) CO-radical, R'₄₃CON(R′₄₄) CO-radical, R'₄₃N(R′₄₄)SO₂N(R′₄₅) CO-group, or R'₄₃N(R′₄₄)CON(R′₄₅) A CO-group.

In the formula (Cp' -8),e is preferably 0 or 1. R'₆₂Preferably is R'₄₁OCON(R′₄₃) -radical, R'₄₁CON(R′₄₃) -a radical, or R'₄₁SO₂N(R′₄₃) -a group. And the substitution position of these substituents is preferably at the (5) position of the naphthol ring.

In formula (Cp '-9), R'₆₃Preferably is R'₄₁CON(R′₄₃) -radical, R'₄₁SO₂N(R′₄₃) -radical, R'₄₁N(R′₄₃)SO₂-radical, R'₄₁SO₂-radical, R'₄₁N(R′₄₃) CO-group, nitro group, or cyano group, and e is preferably 1 or 2.

In formula (Cp '-10), R'₆₃Preferably is R'₄₃N(R′₄₄) CO-radical, R'₄₃OCO-group, or R'₄₃A CO-group. f is preferably 1 or 2.

In formulae (Cp ' -11) and (Cp ' -12), R '₆₄And R'₆₅Are each preferably R'₄₁OCO-group, R'₄₁OSO₂-radical, R'₄₁SO₂-radical, R'₄₄N(R′₄₃) CO-radical, R'₄₄N(R′₄₃)SO₂-a radical, or cyano, most preferably being R'₄₁OCO-group, R'₄₄N(R′₄₃) A CO-group, or a cyano group. R'₆₆Preferably is R'₄₁The same groups. Including the number of carbon atoms of the substituent attached thereto, R'₅₁-R′₆₆The total number of carbon atoms is preferably 18 or less, more preferably 10 or less, respectively.

The photo-useful group represented by B1 or PUG will be described below.

The photo-useful group represented by B1 or PUG can be any photo-useful group known to those skilled in the art.

Examples include development inhibitors, bleach accelerators, dyes, bleach inhibitors, couplers, developers, development aids, reducing agents, silver halide solvents, silver complex formers, fixing agents, image toners, stabilizers, film hardeners, graying agents, ultraviolet absorbers, anti-fog agents, nucleating agents, chemical or spectral sensitizers, desensitizers, and brighteners. However, the PUG is not limited to these examples.

Preferred examples of B1 or PUG are development inhibitors (e.g., development inhibitors described in U.S. Pat. Nos. 3227554, 3384657, 3615506, 3617291, 3733201, and 5200306, and UK patent No. 1450479), bleaching accelerators (e.g., described in research Disclosure 1973, Item No.11449, and European patent No. 193389, and also described in JP-A-61-201247, JP-A-4-350848, JP-A-4-350849, and JP-A-4-350853), development auxiliaries (e.g., development auxiliaries described in U.S. Pat. No. 4859578 and JP-A-10-48787), development accelerators (e.g., development accelerators described in U.S. Pat. No. 4390618 and JP-A- 2-56543), reducing agents (e.g., reducing agents described in JP-A-63-109439 and JP-A-63-12834 2), and whitening agents (e.g., the whitening agents described in U.S. patent nos. 4774181 and 5236804). The pKa of the bound acid of B1 or PUG is preferably 13 or less, and more preferably 11 or less.

B1 or PUG is more preferably a development inhibitor or a bleach promoter.

Preferred development inhibitors are mercaptotetrazole derivatives, mercaptotriazole derivatives, mercaptothiadiazole derivatives, mercaptooxadiazole derivatives, mercaptoimidazole derivatives, mercaptobenzimidazole derivatives, mercaptobenzothiazole derivatives, mercaptobenzoxazole derivatives, tetrazole derivatives, 1,2, 3-triazole derivatives, 1,2, 4-triazole derivatives, and benzotriazole derivatives.

More preferred development inhibitors are represented by the following formulae DI-1 to DI-6:

wherein R'₃₁Represents a halogen atom, R'₄₆O-radical, R'₄₆S-radical, R'₄₇CON(R′₄₈) -radical, R'₄₇N(R′₄₈) CO-radical, R'₄₆OCON(R′₄₇) -radical, R'₄₆O₂(R′₄₇) -radical, R'₄₇N(R′₄₈)SO₂Group R'₄₆SO₂-radical, R'₄₇OCO-group, R'₄₇N(R′₄₈)CON(R′₄₉) -radical, R'₄₇CON(R′₄₈)SO₂-radical, R'₄₇N(R′₄₈)CON(R′₄₉)SO₂-a radical, and R'₄₆Same radicals, R'₄₇N(R′₄₈) -radical, R'₄₆CO₂-radical, R'₄₇OSO₂-a group, cyano, or nitro.

R′₄₆Represents an aliphatic group, an aromatic group, a heterocyclic group. R'₄₇、R′₄₈And R'₄₉Each represents an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom. R'₄₆、R′₄₇、R′₄₈Or R'₄₉The aliphatic groups represented are saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted aliphatic groups of 1 to 32 carbon atoms, preferably 1 to 20 carbon atoms. Representative examples are methyl, cyclopropyl, isopropyl, isopropenyl, n-butyl, tert-butyl, isobutyl, tert-pentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-octyl, 1,3, 3-tetramethylbutyl, and n-decyl.

R′₄₆、R′₄₇、R′₄₈Or R'₄₉The aromatic group represented is an aromatic group of 6 to 32 carbon atoms, preferably a substituted or unsubstituted phenyl cyclic substituted or unsubstituted naphthyl group.

R′₄₆、R′₄₇、R′₄₈Or R'₄₉The heterocyclic group represented is a substituted or unsubstituted heterocyclic group of 1 to 32 carbon atoms, preferably 1 to 20 carbon atoms, preferably 3 to 8-membered ring, the heterocyclic group containing a nitrogen atom, an oxygen atom and a sulfur atomA heteroatom. Representative examples of such heterocyclic groups are 2-pyridyl, 2-benzoxazolyl, 2-imidazolyl, 2-benzimidazolyl, 1-indolyl, 1,3, 4-thiadiazol-2-yl, 1,2, 4-triazol-2-yl, or 1-indolinyl.

R′₃₂Represents and R'₄₆The same groups.

k represents an integer of 1 to 4, g represents 0 or 1, and h represents 1 or 2. V represents an oxygen atom, a sulfur atom, or-N (R'₄₆)-。R′₃₁And R'₃₂May further comprise a substituent. Preferred bleach boosters are as follows. -SCH₂CO₂H

-SCH₂CH₂CO₂H-SCH₂CH₂CH₂CO₂H -S-CH₂CH₂-S-CH₂CH₂CO₂H

(groups attached to COUP by an active bond)

The group represented by TIME will be described below.

The group represented by TIME may be any linking group of the PUG cleavable after cleavage by COUP1 during development. Examples thereof are groups described in U.S. Pat. nos. 4,146,396, 4,652,156, or 4,698,297, in which a cleavage reaction of hemiacetal is used; a light-distributing group described in U.S. Pat. No.4,248,962, 4,847,185, or 4,857,440, which generates a cleavage reaction by using an intramolecular nucleophilic substitution reaction; a light-distributing group described in U.S. Pat. No.4,409,323 or 4,421,845, which generates a cleavage reaction by using an electron transfer reaction; groups described in U.S. Pat. No.4,546,073, which produce a cleavage reaction by a hydrolysis reaction using an imino ketal; and groups described in the patent No. 2626317, which produce cleavage reactions by hydrolysis reactions using esters. At the heteroatom contained therein, preferably an oxygen atom, a sulfur atom or a nitrogen atom, TIME is attached to COUP1 in formula (IIa) or (IIb). Preferred examples of TIME are the following formulae (T-1), (T-2), and (T-3).

^*-W-(X＝Y)j-C(R₂₁)R₂₂-^** (T-1)

^*-W-CO-^** (T-2)

^*-W-LINK-E1-^**(T-3) wherein (A) in the above,^*represents the position of attachment of TIME to COUP1 in formula (IIa) or (IIb),^**represents the position of TIME attached to PUG or other TIME (if m is plural), W represents an oxygen atom, a sulfur atom, or > N-R₂₃X and Y independently represent a methine group or a nitrogen atom, j represents 0,1 or 2, and R₂₁、R₂₂And R₂₃Each represents a hydrogen atom or a substituent. If X and Y represent a substituted methine group, then the substituent is reacted with R₂₁、R₂₂And R₂₃Any two substituents in (a) may be linked to form a cyclic structure (e.g. a benzene ring or a pyrazole ring). In formula (T-3), E1 represents an electrophilic group. LINK represents a linking group that sterically LINKs W to E1 for intramolecular nucleophilic substitution reactions.

Practical examples of TIME represented by the formula (T-1) are as follows:

^*-OCH₂-^{** *}-S-CH₂-^**

practical examples of TIME represented by the formula (T-2) are as follows:

practical examples of TIME represented by the formula (T-3) are as follows: if m in formula (IIa) is 2, (TIME)_mThe practical examples of (a) are as follows:

the group represented by RED in formula (IIb) will be described below. RED is a group that cleaves from COUP1 or TIME to form RED-PUG and is capable of being cross-oxidized by acidic species present during development, such as oxidized forms of developer. RED-PUG can be any compound that cleaves PUG upon oxidation. Examples of RED are hydroquinone, catechol, 1,2, 3-benzenetriol, 1, 4-naphthohydroquinone, 1, 2-naphthohydroquinone, sulfonamidophenol, hydrazine, and sulfonamidophenol. Practical examples of such groups are described in JP-A-61-230135, JP-A-6 2-251746, JP-A-61-27885 2, U.S. Pat. Nos. 3,364,02 2, 3,379,529, 4,618,571, 3,639,617 and 4,684,604, and in J.org.chem., volume 29, page 588 (1964).

Among these compounds, preferred examples of RED are hydroquinone, 1, 4-naphthohydroquinone, 2- (or 4-) sulfonylaminophenol, 1,2, 3-benzenetriol, and hydrazine. In these compounds, a redox group having a phenolic hydroxyl group is bonded to COUP1 or TIME at the oxygen atom of the phenolic group.

In order to fix the compound represented by the formula (IIa) or (IIb) on the photosensitive layer or the non-photosensitive layer, the compound is added to the photosensitive layer or the non-photosensitive layer before the silver halide photosensitive material containing the compound represented by the formula (IIa) or (IIb) is developed, and the compound represented by the formula (IIa) or (IIb) preferably has a non-diffusible group. Most preferably, the non-diffusing group is contained in a TIME or RED. Preferred examples of the non-diffusing group are an alkyl group of 8 to 40 carbon atoms, preferably 12 to 32 carbon atoms, an aromatic group of 8 to 40 carbon atoms, preferably 12 to 32 carbon atoms, and having at least one of an alkyl group (having 3 to 20 carbon atoms), an alkoxy group (having 3 to 20 carbon atoms) or an aryl group (having 6 to 20 carbon atoms).

Methods for synthesizing the compounds represented by the formulｃA (IIｃA) or (IIb) are described, for example, in known patents and documents cited in the explanation of TIME, RED and PUG, and disclosed in JP-A-61-156127, JP-A-58-160954, JP-A-58-162949, JP-A-61-24905 2, JP-A-63-37350, U.S. Pat. No.5,026,628, and European patents 443530A 2 and 444501A 2.

The compound for releasing a photographically useful group represented by formula (III) will be described below:

COUP2-A-E-B2 (III) wherein COUP2 represents a color former group capable of coupling to an oxidized form of a developer; e represents an electrophilic moiety; a represents a linking group capable of releasing B2 by forming a ring through an intramolecular nucleophilic substitution reaction of a nitrogen atom, which is present in the coupling product between COUP2 and the oxidized form of the developer by the developer, and which directly links the coupling site with the nucleophilic moiety E; and B2 represents a photographically useful group or precursor thereof.

As the color former group represented by COUP2, a color former group generally known as a photographic color former may be used. Examples thereof are yellow color-former groups (e.g., open-chain ketone methylene color-former groups such as acyl anilides and malonodianilides), magenta color-former groups (e.g., 5-pyrazolone type, pyrazolotriazole type color-former groups), and cyan color-former groups (e.g., phenol type, naphthol type, pyrrolotriazole type color-former groups). Couplers which form yellow, magentｃA and cyan dyes and have ｃA novel skeleton may also be used, as described in, for example, U.S. Pat. No. 5681689, JP-A-7-128824, JP-A-7-128823, JP-A-6-222526, JP-A-9-258400, JP-A-9-258401, JP-A-9-269573 and JP-A-6-2761 2. Other color former groups may also be used (e.g., the color former groups described in U.S. patent nos. 3632345 and 3928041, which form colorless materials by reaction with oxidized forms of aromatic amine-based developers, and the color former groups described in U.S. patent nos. 1939231 and 2181944, which form black or intermediate colored materials by reaction with oxidized forms of aromatic amine-based developers).

The attachment site of COUP2 and linking group a may be any site provided that after coupling of the color former and the oxidized form of the developer to each other, B may be released as a ring formed by an intramolecular nucleophilic substitution reaction of the nitrogen atom, which is present in the coupled product by the developer and is directly bonded to the coupling site with electrophilic moiety E. This position is preferably at or near the coupling position of COUP2 (an atom adjacent to the coupling position or an atom adjacent to the coupling position), and more preferably at or near the coupling position of COUP2 (an atom adjacent to the coupling position or an atom adjacent to the coupling position).

The couplers of the present invention and ArNH in oxidized form (Ar' ═ NH) when linking group a is bonded to (1) the coupling position of the coupler group represented by COUP2, (2) the atom adjacent to the coupling position, and (3) the atom adjacent to the coupling position₂The reaction between the aromatic amine-based developers represented can be represented by the following formula.

(1) A is bonded to the coupling position of COUP2

(2) A is bonded to an atom adjacent to the coupling position of COUP2

(3) A is bonded to an atom adjacent to the coupling position of COUP2

Andeach represents a colour former residue capable of coupling to an oxidised form of a developer, which is not necessarily a cyclic structure. The symbol denotes a coupling position. Straight line one represents the bond between the non-metallic atoms.

Preferred examples of COUP2 of the present invention are described below, but COUP2 is not limited to these examples. Wherein,^*represents the position at which COUP2 is bonded to A, and X' represents a hydrogen atom or a halogen atom (e.g., fluorine atom or chlorine atom)Atom, bromine atom, or iodine atom), R₁₃₁-、R₁₃₁O-、R₁₃₁S-、R₁₃₁OCOO-、R₁₃₂COO-、R₁₃₂(R₁₃₃) NCOO-, or R₁₃₂CON(R₁₃₃) -, Y' represents an oxygen atom, a sulfur atom, R₁₃₂N ═ or R₁₃₂ON＝。

R₁₃₁Represents an aliphatic group ("aliphatic group" means a saturated or unsaturated, chain or cyclic, straight-chain or branched, substituted or unsubstituted aliphatic hydrocarbon group, and the aliphatic groups used in the following description have the same meaning), an aromatic group, or a heterocyclic group.

R₁₃₁The aliphatic group represented is an aliphatic group preferably having 1 to 32 carbon atoms, more preferably 1 to 22 carbon atoms. Examples thereof are methyl, ethyl, vinyl, ethynyl, propyl, isopropyl, 2-propenyl, 2-propynyl, butyl, isobutyl, tert-butyl, tert-pentyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,3, 3-tetramethylbutyl, decyl, dodecyl, hexadecyl and octadecyl. The "number of carbon atoms" means the total number of carbon atoms including the carbon atoms of the substituents attached to the above aliphatic group. The number of carbon atoms of the other groups than the aliphatic group also means the total number of carbon atoms including the carbon atoms of the substituent.

R₁₃₁The aromatic group represented is a substituted or unsubstituted aryl group, preferably having 6 to 32 carbon atoms, more preferably 6 to 22 carbon atoms. Examples thereof are phenyl, tolyl and naphthyl.

R₁₃₁The heterocyclic groups represented are substituted or unsubstituted heterocyclic groups, preferably having from 1 to 32 carbon atoms, more preferably from 1 to 22 carbon atoms. Examples thereof are 2-furyl, 2-pyrrolyl, 2-thienyl, 3-tetrahydrofuryl, 4-pyridyl, 2-pyrimidyl, 2- (1, 3, 4-thiadiazolyl), 2-benzothiazolyl, 2-benzoxazolyl, 2-benzimidazolyl, 2-benzoselenazolyl, 2-quinolyl, 2-oxazolyl, 2-thiazolyl, 2-selenazolyl, 5-tetrazolyl, 2- (1, 3, 4-oxadiazolyl), and 2-imidazolyl.

R₁₃₂And R₁₃₃Each independently represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. R₁₃₂And R₁₃₃The aliphatic, aromatic and heterocyclic groups represented have the same structure as R₁₃₁The same meaning.

Preferably, X' represents a hydrogen atom, an aliphatic group, an aliphatic oxy group, an aliphatic thio group, or R₁₃₂CON(R₁₃₃) -, and Y' represents an oxygen atom.

Examples of the substituent suitable for the above-mentioned group and the following groups and examples of the "substituent" described below are a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, and iodine atom), a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, a nitro group, an alkyl group (e.g., methyl, ethyl, and hexyl), a fluoroalkyl group (e.g., trifluoromethyl), an aryl group (e.g., phenyl, tolyl, and naphthyl), a heterocyclic group (e.g., having the same structure as R)₁₃₁Heterocyclic groups of the same meaning), alkoxy (methoxy, ethoxy and octyloxy), aryloxy (e.g., phenoxy and naphthyloxy), alkylthio (e.g., methylthio and butylthio), arylthio (e.g., phenylthio), amino (e.g., amino, N-methylamino, N-dimethylamino, and N-phenylamino), acyl (e.g., acetyl, propionyl, and benzoyl), alkylsulfonyl or arylsulfonyl (e.g., methanesulfonyl and benzenesulfonyl), acylamino (e.g., acetylamino and benzoylamino), alkylsulfonylamino or arylsulfonylamino (e.g., methanesulfonylamino and benzenesulfonylamino), carbamoyl (e.g., carbamoyl, N-methylaminocarbonyl, N-dimethylaminocarbonyl, and N-phenylaminocarbonyl), sulfamoyl (e.g., sulfamoyl, N-naphthyloxy, and N-naphthyloxy), alkylthio (e.g., methylthio and butylthio), arylthio (e, N-methylaminosulfonyl, N-dimethylaminosulfonyl, and N-phenylaminosulfonyl), alkoxycarbonyl (such as methoxycarbonyl, ethoxycarbonyl, and octyloxycarbonyl), aryloxycarbonyl (such as phenoxycarbonyl and naphthyloxycarbonyl), acyloxy (such as acetyloxy and benzoyloxy), alkoxycarbonyloxy (such as methoxycarbonyloxy and ethoxycarbonyloxy), aryloxycarbonyloxy (such as phenoxycarbonyloxy), alkoxycarbonylamino (such as methoxycarbonylamino and butyloxycarbonyl)Oxycarbonylamino), aryloxycarbonylamino (e.g., phenoxycarbonylamino), aminocarbonyloxy (e.g., N-methylaminocarbonyloxy and N-phenylaminocarbonyloxy), aminocarbonylamino (e.g., N-methylaminocarbonylamino and N-phenylaminocarbonylamino).

R₁₁₁And R₁₁₂Each independently represents R₁₃₂CO-、R₁₃₁OCO-、R₁₃₂(R₁₃₃)NCO-、R₁₃₃SO_n-、R₁₃₂(R₁₃₃)NSO₂-, or cyano. R₁₃₁、R₁₃₂And R₁₃₃Having the same meaning as described above. n represents 1 or 2.

R₁₁₃Represents and R₁₃₁The same groups.

R₁₁₄Represents R₁₃₂-、R₁₃₂CON(R₁₃₃)-、R₁₃₂(R₁₃₃)N-、R₁₃₁SO₂N(R₁₃₂)-、R₁₃₁S-、R₁₃₁O-、R₁₃₁OCON(R₁₃₂)-、R₁₃₂(R₁₃₃)NCON(R₁₃₄)-、R₁₃₁OCO-、R₁₃₂(R₁₃₃) NCO-, or cyano. R₁₃₁、R₁₃₂And R₁₃₃Having the same meaning as described above. R₁₃₄Represents and R₁₃₂The same groups.

R₁₁₅And R₁₁₆Each independently represents a substituent, preferably R₁₃₂-、R₁₃₂CON(R₁₃₃)-、R₁₃₁SO₂N(R₁₃₂)-、R₁₃₁S-、R₁₃₁O-、R₁₃₁OCON(R₁₃₂)-、R₁₃₂(R₁₃₃)NCON(R₁₃₄)-、R₁₃₁OCO-、R₁₃₂(R₁₃₃) NCO-, halogen atom, or cyano group, more preferably R₁₃₁、R₁₃₂、R₁₃₃And R₁₃₄The groups represented have the same meaning as described above.

R₁₁₇Represents a substituent, p represents an integer of 0 to 4, and q represents 0 to 3Is an integer of (1). R₁₁₇A preferred example of the substituent represented is R₁₃₁-、R₁₃₂CON(R₁₃₃)-、R₁₃₁OCON(R₁₃₂)-、R₁₃₁SO₂N(R₁₃₂)-、R₁₃₂(R₁₃₃)NCON(R₁₃₄)-、R₁₃₁S-、R₁₃₁O-, and halogen. R₁₃₁、R₁₃₂、R₁₃₃And R₁₃₄Having the same meaning as described above. If p and q are 2 or more, a plurality of R₁₁₇May be the same or different and are adjacent to R₁₁₇May be bonded to each other to form a ring. In a preferred form of the formulae (III-1E) and (III-2E), at least one ortho position to the hydroxyl group is replaced by R₁₃₂CONH-、R₁₃₁OCONH-or R₁₃₂(R₁₃₃) NCONH-substitution.

R₁₁₈Represents a substituent, r represents an integer of 0 to 6, and s represents an integer of 0 to 5. R₁₁₈A preferred example of the substituent represented is R₁₃₂CON(R₁₃₃)-、R₁₃₁OCON(R₁₃₂)-、R₁₃₁SO₂N(R₁₃₂)-、R₁₃₂(R₁₃₃)NCON(R₁₃₄)-、R₁₃₁S-、R₁₃₁O-、R₁₃₂(R₁₃₃)NCO-、R₁₃₂(R₁₃₃)NSO₂-、R₁₃₁OCO-, cyano, and halogen atoms. R₁₃₁、R₁₃₂、R₁₃₃And R₁₃₄Having the same meaning as described above. If R and s are 2 or more, a plurality of R₁₁₈May be the same or different and are adjacent to R₁₁₈May be bonded to each other to form a ring. In preferred forms of the formulae (III-1F), (III-2F), and (III-3F), one ortho position to the hydroxy group is replaced by R₁₃₂CONH-、R₁₃₂HNCONH-、R₁₃₂(R₁₃₃)NSO₂-or R₁₃₂NHCO-substitution.

R₁₁₉Represents a substituent, preferably R₁₃₂-、R₁₃₂CON(R₁₃₃)-、R₁₃₁SO₂N(R₁₃₂)-、R₁₃₁S-、R₁₃₁O-、R₁₃₁OCON(R₁₃₂)-、R₁₃₂(R₁₃₃)NCON(R₁₃₄)-、R₁₃₁OCO-、R₁₃₂(R₁₃₃)NSO₂-、R₁₃₂(R₁₃₃) NCO-, halogen atom, or cyano group, more preferably R₁₃₁The group represented. R₁₃₁、R₁₃₂、R₁₃₃And R₁₃₄Having the same meaning as described above.

R₁₂₀And R₁₂₁Each independently represents a substituent, preferably R₁₃₂-、R₁₃₂CON(R₁₃₃)-、R₁₃₁SO₂N(R₁₃₂)-、R₁₃₁S-、R₁₃₁O-、R₁₃₁OCON(R₁₃₂)-、R₁₃₂(R₁₃₃)NCON(R₁₃₄)-、R₁₃₂(R₁₃₃)NCO-、R₁₃₂(R₁₃₃)NSO₂-、R₁₃₁OCO-, a halogen atom, or a cyano group, more preferably R₁₃₂(R₁₃₃)NCO-、R₁₃₂(R₁₃₃)NSO₂-, trifluoromethyl, R₁₃₁OCO-or cyano. R₁₃₁、R₁₃₂、R₁₃₃And R₁₃₄Having the same meaning as described above.

E represents an electrophilic group, such as-CO-, -CS-, -COCO-, -SO-, -SO₂-、-P(＝O)(R₁₅₁) -, or-P (═ S) (R)₁₅₁) - (wherein R)₁₅₁Represents an aliphatic group, an aromatic group, an aliphatic oxy group, an aryloxy group, an aliphatic thio group, or an arylthio group), and is preferably-CO-.

A represents a linking group capable of releasing B2 as a ring (preferably a 3-7 membered ring, more preferably a 5 or 6 membered ring) is formed by an intramolecular nucleophilic substitution reaction of a nitrogen atom, which occurs in the coupling reaction product between COUP2 and an oxidized form of the developer by the developer, and which is bonded to the coupling position with an electrophilic moiety E-. A preferred form of A may be represented by the following formula (IV):

wherein,^*represents a moiety linked to COUP2, and^**represents the moiety attached to E. R₁₄₁、R₁₄₂、R₁₄₃Each independently represents R₁₃₂The same groups. i represents an integer of 0 to 3, and j represents an integer of 0 to 2. R₁₄₁Or R₁₄₂Can be combined with COUP2 or R₁₄₃Combined to form a ring, or R₁₄₁And R₁₄₂Can be combined with each other to form a spiro ring. If i is 2 or 3, then a plurality of R₁₄₁Or R₁₄₂May be the same or different and are adjacent to R₁₄₁Or R₁₄₂May be bonded to each other to form a ring. R₁₄₁And R₁₄₂Each is preferably a hydrogen atom or an (1-20 carbon atoms, preferably 1-10 carbon atoms) aliphatic group, more preferably a hydrogen atom. R₁₄₃Preferably an aliphatic group of 1 to 32 carbon atoms, more preferably an aliphatic group of 1 to 22 carbon atoms, and may be combined with COUP2 to form a ring. If j is 2, then two R₁₄₃May be the same or different and are adjacent to R₁₄₃A ring may be formed. j is preferably 1. In the formulae (III-1) { (III-1A), (III-1B), (III-1C), (III-1D), (III-1E), (III-1F), and (III-1G) }, i is preferably 1 or 2. In the formulae (III-2) { (III-2A), (III-2B), (III-2C), (III-2D), (III-2E), (III-2F), and (III-2G) }, i is preferably 0 or 1. In the formula (III-3) { (III-3F) }, i is preferably 0.

B2 represents a photographically useful compound or a precursor thereof. A preferred form of B2 is represented by the following formula (V):

# - (T) k-PUG (V) wherein, # represents a moiety attached to E, T represents a light-distributing group capable of releasing PUG after release from E, k represents an integer of 0 to 2, preferably 0 or 1, and PUG represents a photo-useful group.

Examples of the light-distributing group represented by T are groups described in U.S. Pat. Nos. 4146396, 4652516 or 4698297, which release PUG by a cleavage reaction using a hemiacetal; groups described in JP-A-9-114058 or U.S. Pat. Nos. 424896 2, 5719017 or 5709987, which release PUG by using an intramolecular ring closure reaction; groups described in JP-B-54-39727, JP-A-57-136640, JP-A-57-154234, JP-A-4-261530, JP-A-4-211246, JP-A-6-324439, JP-A-9-114058, or U.S. Pat. No. 4409323 or 4421845, using electron transfer viｃA pi electrons to release PUG; groups described in JP-A-57-17984 2, JP-A-40261530 or JP-A-5-31332 2, which release PUG by generating carbon dioxide; groups described in U.S. Pat. No. 4546073, which release PUG by hydrolysis reaction using an imino ketal; groups described in the patent publication No. 26261317, which release PUG by hydrolysis reaction using an ester; and groups described in european patent No. 572084, which release PUG by using a reaction with sulfate ions.

Preferred examples of the light-distributing group represented by T in the present invention are as follows. However, T is not limited to these examples.

Where # represents the moiety where T is bonded to the electrophilic moiety E or # # when k is 2, and # # represents the moiety where T is bonded to PUG or # # when k is 2. Z represents an oxygen atom or a sulfur atom, preferably an oxygen atom. R₁₆₁Represents a substituent, preferably R₁₃₁-、R₁₃₂CON(R₁₃₃)-、R₁₃₁SO₂N(R₁₃₂)-、R₁₃₁S-、R₁₃₁O-、R₁₃₁OCON(R₁₃₂)-、R₁₃₂(R₁₃₃)NCON(R₁₃₄)-、R₁₃₂(R₁₃₃)NCO-、R₁₃₂(R₁₃₃)NSO₂-、R₁₃₁OCO-, halogen atom, nitro group, or cyano group. R₁₃₁、R₁₃₂、R₁₃₃And R₁₃₄Having the same meaning as described above. R₁₆₁Can be reacted with R₁₆₂、R₁₆₃And R₁₆₄Any one of which is joined to form a ring. n is₁Represents an integer of 0 to 4. If n is₁Represents 2 or more, then a plurality of R₁₆₁May be the same or different and may be bonded to each other to form a ring.

R₁₆₂、R₁₆₃And R₁₆₄Respectively represent with R₁₃₂The same groups. n is₂Represents 0 or 1. R₁₆₂And R₁₆₃Can be combined with each other to form a spiro ring. R₁₆₂And R₁₆₃Each is preferably a hydrogen atom or an (1-20 carbon atoms, preferably 1-10 carbon atoms) aliphatic group, more preferably a hydrogen atom. R₁₆₄Preferably (1-2)0 carbon atoms, preferably 1 to 10 carbon atoms) aliphatic groups or (6 to 20 carbon atoms, preferably 6 to 10 carbon atoms) aromatic groups. R₁₆₅Represents R₁₃₂-、R₁₃₂(R₁₃₃)NCO-、R₁₃₂(R₁₃₃)NSO₂-、R₁₃₁OCO-or R₁₃₂CO-。R₁₃₁、R₁₃₂And R₁₃₃The same as the above meaning. R₁₆₅Preferably represents R₁₃₂More preferred are aromatic groups of 6 to 20 carbon atoms.

The photographically useful radicals represented by PUG have the same meaning as described above.

The preferred form of the color former used in the present invention is formula (III-2) (wherein A is bound at an atom adjacent to the coupling position of COUP) or formula (III-3) (wherein A is bound at an atom adjacent to the coupling position of COUP), and the most preferred form is formula (III-3). The formula (III-3) is preferably represented by the formula (III-3a), more preferably the formula (III-3b), and most preferably the formula (III-3 c). By ArNH of formula (III-3c) with the oxidized form (Ar' ═ NH)₂The cyclic structure obtained by the reaction of the aromatic amine-based developer represented by the following formula (VI).

Wherein Q is₁And Q₂Respectively, X ', T, k, PUG, R represent non-metallic atoms required to form a 5-or 6-membered ring and to produce a reaction with the developer in oxidized form in the atom at the X' radical₁₁₈、s、R₁₃₂And R₁₄₃The same as above, and R₁₄₄Represents a substituted or unsubstituted aliphatic group of 1 to 32 carbon atoms.

Practical examples of the color former used in the photosensitive material of the present invention are shown below. However, the color former is not limited to these examples.

The silver halide emulsion having a pre-ashing surface will be described below.

The silver halide emulsion having a pre-ashed surface is a silver halide emulsion which can be developed uniformly (imagewise) regardless of the exposure amount in the unexposed and exposed portions of the photosensitive material.

By "developing" is meant that at least 20% of the silver in the ashed silver halide emulsion is developed during standard color development.

The standard color development described herein is a standard color development of the photosensitive material to which the present invention is applied. That is, the develop is C-41 for either Fuji Photo Film Co., Ltd for color negative develop or Eastman Kodat Company color negative develop and RA-4 for either CP-45 for color photographic paper (Fuji Photo Film Co., Ltd.) or Eastman Kodak Company color photographic paper develop.

The surface ashed silver halide emulsion can be prepared by the following method: a method of adding a reducing agent or a gold salt to a silver halide emulsion capable of forming a surface latent image under appropriate pH and pAg conditions, a method of heating at a low pAg, or a method of giving uniform exposure.

As the reducing agent, thiourea dioxide, stannous chloride, a hydrazine-based compound, or ethanolamine can be used.

As the silver halide emulsion for surface ashing, any of silver chloride, silver chlorobromide, silver iodobromide, or silver bromochloroiodide may be used. However, it is preferable that the chloride content is 10 mol% or more, and the upper limit of the chloride content is 100 mol%.

The particle size of the surface-ashed silver halide emulsion is not particularly limited. However, the average particle diameter is preferably 0.01 to 0.75. mu.m, and most preferably 0.05 to 0.6. mu.m.

The particle shape is also not particularly limited. Thus, both conventional and non-conventional particles may be used. The average aspect ratio is not particularly limited.

The particles are preferably monodisperse (the particle size is within ± 40% of the average particle size by weight of the silver halide particles or 95% of the number of particles), although polydisperse particles may also be used.

In the present invention, the non-photosensitive material layer containing the surface-ashed silver halide emulsion may be provided at any position in the photosensitive material. The non-photosensitive layer can be set in an optimum position by the action of the released photographically useful groups.

For example, the non-photosensitive material layer may be formed as a layer between the photosensitive silver halide emulsion layer closest to the support and the support, that is, as an intermediate layer between the photosensitive layers sensitive to different colors, as a protective layer farther from the support than the photosensitive silver halide emulsion layer farthest from the support, or as a layer between silver halide emulsion layers different in sensitivity from each other but having the same color sensitivity.

The surface-ashed silver halide emulsion is preferably contained in the layer containing the black colloidal silver or in a layer adjacent thereto. The coating amount of the black colloidal silver may be determined according to the ability to prevent halation and the light-shielding ability of the photosensitive material. Preferably, the coating amount is 0.01 to 1 g/m²More preferably 0.05 to 0.5g/m²。

A compound which releases a photouseful group or a precursor thereof (hereinafter referred to as "PUG-releasing compound") may be added to the nonphotosensitive layer containing the surface-ashed silver halide emulsion, or to a layer adjacent to the nonphotosensitive layer. The PUG-releasing compound is preferably added in the non-photosensitive layer comprising the surface ashed silver halide emulsion.

When the "PUG-releasing compound" is added in the layer adjacent to the non-photosensitive layer containing the surface-ashed silver halide emulsion, the layer containing the "PUG-releasing compound" preferably does not contain any photosensitive silver halide emulsion.

Typically, the photogenic group acts directly on the photosensitive material (during color development after release). However, the released photographically useful groups may also act on the photosensitive material after being accumulated in the color developer by the replenishment process. In addition, the photouseful group can have the purpose of maintaining the performance of the color developing replenisher. For this purpose, a non-photosensitive material layer containing a surface-ashed silver halide emulsion is provided on the bottom surface (surface of the support with respect to the surface covered with the photosensitive silver halide emulsion layer). In this case, of course, the "PUG-releasing compound" is also present on the bottom surface.

Additives commonly used in the manufacture of photosensitive materials can be added to the non-photosensitive layer comprising the surface-ashed silver halide emulsion and the layer comprising the "PUG-releasing compound", which layers are the same or adjacent to each other. Examples are black colloidal silver that resists halation, minimum density control dyes, ultraviolet absorbers, and anti-fading agents. However, the additive is not limited to these examples.

The amount of the surface-ashed silver halide emulsion used in the present invention may be any amount. However, the preferable range is determined by the coating amount of the "PUG-releasing compound".

As the amount of silver, the coating amount is preferably 0.5 to 200 moles, more preferably 1 to 50 moles, per mole of the "PUG-releasing compound".

The preferred range may also vary depending on the type of photographically useful group released. For example, if the released photographically useful groups have development inhibiting action, the amount of the silver halide emulsion coated with the surface ashing relative to the "PUG-releasing compound" must be larger than in the case where the released photographically useful groups do not have development inhibiting action.

The coating amount of the "PUG-releasing compound" may be any value according to the objective function of photographic properties. In general, the PUG-releasing compound is applied in an amount of 5X 10^-4-2 g/m²Preferably 1X 10^-3-1 g/m²More preferably 5X 10^-3-5×10^-1g/m²。

Also, two or more different types of "PUG-releasing compounds" may be used. In this case, the chemical structures of the released photographically useful groups may be the same or different. Likewise, the photographic function of the released photographically useful groups may also be the same or different.

The non-photosensitive layer comprising the surface-ashed silver halide emulsion and the layer comprising the above-mentioned "PUG-releasing compound" (these layers may be the same or adjacent to each other) are collectively referred to as a "PUG-releasing unit".

The "PUG release unit" releases photographically useful groups in time and rapidly during development. Also, the "PUG releasing unit" minimizes side effects on photographic properties (storage stability of photosensitive material, storage stability from exposure to development, and change in photographic properties due to development variables).

Therefore, this is different from the method of adding the ashing emulsion in the photosensitive silver halide emulsion layer as disclosed in JP-A-63-175850 as the prior art.

Also, the ashed silver halide emulsion in JP-A- 2-504 2 is developed by first development (black-and-white development). Thus, the emulsion forms developed silver (metallic silver) in color development, that is, unlike the present invention, does not produce an oxidized form of color developer. This prior art differs from the present invention substantially in this respect.

The action of the present invention can be obtained by forming at least one "PUG releasing unit". However, two or more units may be formed. In this case, the chemical structures of the photographically useful groups released by these units may be the same or different. Similarly, the photographic function of the released photographically useful groups may be the same or different.

The coupling product produced by the reaction of the "PUG-releasing compound" of the present invention with the oxidized form of the developer is, although not necessarily, chromogenic. However, in directly appreciated photosensitive materials such as color photographic paper, it is preferable that the "PUG-releasing compound" does not cause the coupled product to develop color or to develop color slightly. Most preferably, the coupling product flows out of the photosensitive material.

In a photosensitive material that is not directly appreciated, such as a color negative, the coupled product of the "PUG-releasing compound" can develop color to increase the optical density of the photosensitive material. However, a large increase in optical density is not preferable for printing of color photographic paper. The optical density of the photosensitive material resulting from the color development of the coupled product of the "PUG-releasing compound" is preferably 0.5 or less, more preferably 0.3 or less, and most preferably 0.1 or less.

It is particularly preferred that the "PUG-releasing compound" does not cause the color development of the coupled product with respect to the change in the minimum density value due to color development. Most preferably, the coupling product flows out of the photosensitive material.

The silver halide photographic light-sensitive material of the present invention requires only at least one photosensitive layer formed on a support. A typical example thereof is a silver halide photographic light-sensitive material having, on its support, at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The photosensitive layer includes a unit photosensitive layer that is sensitive to any of blue light, green light, and red light. In the multilayer silver halide color photographic light-sensitive material, these unit light-sensitive layers are usually arranged in order of red, green and blue sensitive layers from the support side. However, depending on the desired application, the order of arrangement may also be reversed, or the order of arrangement may be such that different photosensitive layers are embedded between layers of the same color sensitivity. The non-photosensitive layer may be formed between the silver halide photosensitive layers, and as the uppermost layer and the lowermost layer. They may comprise, for example, color formers, DIR compounds described below, and color mixing inhibitors. As the plurality of silver halide emulsion layers constituting each unit photosensitive layer, it is preferable to provide a two-layer structure of high-speed and low-speed emulsion layers so that the sensitivity is decreased in the order of the carrier direction as described in German patent No.1,121,470 or British patent No. 923,045. Also, as described in JP-A-57-112751, JP-A-6 2-200350, JP-A-6 2-206541 and JP-A-6 2-206543, the layers may also be provided as follows: the low-speed emulsion layer is formed on the side away from the carrier, and the high-speed emulsion layer is formed on the side close to the carrier.

Specifically, the layers are arranged in the order of low-speed blue photosensitive layer (BL)/high-speed blue photosensitive layer (BH)/high-speed green photosensitive layer (GH)/low-speed green photosensitive layer (GL)/high-speed red photosensitive layer (RH)/low-speed red photosensitive layer (RL), BH/BL/GL/GH/RH, or BH/BL/GH/GL/RL/RH from the farthest side of the support.

In addition, as described in JP-B-55-34932, the layers are arranged in the order of blue photosensitive layer/GH/RH/GL/RL from the farthest side from the support. Further, as described in JP-A-56-25738 and JP-A-6 2-63936, the layers are arranged in the order of blue photosensitive layer/GL/RL/GH/RH from the side farthest from the support.

As described in JP-B-49-15495, three layers may be provided such that the silver halide emulsion layer having the highest sensitivity is an upper layer, the silver halide emulsion layer having a lower sensitivity than that of the upper layer is provided as an intermediate layer, and the silver halide emulsion layer having a lower sensitivity than that of the intermediate layer is provided as a lower layer; that is, three layers having different sensitivities are disposed toward the support in the order of decreasing sensitivity. Even when the structure of the layers is constituted by the above-described three layers having different sensitivities, as described in JP- ｃA-59-202464, the layers may be provided in the layer sensitive to one color in the order of medium-speed emulsion layer/high-speed emulsion layer/low-speed emulsion layer from the farthest side from the support.

In addition, a high-speed emulsion layer/low-speed emulsion layer/medium-speed emulsion layer or a low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer may be used in this order. Further, when four or more layers are formed, the arrangement order may also be changed as described above.

To improve color reproducibility, ｃA donor layer (CL) having an interlayer effect having ｃA spectral sensitivity distribution different from that of the main photosensitive layer BL, GL and RL is provided adjacent to or near the main photosensitive layer as described in U.S. patent nos. 4,663,271, 4,705,744, 4,707,436, JP- ｃA-6 2-160448 and JP- ｃA-63-89850.

Silver halide preferably used in the present invention in addition to the above-mentioned silver halide emulsion is silver iodobromide, silver iodochloride or silver iodochlorobromide, which contains about 30 mol% or less of silver iodide. Particularly preferred silver halides are silver iodobromide or silver iodochlorobromide containing about 2 to 10 mol% silver iodide.

The silver halide grains contained in the photographic emulsion used in the photographic material of the present invention may be those having conventional crystals such as cubic, octahedral, or tetradecahedral crystals, those having irregular crystals such as spherical or flaky crystals, or those having crystal defects such as at least one double crystal face, or a complex form thereof.

With respect to particle size, the silver halide may be composed of fine particles having a particle size of about 0.2 μm or less or large particles having a projected area diameter of up to about 10 μm, and the emulsion may be a polydisperse or monodisperse emulsion.

The silver halide photographic emulsion usable in the present invention can be prepared by a method described in, for example, "i.emulsion preparation and types", research disclosure (hereinafter abbreviated as RD) No. 17643 (12 months 1978), pages 22 and 23, "i.emulsion preparation and types"; and RD 18716 (11 months 1979), page 648; RD No. 307105 (11 months 1989), pages 863-865; p, Glafkides, "Chemie et Phisique Photograpphiques", Paul Montel, 1967; duffin, "pharmaceutical emulsion chemistry," Focal Press, 1966; and v. l.zelikman et al, "Making and coating Photographic Emulsion", Focal Press, 1964.

Monodisperse emulsions such as those described in us patent nos. 3,574,628 and 3,655,394 and british patent No.1,413,748 are also preferred.

Likewise, plate-like particles having an aspect ratio of about 3 or greater may be used in the present invention.

Plate-like particles can be readily prepared by the methods described in the following references: gutoff, "Photographic science and Engineering," Vol.14, pp.248-257 (1970); us patent nos. 4,434,226, 4,414,310, 4,433,048, and 4,439,520 and uk patent No.2,112,157.

Also, plate-like particles having an aspect ratio of about 3 or more are particularly preferred for use in the present invention. The major surface of the plate-like particle is a (100) plane or a (111) plane. Particles having a major face of (100) can be prepared by the methods described in U.S. patent nos. 5,320,938, 5,264,337, and 5,292,632. Particles having ｃA main face of (111) can be produced by the method described in JP-A-10-221827 (page 38, line 14 to page 45, line 20). "the principal surface is (100)" means that 50% or more of the outer surface thereof is silver halide grains composed of (100) occupying 50% or more of the total projected area. Likewise, "the main surface is (111)" means that 50% or more of the outer surface thereof is silver halide grains composed of (111) occupying 50% or more of the total projected area.

The crystal structure is uniform, may have a halogen component that is different between the inside and the outside, or may be a layered structure. Alternatively, the silver halide may be combined with silver halide having a different composition by orientation bonding, for example, may be combined with a compound other than silver halide such as rhododenide silver or lead oxide. Mixtures of particles having various crystal forms may also be used.

The emulsion may be any of a surface latent image type emulsion in which a latent image is formed mainly on the surface of the particles, an internal latent image type emulsion in which a latent image is formed inside the particles, and other types of emulsions in which a latent image is formed on the surface and inside of the particles. However, the emulsion must be a negative type emulsion. The internal latent image type emulsion may be ｃA core/shell internal latent image type emulsion described in JP-A-63-264740. A method for producing the core/shell internal latent image type emulsion is described in JP-A-59-13354 2. Although the shell thickness of the emulsion depends on, for example, the development conditions, it is preferably 3 to 40 nm, more preferably 5 to 20 nm.

Silver halide emulsions are typically subjected to physical maturation, chemical maturation and spectral sensitization prior to use. The additives used in these steps are listed in RD nos. 17463, 18716 and 307105, the relevant parts of which are summarized in the table below.

In the photosensitive material of the present invention, two or more photosensitive silver halide emulsions different from each other in at least one property such as particle size, particle size distribution, halogen composition, particle morphology and sensitivity thereof may be mixed together and used in a single layer.

Silver halide grains having an ashed surface as described in U.S. Pat. No.4,082,553, silver halide grains having an ashed inner portion as described in U.S. Pat. No.4,626,498 and JP- ｃA-59-21485 2, and colloidal silver are preferably used in the photosensitive silver halide emulsion layer and/or the substantially non-photosensitive hydrophilic colloid layer. Internally or surface ashed silver halide grains refer to silver halide grains that can be uniformly developed (in an imageless manner) regardless of the exposed or unexposed portions of the photosensitive material. Methods for producing this effect are described in U.S. Pat. No.4,626,498 and JP-A-59-21485 2. The silver halide forming the inner core of the core/shell type silver halide particle, which is ashed inside, may have a different halogen composition. The silver halide whose particle inside or surface is ashed may be any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide. The average particle diameter of these ashed silver halide grains is preferably 0.01 to 0.75. mu.m, more preferably 0.05 to 0.6. mu.m. For particle morphology, conventional particles and continuous polydisperse emulsions can be used. However, monodisperse emulsions are preferred, i.e., at least 95% of the total weight of the silver halide particles or the total number of particles is within 40% of the average particle size.

In the present invention, non-photosensitive fine-particle silver halide is preferably used. The non-photosensitive fine particles of silver halide preferably consist of fine silver halide particles that are not sensitive during image exposure to obtain a dye image and are not substantially developed during the developing step. These silver halide grains are preferably not ashed in advance. In the fine particle silver halide, the content of silver bromide is 0 to 100 mol%, and silver chloride and/or silver iodide may be contained if necessary. The fine particle silver halide preferably contains 0.5 to 10 mol% of silver iodide. The average particle diameter of the silver halide fine particles, that is, the average value of the circular diameters corresponding to the projected area, is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine particle silver halide can be prepared in the same manner as conventional photosensitive silver halide.

The surface of the silver halide grains does not have to be optically or spectrally sensitized. However, before adding the silver halide particles to the coating solution, it is preferable to add thereto a conventionally known stabilizer such as a triazole compound, an azaindene compound, a benzothiazolyl compound, a mercapto compound, or a zinc compound. Colloidal silver may be incorporated into the layer comprising the fine-particle silver halide.

The coating weight of silver of the photosensitive material of the present invention is preferably 6.0 g/m²Or less, most preferably 4.5g/m²Or lower.

Photographic additives useful in the present invention are also described in RD and the relevant description is summarized in the following table.

Additive type	RD17643	RD18716	RD307105
				1. Chemical sensitizer	Page 23	Page 648 right column	866 th page
2. Sensitizer		Page 648 right column
				3. Spectral sensitizer and hypersensitizer	Pages 23 to 24	Page 648 right column-page 649 right column	Pages 866 to 868
4. Whitening agent	Page 24	647 th page right column	868 th page
				5. Light absorbers, light-filtering dyes, UV absorbers	Pages 25 to 26	Page 649 right column-page 650 left column	Page 873
6. Adhesive agent	Page 26	Page 651 left column	Pages 873-874

7. Plasticizers, lubricants	Page 27	Page 650 right column	Page 876
				8. Coating aids, surfactants	Pages 26 to 27	Page 650 right column	Pages 875 to 876
9. Antistatic agent	Page 27	Page 650 right column	Pages 876-877
				10. Light-shading agent			Pages 878-879

Various dyes can be used in the photosensitive material of the present invention to form a color former, and the following color former is particularly preferable.

Yellow color former: couplers of the formulae (I) and (II) in EP 502,424A; color formers represented by formulas (1) and (2) in EP No.513,496A (especially Y-28 on page 18); a color former represented by formula (I) in claim 1 of EP No.568,037A; a color former represented by the general formula (I) in column 1, lines 45-55 of U.S. Pat. No.5,066,576; ｃA color former represented by the general formulｃA (I) in paragraph 0008 of JP-A-4-274425; page 40 of EP No.498,381A1 the colour former described in claim 1 (especially D-35 on page 18); color formers represented by formula (Y) on page 4 of EP No.447,969A1 (particularly Y-1 on page 17 and Y-54 on page 41); and color formers represented by formulas (II) - (IV) at column 7, lines 36-58 of U.S. Pat. No. B4,476,219 (particularly II-17 and II-19 at column 17, and II-24 at column 19).

Magenta color former: JP-A-3-39737L 57 (page 11, lower right column), L-68 (page 1 2, lower right column), and L-77 (page 13, lower right column); EPNo.456,257 [ A-4] -63 (page 134), and [ A-4] -73 and [ A-4] -75 (page 139); m-4 and M-6 (page 26), and M-7 (page 27) in EPNos. 486,965; m-45 in EP No.571,959 (page 19); (M-1) in JP-A-5-204106 (page 6); and M-2 2 in paragraph 0237 of JP-A-4-362631.

Cyan coupler: CX-1, CX-3, CX-4, CX-5, CX-11, CX-1 2, CX-14, and CX-15 in JP-A-4-204843 (pages 14 to 16); c-7 and C-10 (page 35), C-34 and C-35 (page 37), and (I-1) and (I-17) (pages 4 2 and 43) in JP-A-4-43345; and couplers represented by the general formulae (IｃA) and (Ib) in claim 1 of JP-A-6-67385.

Polymeric color former: p-1 and P-5 in JP-A- 2-44345 (page 11).

Couplers for forming coloured dyes with suitable diffusivity are preferably those described in us patent no 4,366,237, GB No.2,125,570, EP no 96,873B and DE no 3,234,533.

Couplers for correcting unwanted absorption of colored dyes are preferably: cyan couplers with yellow color represented by the formulae (CI), (CII), (CIII) and (CIV) described on page 5 of EP No.456,257A1; magenta color formers ExM-7 (page 202), Ex-1 (page 249) and Ex-7 (page 251) with yellow color as described in EP No.456,257A1; cyan couplers CC-9 (column 8) and CC-13 (column 10) with magenta as described in U.S. Pat. No.4,833,069; U.S. Pat. No.4,837,136 (2) (column 8); and colorless hiding color-formers represented by the formula (A) in claim 1 of WO No.92/11575 (in particular examples of compounds on pages 36 to 45).

Examples of compounds (including couplers) that react with the oxidized form of the developer thereby releasing a residue of a photographically useful compound are as follows. Development inhibitor releasing compound: the compounds of formulae (I), (II), (III) and (IV) on page 11 of EP 378,236A1 (in particular, T-101 on page 30, T-104 on page 31, T-113 on page 36, T-131 on page 45, T-144 on page 51 and T-158 on page 58); the compounds of formula (I) on page 7 of EP No.436,938A2 (in particular D-49 on page 51); a compound represented by the formula (1) in EP No.568,037A (particularly (23) on page 11); and compounds represented by the formulae (I), (II) and (III) on pages 5 and 6 of EP No.440,195A2 (in particular I- (1) on page 29). Bleach boosting agent releasing compounds: the compounds represented by the formulae (I) and (I') on page 5 of EP No.310,125A2 (in particular (60) and (61) on page 61); and ｃA compound represented by the formulｃA (I) in claim 1 of JP-A-6-59411 (particularly (7) on page 7). Ligand releasing compounds: the compound of claim 1 of U.S. patent No.4,555,478, represented by LIG-X (particularly the compound in column 12 lines 21-41). Leuco dye releasing compounds: compounds 1-6 in columns 3-8 of U.S. patent No.4,749,641. Fluorescent dye releasing compounds: a compound represented by COUP-DYE in claim 1 of U.S. Pat. No.4,774,181 (particularly, compounds 1 to 11 in columns 7 to 10). Image-promoting or graying agent-releasing compounds: compounds represented by the formulae (1), (2) and (3) in column 3 of U.S. Pat. No.4,656,123 (particularly (I-22) in column 25); and ExZK-2 in page 75, lines 36-38 of EP No.450,637A2. Compounds which release groups which only act as dyes when cleaved: compounds represented by the formula (I) in claim 1 of U.S. Pat. No.4,857,447 (particularly Y-1 to Y-19 in columns 25 to 36).

Preferred examples of the additives other than the color former are as follows.

Dispersion medium of oil-soluble organic compound: p-3, P-5, P-16, P-19, P-25, P-30, P-4 2, P-49, P-54, P-55, P-66, P-81, P-85, P-86, and P-93 in JP-A-6 2-21527 2 (pages 140 to 144). Dipping latex of oil-soluble organic compound: latex described in U.S. patent No.4,199,363. Developer oxidation product scavenger: compounds represented by the formula (I) at column 2, lines 54-62 of U.S. Pat. No.4,978,606 (particularly I- (1), I- (2), I- (6), and I- (12) at columns 4 and 5); and compounds from column 2, lines 5-10 in U.S. patent No.4,923,787 (especially compound 1 in column 3). A pollution inhibitor: pages 4 lines 30 to 33 of EP No.298321A, formulae (I) to (III), in particular I-47, I-72, III-1 and III-27 (pages 24 to 48). Fading inhibitor: EP 298,321A1A-6, A-7, A-20, A-21, A-23, A-24, A-25, A-26, A-30, A-37, A-40, A-42, A-48, A-63, A-90, A-92, A-94, and A-164 (pages 69-118); column II-1 to III-23, especially III-10, of U.S. Pat. No. 25-38 of 5,112,444; pages I-1 to III-4, especially II-2, 8-12 of EP 471,347A1; and columns 32-40 of U.S. Pat. No.5,139,931A-1 to A-48, specifically A-39 and A-42. Substances which reduce the amount of colour enhancer or colour-mixing inhibitor used: EP No.411,324A, pages 5-24, I-1 to II-15, in particular I-46. Formalin scavenger: pages 24-29 of EP No.477,932A are SCV-1 to SCV-28, especially SCV-8. Film hardener: h-1, H-4, H-6, H-8 and H-14 on page 17 of JP-A-1-214845; compounds (H-1 to H-54) represented by the formulae (VII) to (XII) in columns 13 to 23 of U.S. Pat. No.4,618,573; the compounds represented by the formulｃA (6) (H-1 to H-76) in the lower right column on page 8 of JP-A- 2-21485 2, particularly H-14; and a compound described in claim 1 of U.S. patent No.3,325,287. Development inhibitor precursor: p-24, P-37 and P-39 in JP-A-6 2-168139 (pages 6 and 7); and 5,019,492, in particular column 7, 28 and 29. Preservatives and mildewcides: column 3-15 of U.S. Pat. No.4,923,790 shows columns I-1 to III-43, specifically II-1, II-9, II-10, II-18, and II-25. Stabilizers and antifog agents: column 6-16 of U.S. Pat. No.4,923,793 shows I-1 to (14), specifically I-1, I-60, (2), and (13); and compounds 1-65, especially compound 36, in columns 25-32 of U.S. patent No.4,952,483. Chemical sensitizer: triphenylphosphine, selenide, and compound 50 of JP-A-5-40324. Dye: ｃA-1 to b-20, particularly ｃA-1, ｃA-1 2, ｃA-18, ｃA-27, ｃA-35, ｃA-36, and b-5 on pages 15 to 18, and V-1 to V-23, particularly V-1, on pages 27 to 29 in JP-A-3-156450; EP No.445,627A, pages 33-55, F-I-1 to F-II-43, in particular F-I-11 and F-II-18; pages 17-28 of EP No.457,153A, III-1 to III-36, in particular III-1 and III-3; microcrystalline dispersions of dye-1 to dye-124 on pages 8-26 of WO No. 88/04794; compounds 1 to 22, in particular Compound 1, on pages 6 to 11 of EP No.319,999A; compounds D-1 to D-87 (pages 3 to 28) represented by the formulae (1) to (3) in EP 519,306A; 4,268,622 Compound 1-22 (column 3-10) represented by the general formula (I); and compounds (1) to (31) represented by formula (I) in U.S. Pat. No.4,923,788 (columns 2 to 9). UV absorber: compounds (18b) to (18r) and 101 to 427 (pages 6 to 9) represented by the formulｃA (1) in JP-A-46-3335; compounds (3) to (66) represented by formula (I) in EP No.520,938A (pages 10 to 44) and compounds HBT-1 to HBT-10 (page 14) represented by formula (III); and compounds (1) to (31) represented by formula (1) in EP No.521,823A (columns 2 to 9).

The photographically useful compounds of the present invention can be applied to a variety of color photosensitive materials, such as color negative films for general purposes or movies, color reversal films for slides and TVs, color photographic paper, color positive films, and color reversal photographic paper. In addition, the photographic material of the present invention is suitable for a film unit with a lens as described in JP-B-32615 and Kokoku No. 3-39784.

Vectors that may be suitably used in the present invention are described, for example, in RD No. 17643, page 28; RD No. 18716, page 647, right column to page 648, left column; and RD No. 307105 page 879.

In the photosensitive material of the present invention, the total film thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or moreLower, more preferably 23 μm or lower, still more preferably 18 μm or lower, and most preferably 16 μm or lower. Membrane swelling velocity T_1/2Preferably 30 seconds or less, more preferably 20 seconds or less. Membrane swelling velocity T_1/2As defined below: when the saturated film thickness is 90% of the maximum swelling film thickness reached after rinsing in a color developer at 30 ℃ for 3 minutes and 15 seconds, the time required for the film thickness to reach 1/2 of the saturated film thickness is obtained. The film thickness is the value measured (2 days) under humid conditions at 25 ℃ and 55% relative humidity. Membrane swelling velocity T_1/2Can be determined by using a swelling instrument (a.green et al, photo gr.sci.eng., vol 19, p.124-129). Membrane swelling velocity T_1/2Can be adjusted by adding a film hardener to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness measured under the above conditions according to the following formula:

(maximum swelling film thickness-film thickness)/film thickness

In the photosensitive material of the present invention, it is preferable to form a hydrophilic colloid layer (referred to as "black layer") having a total dry film thickness of 2 to 20 μm on the opposite side to the side having the emulsion layer. The under layer preferably contains the above-mentioned light absorbers, light-filtering dyes, ultraviolet absorbers, antistatic agents, film hardeners, adhesives, plasticizers, lubricants, coating aids, and surfactants. The swelling ratio of the under layer is preferably 150 to 500%.

The photosensitive material according to the present invention can be developed by the conventional methods described in the above-mentioned RD 17643, pages 28 and 29, RD 18716, page 651, left-right columns, and RD 307105, pages 880 and 881.

The color negative film rinse used in the present invention will be described below.

The compounds listed in the upper right column, line 1 of page 9 to the lower left column, line 14 of page 11 of JP-A-4-121739 can be used in the color developer used in the present invention. Preferred color developers for particularly rapid development are, for example, 2-methyl-4- [ N-ethyl-N- (2-hydroxyethyl) amino ] aniline, 2-methyl-4- [ N-ethyl-N- (3-hydroxypropyl) amino ] aniline, and 2-methyl-4- [ N-ethyl-N- (4-hydroxybutyl) amino ] aniline.

These color developers are preferably used in an amount of 0.01 to 0.08 mol, more preferably 0.015 to 0.06 mol, and most preferably 0.02 to 0.05 mol per liter (hereinafter referred to as "L") of color developer. The replenishment liquid for the color developing solution preferably contains a color developer in an amount corresponding to 1.1 to 3 times, more preferably 1.3 to 2.5 times, the above concentration.

Hydroxylamine is widely used as a preservative for color developers. When a stronger corrosion preventing property is required, hydroxylamine derivatives having a substituent such as an alkyl group, a hydroxyalkyl group, a sulfoalkyl group and a carboxyalkyl group are preferably used, and examples thereof include N, N-bis (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, and N, N-bis (carboxyethyl) hydroxylamine. Of these compounds, the most preferred is N, N-bis (sulfoethyl) hydroxylamine. Although these compounds may be used in combination with hydroxylamine, it is preferable to use one or at least two of the above compounds in place of hydroxylamine.

These preservatives are preferably used in an amount of 0.02 to 0.2 mol, more preferably 0.03 to 0.15mol, and most preferably 0.04 to 0.1 mol per liter of the color developing solution. The replenishment liquid for the color developing solution contains the preservative in an amount equivalent to 1.1 to 3 times the concentration of the mother liquid (rinse tank solution) of the color developing agent.

Sulfite is used as a tarring preventive agent for an oxidized form of color developer in a color developing solution. The amount of each sulfite in the color developing solution is preferably 0.01 to 0.05 mol, more preferably 0.02 to 0.04 mol per liter, and the amount in the replenisher solution is preferably 1.1 to 3 times the above concentration.

The pH of the color developing solution is preferably in the range of 9.8 to 11.0, more preferably 10.0 to 10.5. The pH of the replenishment solution is preferably set to be higher than the above value by 0.1 to 1.0. To stabilize the above pH, conventional buffers such as carbonate, phosphate, sulfosalicylate and borate may be used.

Although the amount of the replenishment liquid for the color developing solution is preferably 80 to 1300 ml (hereinafter also referred to as "ml") per square meter of the photosensitive material, it is desirable that the amount is smaller from the viewpoint of reducing environmental pollution. Specifically, the amount of the replenishment liquid is more preferably 80 to 600 ml, and most preferably 80 to 400 ml.

Although the bromine ion concentration of the color developing solution is usually 0.01 to 0.06 mol/L, it is preferable to set the above concentration to 0.015 to 0.03 mol/L in order to suppress ashing while maintaining sensitivity, thereby improving resolution and better particle size. When the concentration of bromide ions is set within the above range, the replenishment solution preferably contains bromide ions at a concentration calculated by the following formula. However, when C is negative, it is preferable that the replenishment solution contains no bromide ions.

C-a-W/V wherein: c is the concentration (mol/L) of bromide ions in the color developing supplementary liquid,

a is the concentration (mol/L) of target bromide ions in the color developing supplementary solution,

w is when the photosensitive material has a thickness of 1 m²The amount (mol) of bromide ions leached from the photosensitive material into the color developing solution, and

v is per m²The amount of color developer replenisher (L) provided by the photosensitive material.

When the amount of the replenishment liquid is reduced or a high bromide ion concentration is set, it is preferable to use the following development accelerator for enhancing the sensitivity: pyrazolidinones, such as 1-phenyl-3-pyrazolidinone and 1-phenyl-2-methyl-2-hydroxymethyl-3-pyrazolidinone, and thioethers, such as 3, 6-dithio-1, 8-octanediol.

The compounds and rinsing conditions described in the lower left column line 16 on page 4 to lower left column line 6 on page 7 of JP-A-4-125558 can be applied to the rinse liquid having bleaching ability of the present invention.

The bleaching agents preferably used have a redox potential of at least 150 mV. Specifically, suitable examples thereof are those described in JP-A-5-72694 and JP-A-5-17331 2, and particularly suitable examples thereof are 1, 3-diaminopropane tetraacetic acid and an iron complex salt of the compound of example 1 listed on page 7 of JP-A-5-17331 2.

In order to improve the biodegradability of the bleaching agent, it is preferable to use, as the bleaching agent, iron complex salts of the compounds listed in JP-A-4-251845, JP-A-4-26855 2, EP-No. 588,289, EP-No. 591,934 and JP-A-6-208213. The concentration of the above bleaching agent is preferably 0.05 to 0.3 mol per liter of the solution having bleaching ability, and particularly preferably is designed to be 0.1 to 0.15mol per liter for reducing the stress to the environment. When the solution having bleaching power is a bleaching liquor, it is preferred to incorporate bromide therein in an amount of 0.2 to 1 mol, more preferably 0.3 to 0.8mol per liter.

The concentration of each component incorporated in the replenisher solution for the solution having bleaching power is calculated substantially according to the following formula. This enables the concentration of the mother liquor to be kept constant.

CR ═ CT × (V1+ V2)/V1+ CP wherein: CR is the concentration of each component in the make-up solution,

CT is the concentration of the components in the mother liquor (wash tank solution),

the concentration of components consumed during the CP carboxyl flush,

v1 is the amount (ml) of replenishment liquid having bleaching power provided per square meter of photosensitive material, an

V2 is the amount (ml) performed in a preliminary bath of 1 square meter of photosensitive material.

In addition, it is preferred to incorporate a pH buffer in the bleaching liquor, with small amounts of carbonic acid, succinic acid, maleic acid, malonic acid, glutaric acid and adipic acid being particularly preferred. It is also preferable to use conventional bleaching accelerators as listed in JP-A-53-95630, RD 17129 and 3,893,858.

Preferred levels of bleach liquor are from 50 to 1000 ml, more preferably from 80 to 500 ml and most preferably from 100 to 300ml of bleach liquor per square metre of photosensitive material. In addition, the bleaching liquor is preferably aerated.

The compounds and rinsing conditions described in JP-A-4-125558 from page 7, lower left column, line 10 to page 8, lower right column, line 19 may be applied in ｃA rinsing liquid having fixing ability.

In order to enhance the fixing speed and the storage stability, it is particularly preferable to incorporate the compounds represented by the general formulae (I) and (II) of JP-A-6-301169, either alone or in combination, in ｃA washing liquid having fixing ability. In addition, from the viewpoint of enhancing the preservability, it is preferable to use p-toluenesulfinic acid salts and sulfinic acid salts listed in JP-A-1-22476 2.

Although it is preferable to incorporate ammonium ions in a solution having bleaching ability or a solution having fixing ability in view of enhancing bleaching ability, it is preferable to reduce or not use the amount of ammonium from the viewpoint of minimizing environmental pollution.

In the bleaching, bleach-fixing and fixing steps, the jet agitation described in JP-A-1-309059 is particularly preferably performed.

The amount of the replenishment liquid provided in the bleach-fixing or fixing step is 100 to 1000 ml, preferably 150 to 700ml, more preferably 200 to 600 ml per square meter of the photosensitive material.

Any of various silver recovery devices are preferably provided in the bleach-fixing or fixing step in an on-line or off-line manner, whereby the silver is recovered. The in-line device enables the silver concentration of the rinse solution to be reduced so that the amount of make-up fluid can be reduced. It is also suitable to perform off-line silver recovery and reuse the remaining solution for make-up.

The bleach-fixing and fixing steps may each be constituted by a plurality of rinse tanks. Preferably, the tank is provided with a drip line and a multi-stage convection system is used. The cascade structure of 2 tanks is generally effective from the viewpoint of balancing with the size of the developing machine. The ratio of the flushing time in the preceding-stage tank to the flushing time in the succeeding-stage tank is preferably 0.5: 1 to 1: 0.5, more preferably 0.8: 1 to 1: 0.8.

From the viewpoint of enhancing the preservation property, it is preferable that a free chelating agent, which does not form any metal complex, is present in the bleach-fixing and fixing fluid. It is preferred to use as the chelating agent a biodegradable chelating agent in connection with bleaching liquors.

It is preferable to use the descriptions in page 1 2, right lower column line 6 to page 13, right lower column line 16 of JP-A-4-125558 in the water-washing and stabilizing step. Specifically, for the stabilizing liquid, it is preferable from the viewpoint of protection of working environment to replace formaldehyde with pyrrolylmethylamines described in EP Nos. 504,609 and 519,190 and N-hydroxymethylpyrrole compounds described in JP-A-4-362943, and dimerize magentｃA couplers into ｃA surfactant solution containing no image stabilizer such as formaldehyde.

In addition, the stabilizing liquid described in JP-A-6-289559 is preferably used to reduce the adhesion of the fuse to the magentｃA recording layer applied on the photosensitive material.

The amount of the water washing and stabilizing solution to be supplemented is preferably 80 to 1000 ml, more preferably 100 to 500 ml, and most preferably 150 to 300ml per square meter of the photosensitive material, from the viewpoint of ensuring the water washing and stabilizing function and contributing to environmental protection by reducing the amount of waste liquid. In order to prevent the propagation of bacteria and mold when rinsing with the above supplementary amounts, it is preferable to use known mildewcides such as thiabenzazole, 1, 2-benzisothiazolin-3-one and 5-chloro-2-methylisothiazolin-3-one, antibiotics such as gentamicin, and water deionized by using, for example, an ion exchange resin. The combined use of deionized water, a mildewcide, and an antibiotic is more effective than the use alone.

For the solution placed in the water washing or stabilization tank, it is also preferable to reduce the replenishment amount by performing the reverse osmosis membrane treatment as described in JP-A-3-4665 2, JP-A-3-53246, JP-A-3-5554 2, JP-A-3-121448 and JP-A-3-126030. It is preferable to use a low-pressure reverse osmosis membrane in the above treatment.

In the rinsing of the present invention, it is particularly preferable to carry out evaporation correction of the rinsing liquid as disclosed in JIII (Japan Institute of Inventionand Innovation) Journal of Technical Disclosure No. 94-4992. Specifically, a preferable method is to perform correction using information on the temperature and humidity of the developer apparatus environment according to equation 1 on page 2 thereof. The water used for evaporation correction is preferably collected from the wash make-up tank. In this case, deionized water is preferably used as the washing makeup water.

The rinse described in the above-mentioned technical publication journal, page 3, right column, line 15 to page 4, left column, line 32, is preferably used in the present invention. Preferably, a film processor as described in page 3, right column, lines 22-28, is used as the processor used in the processing of the present invention.

Specific examples of the rinse, the automatic developing machine and the evaporation correction scheme preferably used when carrying out the present invention are shown on the right column, page 5, line 11 to the right column, page 7, line last of the above-mentioned journal of technical disclosure.

The flushing agent for the photographic material of the present invention may be provided in any form, such as a liquid or concentrated agent, granules, powder, tablets, paste or emulsion, in the same concentration as used. For example, JP-A-63-17453 discloses liquid agents stored in ｃA container having low oxygen permeability, JP-A-4-19655 and JP-A-4-23078 disclose vacuum-packed powders, JP-A-4-221951 discloses granules comprising ｃA water-soluble polymer, JP-A-51-61837 and JP-A-6-102628 disclose tablets, and PCT national publication 57-5000485 discloses pastes. Although any of the above may be suitably used, it is preferable to use a liquid having the same concentration as that at the time of use from the viewpoint of ease of use.

The container for storing the above-mentioned flushing agent is composed of, for example, any one of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, and nylon, or a mixture thereof. Can be selected according to the desired oxygen permeability. A material having low oxygen permeability, such as polyethylene terephthalate or a composite material of polyethylene and nylon, is preferably used as a liquid that is easily oxidized, such as a color developing solution. Preferably, these materials are used in containers each having a thickness of 500 to 1500 μm so that the overall oxygen permeability is 20 ml/m²24 hrs. atm or less.

The following will describe a developing solution for color reversal film suitable for use in the present invention.

For color reversal film processing, the following detailed description is preferably used: published public technology No.6 by Aztek (4/1, 1991), page 1, line 5 to page 10, line 5, and page 15, line 8 to page 24, line 2. In color reversal film processing, an image stabilizer is added to the conditioning bath and the final bath. Examples of suitable image stabilizers include formalin, formaldehyde sodium bisulfite and N-hydroxymethylpyrrole compounds. From the viewpoint of working environment, formaldehyde sodium bisulfite and N-hydroxymethylpyrrole compounds are preferable. Among N-hydroxymethylpyrrole compounds, N-hydroxymethyltriazole is particularly preferred. Color developers, bleaches, fixatives, and washing water are also preferred for color negative film development.

As preferred color reversal Film developers including the above features, a developer E-6 available from Eastman Kodak and a developer CR-56 available from Fuji Photo Film co.

The color photographic photosensitive material used in the present invention is suitable for use as a negative film for an advanced photographic system (hereinafter referred to as "AP system"). For example, films are processed into an AP system format and loaded into special purpose cartridges such as NEXIA, NEXIA F or NEXIA H (in the ISO200/100/400 sequence) manufactured by Fuji Photo Film Co., Ltd. (hereinafter "Fujifilm"). The Film cartridge for AP system is put into a camera for AP system such as the Epion series manufactured by Fuji Film, for example, Epion 300Z, and then used in actual use. Further, the Color photographic light-sensitive material of the present invention is suitable for a lens-fitted Film such as Fuji Color Utunmdesu Super Slim manufactured by Fuji Film.

The films thus photographed were printed in a mini-lab system by the following steps:

(1) acceptance (acceptance of exposed film cartridge by customer);

(2) disassembling (transferring the film from the cartridge to an intermediate cartridge for development);

(3) developing the film;

(4) back contact (return developed negative to original cassette);

(5) printing (continuously and automatically printing three types of C/H/P photos and index photos (preferably Super FA8 manufactured by Fuji Film)) on color photographic paper; then the

(6) Collation and dispatch (collation of the cassette and index photograph with the ID number, and dispatch of the photograph).

The System is preferably Fuji Film Minilabo Champion Super FA-298/FA-278/FA-258/FA-238 or Fuji Film Digital laboratory System Frontier. The film processors of the MinilaboChampion are for example FP922AL/FP562B/FP562BL, AL/FP362B/FP3622B, AL, and the recommended processing chemicals are Fuji Color Just It CN-16L or CN-16Q. Film processing machines are for example PP3008AR/PP3008A/PP1828AR/PP1828A/PP1258AR/PP1258A/PP728AR/PP728A, and the recommended processing chemicals are FujiColor Just It CP-47L or CP-40 FAII. In the Frontier system, a scanning and image processor SP-1000 and a laser printer and paper processor LP-1000P or a laser printer L-1000W are used. Fuji Film DT200/DT100 and AT200/AT100 are preferably used as the detacher in the detaching step and the rear contactor in the rear contact step, respectively. In addition, the adadin 1000 can output digital information directly to a floppy disk, Zip disk, or onto a CD via a CD reader/writer.

The AP system can be appreciated by photo joy system (photo joy system), the central unit of which is the Fuji Film digital image workstation Aladin 1000. For example, developed AP system cassette films are placed directly into Aladdin 1000, or negative, positive or photographic image information is input using the 35 mm film scanner FE-550 or flat head scanner PE-550 therein, and the resulting digital image data can then be readily processed and edited. The resulting data can be output photographically with current laboratory equipment, for example, via digital color printer NC-550AL based on a photo-permanent thermal color printing system or via Pictrograph 3000 based on a laser exposure thermal development transfer system or via a film recorder.

On the other hand, if at home, a picture can be enjoyed on a television by simply placing the developed AP system cassette Film in a photo player (photoplayer) AP-1 manufactured by Fuji Film. It is also possible to continuously input image information into a personal computer at high speed by putting it into a photo scanner AS-1 manufactured by Fuji Film. In addition, films, photographs, or stereographic articles can be input into a personal computer using the photo vision FV-10/FV-5 manufactured by Fuji Film. Further, various processes are performed on a personal computer using FujiFilm Application Soft optics, whereby video information recorded on a flexible disk, a Zip disk, a CD-R, or a hard disk can be enjoyed. The digital color printer NC-2/NC-2D based on the photographic fixing type thermal color printing system manufactured by Fuji Film is suitable for outputting high-quality photographs by a personal computer.

Fuji Color Pocket Album AP-5 Pop L, AP-1Pop L or AP-1Pop KG or card File16 are preferably used for storage of developed AP system film.

The present invention will be described in more detail below by way of examples. Example 1

In example 1, the case where the compound released as a photographically useful group is a bleach accelerator will be described. Preparation of sample 101

The following photosensitive material was produced. Note that the ashed emulsion Z in the first layer is produced as follows. Preparation of ashed emulsion Z preparation of emulsion Z

2.0L of a 1% inert gelatin aqueous solution was maintained at 40 ℃ and then 0.1 g of chloroauric acid was added and dissolved with stirring. 0.6 mol of potassium bromide, 0.006 mol of potassium iodide, and 0.6 mol of silver nitrate were added by the double spray method at the same fixed flow rate over a period of 4 minutes. 0.1 g of chloroauric acid and 0.02 mol of sodium hydroxide were added, and then the resultant was stirred. Thereafter, 0.1 mol of potassium bromide was added to obtain particles having an average particle diameter of 0.08. mu.m. After washing these particles with water, 100 g of inert gelatin was added to disperse the particles, thereby preparing an emulsion Z having a surface-ashed core.

The film support which had been bottom-coated with cellulose triacetate was coated with a plurality of layers having the following composition to produce sample 101 as a multilayer color photosensitive material. Composition of photosensitive layer

The main materials used in the individual layers are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high-boiling organic solvent ExY: yellow color former H: gelatin hardener ExS: sensitizing dye

The numbers corresponding to the components are expressed in g/m²Is the coating weight in units. The coating amount of silver halide is expressed in terms of the amount of silver. The coating amount of each sensitizing dye is expressed in units of mol per mol of silver halide in the same layer. Sample 101 first layer (first antihalation layer)

Black colloidal silver	Silver 0.155
		Ashed emulsion Z	Silver 0.2
Gelatin	0.87
		ExC-1	0.04
ExC-3	0.04
		Cpd-2	0.001
HBS-1	0.004
		HBS-2	0.002

Second layer (second antihalation layer)

Black colloidal silver	Silver 0.066
		Gelatin	0.407
ExM-1	0.050
		ExF-1	2.0×10-3
HBS-1	0.074
		Solid disperse dye ExF-2	0.015
Solid disperse dye ExF-3	0.020

Third layer (middle layer)

Iodine silver bromide emulsion O	0.020
		ExC-2	0.022
Polyacrylic acid ethyl ester latex	0.085
		Gelatin	0.294

Fourth layer (Low speed red photosensitive emulsion layer)

Iodine silver bromide emulsion A	Silver 0.40
		ExS-1	5.5×10-4
ExS-2	1.0×10-5
		ExS-3	2.4×10-4
ExC-1	0.109
		ExC-3	0.044
ExC-4	0.072
		ExC-5	0.011
ExC-6	0.003
		Cpd-2	0.025
Cpd-4	0.025
		HBS-1	0.17
Gelatin	0.80

Fifth layer (Medium speed red emulsion layer)

Iodine silver bromide emulsion B	Silver 0.30
		Iodine silver bromide emulsion C	0.60 silver
ExS-1	5.0×10-4
		ExS-2	1.0×10-5

ExS-3	2.0×10-4
		ExC-1	0.15
ExC-2	0.026
		ExC-3	0.025
ExC-4	0.12
		ExC-5	0.016
ExC-6	0.007
		Cpd-2	0.036
Cpd-4	0.028
		HBS-1	0.16
Gelatin	1.18

Sixth layer (high speed red emulsion layer)

Iodine silver bromide emulsion layer D	Silver 1.50
		ExS-1	3.7×10-4
ExS-2	1×10-5
		ExS-3	1.8×10-4
ExC-1	0.18
		ExC-3	0.07
ExC-6	0.029
		ExC-7	0.010
ExY-5	0.008
		Cpd-2	0.046
Cpd-4	0.077
		HBS-1	0.25
HBS-2	0.12

Gelatin

2.12

Seventh layer (middle layer)

Cpd-1	0.012
		Solid disperse dye ExF-4	0.030
HBS-1	0.050
		Polyacrylic acid ethyl ester latex	0.83
Gelatin	0.84

Eighth layer (layer providing intermediate image effect to red photosensitive layer)

Iodine silver bromide emulsion E	Silver 0.59
		ExS-6	1.7×10-4
ExS-10	4.6×10-4
		Cpd-4	0.030
ExM-2	0.096
		ExM-3	0.028
ExY-1	0.031
		HBS-1	0.085
HBS-3	0.003
		Gelatin	0.58

Ninth layer (Low-speed Green emulsion layer)

Iodine silver bromide emulsion F	Silver 0.42
		Iodine silver bromide emulsion G	Silver 0.30

Iodine silver bromide emulsion H	0.38 silver
		ExS-4	2.4×10-5
ExS-5	1.0×10-4
		ExS-6	3.9×10-4
ExS-7	7.7×10-5
		ExS-8	3.3×10-4
ExM-2	0.36
		ExM-3	0.045
HBS-1	0.28
		HBS-3	0.01
HBS-4	0.27
		Gelatin	1.39

Tenth layer (Medium speed green emulsion layer)

Iodine silver bromide emulsion I	0.60 silver
		ExS-4	5.3×10-5
ExS-7	1.5×10-4
		ExS-8	6.3×10-4
ExC-6	0.009
		ExM-2	0.031
ExM-3	0.029
		ExY-1	0.006
ExM-4	0.028
		HBS-1	0.064
HBS-3	2.1×10-3

Gelatin

0.44

Eleventh layer (high speed green emulsion layer)

Iodine silver bromide emulsion I	Silver 0.20
		Iodine silver bromide emulsion J	Silver 0.75
ExS-4	4.1×10-5
		ExS-7	1.1×10-4
ExS-8	4.9×10-4
		ExC-6	0.004
ExM-1	0.016
		ExM-3	0.036
ExM-4	0.020
		ExM-5	0.004
ExY-5	0.003
		ExM-2	0.013
Cpd-3	0.004
		Cpd-4	0.007
HBS-1	0.18
		Polyacrylic acid ethyl ester latex	0.099
Gelatin	1.11

Twelfth layer (yellow filter layer)

Yellow colloidal silver	Silver 0.05
		Cpd-1	0.16
Solid disperse dye ExF-5	0.020

Solid disperse dye ExF-6	0.020
		Oil soluble dye ExF-7	0.010
HBS-1	0.082
		Gelatin	1.057

The tenth layer (Low speed blue emulsion layer)

Iodine silver bromide emulsion K	Silver 0.18
		Iodine silver bromide emulsion L	Silver 0.20
Iodine silver bromide emulsion M	Silver 0.07
		ExS-9	4.4×10-4
ExS-10	4.0×10-4
		ExC-1	0.041
ExC-8	0.012
		ExY-1	0.035
ExY-2	0.71
		ExY-3	0.10
ExY-4	0.005
		Cpd-2	0.10
Cpd-3	4.0×10-3
		HBS-1	0.24
Gelatin	1.41

Fourteenth layer (high speed blue emulsion layer)

Iodine silver bromide emulsion N	Silver 0.81
		ExS-9	3.6×10-4

ExC-1	0.013
		ExY-2	0.31
ExY-3	0.05
		ExY-6	0.062
Cpd-2	0.075
		Cpd-3	1.0×10-3
HBS-1	0.10
		Gelatin	0.91

The fifteenth layer (first protective layer)

Iodine silver bromide emulsion O	Silver 0.30
		UV-1	0.21
UV-2	0.13
		UV-3	0.20
UV-4	0.025
		F-18	0.009
HBS-1	0.12
		HBS-4	5.0×10-2
Gelatin	2.3

Sixteenth layer (second protective layer)

H-1	0.40
		B-1 (diameter 1.7 μm)	5.0×10-2
B-2 (diameter 1.7 μm)	0.15
		B-3	0.05

S-1	0.20
		Gelatin	0.75

In addition to the above components, the individual layers may contain W-1 to W-5, for the purpose of improving storage stability, handleability, pressure resistance, antibacterial and antifungal properties, antistatic properties, and coating properties,B-4 to B-6, F-1 to F-18, iron salts, lead salts, gold salts, platinum salts, palladium salts, iridium salts, ruthenium salts, and rhodium salts. In addition, 8.5X 10 calcium in the form of an aqueous calcium nitrate solution was added to the coating solutions of the eighth and tenth layers, respectively, on a per mole silver halide basis^-3g to 7.9X 10^-3g, thereby preparing a sample.

Table 1 below shows the AgI content, particle size, surface iodine content, and the like of the emulsion abbreviated in this example. The surface iodine content can be checked by using XPS as follows. Each sample was cooled to-115 ℃ in a vacuum of 1X 10 Torr or less, and then MgK α was excited at an X-ray source voltage of 8 kV and an X-ray current of 20 mA, whereby Ag3d5/2, Br3d and I3d5/2 electrons were measured. The overall density of the measurement peaks was corrected by the sensitivity factor. From these density ratios, the surface iodine content can be calculated.

TABLE 1

Name of emulsion	Average iodine content (mol%)	Coefficient of variation relating to iodine distribution among particles	Average particle diameter (equivalent to spherical diameter. mu.m)	Coefficient of variation (%) corresponding to the diameter of sphere	Projected area diameter (equivalent to circular diameter, mum)	Diameter/thickness ratio	Surface iodine content (mol%)	Particle shape
									A	3.9	20	0.37	19	0.40	2.7	2.3	Flaky particles
B	5.1	17	0.52	21	0.67	5.2	3.5	Flaky particles
									C	7.0	18	0.86	22	1.27	5.9	5.2	Flaky particles
D	4.2	17	1.00	18	1.53	6.5	2.8	Flaky particles
									E	7.2	22	0.87	22	1.27	5.7	5.3	Flaky particles
F	2.6	18	0.28	19	0.28	1.3	1.7	Flaky particles
									G	4.0	17	0.4 3	19	0.58	3.3	2.3	Flaky particles
H	5.3	18	0.52	17	0.79	6.5	4.7	Flaky particles
									I	5.5	16	0.73	15	1.03	5.5	3.1	Flaky particles
J	7.2	19	0.93	18	1.45	5.5	5.4	Flaky particles
									K	1.7	18	0.40	16	0.52	6.0	2.1	Flaky particles
L	8.7	22	0.64	18	0.86	6.3	5.8	Flaky particles
									M	7.0	20	0.51	19	0.82	5.0	4.9	Flaky particles
N	6.5	22	1.07	24	1.52	7.3	3.2	Flaky particles
									O	1.0	-	0.07	-	0.07	1.0	-	Uniform structure
P	0.9	-	0.07	-	0.07	1.0	-	Uniform structure

In table 1:

(1) emulsion L-O is reductively sensitized with thioureｃA dioxide and thiosulfonic acid during the preparation of the granules according to the examples of JP-A- 2-191938.

(2) Emulsion A-O gold sensitization, sulfur sensitization and selenium sensitization were carried out in the presence of ｃA spectral sensitizing dye and sodium thiocyanate as described in the individual photosensitive layers according to the examples of JP-A-3-237450.

(3) Flaky particles were prepared from low molecular weight gelatin according to JP-A-1-158426.

(4) Dislocation lines as described in JP-A-3-237450 were observed in the plate-like particles when ｃA high-pressure electron microscope was used. Preparation of dispersions of organic solid disperse dyes

ExF-2 was dispersed as follows. That is, 21.7ml of water, 3ml of a 5% aqueous solution of p-octylphenoxyethoxyethanesulfonic acid soda, and 0.5g of a 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) were placed in a 700ml ball mill, and then 5.0g of the dye ExF-2 and 500 ml of zirconia balls (diameter 1 mm) were added to the mill. The contents were dispersed for 2 hours. The dispersion was prepared by using a BO type vibratory ball mill manufactured by Chuo Koki k.k. The dispersion was removed from the mill and then added to 8g of a 12.5% aqueous gelatin solution. The zirconia balls were filtered off to give a gelatin dispersion of the dye. The fine dye particles had an average particle diameter of 0.44. mu.m.

Solid dispersions ExF-3, ExF-4 and ExF-6 were prepared in the same manner as above. The average particle diameters of these fine dye particles were 0.24, 0.45, and 0.52 μm, respectively. ExF-5 was dispersed by the microprecipitation dispersion method described in the examples of EP 549,489A. The average particle size was 0.06. mu.m.

The solid dispersion ExF-8 was dispersed in the following manner.

70g of water and W-2 were added to 1400g of ExF-8 wet cake containing 30% water, and the resulting mass was stirred to form a 30% strength ExF-8 slurry. Next, ULTRAVISO MILL (UVM-2) manufactured by Imex k.k. was filled with 1700ml of zirconia balls having an average particle diameter of 0.5 mm. The slurry was ground for 8 hours by passing the slurry through the mill, the peripheral speed of the mill was about 10m/sec, and the filling amount was 0.5L/min.

The compounds used to form each layer are as follows.

HBS-1 Trihydroxymethylphenyl phosphate HBS-2 di-n-butyl phthalate

HBS-4 phosphoric acid tris (2-ethylhexyl) ester

Fabrication of sample 102

Sample 102 was prepared in the same manner as sample 101 in example 1 except that ExC-1 and ExC-3 in the first layer were replaced with equimolar amounts of the compound (A-21). Production of samples 103-105

Samples 103-105 were made in the same manner as sample 102, except that the compound (A-21) was replaced with equimolar amounts of the compounds shown in Table 2. Fabrication of sample 106

Sample 106 was produced in the same manner as sample 102, except that the compound (A-21) and the ashed emulsion Z in the first layer were transferred to the fourth layer. Manufacture of sample 107

Sample 107 was produced in the same manner as sample 103 except that the compound (a-21) and the ashed emulsion Z in the first layer were transferred to the fourth layer. Manufacture of sample 108

Sample 108 was produced in the same manner as sample 102, except that compound (A-21) in the first layer was transferred to the second layer. In this sample, a layer adjacent to the layer to which the ashed emulsion was added was coated with "the PUG-releasing compound" (a-21). Evaluation of desilvering Properties

In this example, a bleach accelerator was used as the photogenic group. Therefore, the release characteristics were evaluated by evaluating the desilvering characteristics of the photosensitive material.

The above sample was subjected to wedge exposure and then developed by the following development procedure (1). Meanwhile, the developing process (2) is performed only when a relatively low-order solution is used in the bleaching step of the developing process (1).

After development, density measurements were taken. The desilvering property was evaluated by the increase of the yellow density in the developing procedure (2) at the exposure amount at which the density was the minimum yellow density +1.8 in the developing procedure (1). (residual silver under minor conditions was evaluated by optical density change).

The results are shown in Table 2.

The method of developing each sample is described below. Program (1)

Step (ii) of	Time	Temperature (. degree.C.)
			Color development	3 minutes and 15 seconds	38
Bleaching	3 min 00 s	38
			Washing machine	30 seconds	24
Fixing device	3 min 00 s	38
			Washing (1)	30 seconds	24
Washing (2)	30 seconds	24
			Stabilization	30 seconds	38
Drying	4 minutes and 20 seconds	55

In procedure (2), the bleaching time was 2 minutes and 30 seconds.

The composition of the rinse solution was as follows. Color developing agent

Diethylenetriaminepentaacetic acid	1.0g
		1-hydroxyethylidene-1, 1-diphosphonic acid	2.0g
Sulfurous acidSodium salt	4.0g
		Potassium carbonate	30.0g
Potassium bromide	1.4g
		Potassium iodide	1.5mg
Hydroxylamine sulfate	2.4g
		4- [ N-Ethyl-N- (. beta. -hydroxyethylamino)]-2-methylaniline sulfate	4.5g
Adding water to	1.0L
		pH (controlled with Potassium hydroxide and sulfuric acid)	10.05

Bleach-fixing liquid

Ethylenediaminetetraacetic acid ferric sodium trihydrate	100.0g
		Ethylenediaminetetraacetic acid disodium salt	10.0g
3-mercapto-1, 2, 4-triazoles	0.03g
		Ammonium bromide	140.0 g
Ammonium nitrate	30.0 g
		Ammonia (27%)	6.5 ml
Adding water to	1.0 L
		pH (controlled with ammonia and nitric acid)	6.0

Fixing agent

Ethylenediaminetetraacetic acid disodium salt	0.5 g
		Ammonium sulfite	20.0 g
Aqueous ammonium thiosulfate solution (700 g/L)	295.0 ml
		Acetic acid (90%)	3.3 g
Adding water to	1.0 L
		pH (control with Ammonia and acetic acid)	6.7

Stabilizer

Para nonyl phenoxy polyglycidyl (glycidol average degree of polymerization 10)	0.2g
		Ethylenediaminetetraacetic acid	0.05g
1,2, 4-triazoles	1.3g
		1, 4-bis (1, 2, 4-triazol-1-ylmethyl) piperazine	0.75g
Glycolic acid	0.02g
		Hydroxyethyl cellulose (DAISERU KAGAKUHUC SP-2000)	0.1g
1, 2-benzisothiazolin-3-ones	0.05g
		Adding water to	1.0L
pH	8.5

Evaluation of storage stability of photosensitive Material

In the development procedure (1) for evaluating the desilvering characteristics as described above, the photosensitive material was left for 4 days under the conditions of 50 ℃ and 55% RH before exposure, and then the thus-obtained sample was subjected to exposure and development simultaneously, thereby evaluating the change in sensitivity of the cyan image during storage. The sensitivity was obtained with the logarithm of the reciprocal of the exposure given by the minimum cyan density +1.2, whereby the change in sensitivity during storage was examined.

The results are also shown in table 2. Evaluation of color development process fluctuations

In the developing procedure (1) for evaluating the desilvering property as described above, similar evaluation was made using a color developer in which the concentration of potassium bromide was changed to 90% in the above color developer. In this way, the value of the ashing fluctuation in the cyan image was evaluated.

The process fluctuation is represented by a relative value assuming that the density fluctuation of the sample 101 is 1.

The results are also shown in table 2.

TABLE 2

Sample number	Additive layer of ashed emulsion	Type of PUG releasing compound and additive layer	Desilvering characteristics	Storage characteristics	Handling fluctuations
						101 comparative example	Layer 1	Is free of	+0.27	-0.03	1.0 (control)
102 invention	Layer 1	Layer 1A-21	+0.03	-0.03	1.0
						103 the invention	Layer 1	Layer 1A-24	+0.03	-0.03	1.0
104 invention	Layer 1	Layer 1 (46)	+0.02	-0.03	0.7
						105 the invention	Layer 1	Layer 1 (123)	+0.02	-0.03	0.7
106 comparative example	Layer 4	Layer 4A-21	+0.05	-0.23	1.3
						107 comparative example	Layer 4	Layer 4A-24	+0.05	-0.24	1.3
108 invention	Layer 1	Layer 2A-21	+0.09	-0.03	0.7

As shown in table 2, each of the inventive samples had a slightly increased density and good desilvering characteristics even when a lesser amount of bleach was used.

Table 2 also shows that this effect is reduced when ashed emulsion and "PUG-releasing compound" are present in the adjacent layer (sample 108). In this respect, the ashed emulsion and the "PUG-releasing compound" are preferably in the same layer. Samples 102 and 103 contained "PUG-releasing compounds" that produced a cyan color. Although the desilvering property and the storage stability are good, the ashing fluctuation due to the color development fluctuation is large. In this respect, it is more preferable that the "PUG-releasing compound" is a compound that does not develop a color (does not generate any color-forming dye in the photosensitive material).

In samples 106 and 107, the ashing emulsion was added to the light-sensitive silver halide emulsion layer. These samples are in the range of JP-A-63-175850. However, the change in photographic properties (change in sensitivity) due to storage is large, so that further improvement is required for putting these photosensitive materials into practical use. Example 2

In example 2, a compound that releases the development inhibitor will be described below. Production of samples 201-204

Samples 201 to 204 were produced by following the same procedure as sample 102 of example 1 except that the compound (a-21) in the first layer was changed to the compound shown in table 3. Note that the coating amount was 0.1 times (mol) the coating amount of the compound in the first layer of sample 102. Manufacture of sample 205

In sample 101 of example 1, the silver iodobromide emulsion O in the third layer was removed. Instead, the third layer uses 0.1 g/m²Ashed emulsion Z formed in example 1 was applied. The third layer also used 0.01 g/m²Compound (12) of (2). Manufacture of sample 206

In sample 205, ashed emulsion Z and compound (12) in the third layer were removed. Instead, the comparative compound (a) and the comparative compound (a) are added in the same molar amount as the compound (12)(Compound described in JP-B-4-73573) minimum fluctuation in density due to color development

The evaluation was made similarly to "evaluation of color development fluctuation" in example 1.

In addition, the amount of hydroxylamine sulfate in the developing procedure (1) of example 1 was coated plural times, 0.7 times, thereby performing similar evaluation. Evaluation of storage stability

Evaluation was performed similarly to "evaluation of storage stability of photosensitive material" in example 1.

TABLE 3

Sample number	Additive layer of ashed emulsion	Type of PUG releasing compound and additive layer	Ashing fluctuation	Ashing fluctuation	Storage characteristics
						101 comparative example	Layer 1	Is free of	1.0 (ref)	1.0 (ref)	-0.03
201 the invention	Layer 1	Layer 1 (12)	0.50	0.8	-0.03
						202 invention	Layer 1	Layer 1 (106)	0.52	0.8	-0.04
203 invention	Layer 1	Layer 1A-4	0.6	0.8	-0.04
						204 comparative example	Layer 1	Comparative Compound (a) described in JP-B-4-73573 layer 1	0.8	1.1	-0.25
205 invention of the invention	Layer 3	Layer 3 (12)	0.7	0.8	-0.03
						206 comparative example	Without adding	Comparative Compound (a) described in JP-B-4-73573 layer 3	0.9	1.1	-0.27

The results of example 2 show that each of the samples of the present invention has small ashing fluctuation and high storage stability.

In contrast, although the compound described in JP-B-4-73573 has an effect on ashing fluctuation (fluctuation in the concentration of potassium bromide), its effect of improving the density dependence of hydroxylamine sulfate is not so great. Also, the compound still needs to be improved in storage stability. Example 3

Samples 301 and 302 (color photographic paper) described below were manufactured.

Corona discharge was performed on the surface of the support formed by coating both surfaces of the paper with polyethylene resin. Thereafter, a gelatin base layer comprising sodium dodecylbenzenesulfonate was formed. In addition, first to seventh photographic constituent layers were formed by the coating sequence, thereby producing a sample (301) having a silver halide color photosensitive material disposed in the following layers. The coating solution of the individual photographic constituting layers was prepared as follows. Preparation of fifth layer coating solution

300 g of cyan coupler (ExC-1), 250 g of color image stabilizer (Cpd-1), 10 g of color image stabilizer (Cpd-10), 20 g of color image stabilizer (Cpd-12), 14 g of ultraviolet absorber (UV-1), 50 g of ultraviolet absorber (UV-2), 40 g of ultraviolet absorber (UV-3) and 60 g of ultraviolet absorber (UV-4) were dissolved in 230 g of solvent (Solv-6) and 350 ml of ethyl acetate. The resulting solution was dispersed by emulsion in 6500 g of a 10% aqueous gelatin solution containing 25 g of a surfactant (Cpd-20) to prepare emulsion dispersion C.

Silver chlorobromide emulsion C (cubic, 5: 5 mixture (molar ratio of silver) of large-size emulsion C having an average particle diameter of 0.40 μm and small-size emulsion C having an average particle diameter of 0.30 μm; the coefficients of variation of particle size distribution of the two emulsions are 0.09 and 0.11, respectively; in the two emulsions, 0.5 mol% of silver bromide is locally contained in a portion of the surface of the particles having silver halide as a substrate) is separately prepared.

The red sensitizing dyes G and H shown below were each used at 9.0X 10 per mol of silver^-5mol and 12.0X 10^-5The amount of mol is added in the large size emulsion C and the small size emulsion C. The emulsion is optimally chemically matured by adding a sulfur sensitizer and a gold sensitizer.

The emulsion dispersion C and the silver chlorobromide emulsion C were mixed and then dissolved to prepare a fifth layer coating solution having the following composition. The coating solutions for the first to fourth layers and the sixth and seventh layers were prepared in the same manner as the fifth layer coating solution. H-1, H-2 and H-3 were used as gelatin hardeners in each layer.

Similarly, 15.0, 60.0, 5.0 and 10.0 mg/m were added to each layer, respectively²Ab-1, Ab-2, Ab-3 and Ab-4. (H-1) curing agent

(used in an amount of 0.50 wt% of gelatin) (H-2) hardener(the usage amount is 1.20 wt% of the gelatin) (H-3) hardener

(the usage amount is 0.40 wt% of gelatin%) (Ab-1) antibacterial agent (Ab-2) antibacterial agent (Ab-3) antibacterial agent

(Ab-4) antibacterial agent

a: b: c: d in a molar ratio of 1: 1

A spectral sensitizing dye and a crystal phase controlling agent 1 were used in the silver chlorobromide emulsion of each emulsion layer. Blue sensitive emulsion layer sensitizing dye ASensitizing dye BSensitizing dye C

Crystal controller 1(sensitizing dyes A and C were added in an amount of 0.42X 10 per mole of silver halide in the large-size emulsion and the small-size emulsion, respectively^-4mol and 0.05X 10^-4And (mol). The addition amount of the sensitizing dye B in the large-size emulsion and the small-size emulsion is 3.4 multiplied by 10 respectively per mol of silver halide^-4mol and 4.1X 10^-4And (mol). ) Green emulsion layer sensitizing dye D

Sensitizing dye E

Sensitizing dye F(the amount of the sensitizing dye D added in the large-size emulsion and the small-size emulsion was 3.0X 10, respectively, per mole of silver halide^-4mol and 3.6X 10^-4And (mol). The addition amount of the sensitizing dye E in the large-size emulsion and the small-size emulsion is 4.0X 10 per mol of silver halide^-5mol and 7.0X 10^-5And (mol). The addition amount of the sensitizing dye F in the large-size emulsion and the small-size emulsion is 2.0X 10 per mol of silver halide^-4mol and 2.8X 10^-4And (mol). ) Red photosensitive emulsion layer sensitizing dye G

Sensitizing dye H(infection by infection with an increased amount ofThe addition amounts of materials G and H in the large-size emulsion and the small-size emulsion were 8.0X 10, respectively, per mole of silver halide^-5mol and 10.7X 10^-5 mol。)

In addition, the red photosensitive layer is prepared by 3.0 × 10 per mol of silver halide^-3The following compound I is added in mol amounts. Compound I

Similarly, each of the blue, green and red emulsion layers was coated with 3.3X 10 silver halide per mole^-4mol、1.0×10^-3mol and 5.9X 10^-41- (3-methylureidophenyl) -5-mercaptotetrazole is added in mol.

In addition, 0.2, 0.6 and 0.1 mg/m were added to the second, fourth, sixth and seventh layers, respectively²The same compound of (1).

In the blue and green emulsion layers, 4-hydroxy-6-methyl-1, 3, 3a, 7-tetraazaindene was added in an amount of 1X 10 per mole of silver halide^-4mol and 2X 10^-4 mol。

Adding 0.05 g/m into red photosensitive emulsion layer²Is a copolymer latex of methacrylic acid and butyl acrylate (weight ratio 1: 1, average molecular weight 200000-400000).

Adding 6,6 and 18 mg/m in the second, fourth and sixth layers respectively²Amount of disodium catechol-3, 5-disulfonate.

To prevent irradiation, the following dyes were added (numbers in parentheses indicate the coating amounts).

Layer arrangement

The composition of each layer will be described below. The numbers represent the coating weight (g/m)²). The coating amount of each silver halide emulsion is expressed by the coating amount of silver. Carrier

Polyethylene resin laminated paper { polyethylene resin containing white pigment (titanium dioxide, content 16 wt%, zinc oxide, content 4 wt%)) Brightener (4, 4' -bis- (5-methylbenzoxazolyl) stilbene, content 0.03 wt%), and blue dye (ultramarine) } first layer (blue emulsion layer)

Silver chlorobromide emulsion A (cubic, 5: 5 mixture (molar ratio of silver) of large-size emulsion A having an average particle diameter of 0.72 μm and small-size emulsion A having an average particle diameter of 0.06 μm; coefficient of variation of particle diameter distribution of both emulsions is 0.08 and 0.10, respectively; in both emulsions, 0.3 mol% of silver bromide is contained locally in the surface of a part of the particles having silver halide as a substrate)	0.24
		Gelatin	1.25
Yellow color former (ExY)	0.57
		Color image stabilizer (Cpd-1)	0.07
Color image stabilizer (Cpd-2)	0.04
		Color image stabilizer (Cpd-3)	0.07
Color image stabilizer (Cpd-8)	0.02
		Solvent (Solv-1)	0.21

Second layer (color mixing prevention layer)

Gelatin	0.99
		Color mixing inhibitor (Cpd-4)	0.09
Color image stabilizer (Cpd-5)	0.018
		Color image stabilizer (Cpd-6)	0.13
Color image stabilizer (Cpd-7)	0.01
		Solvent (Solv-1)	0.06
Solvent (Solv-2)	0.22

Third layer (Green emulsion layer)

Silver chlorobromide emulsion B (cubic, 1: 3 mixture (molar ratio of silver) of large-size emulsion B having an average particle diameter of 0.45 μm and small-size emulsion B having an average particle diameter of 0.35 μm; the coefficients of variation of particle size distribution of the two emulsions are 0.10 and 0.08, respectively; in the two emulsions, 0.4 mol% of silver bromide is partially contained in the surface of a part of the particles having silver halide as a substrate)	0.14
		Gelatin	1.36
Magenta color former (ExM)	0.15
		Ultraviolet absorber (UV-A)	0.14
Color image stabilizer (Cpd-2)	0.02
		Color image stabilizer (Cpd-4)	0.002
Color image stabilizer (Cpd-6)	0.09
		Color image stabilizer (Cpd-8)	0.02
Color image stabilizer (Cpd-9)	0.03
		Color image stabilizer (Cpd-10)	0.01

Color image stabilizer (Cpd-11)	0.0001
		Solvent (Solv-3)	0.1 1
Solvent (Solv-4)	0.22
		Solvent (Solv-5)	0.20

Fourth layer (color mixing prevention layer)

Gelatin	0.71
		Color mixing inhibitor (Cpd-4)	0.06
Color image stabilizer (Cpd-5)	0.013
		Color image stabilizer (Cpd-6)	0.10
Color image stabilizer (Cpd-7)	0.007
		Solvent (Solv-1)	0.04
Solvent (Solv-2)	0.16

Fifth layer (Red photosensitive emulsion layer)

Silver chlorobromide emulsion C (cubic, large size emulsion C with average particle size of 0.40 μm and small size emulsion C with average particle size of 0.30 μm5: 5 mixture of size emulsion C (molar ratio of silver); the coefficient of variation of the particle size distribution of the two emulsions was 0.09 and 0.11, respectively; in both emulsions, 0.5 mol% of silver bromide was locally contained in the surface of a part of the particles having silver halide as a substrate)	0.20
		Gelatin	1.11
Cyan color former (ExC-1)	0.30
		Ultraviolet absorber (UV-A)	0.29

Color image stabilizer (Cpd-1)	0.25
		Color image stabilizer (Cpd-9)	0.01
Color image stabilizer (Cpd-10)	0.01
		Color image stabilizer (Cpd-12)	0.02
Solvent (Solv-6)	0.23

Sixth layer (ultraviolet absorption layer)

Gelatin	0.46
		Ultraviolet absorber (UV-B)	0.45
Solvent (Solv-7)	0.25

Seventh layer (protective layer)

Gelatin	1.00
		Acryloyl group-modified polyvinyl alcohol copolymer (degree of modification: 17%)	0.04
Liquid paraffin	0.02
		Surfactant (Cpd-13)	0.01

Manufacture of sample 302

The composition of the fifth layer of the silver halide color photosensitive material 301 prepared as described above was changed as shown below, thereby preparing a sample 302. Fifth layer (Red photosensitive emulsion layer)

Silver chlorobromide emulsion C (cubic, 5: 5 mixture (molar ratio of silver) of large-size emulsion C having an average particle size of 0.40 μm and small-size emulsion C having an average particle size of 0.30 μm)The coefficient of variation of the particle size distribution was 0.09 and 0.11: in both emulsions, 0.8 mol% of silver bromide was locally contained in the surface of a part of the particles having silver halide as a substrate)	0.12
		Gelatin	1.11
Cyan color former (ExC-2)	0.13
		Cyan color former (ExC-3)	0.03
Color image stabilizer (Cpd-1)	0.05
		Color image stabilizer (Cpd-6)	0.06
Color image stabilizer (Cpd-7)	0.02
		Color image stabilizer (Cpd-9)	0.04
Color image stabilizer (Cpd-10)	0.01
		Color image stabilizer (Cpd-14)	0.01
Color image stabilizer (Cpd-15)	0.12
		Color image stabilizer (Cpd-16)	0.03
Color image stabilizer (Cpd-17)	0.09
		Color image stabilizer (Cpd-18)	0.07
Solvent (Solv-5)	0.15
		Solvent (Solv-8)	0.05

The structures of the compounds in samples 301 and 302 are shown below. (ExY) yellow coupler: mixtures of(ExM) magenta coupler: a mixture of:

(ExC-1) cyan coupler: a mixture of:and

(ExC-2) cyan coupler at a molar ratio of 15: 85

(ExC-3) cyan coupler: a mixture of:

and

(Cpd-1) colour image stabilizer (Cpd-2) colour image stabilization in a molar ratio of 50: 25Agent for treating cancer

Number average molecular weight

60,000(Cpd-3) color image stabilizers

n-7-8 (average) (Cpd-4) melange inhibitors

(Cpd-5) colour-mixing inhibitor (Cpd-6) stabilizer

Number average molecular weight of

600

Color image stabilizers as m/n 10/90(Cpd-7) color mixing inhibitors (Cpd-8)

(Cpd-9) color image stabilizer (Cpd-10) color image stabilizer (Cpd-12) color image stabilizer(Cpd-13) surfactant: 7: 3 mixture of

And(Cpd-20) surfactant: mixture of the following substances in a molar ratio of 1: 4

(UV-1) UV absorber (UV-2) UV absorber

(UV-3) UV absorber (UV-4) UV absorber

UV-A: mixture UV-1/UV-2/UV-3/UV-4 ═ 4/2/2/3 UV-B:

mixture UV-C of UV-1/UV-2/UV-3/UV-4/UV-5/UV-6 ═ 9/3/3/4/5/3: mixture of UV-2/UV-3/UV-6/UV-7 ═ 1/1/1/2

Sample 303 was made following the same procedure as sample 301, but forming a layer comprising 0.6 g/m between the support and the first layer²Gelatin, 0.06 g/m²Ashed emulsion Y and 0.01 g/m (in terms of silver amount)²Layer of compound (12) (PUG release unit).

Sample 304 was made following the same procedure as sample 302, but forming a layer comprising 0.6 g/m between the support and the first layer²Gelatin, 0.06 g/m²Ashed emulsion Y and 0.01 g/m (in terms of silver amount)²Compound (I)(12) Layer (PUG release unit). The method for preparing the ashed emulsion Y will be described below.

Sample 305 was made following the same procedure as sample 301, except that 0.06 g/m was added to the seventh layer²Ashed emulsion Y and 0.01 g/m (in terms of silver amount)²Compound (106).

Sample 306 was made following the same procedure as sample 302, except that 0.06 g/m was added in the seventh layer²Ashed emulsion Y and 0.01 g/m (in terms of silver amount)²Compound (106).

These samples produced as above were uniformly exposed and developed, with purposefully reduced agitation during the color development step. Changes in the process were observed and evaluated.

As a result, the process fluctuation in the photosensitive material of the present invention is significantly small. Preparation of emulsion Y

2.0L of a 1% inert gelatin solution was stirred and dissolved at 35 ℃. 0.66 mol of sodium chloride and 0.6 mol of nitrate are added by the double-injection method at the same fixed flow rate over a period of 4 minutes. 0.1 g of chloroauric acid and 0.02 mol of sodium hydroxide were added, and then the resultant was stirred for 10 minutes. Thereafter, 0.4mol of sodium chloride was added to obtain particles having an average particle diameter of 0.1. mu.m. These particles were washed with water, and then 100 g of inert gelatin was added to disperse the particles, thereby preparing an emulsion Y having a surface-ashed core. Treatment A

The photosensitive material 305 was rolled into a 127 mm wide roll and then image exposed using a small laboratory photo processor PP1258AR available from Fuji PhotoFilm co. After that, the rinsing (running experiment) was continuously performed in the lower rinsing step until the replenishment liquid was replenished twice the volume of the color developing tank. The rinse with the replenishment solution was treatment A.

Step (ii) of	Temperature (. degree.C.)	Time (seconds)	Replenishment rate*
				Color development	38.5	45	45 ml
Bleach-fixing	38.0	45	35 ml
				Rinsing (1)	38.0	20	-
Rinsing (2)	38.0	20	-
				Rinsing (3)	38.0**	20	-
Rinsing (4)	38.0**	30	121 ml

^*Replenishment rate of photosensitive material per square meter^**The cleaning system was rinsed in rinse (3) using RC50D manufactured by Fuji Photo Film co., ltd. to extract the rinse solution from rinse (3) and provide the solution to the reverse osmosis membrane module (RC50D) by a pump. The transfer water obtained in the tank is supplied to the rinse (4) and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of water delivered to the reverse osmosis module was maintained at 5-300 ml/min. The water was circulated for 10 hours a day at controlled temperature (rinsing by the tank convection system from (1) to (4)).

The composition of each rinse was as follows.

Color developing agent	Tank solution	Supplementary liquid
			Water (W)	800 ml	800ml

Dimethylpolysiloxane based surface Activity (SILICONE KF 351A/shin-Etsu chemical Co., Ltd.)	0.1 g	0.1 g
			Tris (isopropanolamine) amine	8.8 g	8.8 g
Ethylenediaminetetraacetic acid	4.0 g	4.0 g
			Polyethylene glycol (molecular weight 300)	10.0 g	10.0 g
4, 5-Dihydroxybenzene-1, 3-disulfonic acid sodium salt	0.5 g	0.5 g
			Potassium chloride	10.0 g	-
Potassium iodide	0.040 g	0.010 g
			Triazazinylaminostilbene whitening agent (HAKKOL FWA-SF/Showa Kagaku K.K.)	2.5 g	5.0 g
Sodium sulfite	0.1 g	0.1 g
			N, N-bis (sulfoester) hydroxylamine disodium salt	8.5 g	11.1 g
N-ethyl-N- (. beta. -methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoanilino-3/2-sulfuric acid monohydrate	5.0 g	15.7 g
			Potassium carbonate	26.3 g	26.3 g
Adding water to	1000 ml	1000 ml
			pH (25 ℃/adjusted with potassium hydroxide and sulfuric acid)	10.15	12.50

Bleach-fixing liquid	Tank solution	Supplementary liquid
			Water (W)	700 ml	600ml
Ethylenediaminetetraacetic acid ferric ammonium (III)	47.0 g	94.0 g
			Ethylenediaminetetraacetic acid	1.4 g	2.8 g
O-carboxybenzene sulfinic acid	8.3 g	16.5 g

Acetic acid (67%)	16.5	33.0 g
			Imidazole	14.6 g	29.2 g
Ammonium thiosulfate (750 g/L)	107.0 ml	214.0 ml
			Ammonium sulfite	16.0 g	32.0 g
Ammonium bisulfite	23.1 g	46.2 g
			Adding water to	1000 ml	1000 ml
pH (25 ℃/adjusted with acetic acid and ammonia)	6.0	6.0

Rinsing liquid	Tank solution	Supplementary liquid
			Chlorinated sodium isocyanurates	0.02 g	0.02 g
Deionized water	1000 ml	1000ml
			pH	6.5	6.5

Example 4

A support whose bottom layer was a cellulose triacetate film was coated with a plurality of layers having the following composition to manufacture a sample 401 as a multi-layer color photosensitive material. Composition of photosensitive layer

The numbers corresponding to the components are expressed in g/m²Is the coating weight in units. The coating amount of silver halide is expressed by the amount of silver. The coating amount of each sensitizing dye is represented by the number of moles added per mole of silver halide in the same layer. Sample 401 first layer (first antihalation layer)

Iodine silver bromide emulsion P	Silver 0.01
		Black colloidal silver	Silver 0.05
Gelatin	0.87
		ExC-1	0.002
ExC-3	0.002
		Cpd-2	0.001
HBS-1	0.004
		HBS-2	0.002

Second layer (second antihalation layer)

Black colloidal silver	Silver 0.04
		Gelatin	0.407
ExM-1	0.050
		ExF-1	2.0×10-3
HBS-1	0.074
		Solid disperse dye ExF-2	0.030

Third layer (middle layer)

Polyacrylic acid ethyl ester latex	0.085
		Gelatin	0.294

Fourth layer (Low speed red photosensitive emulsion layer)

Iodine silver bromide emulsion A	Silver 0.300
		ExS-1	3.8×10-4
ExS-2	1.0×10-5
		ExS-3	2.4×10-4
ExS-4	1.0×10-4
		ExS-12	2.7×10-4
ExC-1	0.109
		ExC-3	0.044
ExC-4	0.72
		ExC-5	0.011
ExC-6	0.003
		Cpd-2	0.025
Cpd-4	0.025
		HBS-1	0.17
Gelatin	0.80

Fifth layer (Medium speed red emulsion layer)

Iodine silver bromide emulsion B	Silver 0.24
		Iodine silver bromide emulsion C	0.60 silver
ExS-1	4.8×10-4
		ExS-2	1.8×10-5
ExS-3	2.8×10-4
		ExS-4	0.7×10-4
ExS-12	1.8×10-4
		ExC-2	0.026

ExC-3	0.020
		ExC-4	0.12
ExC-5	0.016
		ExC-6	0.007
Cpd-2	0.036
		Cpd-4	0.028
HBS-1	0.16
		Gelatin	1.18

Sixth layer (high speed red emulsion layer)

Iodine silver bromide emulsion D	Silver 1.20
		ExS-1	3.4×10-4
ExS-2	1.4×10-5
		ExS-3	2.2×10-4
ExS-4	0.5×10-4
		ExS-12	1.8×10-4
ExC-3	0.07
		ExC-6	0.029
ExC-7	0.010
		ExY-5	0.008
Cpd-2	0.046
		Cpd-4	0.077
HBS-1	0.25
		HBS-2	0.12
Gelatin	2.12

Seventh layer (middle layer)

Cpd-1	0.089
		Solid disperse dye ExF-4	0.030
HBS-1	0.050
		Polyacrylic acid ethyl ester latex	0.83
Gelatin	0.84

Eighth layer (layer for providing interlayer function to red photosensitive layer)

Iodine silver bromide emulsion E	Silver 0.560
		ExS-6	2.8×10-4
ExS-10	5.9×10-4
		Cpd-4	0.030
ExM-2	0.096
		ExM-3	0.028
ExC-9	0.020
		ExY-1	0.020
HBS-1	0.085
		HBS-3	0.003
Gelatin	0.58

Ninth layer (Low-speed Green emulsion layer)

Silver bromochloroiodide emulsion F	Silver 0.45
		Emulsion G of silver bromochloroiodide	Silver 0.30
Bromochloroiodosilver emulsion H	0.38 silver
		ExS-4	1.4×10-5

ExS-5	1.0×10-4
		ExS-6	1.9×10-4
ExS-7	3.7×10-5
		ExS-8	1.0×10-4
ExS-12	1.0×10-4
		ExS-13	6.2×10-4
HBS-1	0.28
		HBS-3	0.01
HBS-4	0.27
		Gelatin	1.39

Tenth layer (Medium speed green emulsion layer)

Emulsion of silver bromochloroiodide I	Silver 0.45
		Exs-4	2.3×10-5
ExS-7	1.0×10-4
		ExS-8	2.3×10-4
ExS-12	1.0×10-4
		ExS-13	8.2×10-4
ExC-9	0.02
		ExM-2	0.031
ExM-3	0.029
		ExY-1	0.002
ExM-4	0.028
		HBS-1	0.062
HBS-3	2.1×10-3

Gelatin

0.44

Eleventh layer (high speed green emulsion layer)

Emulsion of silver bromochloroiodide I	Silver 0.19
		Bromochloroiodosilver emulsion J	Silver 0.80
ExS-4	2.1×10-5
		ExS-7	1.0×10-4
ExS-8	1.9×10-4
		ExS-12	1.0×10-4
ExS-13	5.2×10-4
		ExC-6	0.004
ExC-9	0.030
		ExM-1	0.016
ExM-3	0.036
		ExM-4	0.020
ExM-5	0.004
		ExY-5	0.001
ExM-2	0.013
		Cpd-3	0.004
Cpd-4	0.007
		HBS-1	0.18
Polyacrylic acid ethyl ester latex	0.099
		Gelatin	1.11

Twelfth layer (middle layer)

Cpd-1	0.16
		HBS-1	0.082
Gelatin	1.057

The tenth layer (Low speed blue emulsion layer)

Bromochloroiodosilver emulsion K	Silver 0.28
		Silver bromochloroiodide emulsion L	Silver 0.30
Emulsion M of silver bromochloroiodide	Silver 0.10
		ExS-9	1.0×10-4
ExS-11	1.2×10-4
		ExS-14	4.2×10-4
ExC-8	0.012
		ExY-1	0.035
ExY-2	0.71
		ExY-3	0.10
ExY-4	0.005
		Cpd-2	0.10
Cpd-3	4.0×10-3
		HBS-1	0.24
Gelatin	1.41

Fourteenth layer (high speed blue emulsion layer)

Emulsion of silver bromochloroiodide N	Silver 1.05
		ExS-9	1.6×10-4

ExS-14	4.5×10-4
		ExY-2	0.31
ExY-3	0.05
		ExY-6	0.062
Cpd-2	0.075
		Cpd-3	1.0×10-3
HBS-1	0.10
		Gelatin	0.91

The fifteenth layer (first protective layer)

UV-1	0.21
		UV-2	0.13
UV-3	0.20
		UV-4	0.025
F-18	0.009
		HBS-1	0.12
HBS-4	5.0×10-2
		Gelatin	2.3

Sixteenth layer (second protective layer)

H-1	0.40
		B-1 (diameter 1.7 μm)	5.0×10-2
B-2 (diameter 1.7 μm)	0.15
		B-3	0.05
S-1	0.20

Gelatin

0.75

In addition to the above components, the individual layers may contain W-1 to W-3, B-4 to B-6, F-1 to F-19, iron salt, lead salt, gold salt, platinum salt, palladium salt, iridium salt, ruthenium salt, rhodium salt, and calcium salt in order to improve storage stability, handleability, pressure resistance, antibacterial and antifungal properties, antistatic properties, and coating properties.

Table 4 below shows Br content, I content, particle size, and the like of each emulsion abbreviated in the above description.

TABLE 4

Name of emulsion	Coefficient of variation (mol%) of iodine distribution between particles	Br content (mol%)	I content (mol%)	Average particle diameter (equivalent to spherical diameter. mu.m)	Coefficient of variation (%) corresponding to the diameter of sphere	Projected area diameter (equivalent to circular diameter, mum)	Projected area diameter/thickness ratio	Particle shape
									A	20	3.0	0.02	0.40	19	0.55	4.0	Flaky particles
B	17	2.0	0.01	0.54	21	0.86	6.0	Flaky particles
									C	18	3.0	0.01	0.90	22	1.50	7.0	Flaky particles
D	17	2.0	0.03	1.10	18	2.07	10.0	Flaky particles
									E	22	2.0	0.03	0.90	22	1.50	7.0	Flaky particles
F	18	3.0	0.02	0.30	19	0.38	3.0	Flaky particles
									G	17	2.0	0.02	0.50	1 9	0.70	4.2	Flaky particles
H	18	1.0	0.02	0.60	17	1.00	7.0	Flaky particles
									I	16	3.0	0.02	0.78	15	1.30	7.0	Flaky particles
J	19	3.0	0.02	0.97	18	1.8 8	11.0	Flaky particles
									K	18	4.0	0.02	0.40	16	0.55	4.0	Flaky particles
L	22	4.0	0.03	0.60	18	1.05	8.0	Flaky particles
									M	20	5.0	0.02	0.80	19	1.34	7.0	Flaky particles
N	22	6.0	0.04	1.40	24	2.80	12.0	Flaky particles
									P	-	1.0	0	0.07	-	0.07	1.0	Uniform structure

In table 4:

(2) as for the emulsion A-N, gold sensitization, sulfur sensitization, and selenium sensitization were optimally performed according to example 6 of JP-A-10-221827.

(3) The main surface of the plate-like particles is ｃA (111) surface, and the plate-like particles can be produced by changing the addition conditions, addition amounts, and the like in JP-A-10-221827. The added spectral sensitizing dye is the compound described in each photosensitive layer.

(4) The dislocation lines described in JP-A-3-237450 were observed in the flaky particles using ｃA high-pressure electron microscope. Preparation of organic solid disperse dye dispersions

ExF-2 was dispersed as follows. That is, 21.7ml of water, 3ml of a 5% aqueous solution of p-octylphenoxyethoxyethanesulfonic acid soda, and 0.5g of a 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) were placed in a 700ml ball mill, and then 5.0g of the dye ExF-2 and 500 ml of zirconia balls (diameter 1 mm) were added to the mill. The contents were dispersed for 2 hours. The dispersion was prepared by using a BO type vibratory ball mill manufactured by Chuo Koki k.k. The dispersion was removed from the mill and then added to 8g of a 12.5% aqueous gelatin solution. The zirconia balls were filtered off to give a gelatin dispersion of the dye. The fine dye particles had an average particle diameter of 0.44. mu.m.

According to the same manner as above, solid dispersion ExF-4 was obtained. The fine dye particles had an average particle diameter of 0.45. mu.m. The compounds used for forming the above layers are as follows.

HBS-1 Trihydroxymethylphenyl phosphate HBS-2 di-n-butyl phthalateHBS-4 phosphoric acid tris (2-ethylhexyl) ester

Manufacture sample 402

Sample 402 was made following the same procedure as sample 401, except that 0.08g/m was added to the third layer²Previously ashed emulsion Y and 0.02 g/m in example 3²The compound (12) of (1).

The compound (12) of sample 401 was added as an emulsion dispersion using a high boiling point organic solvent (HBS-1) and a surfactant (W-4) in an amount of 0.5 times as much as the color former. Production of samples 403-405

Samples 403-405 were prepared following the same procedure as sample 402, except that the compounds in the third layer were changed to those shown in table 5 below. Evaluation of ashing Density fluctuation due to rinsing

Samples 401-405 were wedge exposed and developed under white light using treatments a and B below. The magenta image was evaluated for fluctuation in the ashing density (difference between the ashing density in process a and the ashing density in process B).

Treatment B was the same as treatment a, but the time and temperature of the color development step were changed to 2 minutes 10 seconds and 44 ℃.

The smaller the value, the smaller the ashing fluctuation caused by the treatment, and is preferable.

The results are shown in Table 5 below. Table 5 shows that the samples having the PUG releasing units of the present invention have small ashing fluctuation and are preferable.

TABLE 5

Sample number	Color former in third layer	Ashing fluctuation	Description of the invention
				401	Is free of	0.20	Comparative example
402	Compound (12)	0.07	The invention
				403	Compound (13)	0.09	The invention
404	Compound (10)	0.11	The invention
				405	Compound (106)	0.12	The invention
406	ExC-6	0.10	The invention

The treatment and rinse compositions are as follows. Treatment A

Step (ii) of	Time	Temperature (. degree.C.)	Replenishment rate	Volume of tank
					Color development	1 minute and 30 seconds	41	10 ml	10.3 L
Bleaching	20 seconds	41	5 ml	3.6 L
					Photographic fixing (1)	20 seconds	41	-	3.6 L
Photographic fixing (2)	20 seconds	41	7.5 ml	3.6 L
					Stable (1)	10 seconds	41	-	1.9 L
Stable (2)	10 seconds	41	-	1.9 L
					Stable (3)	10 seconds	41	30 ml	1.9 L
Drying	30 seconds	60

^*The replenishment rate was relative to a 35 mm wide photosensitive material of 1.1 m (equivalent to a 24-inch thick photosensitive material)Example 1).

The stabilizer is caused to flow in the order of (3) to (2) to (1), and the fixer is connected from (2) to (1) through a convection duct. Also, a tank solution of the stabilizer (2) was supplied to the fixer (2) at a replenishment rate of 15 ml. Note that the amounts of the developer, the bleaching liquid, and the fixer were kept at 2.0 ml for a 35 mm-wide photosensitive material of 1.1 m in the bleaching step, the fixing step, and the washing step, respectively. It is also noted that each switching time is 6 seconds, and this time is included in the rinsing time of each rinsing step.

The composition of the rinse solution is as follows.

Color developing agent	Tank solution	Supplementary liquid
			Diethylenetriaminepentaacetic acid	3.0 g	5.0 g
4, 5-Dihydroxybenzene-1, 3-disulfonic acid sodium salt	0.5 g	0.5 g
			N, N-bis (sulfoethyl) hydroxylamine disodium salt	10.0 g	15.0 g
Sodium sulfite	4.0 g	10.0 g
			Hydroxylamine sulfate	1.5 g	3.0 g
Potassium chloride	2.0 g	-
			Diethylene glycol	10.0 g	10.0 g
Ethyl urea	3.0 g	3.0 g
			2-ethyl-4- [ N-ethyl-N- (. beta. -hydroxyethyl) amino]Aniline sulfates	6.0 g	11.4 g
Potassium carbonate	35 g	35 g
			Adding water to	1.0 L	1.0 L
pH (adjusted with Potassium hydroxide and sulfuric acid)	10.10	10.60

Bleaching liquor	Tank solution	Supplementary liquid
			1, 2-diaminopropane tetraacetic acid ammonium iron monohydrate	140 g	200 g

Ammonium bromide	50 g	70 g
			Succinic acid	10 g	15 g
Maleic acid	40 g	60 g
			Imidazole	60 g	90 g
Adding water to	1.0 L	1.0 L
			pH (adjusted with nitric acid and ammonia water)	4.2	3.8

Fixing liquid	Tank solution	Supplementary liquid
			Ammonium thiosulfate (750 g/L)	280ml	750ml
Ammonium bisulfite aqueous solution (72%)	20 g	80 g
			Imidazole	10 g	45 g
1-mercapto-2- (N, N-dimethylaminoethyl-tetrazole	1 g	3 g
			Ethylenediaminetetraacetic acid	3 g	9 g
Adding water to	1.0 L	1.0 L
			pH (controlled with ammonia and nitric acid)	7.0	7.0

A stabilizer: the tank solution is the same as the make-up solution
		Sodium p-toluenesulfinate	0.03 g
Para nonyl phenoxy polyglycidyl (glycidol average degree of polymerization 10)	0.4 g
		Ethylenediaminetetraacetic acid disodium salt	0.05 g
1,2, 4-triazoles	1.3 g
		1, 4-bis (1, 2, 4-triazole-1-iso-isomer	0.75 g

Methyl) piperazine
		1, 2-benzisothiazolin-3-ones	0.10 g
Adding water to	1.0 L
		pH	8.5

Other advantages and variations will be apparent to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described above. And various modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims and their equivalents.

Claims (10)

1. A silver halide color photosensitive photographic material comprising at least one photosensitive silver halide emulsion layer and at least one nonphotosensitive layer on a support,

wherein at least one layer of the non-photosensitive layer comprises a pre-ashed silver halide emulsion comprising particles having a pre-ashed surface, and the non-photosensitive layer comprising the pre-ashed emulsion and/or a layer adjacent thereto comprises a compound capable of releasing a photographically useful group or a precursor thereof by a coupling reaction with a developer in an oxidised form; and also

The pre-ashed emulsion is developed during color development to uniformly form an oxidized form of the color developer, while the photographically useful groups or precursors thereof are released imagewise by a coupling reaction.

2. A photosensitive material according to claim 1 wherein the compound capable of releasing a photographically useful group or precursor thereof forms substantially no image upon coupling reaction with an oxidized form of a developer.

3. A photosensitive material according to claim 2, wherein the compound capable of releasing a photographically useful group or a precursor thereof is represented by the following formula (II):

COUP1-B1 (II) wherein COUP1 represents a color former group capable of liberating B1 by a coupling reaction with an oxidized form of a developer and also forming a water-soluble or alkali-soluble compound, and B1 represents a photographically useful group or a precursor thereof attached at the coupling position of COUP 1.

4. A photosensitive material according to claim 3, wherein the compound represented by formula (II) is a compound represented by the following formula (III):

COUP2-A-E-B2 (III) wherein COUP2 represents a color former group capable of coupling to an oxidized form of a developer; e represents an electrophilic moiety; a represents a linking group capable of releasing B2 by forming a ring through an intramolecular nucleophilic substitution reaction of a nitrogen atom, which is present in the coupling product between COUP2 and the oxidized form of the developer by the developer, and which directly links the coupling site with the nucleophilic moiety E; and B2 represents a photographically useful group or precursor thereof.

5. A photosensitive material according to any one of claims 1 to 4, wherein the pre-ashed silver halide emulsion and the compound are contained in the same layer.

6. A photosensitive material according to any one of claims 1 to 5, wherein the nonphotosensitive layer containing the preliminarily ashed silver halide emulsion or a layer adjacent to the nonphotosensitive layer contains black colloidal silver.

7. A photosensitive material according to claim 5 wherein the photogenic group is a bleach promoter.

8. The photosensitive material of claim 5, wherein the photogenic group is a development inhibitor.

9. The photosensitive material of claim 5, wherein at least one of the photosensitive silver halide emulsions contained in the at least one photosensitive silver halide emulsion layer is an emulsion having a silver chloride content of at least 10 mol%.

10. The photosensitive material according to claim 5, wherein at least one of the pre-ashed silver halide emulsions contained in the at least one nonphotosensitive layer is an emulsion having a silver chloride content of at least 10 mol%.