CN1208682C - Silver halide colour photosensitive material - Google Patents

Abstract

The present invention discloses a silver halide colored photosensitive photographic material comprising at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer on a carrier, wherein at least one layer of the non-photosensitive layer contains incinerated silver halide emulsion, the emulsion contains granules with surface previously incinerated, and the non-photosensitive layer and/or the adjacent layer thereof contain a compound capable of carrying out a reaction with a developing agent in an oxidation form to release photographic useful groups; the incinerated emulsion is developed during color development to form a color developing agent in an oxidation form, and the photographic useful compound is released in the non-image mode by means of a coupling reaction. The photosensitive material has excellent storage stability and is capable of stably and quickly releasing the photographic useful groups.

Description

Silver-halide color photoelement

Technical field

The present invention relates to the silver-halide color sensitive photographic material, this material have height storage stability, and can during colour development, stablize and discharge the useful group of photograph apace.

Background technology

Type according to the useful group of photograph that discharges during the colour development can obtain various effects.

The necessary useful compound of photograph is added on (promptly, compound is added on and replenishes in the liquid, to guarantee necessary concentration in the flow equilibrium) in the developer solution usually during the development.

But when the useful compound of will taking a picture is added in developer solution or the additional liquid, under the influence of standing storage (storage of additional liquid or additional), can lose its effect sometimes.

For preventing this point, can in photosensitive material, add the useful compound of taking a picture in advance, and during developing, realize its effect.The advantage of this method is that the only described effect of realization in necessary position is for example located the contiguous of specific layer and multilayer photosensitive material thereof.But if be added in the photosensitive material with the activity form useful compound of will taking a picture, this compound decomposes under the effect of heat, moisture or oxygen in the time of can storing photosensitive material before developing.Its consequence is to realize its effect during developing.In addition, decomposition product produces not preferred photographic property variation to photosensitive material sometimes.Therefore, this method depends on that the type of compound is inapplicable.

Special fair (being called JP-B-later on) 4-73573 discloses a kind of method that addresses this problem.In the method, be added in the photosensitive material with the inactive in fact form useful compound (as the useful compound precursor of taking a picture) of will taking a picture by blocking its reactive group, and this precursor plays the effect of the active useful compound of taking a picture in developer solution.

This JP-B-4-73573 had both realized during developing having realized the high storage stability of photosensitive material again from the active useful compound of taking a picture of precursor snap-out release.But, still need further to improve the storage stability of photosensitive material.In addition, the reaction with azanol has been used in developer solution in active release of taking a picture useful compound.Because the variation of azanol concentration, this makes photographic property also produce very big variation.

Te Kaiping (hereinafter referred to as JP-A-) 8-339058, it is corresponding to the present the 5th, 561, No. 031 United States Patent (USP), the color inversion photography monomer is disclosed, wherein add non-photosensitive emulsion in single identical layer or the layer that merges and bleach boosters discharges compound, this compound can discharge bleach boosters by the developer reaction with oxidised form.

This is a very excellent method, and wherein bleach boosters (the useful compound of taking a picture) is released in the askiatic mode during colour development.But non-photosensitive emulsion is being bathed in (cineration step) by chemical ashing in counter-rotating before the colour development.Therefore, this method can not be used for the colour negative photosensitive material or not use the colour paper photosensitive material that reverses and bathe.

JP-A-63-175850 discloses a kind of photosensitive material that comprises silver halide particle in silver emulsion, and this silver halide particle has ashing nuclear on its surface or inferior surface.This photosensitive material also comprises bleach boosters (photograph is used for compound) and is released into toner.The excellent part of this method is to realize the height ageing stability of photosensitive material and good desilverization feature.But the silver halide particle that has ashing nuclear on its surface or inferior surface is present in the silver halide emulsion layer jointly.According to the type of silver emulsion, this has a negative impact to the ageing stability of photosensitive material sometimes.Equally, in the method, the silver halide particle with ashing nuclear is present in the silver halide emulsion layer jointly, makes bleach boosters be released in the image mode on some degree.Therefore, because the storage of the common silver emulsion that exists, burst size and similar factor are easy to casual qualitative changeization and change.

JP-A-2-5042 discloses a kind of silver emulsion of surperficial ashing and colour reversal material that bleach boosters discharges compound of comprising.Because this colour reversal material needed before colour development through black-and-white development, the silver emulsion of ashing forms developed silver during colour development, and making does not have the developer of oxidised form to form.Its consequence is to produce the useful group of taking a picture during developing.

Therefore, the purpose of this invention is to provide photosensitive silve halide material, this photosensitive material has high storage stability, and comprises and can stablize during colour development and the take a picture compound of useful group of snap-out release.

Summary of the invention

Above-mentioned purpose of the present invention realizes by following photosensitive silve halide material.That is to say,

(1) a kind of silver-halide color photoelement that is included at least one photosensitive silver halide emulsion layer on the carrier and at least one non-photographic layer,

Wherein, have at least a layer to comprise the silver emulsion of ashing in advance in the non-photographic layer, this emulsion comprises and has the particle on ashing surface in advance, and comprises the non-photographic layer of ashing emulsion in advance and/or its adjacent layer and comprise the compound that can discharge take a picture useful group or its precursor by the coupling reaction with the developer of oxidised form; The emulsion of ashing in advance is developed during colour development, and with the color developer of even formation oxidised form, and take a picture useful group or its precursor are d/d in the askiatic mode by coupling reaction.

(2) silver-halide color photoelement of describing in the above-mentioned project (1), wherein, the compound that can discharge take a picture useful group or its precursor does not form image basically when the developer with oxidised form carries out coupling reaction.

(3) silver-halide color photoelement of describing in the above-mentioned project (2), wherein, the compound that can discharge take a picture useful group or its precursor is represented in order to following formula (II):

COUP1-B1 (II)

Wherein, COUP1 represents to discharge B1 by the coupling reaction with the developer of oxidised form but also the colour coupler group that forms water-soluble or alkali solubility compound, and the B1 representative is connected the useful group of photograph or its precursor of the coupling position of COUP1.

(4) silver-halide color photoelement of describing in the above-mentioned project (3), wherein, the compound of formula (II) expression is the compound with following formula (III) expression:

COUP2-A-E-B2 (III)

Wherein, COUP2 representative can with the colour coupler group of the developer coupling of oxidised form; E represents electrophilic moiety; The A representative can form the linking group that ring discharges B2 by the intramolecular nucleophilic substitution reaction of nitrogen-atoms, it is appeared at by developer in the coupled product between the developer of COUP2 and oxidised form, and directly coupling position and nucleophilic part E is linked together; And useful group or its precursor of B2 representative photograph.

(5) silver-halide color photoelement described in any one of above-mentioned project (1)-(4), wherein, the silver emulsion of ashing in advance is included in the identical layer with compound.

(6) silver-halide color photoelement described in any one of above-mentioned project (1)-(5), wherein, the non-photographic layer that comprises the silver emulsion of ashing in advance comprises the black collargol.

(7) silver-halide color photoelement described in any one of above-mentioned project (1)-(5), wherein, the layer of the non-photographic layer of the contiguous silver emulsion that comprises ashing in advance comprises the black collargol.

(8) silver-halide color photoelement described in any one of above-mentioned project (1)-(7), wherein, the useful group of taking a picture is a bleach boosters.

(9) silver-halide color photoelement described in any one of above-mentioned project (1)-(7), wherein, the useful group of taking a picture is a development restrainer.

(10) silver-halide color photoelement described in any one of above-mentioned project (1)-(9), wherein, at least one that is included in the photosensitive silver halide emulsion at least one photosensitive silver halide emulsion layer is the emulsion that silver chloride content is at least 10mol%.

(11) silver-halide color photoelement described in any one of above-mentioned project (1)-(10), wherein, at least one that is included in the silver emulsion of the ashing in advance at least one non-photographic layer is the emulsion that silver chloride content is at least 10mol%.

Embodiment

Below the present invention will be described in more detail.

The compound that can discharge take a picture useful group or its precursor by the coupling reaction with the developer of oxidised form is below described among the present invention.

The compound that this compound that can discharge take a picture useful group or its precursor by the coupling reaction with the developer of oxidised form is preferably represented with A-B.

A represents the colour coupler group, and preferred example is as follows.

The example of colour coupler group be the yellow colour former group (for example; open chain ketone methylene colour coupler group; as acyl group monoacetylaniline and malonyl diphenylamine); magenta colour coupler is (as the 5-pyrazolone-type; the Pyrazolotriazole type; imidazolopyrazole type colour coupler group); the cyan colour coupler group is (as phenol type colour coupler group; naphthol type colour coupler group; the and the 249th; the imidazole type colour coupler group of describing during No. 453 European patent is open; EP 304; and the colour coupler group (as imidanone type and acetophenone type colour coupler group) that forms of non-dyestuff the pyrazolopyrimidine type colour coupler group of describing in 001).Can also use the 4th, 315,070,4,183,752,4,174,969,3,961,959 and 4,171, the heterocyclic coupler agent group of describing among No. 223 United States Patent (USP)s and the JP-A-52-82423.

Preferred example is formula (Cp-1), (Cp-2), (Cp-3), (Cp-4), (Cp-5), (Cp-6), (Cp-7), (Cp-8), (Cp-9), (Cp-10) and (Cp-11) the colour coupler group of expression.These colour couplers are preferred, and its reason is because their high-purity speed.

In above-mentioned formula, stem from the symbol of coupling position ^*Represent colour coupler to be connected position on the B among the formula A-B.

In above-mentioned formula, if 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, or R ₆₅Comprise non-diffusion group, then should to make total carbon number be 8-40 in the selection of this non-diffusion group, is preferably 10-30.In another under situation, the sum of carbon is preferably 15 or still less.

R ₅₁-R ₆₅, Z ₁, Z ₂, j, d, e and f detail will be in following description.In the following description, R ₄₁Represent aliphatic group, aromatic group or heterocyclic group.R ₄₂Represent aromatic group or heterocyclic group.R ₄₃, R ₄₄And R ₄₅Represent hydrogen atom, aliphatic group, aromatic group or heterocyclic group respectively.

R ₅₁Representative and R ₄₁Identical group.R ₅₂And R ₅₃Represent respectively and R ₄₂Identical group.J represents 0 or 1.R ₅₄Representative and R ₄₁Identical group, R ₄₁CON (R ₄₃)-group, R ₄₁R ₄₃N-group, R ₄₁SO ₂N (R ₄₃)-group, R ₄₁S-group, R ₄₃O-group, R ₄₅N (R ₄₃) CON (R ₄₄)-group or R ₄₁OCON (R ₄₃)-group.R ₅₅Representative and R ₄₁Identical group.R ₅₆And R ₅₇Represent respectively and R ₄₃Identical group, R ₄₁S-group, R ₄₃O-group, R ₄₁CON (R ₄₃)-group or R ₄₁SO ₂N (R ₄₃)-group.R ₅₈Representative and R ₄₁Identical group.R ₅₉Representative and R ₄₁Identical group, R ₄₁CON (R ₄₃)-group, R ₄₁OCON (R ₄₃)-group, R ₄₁SO ₂N (R ₄₃)-group, R ₄₃R ₄₄NCON (R ₄₅)-group, R ₄₁O-group, R ₄₁S-group, halogen atom or R ₄₁R ₄₃The N-group.

D represents 0-3.If d is a plural number, then a plurality of R ₅₉Represent identical substituting group or different substituting groups.

In addition, these R ₅₉Can be used as the covalency group and be interconnected to form ring texture.The example of this ring texture is pyridine ring and pyrrole ring.

R ₆₀Representative and R ₄₁Identical group.R ₆₁Representative and R ₄₁Identical group.R ₆₂Representative and R ₄₁Identical group, R ₄₁OCONH-group, R ₄₁SO ₂NH-group, R ₄₃R ₄₄NCON (R ₄₅)-group, R ₄₃R ₄₄NSO ₂N (R ₄₅)-group, R ₄₃O-group, R ₄₁S-group, halogen atom or R ₄₁R ₄₃The N-group.R ₆₃Representative and R ₄₁Identical group, R ₄₃CON (R ₄₅)-group, R ₄₃R ₄₄NCO-group, R ₄₁SO ₂N (R ₄₄)-group, R ₄₃R ₄₄NSO ₂-group, R ₄₁SO _2-Group, R ₄₃OCO-group, R ₄₃O-SO ₂-group, halogen atom, nitro, cyano group or R ₄₃The CO-group.

E represents the integer of 0-4.If there are a plurality of R ₆₂Perhaps R ₆₃, then their represent identical group or different groups.

R ₆₄And R ₆₅Represent R respectively ₄₃R ₄₄NCO-group, R ₄₁CO-group, R ₄₃R ₄₄NSO ₂-group, R ₄₁OCO-group, R ₄₁SO ₂-group, nitro or cyano group.

Z ₁Represent nitrogen-atoms or=C (R ₆₆)-group (R ₆₆Represent hydrogen atom or and R ₆₃Identical group).Z ₂Represent sulphur atom or oxygen atom.

F represents 0 or 1.

In the foregoing description, aliphatic group is the aliphatic hydrocarbyl that has 1-32 carbon atom, preferred 1-22 carbon atom, saturated or unsaturated, chain or ring-type, straight or branched, is substituted or is unsubstituted.Representational example is methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group, isobutyl, tertiary pentyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl group, 1,1,3,3-tetramethyl butyl, decyl, dodecyl, cetyl or octadecyl.

Aromatic group is 6-20 carbon atom, preferably is substituted or unsubstituted phenyl or the naphthyl that is substituted or is unsubstituted.

Heterocyclic group is the replacement or the unsubstituted heterocyclic group of 1-20 carbon atom, preferred 1-7 carbon atom, preferred 3-8 unit, and it comprises the heteroatoms that is selected from nitrogen-atoms, oxygen atom and sulphur atom.The representative example of this heterocyclic group is 2-pyridine radicals, 2-furyl, 2-imidazole radicals, 1-indyl, 2,4-dioxy-1,3-imidazoline-5-base, 2-benzoxazolyl, 1,2,4-triazole-3-base and 4-pyrazolyl.

If any one in these aliphatic hydrocarbyls, aromatic group and the heterocyclic group has substituting group, then representational example is halogen atom, R ₄₇O-group, R ₄₆S-group, R ₄₇CON (R ₄₈)-group, R ₄₇N (R ₄₈) CO-group, R ₄₆OCON (R ₄₇)-group, R ₄₆SO ₂N (R ₄₇)-group, R ₄₇R ₄₈NSO ₂-group, R ₄₆SO ₂-group, R ₄₇OCO-group, R ₄₇R ₄₈NCON (R ₄₉)-group and R ₄₆Identical group, R ₄₆COO-group, R ₄₇OSO ₂-group, cyano group and nitro.R ₄₆Represent aliphatic group, aromatic group or heterocyclic group.R ₄₇, R ₄₈And R ₄₉Represent aliphatic group, aromatic group, heterocyclic group or hydrogen atom respectively.These aliphatic groups, aromatic group and heterocyclic group are identical with above-mentioned definition.

Next R will be described ₅₁-R ₆₅, j, d, e and f preferable range.

R ₅₁Preferably aliphatic group or aromatic group.R ₅₂And R ₅₅Difference is aromatic group preferably.R ₅₃Preferably aromatic group or heterocyclic group.

In formula (Cp-3), R ₅₄R preferably ₄₁CONH-group or R ₄₁R ₄₃The N-group.R ₅₆And R ₅₇Difference is aliphatic group, aromatic group, R preferably ₄₁O-group or R ₄₁The S-group.R ₅₈Preferably aliphatic group or aromatic group.In formula (Cp-6), R ₅₉Preferably chlorine atom, aliphatic group or R ₄₁The CONH-group.D preferably 1 or 2.R ₆₀Aromatic group preferably.In formula (Cp-7), R ₅₉R preferably ₄₁The CONH-group.D preferably 1.R ₆₁Preferably aliphatic group or aromatic group.In formula (Cp-8), e preferably 0 or 1.R ₆₂R preferably ₄₁OCONH-group, R ₄₁CONH-group or R ₄₁SO ₂The NH-group.The position of substitution of these groups is (5) position of naphthols ring preferably.In formula (Cp-9), R ₆₃R preferably ₄₁CONH-group, R ₄₁SO ₂NH-group, R ₄₁R ₄₃NSO ₂-group, R ₄₁SO ₂-group, R ₄₁R ₄₃NCO-group, nitro or cyano group, and e preferably 1 or 2.In formula (Cp-10), R ₆₃(R preferably ₄₃) ₂NCO-group, R ₄₃OCO-group or R ₄₃CO-group, and e preferably 1 or 2.In formula (Cp-11), R ₅₄Preferably aliphatic group, aromatic group or R ₄₁CONH-group, and f preferably 1.Equally, the colour coupler group of A representative preferably has non-diffusion group.

The useful group of photograph of B representative or its precursor with following formula (II) with identical (III) to the explanation of B1 and B2.

The preferred example of the compound of A-B representative is development inhibitor releasing coupler and bleach accelerator releasing coupler.But this compound is not limited to these examples.

The example of development inhibitor releasing coupler is described among JP-A-62-34158, JP-A-63-37346, US-4782012, JP-A-60-191241 and the EP-252376.

The example that bleach boosters discharges compound is described among JP-A-60-191241, JP-A-64-31159, JP-A-1-185631, JP-A-7-152122, JP-A-8-339058 and the JP-A-61-201247.

The example of these compounds is as follows.But the present invention is not limited in these examples.

The release that below will describe formula (II) the expression compound of useful group of taking a picture:

COUP1-B1 (II)

Wherein, COUP1 represents to discharge B1 by the coupling reaction with the developer of oxidised form but also the colour coupler group that forms water-soluble or alkali solubility compound, and the B1 representative is connected the useful group of photograph or its precursor of the coupling position of COUP1.)

The release that below will describe formula (II) the expression compound of useful group of taking a picture.

More specifically, the release of formula (II) expression is taken a picture the compound of useful group in order to following formula (IIa) or (IIb) expression:

COUP1-(TIME) _m-PUG (IIa)

COUP1-(TIME) _i-RED-PUG (IIb)

Wherein, the COUP1 representative is by dividing to fall (TIME) with the developer coupling of oxidised form _m-PUG or (TIME) _i-RED-PUG also forms the colour coupler group of water-soluble or alkali solubility compound, the TIME representative is at luminous intensity distribution (timing) group that divides to fall back fracture PUG or RED-PUG by coupling reaction from COUP1, RED representative divide to fall by COUP1 or TIME and fracture PUG after with the group of the developer reaction of oxidised form, the useful group of PUG representative photograph, m represents the integer of 0-2, and i represents 0 or 1.If m is 2,2 identical or different groups of TIME representative.

If COUP1 represents the yellow colour former group, the example of this colour coupler group is a valeryl monoacetylaniline type colour coupler group; benzoyl monoacetylaniline type colour coupler group; diester malonate type colour coupler group; malonic acid diamides type colour coupler group; dibenzoyl methane type colour coupler group; benzothiazole yl acetamide type colour coupler group; malonate monoamides type colour coupler group; benzoxazoles yl acetamide type colour coupler group; benzimidazole yl acetamide type colour coupler group; quinazoline-4-one-2-base monoacetylaniline type colour coupler group; and cycloalkanes acyl group acetamide type colour coupler group.

If COUP1 represents the magenta colour coupler group, the example of this colour coupler group is 5-pyrazolone-type colour coupler group, pyrazolo [1,5-a] benzimidazole type colour coupler group, pyrazolo [1,5-b] [1,2,4] triazole type colour coupler group, pyrazolo [5,1-c] [1,2,4] triazole type colour coupler group, imidazo [1,2-b] pyrazoles type colour coupler group, pyrrolo-[1,2-b] [1,2,4] triazole type colour coupler group, pyrazolo [1,5-b] pyrazoles type colour coupler group and cyano-acetophenone type colour coupler group.

If COUP1 represents cyan colour coupler, then the example of this colour coupler group is phenol type colour coupler group, naphthol type colour coupler group, pyrrolo-[1,2-b] [1,2,4] triazole type colour coupler group, pyrrolo-[2,1-c] [1,2,4] triazole type colour coupler group and 2,4-diphenyl-imidazole type colour coupler group.

COUP1 also can be the colour coupler group that does not stay any chromatic image basically.The example of the type colour coupler group is indone type and acetophenone type colour coupler group.

The preferred example of COUP1 is the colour coupler group with following formula (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) representative.These colour couplers are preferred, and its reason is their high-purity speed.

In above-mentioned formula, the free linkage that is derived from the coupling position is represented the bonding position of coupling split-off group.

In above-mentioned 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 ' ₆₅, and R ' ₆₆Preferably 10 or still less respectively of carbon numbers.

The colour coupler group of COUP1 representative preferably has at least one and is selected from R ₇₁OCO-group, HOSO ₂-group, HO-group, R ₇₂NHCO-group and R ₇₂NHSO ₂The substituting group of-group.That is to say the R ' of formula (Cp '-1) ₅₁And R ' ₅₂In have one at least, the R ' of formula (Cp '-2) ₅₁, R ' ₅₂And R ' ₅₃In have one at least, the R ' of formula (Cp '-3) ₅₄And R ' ₅₅In have one at least, the R ' of formula (Cp '-4) and (Cp '-5) ₅₆And R ' ₅₇In have one at least, the R ' of formula (Cp '-6) ₅₈And R ' ₅₉In have one at least, the R ' of formula (Cp '-7) ₅₉And R ' ₆₀In have one at least, the R ' of formula (Cp '-8) ₆₁And R ' ₆₂In have one at least, at least one R ' of formula (Cp '-9) and (Cp '-10) ₆₃, and the R ' of formula (Cp '-11) and (Cp '-12) ₆₄, R ' ₆₅And R ' ₆₆In have one at least, have at least one and be selected from R ₇₁OCO-group, HOSO ₂-group, HO-group, R ₇₂NHCO-group and R ₇₂NHSO ₂The substituting group of-group.R ₇₁Represent hydrogen atom, have 6 or still less alkyl of carbon atom (as methyl, ethyl, propyl group, isopropyl, butyl and the tert-butyl group) or phenyl.R ₇₂Represent R ₇₁Represented group, R ₇₄CO-group, R ₇₄N (R ₇₅) CO-group, R ₇₃SO ₂-group or R ₇₄N (R ₇₅) SO ₂-group.R ₇₃Representative has 6 or still less alkyl of carbon atom (as methyl, ethyl, propyl group, isopropyl, butyl and the tert-butyl group) or phenyl.R ₇₄And R ₇₅Represent by R respectively ₇₁Represented group.

These groups also can have substituting group.

Below will describe R ' in detail ₅₁-R ' ₆₆, a, b, d, e and f.In the following description, R ' ₄₁Represent alkyl, aryl or heterocyclic group.R ' ₄₂Represent aryl or heterocyclic group.R ' ₄₃, R ' ₄₄And R ' ₄₅Represent hydrogen atom, alkyl, aryl or heterocyclic group respectively.

R ' ₅₁Representative and R ' ₄₁Identical group.A represents 0 or 1.R ' ₅₂And R ' ₅₃Representative and R ' respectively ₄₃Identical group.If R ' ₅₂In formula (Cp '-2) is not hydrogen atom, then R ' ₅₂And R ' ₅₁Can mutually combine and form 5-7 unit ring.B represents 0 or 1.

R ' ₅₄Representative and R ' ₄₁Identical group, R ' ₄₁CON (R ' ₄₃)-group, R ' ₄₁SO ₂N (R ' ₄₃)-group, R ' ₄₁N (R ' ₄₃)-group, R ' ₄₁S-group, R ' ₄₃O-group or R ' ₄₅N (R ' ₄₃) CON (R ' ₄₄)-group.R ' ₅₅Representative and R ' ₄₁Identical group.

R ' ₅₆And R ' ₅₇Representative and R ' independently respectively ₄₃Identical group, R ' ₄₁S-group, R ' ₄₃O-group, R ' ₄₁CON (R ' ₄₃)-group, R ' ₄₁OCON (R ' ₄₃)-group or R ' ₄₁SO ₂N (R ' ₄₃)-group.

R ' ₅₈Representative and R ' ₄₃Identical group.R ' ₅₉Representative and R ' ₄₁Identical group, R ' ₄₁CON (R ' ₄₃)-group, R ' ₄₁OCON (R ' ₄₃)-group, R ' ₄₁SO ₂N (R ' ₄₃)-group, R ' ₄₃N (R ' ₄₄) CON (R ' ₄₅)-group, R ' ₄₁O-group, R ' ₄₁S-group, halogen atom or R ' ₄₁N (R ' ₄₃)-group.D represents 0-3.If d is a plural number, then a plurality of R ' ₅₉Represent identical substituting group or different substituting groups.

R ' ₆₀Representative and R ' ₄₃Identical group.

R ' ₆₁Representative and R ' ₄₃Identical group, R ' ₄₃OSO ₂-group, R ' ₄₃N (R ' ₄₄) SO ₂-group, R ' ₄₃OCO-group, R ' ₄₃N (R ' ₄₄) CO-group, cyano group, R ' ₄₁SO ₂(R ' ₄₃) CO-group, R ' ₄₃CON (R ' ₄₄) CO-group, R ' ₄₃N (R ' ₄₄) SO ₂N (R ' ₄₅) CO-group, R ' ₄₃N (R ' ₄₄) CON (R ' ₄₅) CO-group, R ' ₄₃N (R ' ₄₄) SO ₂N (R ' ₄₅) SO ₂-group or R ' ₄₃N (R ' ₄₄) CON (R ' ₄₅) SO ₂-group.

R ' ₆₂Representative and R ' ₄₁Identical group, R ' ₄₁CONH-group, R ' ₄₁OCONH-group, R ' ₄₁SO ₂NH-group, R ' ₄₃N (R ' ₄₄) CONH-group, R ' ₄₃N (R ' ₄₄) SO ₂NH-group, R ' ₄₃O-group, R ' ₄₁S-group, halogen atom or R ' ₄₁N (R ' ₄₃)-group.In formula (Cp '-8), e represents the integer of 0-4.If e is 2 or bigger, then a plurality of R ' ₆₂Represent identical substituting group or different substituting groups.

R ' ₆₃Representative and R ' ₄₁Identical group, R ' ₄₃CON (R ' ₄₄)-group, R ' ₄₃N (R ' ₄₄) CO-group, R ' ₄₁SO ₂N (R ' ₄₃)-group, R ' ₄₁N (R ' ₄₃) SO ₂-group, R ' ₄₁SO ₂-group, R ' ₄₃OCO-group, R ' ₄₃OSO ₂-group, halogen atom, nitro, cyano group or R ' ₄₃The CO-group.In formula (Cp '-9), e represents the integer of 0-4.If e is 2 or bigger, then a plurality of R ' ₆₃Represent identical substituting group or different substituting groups.In formula (Cp '-10), f represents the integer of 0-3.If f is 2 or bigger, then a plurality of R ' ₆₃Represent identical substituting group or different substituting groups.

R ' ₆₄, R ' ₆₅And R ' ₆₆Representative and R ' independently respectively ₄₃Identical group, R ' ₄₁S-group, R ' ₄₃O-group, R ' ₄₁CON (R ' ₄₃)-group, R ' ₄₁SO ₂N (R ' ₄₃)-group, R ' ₄₁OCO-group, R ' ₄₁OSO ₂-group, R ' ₄₁SO ₂-group, R ' ₄₁N (R ' ₄₃) CO-group, R ' ₄₁N (R ' ₄₃) SO ₂-group, nitro or cyano group.

In the foregoing description, R ' ₄₁, R ' ₄₃, R ' ₄₄, or R ' ₄₅The aliphatic group that the aliphatic group of representative is 1-10 carbon atom, preferred 1-6 carbon atom, saturated or unsaturated, chain or ring-type, straight or branched, be substituted or be unsubstituted.The representational example of this aliphatic group is methyl, 1-propenyl, cyclopropyl, isopropyl, normal-butyl, the tert-butyl group, isobutyl, tertiary pentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-octyl, 1,1,3,3-tetramethyl butyl and positive decyl.

R ' ₄₁, R ' ₄₂, R ' ₄₃, R ' ₄₄Perhaps R ' ₄₅The aryl of representative is the aryl of 6-10 carbon atom, phenyl that preferably is substituted or is unsubstituted or the naphthyl that is substituted or is unsubstituted.

R ' ₄₁, R ' ₄₂, R ' ₄₃, R ' ₄₄Perhaps R ' ₄₅The heterocyclic group of representative is the heterocyclic group that is substituted or is unsubstituted of 1-10 carbon atom, preferred 1-6 carbon atom, preferred 3-8 unit, and it comprises the heteroatoms that is selected from nitrogen-atoms, oxygen atom and sulphur atom.The representational example of this heterocyclic group is 2-pyridine radicals, 2-benzoxazolyl, 2-imidazole radicals, 2-benzimidazolyl, 1-indyl, 1,3,4-thiadiazoles-2-base, 1,2,4-triazole-2-base and 1-indolinyl.

If above-mentioned aliphatic group, aromatic group and heterocyclic group have substituting group, then substituent representative example is halogen atom, R ' ₄₃O-group, R ' ₄₁S-group, R ' ₄₃CON (R ' ₄₄)-group, R ' ₄₃N (R ' ₄₄) CO-group, R ' ₄₁OCON (R ' ₄₃)-group, R ' ₄₁SO ₂N (R ' ₄₃)-group, R ' ₄₃N (R ' ₄₄) SO ₂-group, R ' ₄₁SO ₂-group, R ' ₄₃OCO-group, R ' ₄₁SO ₂The O-group, with R ' ₄₁Identical group, R ' ₄₃N (R ' ₄₄)-group, R ' ₄₁CO ₂-group, R ' ₄₁OSO ₂-group, cyano group and nitro.

Below R ' will be described ₅₁-R ' ₆₅, a, b, d, e and f preferable range.

R ' ₅₁Preferably aliphatic group or aromatic group.A most preferably is 1.R ' ₅₂And R ' ₅₅Difference is aromatic group preferably.If b is 1, R ' ₅₃Aromatic group preferably; If b is 0, R ' ₅₃Heterocyclic group preferably.R ' ₅₄R ' preferably ₄₁CON (R ' ₄₃)-group or R ' ₄₁N (R ' ₄₃)-group.R ' ₅₆And R ' ₅₇Difference is aliphatic group, aromatic group, R ' preferably ₄₁O-group or R ' ₄₁The S-group.R ' ₅₈Preferably aliphatic group or aromatic group.

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

R ' ₆₁R ' preferably ₄₃OSO ₂-group, R ' ₄₃N (R ' ₄₄) SO ₂-group, R ' ₄₃OCO-group, R ' ₄₃N (R ' ₄₄) CO-group, cyano group, R ' ₄₁SO ₂N (R ' ₄₃) CO-group, R ' ₄₃CON (R ' ₄₄) CO-group, R ' ₄₃N (R ' ₄₄) SO ₂N (R ' ₄₅) CO-group or R ' ₄₃N (R ' ₄₄) CON (R ' ₄₅) the CO-group.

In formula (Cp '-8), e preferably 0 or 1.R ' ₆₂R ' preferably ₄₁OCON (R ' ₄₃)-group, R ' ₄₁CON (R ' ₄₃)-group or R ' ₄₁SO ₂N (R ' ₄₃)-group.And these substituent the position of substitution are preferably located in (5) position of naphthols ring.

In formula (Cp '-9), R ' ₆₃R ' preferably ₄₁CON (R ' ₄₃)-group, R ' ₄₁SO ₂N (R ' ₄₃)-group, R ' ₄₁N (R ' ₄₃) SO ₂-group, R ' ₄₁SO ₂-group, R ' ₄₁N (R ' ₄₃) CO-group, nitro or cyano group, and e preferably 1 or 2.

In formula (Cp '-10), R ' ₆₃R ' preferably ₄₃N (R ' ₄₄) CO-group, R ' ₄₃OCO-group or R ' ₄₃The CO-group.F preferably 1 or 2.

In formula (Cp '-11) and (Cp '-12), R ' ₆₄And R ' ₆₅Difference is R ' preferably ₄₁OCO-group, R ' ₄₁OSO ₂-group, R ' ₄₁SO ₂-group, R ' ₄₄N (R ' ₄₃) CO-group, R ' ₄₄N (R ' ₄₃) SO ₂-group or cyano group most preferably are R ' ₄₁OCO-group, R ' ₄₄N (R ' ₄₃) CO--group or cyano group.R ' ₆₆Preferably with R ' ₄₁Identical group.Comprise connection substituent carbon number thereon, R ' ₅₁-R ' ₆₆Preferably 18 or still less respectively of total carbon numbers, more preferably 10 or still less.

The useful group of photograph that B1 or PUG represent below will be described.

The useful group of the photograph that B1 or PUG represent can be the useful group of any photograph well known by persons skilled in the art.

Its example comprises that development restrainer, bleach boosters, dyestuff, bleaching inhibitor, colour coupler, developer, development assistant agent, reductive agent, ag halide solvent, silver complex form agent, fixer, image toner, stabilizing agent, film rigidizer, hardener, fogging agent, ultraviolet absorber, anti-photographic fog agent, nucleator, chemistry or spectral sensitizer, desensitiser and whitening agent.But PUG is not limited to these examples.

The preferred example of B1 or PUG be development restrainer (for example, the 3227554th, 3384657,3615506,3617291,3733201, with No. 5200306 United States Patent (USP)s, and the development restrainer of describing in No. 1450479 BrP), bleach boosters (for example, at ResearchDisclosure 1973, the bleach boosters of describing in Item No.11449 and No. 193389 European patent, and JP-A-61-201247, JP-A-4-350848, JP-A-4-350849, and described in the JP-A-4-350853), the development assistant agent (for example, the development assistant agent of describing among No. 4859578 United States Patent (USP) and the JP-A-10-48787), development accelerant (for example, the development accelerant of in No. 4390618 United States Patent (USP) and JP-A-2-56543, describing), reductive agent (for example, and whitening agent (for example whitening agent of describing in the 4774181st and No. 5236804 United States Patent (USP)) reductive agent of in JP-A-63-109439 and JP-A-63-128342, describing).The pKa in conjunction with acid of B1 or PUG is preferably 13 or lower, and more preferably 11 or lower.

B1 or PUG are more preferably development restrainer or bleach boosters.

Preferred development restrainer is mercapto-tetrazole derivant, mercapto-triazole derivant, dimercaptothiodiazole derivant, sulfydryl oxadiazoles derivant, mercaptoimidazole derivant, sulfhydryl benzimidazole derivative, mercaptobenzothiazolderivative derivative, mercaptobenzoxazole derivant, terazole derivatives, 1,2,3-triazole derivative, 1,2,4-triazole derivative and benzotriazole derivatives.

Preferred development restrainer is represented in order to following formula DI-1 to DI-6:

Wherein, R ' ₃₁Represent halogen atom, R ' ₄₆O-group, R ' ₄₆S-group, R ' ₄₇CON (R ' ₄₈)-group, R ' ₄₇N (R ' ₄₈) CO-group, R ' ₄₆OCON (R ' ₄₇)-group, R ' ₄₆O ₂(R ' ₄₇)-group, R ' ₄₇N (R ' ₄₈) SO ₂Group, R ' ₄₆SO ₂-group, R ' ₄₇OCO-group, R ' ₄₇N (R ' ₄₈) CON (R ' ₄₉)-group, R ' ₄₇CON (R ' ₄₈) SO ₂-group, R ' ₄₇N (R ' ₄₈) CON (R ' ₄₉) SO ₂-group, with R ' ₄₆Identical group, R ' ₄₇N (R ' ₄₈)-group, R ' ₄₆CO ₂-group, R ' ₄₇OSO ₂-group, cyano group or nitro.

R ' ₄₆Represent aliphatic group, aromatic group, heterocyclic group.R ' ₄₇, R ' ₄₈, and R ' ₄₉Represent aliphatic group, aromatic group, heterocyclic group or hydrogen atom respectively.R ' ₄₆, R ' ₄₇, R ' ₄₈, or R ' ₄₉The aliphatic group that the aliphatic group of representative is 1-32 carbon atom, preferred 1-20 carbon atom, saturated or unsaturated, chain or ring-type, straight or branched, be substituted or be unsubstituted.Representational example is methyl, cyclopropyl, isopropyl, isopropenyl, normal-butyl, the tert-butyl group, isobutyl, tertiary pentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-octyl, 1,1,3,3-tetramethyl butyl, and positive decyl.

R ' ₄₆, R ' ₄₇, R ' ₄₈, or R ' ₄₉The aromatic group of representative is the aromatic group of 6-32 carbon atom, the naphthyl that the phenyl ring-type that preferably is substituted or is unsubstituted is substituted or is unsubstituted.

R ' ₄₆, R ' ₄₇, R ' ₄₈, or R ' ₄₉The heterocyclic group of representative is 1-32 carbon atom, preferred 1-20 carbon atom, the preferred 3-8 unit heterocyclic group that is substituted or is unsubstituted, and this heterocycle comprises the heteroatoms that is selected from nitrogen-atoms, oxygen atom and sulphur atom.The representative example of this heterocyclic group is 2-pyridine radicals, 2-benzoxazolyl, 2-imidazole radicals, 2-benzimidazolyl, 1-indyl, 1,3,4-thiadiazoles-2-base, 1,2,4-triazole-2-base or 1-indolinyl.

R ' ₃₂Representative and R ' ₄₆Identical group.

K represents the integer of 1-4, and g represents 0 or 1, and h represents 1 or 2.

V represention oxygen atom, sulphur atom or-N (R ' ₄₆)-.

R ' ₃₁And R ' ₃₂Can further comprise substituting group.

Preferred bleach boosters is as follows.

-SCH ₂CO ₂H

-SCH ₂CH ₂CO ₂H

-SCH ₂CH ₂CH ₂CO ₂H -S-CH ₂CH ₂-S-CH ₂CH ₂CO ₂H

(group is connected on the COUP by the effect key)

The group of TIME representative below will be described.

The group of TIME representative can be by any linking group of the PUG that can rupture after the COUP1 fracture during developing.Its example is the 4th, 146,396,4,652,156 or 4,698, and the group of describing in No. 297 United States Patent (USP)s has wherein used the cleavage reaction of hemiacetal; The 4th, 248,962,4,847,185 or 4,857, the luminous intensity distribution group of describing in No. 440 United States Patent (USP)s, it produces cleavage reaction by using intramolecular nucleophilic substitution reaction; The 4th, 409,323 or 4, the luminous intensity distribution group of describing in 421, No. 845 United States Patent (USP)s, it produces cleavage reaction by using electron transfer reaction: the 4th, the group of describing in 546, No. 073 United States Patent (USP)s, it produces cleavage reaction by the hydrolysis reaction that uses the imino group ketal; And the group of describing in No. 2626317 Deutsches Reichs-Patent, it produces cleavage reaction by the hydrolysis reaction that uses ester.At the heteroatoms place that is contained in wherein, preferred oxygen atom, sulphur atom or nitrogen-atoms, TIME be connected formula (IIa) or (IIb) in COUP1 on.The preferred example of TIME is with following formula (T-1), (T-2) and (T-3).

^*-W-(X＝Y)j-C(R ₂₁)R ₂₂- ^** (T-1)

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

^*-W-LINK-E1- ^** (T-3)

Wherein, ^*Represent TIME be connected formula (IIa) or (IIb) in COUP1 on the position, ^*Represent TIME to be connected position on PUG or other TIME (if m is a plural number), W represention oxygen atom, sulphur atom or＞N-R ₂₃, X and Y represent methine or nitrogen-atoms respectively, and j represents 0,1 or 2, and R ₂₁, R ₂₂And R ₂₃Represent hydrogen atom or substituting group respectively.If the methine that X and Y representative are substituted, then this substituting group and R ₂₁, R ₂₂And R ₂₃In any two substituting groups can be connected to form ring texture (as phenyl ring or pyrazoles ring).In formula (T-3), E1 represents electrophilic group.LINK represents linking group, and its three-dimensional ground is connected W on the E1, to carry out intramolecular nucleophilic substitution reaction.

The concrete instance of the TIME of formula (T-1) representative is as follows:

^*-OCH ₂- ^{** *}-S-CH ₂- ^**

The concrete instance of the TIME of formula (T-2) representative is as follows:

The concrete instance of the TIME of formula (T-3) representative is as follows:

If m is 2 in the formula (IIa), then (TIME) _mConcrete instance as follows:

The group of RED representative in the formula (IIb) below will be described.RED be from COUP1 or TIME break to form RED-PUG and also can be developed during the group of developer cross-over oxidation of the acidic materials that exist such as oxidised form.RED-PUG can be the compound of any PUG that ruptures when oxidation.The example of RED is quinhydrones, catechol, 1,2,3-benzenetriol, 1,4-naphthalene quinhydrones, 1,2-naphthalene quinhydrones, sulfonamido phenol, hydrazine and sulfonamido naphthols.The concrete instance of these groups is described in JP-A-61-230135, JP-A-62-251746, JP-A-61-278852, the 3rd, 364,022,3,379,529,4,618,571,3,639,617 and 4,684, No. 604 United States Patent (USP)s and J.Org.Chem., the 29th volume is in 588 pages (1964).

In these compounds, the preferred example of RED is a quinhydrones, 1,4-naphthalene quinhydrones, 2-(perhaps 4-) sulfonamido phenol, 1,2,3-benzenetriol and hydrazine.In these compounds, the oxidizing reducing group with phenolic hydroxyl group combines with COUP1 or TIME at the oxygen atom place of phenolic group group.

For the compound that makes formula (IIa) or (IIb) represent is fixed on photographic layer or the non-photographic layer, in described photographic layer or non-photographic layer in comprise formula (IIa) or (IIb) photosensitive silve halide material of compound of expression added described compound before being developed, and formula (IIa) or (IIb) compound of expression preferably have non-diffusion group.Most preferably, this non-diffusion group is included among TIME or the RED.The preferred example of non-diffusion group is the alkyl of 8-40 carbon atom, preferred 12-32 carbon atom, and 8-40 carbon atom, preferred 12-32 carbon atom also have the aromatic group of an alkyl (having 3-20 carbon atom), alkoxy (having 3-20 carbon atom) or aryl (having 6-20 carbon atom) at least.

Synthesis type (IIa) or (IIb) method of compound of expression for example be described in the known patent of quoting when explaining TIME, RED and PUG and document, JP-A-61-156127, JP-A-58-160954, JP-A-58-162949, JP-A-61-249052, JP-A-63-37350, the 5th, 026, No. 628 United States Patent (USP) and the 443530th A2 and 444501 A2 European patents are open.

The release that below will describe formula (III) the expression compound of useful group of taking a picture:

COUP2-A-E-B2 (III)

Wherein COUP2 representative can with the colour coupler group of the developer coupling of oxidised form; E represents electrophilic moiety; The A representative can form the linking group that ring discharges B2 by the intramolecular nucleophilic substitution reaction of nitrogen-atoms, it is appeared at by developer in the coupled product between the developer of COUP2 and oxidised form, and directly coupling position and nucleophilic part E is linked together; And useful group or its precursor of B2 representative photograph.

As the colour coupler group that COUP2 represents, can use the colour coupler group that is known as the photograph colour coupler usually.Its example be the yellow colour former group (for example; open chain ketone methylene colour coupler group; as acyl group monoacetylaniline and malonyl diphenylamine); magenta colour coupler (as 5-pyrazolone-type, Pyrazolotriazole type colour coupler group), and cyan colour coupler group (as phenol type, naphthol type, pyrrolo-triazole type colour coupler group).Also can use the colour coupler that forms yellow, pinkish red and blue or green dyestuff and have novel skeleton, for example be described among No. 5681689 United States Patent (USP), 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 the JP-A-6-27612.Also can use other colour coupler groups (for example to be described in the colour coupler group in the United States Patent (USP) the 3632345th and No. 3928041, they form colourless substance by the reaction with the aromatic amino developer of oxidised form, and be described in the colour coupler group in the United States Patent (USP) the 1939231st and No. 2181944, they form the material of black or Neutral colour by the reaction with the aromatic amino developer of oxidised form).

The link position of COUP2 and linking group A can be any position, after its condition is the mutual coupling of the developer of colour coupler and oxidised form, B can form ring and be released with the intramolecular nucleophilic substitution reaction of nitrogen-atoms, it is appeared in the coupling product by developer, and with electrophilic moiety E Direct Bonding on the coupling position.This optimum seeking site is the coupling position of COUP2 or near position it (atom of contiguous coupling position or be adjacent to the atom of the atom of this vicinity coupling position), and is more preferably near the position (be close to the atom of coupling position or be adjacent to the atom of the atom of this vicinity coupling position) of the coupling position of COUP2.

Be bonded to the coupling position of the colour coupler group that (1) COUP2 represents as linking group A, (2) be close to the atom of this coupling position, and (3) when being adjacent on the atom of atom of this vicinity coupling position, colour coupler of the present invention and oxidised form (Ar '=NH) ArNH ₂Reaction between the aromatic amino developer of expression is available to be represented with following formula.

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

(2) A is bonded on the atom of coupling position of contiguous COUP2

(3) A is bonded on the atom of contiguous atom of the coupling position that is adjacent to COUP2

With Respectively representative can with the colour coupler residue of the developer coupling of oxidised form, it is ring texture not necessarily.Symbolic representation coupling position.Bonding between straight line portion-expression non-metallic atom.

Below describe the preferred example of the present invention's COUP2, but COUP2 is not limited to these examples.

Wherein, ^*Represent COUP2 to be bonded to position on the A, X ' represents hydrogen atom, halogen atom (as fluorine atom, chlorine atom, bromine atoms or iodine atom), R ₁₃₁-, R ₁₃₁O-, R ₁₃₁S-, R ₁₃₁OCOO-, R ₁₃₂COO-, R ₁₃₂(R ₁₃₃) NCOO-or R ₁₃₂CON (R ₁₃₃)-, Y ' represention oxygen atom, sulphur atom, R ₁₃₂N=or R ₁₃₂ON=.

R ₁₃₁Represent aliphatic group (" aliphatic group " is meant saturated or unsaturated, chain or ring-type, straight or branched, the aliphatic hydrocarbyl that is substituted or is unsubstituted, and used aliphatic group has identical connotation in below describing), aromatic group or heterocyclic group.

R ₁₃₁The aliphatic group of representative is preferably to have 1-32 carbon atom, the more preferably aliphatic group of 1-22 carbon atom.Its example is methyl, ethyl, vinyl, ethinyl, propyl group, isopropyl, 2-propenyl, 2-propynyl, butyl, isobutyl, the tert-butyl group, tertiary pentyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl group, 1,1,3,3-tetramethyl butyl, decyl, dodecyl, cetyl and octadecyl." carbon number " is meant and comprises the total number of carbon atoms that is connected the substituent carbon atom on the above-mentioned aliphatic group.The carbon number of other groups except that aliphatic group also is meant the total number of carbon atoms that comprises substituent carbon atom.

R ₁₃₁The aromatic group of expression is the aryl that is substituted or is unsubstituted, and preferably has 6-32 carbon atom, more preferably 6-22 carbon atom.Its example is phenyl, tolyl and naphthyl.

R ₁₃₁The heterocyclic group of expression is the heterocyclic group that is substituted or is unsubstituted, and preferably has 1-32 carbon atom, more preferably 1-22 carbon atom.Its example is 2-furyl, 2-pyrrole radicals, 2-thienyl, 3-tetrahydrofuran base, 4-pyridine radicals, 2-pyrimidine radicals, 2-(1,3, the 4-thiadiazolyl group), 2-[4-morpholinodithio base, 2-benzoxazolyl, 2-benzimidazolyl, 2-benzo selenazoles base, 2-quinolyl, 2-oxazolyl, 2-thiazolyl, 2-selenazoles base, 5-tetrazole radical, 2-(1,3,4-oxadiazoles base) and the 2-imidazole radicals.

R ₁₃₂And R ₁₃₃Represent hydrogen atom, aliphatic group, aromatic group or heterocyclic group respectively independently.R ₁₃₂And R ₁₃₃The aliphatic group of representative, aromatic group and heterocyclic group have and R ₁₃₁Identical connotation.

Preferably, X ' represents hydrogen atom, aliphatic group, aliphatic oxygen base, aliphatic sulfenyl or R ₁₃₂CON (R ₁₃₃)-, and Y ' represention oxygen atom.

The example that is applicable to " substituting group " of the substituent example of above-mentioned group and following radicals and the following stated is that halogen atom (as fluorine atom, chlorine atom, bromine atoms and iodine atom), hydroxyl, carboxyl, sulfo group, cyano group, nitro, alkyl (as methyl, ethyl and hexyl), fluoroalkyl (as trifluoromethyl), aryl (as phenyl, tolyl and naphthyl), heterocyclic group (as have and R ₁₃₁The heterocyclic group of synonymous); alkoxy (methoxyl; ethoxy and octyloxy); aryloxy group (as phenoxy group and naphthoxy); alkylthio group (as methyl mercapto and butylthio); arylthio (as thiophenyl); amino (as amino; the N-methylamino; N; the N-dimethylamino; with the N-phenyl amino); acyl group is (as acetyl group; propiono; and benzoyl); alkyl sulphonyl or aryl sulfonyl (as mesyl and benzenesulfonyl); acyl amino (as acetyl-amino and benzoyl-amido); alkyl sulfonyl-amino or arlysulfonylamino (amino and benzenesulfonyl amino) as mesyl; carbamyl is (as carbamyl; N-methylamino carbonyl; N; N-dimethylamino carbonyl; with N-phenyl amino carbonyl); sulfamoyl is (as sulfamoyl; N-methylamino sulfonyl; N, N-dimethylamino sulfonyl; with N-phenyl amino sulfonyl); alkoxy carbonyl is (as methoxycarbonyl; ethoxy carbonyl and carbonyl octyloxy); aryloxycarbonyl (as phenyloxycarbonyl and naphthoxy carbonyl); acyloxy (as acetyl group oxygen base and benzoyl oxygen base); alkoxy-carbonyl oxy (as methoxycarbonyl oxygen base and ethoxy carbonyl oxygen base); aryloxycarbonyl oxygen base (as phenyloxycarbonyl oxygen base); alkoxycarbonyl amino (amino and butoxy carbonyl amino) as methoxycarbonyl; aryloxycarbonyl amino (as phenyloxycarbonyl amino); amino carbonyl oxygen base (as N-methylamino ketonic oxygen base and N-phenyl amino ketonic oxygen base); amino carbonyl amino (as N-methylamino carbonylamino and N-phenyl amino carbonylamino).

R ₁₁₁And R ₁₁₂Represent R respectively independently ₁₃₂CO-, R ₁₃₁OCO-, R ₁₃₂(R ₁₃₃) NCO-, R ₁₃₃SO _n-, R ₁₃₂(R ₁₃₃) NSO ₂-or cyano group.R ₁₃₁, R ₁₃₂And R ₁₃₃Has connotation same as described above.N represents 1 or 2.

R ₁₁₃Representative and R ₁₃₁Identical group.

R ₁₁₄Represent R ₁₃₂-, R ₁₃₂CON (R ₁₃₃)-, R ₁₃₂(R ₁₃₃) N-, R ₁₃₁SO ₂N (R ₁₃₂)-, R ₁₃₁S-, R ₁₃₁O-, R ₁₃₁OCON (R ₁₃₂)-, R ₁₃₂(R ₁₃₃) NCON (R ₁₃₄)-, R ₁₃₁OCO-, R ₁₃₂(R ₁₃₃) NCO-or cyano group.R ₁₃₁, R ₁₃₂, and R ₁₃₃Has connotation same as described above.R ₁₃₄Representative and R ₁₃₂Identical group.

R ₁₁₅And R ₁₁₆Represent a substituting group respectively independently, preferred R ₁₃₂-, R ₁₃₂CON (R ₁₃₃)-, R ₁₃₁SO ₂N (R ₁₃₂)-, R ₁₃₁S-, R ₁₃₁O-, R ₁₃₁OCON (R ₁₃₂)-, R ₁₃₂(R ₁₃₃) NCON (R ₁₃₄)-, R ₁₃₁OCO-, R ₁₃₂(R ₁₃₃) NCO-, halogen atom or cyano group, more preferably R ₁₃₁, R ₁₃₂, R ₁₃₃, and R ₁₃₄The group of representative has connotation same as described above.

R ₁₁₇Represent a substituting group, p represents the integer of 0-4, and q represents the integer of 0-3.R ₁₁₇The substituent preferred example of representative is R ₁₃₁-, R ₁₃₂CON (R ₁₃₃)-, R ₁₃₁OCON (R ₁₃₂)-, R ₁₃₁SO ₂N (R ₁₃₂)-, R ₁₃₂(R ₁₃₃) NCON (R ₁₃₄)-, R ₁₃₁S-, R ₁₃₁O-and halogen.R ₁₃₁, R ₁₃₂, R ₁₃₃And R ₁₃₄Has connotation same as described above.If p and q are 2 or bigger, then a plurality of R ₁₁₇Can be identical or different, and contiguous R ₁₁₇Can mutually combine and form ring.In the formula (III-1E) of preferred form with (III-2E), at least one ortho position of hydroxyl is by R ₁₃₂CONH-, R ₁₃₁OCONH-or R ₁₃₂(R ₁₃₃) the NCONH-replacement.

R ₁₁₈Represent substituting group, r represents the integer of 0-6, and s represents the integer of 0-5.R ₁₁₈The substituent preferred example of representative is R ₁₃₂CON (R ₁₃₃)-, R ₁₃₁OCON (R ₁₃₂)-, R ₁₃₁SO ₂N (R ₁₃₂)-, R ₁₃₂(R ₁₃₃) NCON (R ₁₃₄)-, R ₁₃₁S-, R ₁₃₁O-, R ₁₃₂(R ₁₃₃) NCO-, R ₁₃₂(R ₁₃₃) NSO ₂-, R ₁₃₁OCO-, cyano group and halogen atom.R ₁₃₁, R ₁₃₂, R ₁₃₃, and R ₁₃₄Has connotation same as described above.If r and s are 2 or bigger, then a plurality of R ₁₁₈Can be identical or different, and contiguous R ₁₁₈Can mutually combine and form ring.In the formula (III-1F) of preferred form, (III-2F) with (III-3F), an ortho position of hydroxyl is by R ₁₃₂CONH-, R ₁₃₂HNCONH-, R ₁₃₂(R ₁₃₃) NSO ₂-or R ₁₃₂NHCO-replaces.

R ₁₁₉Represent substituting group, preferably R ₁₃₂-, R ₁₃₂CON (R ₁₃₃)-, R ₁₃₁SO ₂N (R ₁₃₂)-, R ₁₃₁S-, R ₁₃₁O-, R ₁₃₁OCON (R ₁₃₂)-, R ₁₃₂(R ₁₃₃) NCON (R ₁₃₄)-, R ₁₃₁OCO-, R ₁₃₂(R ₁₃₃) NSO ₂-, R ₁₃₂(R ₁₃₃) NCO-, halogen atom or cyano group, be more preferably R ₁₃₁The group of representative.R ₁₃₁, R ₁₃₂, R ₁₃₃And R ₁₃₄Has connotation same as described above.

R ₁₂₀And R ₁₂₁Represent substituting group, preferably a R respectively independently ₁₃₂-, R ₁₃₂CON (R ₁₃₃)-, R ₁₃₁SO ₂N (R ₁₃₂)-, R ₁₃₁S-, R ₁₃₁O-, R ₁₃₁OCON (R ₁₃₂)-, R ₁₃₂(R ₁₃₃) NCON (R ₁₃₄)-, R ₁₃₂(R ₁₃₃) NCO-, R ₁₃₂(R ₁₃₃) NSO ₂-, R ₁₃₁OCO-, halogen atom or cyano group are more preferably R ₁₃₂(R ₁₃₃) NCO-, R ₁₃₂(R ₁₃₃) NSO ₂-, trifluoromethyl, R ₁₃₁OCO-or cyano group.R ₁₃₁, R ₁₃₂, R ₁₃₃And R ₁₃₄Has connotation same as described above.

E represents electrophilic group, as-CO-,-CS-,-COCO-,-SO-,-SO ₂-,-P (=O) (R ₁₅₁)-or-P (=S) (R ₁₅₁)-(be R wherein ₁₅₁Represent aliphatic group, aromatic group, aliphatic oxygen base, aryloxy group, aliphatic sulfenyl or arylthio), and preferably-CO-.

The A representative can form ring (the first ring of preferred 3-7 along with the intramolecular nucleophilic substitution reaction of nitrogen-atoms, more preferably 5 or 6 yuan of rings) discharge the linking group of B2, it is appeared at by developer in the coupling reaction product between the developer of COUP2 and oxidised form, and is bonded on the coupling position with electrophilic moiety E.The preferred form of A can be used with following formula (IV) and represent:

Wherein, ^*The part that representative is connected with COUP2, and ^*The part that representative is connected with E.R ₁₄₁, R ₁₄₂, R ₁₄₃Represent independently respectively and R ₁₃₂Identical group.I represents the integer of 0-3, and j represents the integer of 0-2.R ₁₄₁Or R ₁₄₂Can with COUP2 or R ₁₄₃In conjunction with forming ring, perhaps R ₁₄₁And R ₁₄₂The formation volution can mutually combine.If i is 2 or 3, then a plurality of R ₁₄₁Or R ₁₄₂Can be identical or different, and contiguous R ₁₄₁Or R ₁₄₂Can mutually combine and form ring.R ₁₄₁And R ₁₄₂Be preferably hydrogen atom or (1-20 carbon atom, preferred 1-10 carbon atom) aliphatic group respectively, be more preferably hydrogen atom.R ₁₄₃The aliphatic group of 1-32 carbon atom preferably, the more preferably aliphatic group of 1-22 carbon atom, and can combine with COUP2 and form ring.If j is 2, two R then ₁₄₃Can be identical or different, and contiguous R ₁₄₃Can form ring.J preferably 1.In formula (III-1) { (III-1A), (III-1B), (III-1C), (III-1D), (III-1E), (III-1F) and (III-1G) }, i preferably 1 or 2.In formula (III-2) { (III-2A), (III-2B), (III-2C), (III-2D), (III-2E), (III-2F) and (III-2G) }, i preferably 0 or 1.In formula (III-3) { (III-3F) }, i preferably 0.

The B2 representative useful compound of photograph or its precursor.The B2 of preferred form represents in order to following formula (V):

#-(T)k-PUG (V)

Wherein, the part that # representative is connected with E, the T representative can discharge the luminous intensity distribution group that the back discharges PUG by E, k represent 0-2 integer, be preferably 0 or 1, and PUG represents the useful group of photograph.

The example of the luminous intensity distribution group of T representative is the 4146396th, 4652516 or No. 4698297 group described in the United States Patent (USP), and it discharges PUG by the cleavage reaction that uses hemiacetal; The group of in JP-A-9-114058 or the 4248962nd, 5719017 or No. 5709987 United States Patent (USP), describing, it discharges PUG by using intramolecular ring-closing reaction; The group of describing 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 the 4409323rd or No. 4421845 United States Patent (USP) uses to discharge PUG via the electron transfer of pi-electron; The group of in JP-A-57-179842, JP-A-40261530 or JP-A-5-313322, describing, it discharges PUG by producing carbon dioxide; The group of describing in No. 4546073 United States Patent (USP), it discharges PUG by the hydrolysis reaction that uses the imino group ketal; The group of describing during No. 26261317 Deutsches Reichs-Patent is open, it discharges PUG by the hydrolysis reaction that uses ester; And the group of describing in No. 572084 European patent, it discharges PUG by using the reaction with sulfate ion.

The preferred example of the luminous intensity distribution group of the present invention's T representative is as follows.But T is not limited to these examples.

Wherein, # representative T when k is 2 is bonded to the part on electrophilic moiety E or the ##, and ## representative T when k is 2 is bonded to the part on PUG or the #.Z represention oxygen atom or sulphur atom are preferably oxygen atom.R ₁₆₁Represent substituting group, preferably R ₁₃₁-, R ₁₃₂CON (R ₁₃₃)-, R ₁₃₁SO ₂N (R ₁₃₂)-, R ₁₃₁S-, R ₁₃₁O-, R ₁₃₁OCON (R ₁₃₂)-, R ₁₃₂(R ₁₃₃) NCON (R ₁₃₄)-, R ₁₃₂(R ₁₃₃) NCO-, R ₁₃₂(R ₁₃₃) NSO ₂-, R ₁₃₁OCO-, halogen atom, nitro or cyano group.R ₁₃₁, R ₁₃₂, R ₁₃₃And R ₁₃₄Has connotation same as described above.R ₁₆₁Can with R ₁₆₂, R ₁₆₃And R ₁₆₄In any one in conjunction with forming ring.n ₁Represent the integer of 0-4.If n ₁Represent 2 or bigger, then a plurality of R ₁₆₁Can be identical or different, and the formation ring that can mutually combine.

R ₁₆₂, R ₁₆₃And R ₁₆₄Represent respectively and R ₁₃₂Identical group.n ₂Represent 0 or 1.R ₁₆₂And R ₁₆₃The formation volution can mutually combine.R ₁₆₂And R ₁₆₃Be preferably hydrogen atom or (1-20 carbon atom, preferred 1-10 carbon atom) aliphatic group respectively, be more preferably hydrogen atom.R ₁₆₄Be preferably (1-20 carbon atom, preferred 1-10 carbon atom) aliphatic group or (6-20 carbon atom, preferably 6-10 carbon atom) aromatic group.R ₁₆₅Represent R ₁₃₂-, R ₁₃₂(R ₁₃₃) NCO-, R ₁₃₂(R ₁₃₃) NSO ₂-, R ₁₃₁OCO-or R ₁₃₂CO-.R ₁₃₁, R ₁₃₂And R ₁₃₃Identical with above-mentioned connotation.R ₁₆₅The preferred R that represents ₁₃₂, the aromatic group of 6-20 carbon atom more preferably.

The useful group of the photograph that PUG represents is identical with above-mentioned connotation.

The preferred form of used colour coupler is formula (III-2) (wherein A is combined in the atom place of the coupling position that is adjacent to COUP) or formula (III-3) (wherein A is combined in the atom place of the contiguous atom of the coupling position that is adjacent to COUP) among the present invention, and most preferred form is formula (III-3).Formula (III-3) is preferably with formula (III-3a) expression, more preferably formula (III-3b), and formula (III-3c) most preferably.Through type (III-3c) and oxidised form (Ar '=NH) use ArNH ₂The reaction of the aromatic amino developer of expression and the ring texture that obtains can be used with following formula (VI) and represent.

Wherein, Q ₁And Q ₂Representative forms 5 or 6 yuan of rings and produces the needed non-metallic atom of reaction with the developer of oxidised form in the atom at X ' root place, X ', T, k, PUG, R respectively ₁₁₈, s, R ₁₃₂And R ₁₄₃Identical with above-mentioned connotation, and R ₁₄₄The aliphatic group that represent 1-32 carbon atom, is substituted or is unsubstituted.

The concrete instance of used colour coupler is as follows in the present invention's the photosensitive material.But colour coupler is not limited in these examples.

Below description is had the silver emulsion on ashing surface in advance.

This has exposure even (askiatic mode) silver emulsion that develops all in the unexposed and exposed portion that the silver emulsion on ashing surface in advance is a photosensitive material.

" development " is meant during the standard colour development to have at least 20% silver to be developed in the silver emulsion of ashing.

The standard colour development that standard colour development described herein is the applied photosensitive material of the present invention.That is to say, flushing is CN-16 (the Fuji Photo Film Co. that is used for colour negative, Ltd.) or the C-41 of Eastman Kodat Company colour negative flushing and be used for colour paper CP-45 (Fuji Photo Film Co., Ltd.) or the RA-4 of Eastman Kodak Company colour paper flushing.

The surface fogged silver halide emulsion can make with following method: reductive agent or golden salt is added on the method in the silver emulsion that can form surface latent image under suitable pH and pAg condition, the method that heats when low pAG perhaps provides the method for uniform exposure.

As reductive agent, can use thiourea dioxide, stannous chloride, based on the compound or the monoethanolamine of hydrazine.

As the silver emulsion of surperficial ashing, can use any in silver chloride, chlorine silver bromide, iodine silver bromide or the bromine chlorosulfonylation silver.But preferred chloride content is 10mol% or higher, and the upper limit of chloride content is 100mol%.

The particle diameter of the silver emulsion of this surface ashing does not have concrete restriction.But mean grain size is preferably 0.01-0.75 μ m, and most preferably is 0.05-0.6 μ m.

Particle shape does not have concrete restriction yet.Therefore, can use conventional and unconventional particle.Average depth-width ratio does not have concrete restriction.

Though the polydispersion particle also can use, that particle is preferably is monodispersed (95% particle diameter of silver halide particle weight or amounts of particles is in ± 40% mean grain size).

In the present invention, the non-photosensitive material layer that comprises the silver emulsion of surperficial ashing can be arranged on any position in the photosensitive material.The effect that this non-photographic layer can pass through the useful group of photograph that discharged is arranged in the best position.

For example; this non-photosensitive material layer can form near the photosensitive silver halide emulsion layer of carrier and the layer between the carrier; promptly, so-called to the middle layer between the photographic layer of different color sensitivity; so-called than away from the photosensitive silver halide emulsion layer of carrier protective seam further from carrier, perhaps different but have layer between the silver halide emulsion layer of same hue sensitivity in light sensitivity each other.

The silver emulsion of surface ashing preferably is contained in the layer that contains the black collargol or in its adjacent layer.The coating weight of black collargol can decide according to the light shielding ability of ability that prevents halation and photosensitive material.Preferably, coating weight is 0.01-1g/m ², 0.05-0.5g/m more preferably ²

The compound (following finger " discharges the compound of PUG ") that discharges take a picture useful group or its precursor can be added in the non-photographic layer of the silver emulsion that comprises surperficial ashing, perhaps be added in the layer of contiguous this non-photographic layer.The compound that discharges PUG preferably is added in the non-photographic layer of the silver emulsion that comprises surperficial ashing.

When being somebody's turn to do " discharge PUG compound " when being added in the layer of non-photographic layer of the contiguous silver emulsion that comprises surperficial ashing, the layer that comprises " compound that discharges PUG " does not preferably comprise any photosensitive silver halide emulsion.

Generally, the useful group of taking a picture acts directly on the photosensitive material (during colour development after the release).But the useful group of the photograph that is discharged also can act on the photosensitive material after processing is accumulated in the color developer by replenishing.In addition, this useful group of taking a picture can have the purpose that the colour development kept replenishes the performance of liquid.For this purpose, the non-photosensitive material layer that comprises the silver emulsion of surperficial ashing is arranged on the basal surface surface of the surface that is covered by photosensitive silver halide emulsion layer (in the carrier with respect to).In this case, " discharging the compound of PUG " also is present on this basal surface certainly.

Making in the photosensitive material normally used adjuvant can be added on the non-photographic layer of the silver emulsion that comprises surperficial ashing and comprise in the layer (these layers are identical or are close to mutually) of " compound that discharges PUG ".Example is black collargol, minimum density control dyestuff, ultraviolet absorber and the anti-fading agent of anti-halation.But adjuvant is not limited in these examples.

The coating weight of the silver emulsion of used surperficial ashing can be any value among the present invention.But preferable range is determined by the coating weight of " discharging the compound of PUG ".

As the silver amount, this coating weight preferred every mole " discharging the compound of PUG " is the 0.5-200 mole, more preferably the 1-50 mole.

This preferable range also can change according to the type of the useful group of photograph that is discharged.For example, if the useful group of the photograph that is discharged has the development inhibiting effect, the silver emulsion of then surperficial ashing must not have the inhibiting situation of development greater than the useful group of the photograph that is discharged with respect to the coating weight of " discharging the compound of PUG ".

The coating weight that " discharges the compound of PUG " can be any value according to the objective function of photograph character.Generally, the coating weight of the compound of release PUG is 5 * 10 ^-4-2g/m ², be preferably 1 * 10 ^-3-1g/m ², more preferably 5 * 10 ^-3-5 * 10 ^-1G/m ²

Equally, can use two or more dissimilar " discharging the compound of PUG ".The chemical constitution of the useful group of photograph that is discharged in the case, can be identical or different.The camera function of the useful group of photograph that is discharged equally, also can be identical or different.

Non-photographic layer and the layer that comprises above-mentioned " discharge PUG compound " (these layers can identical or mutual vicinity) that comprise the silver emulsion of surperficial ashing be referred to as one " PUG releasing unit ".

Should " PUG releasing unit " during developing, in time and apace discharge the useful group of taking a picture.Equally, " PUG releasing unit " makes the spinoff of contrast phase character (storage stability of photosensitive material, by the storage stability and because the variation of the photograph character that the flushing variable causes that expose when developing) minimize.

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

Equally, the fogged silver halide emulsion in JP-A-2-5042 is developed by first development (black-and-white development).Therefore, this emulsion forms the silver (argent) that has developed in colour development, that is to say the different color developers that can not produce oxidised form with the present invention.The prior art is different from the present invention basically in this regard.

Effect of the present invention can obtain by forming at least one " PUG releasing unit ".But, also can form two or more unit.In the case, the chemical constitution of the useful group of photograph that is discharged by these unit can be identical or different.The camera function of the useful group of photograph that is discharged similarly, can be identical or different.

The coupled product that reaction by " discharge PUG compound " of the present invention and the developer of oxidised form produces is a color development, though must not be color development.But in photosensitive material of directly appreciating such as colour paper, preferred " discharging the compound of PUG " do not make coupled product color development or color development slightly.Most preferably, coupled product flows out from photosensitive material.

In the photosensitive material such as colour negative directly do not appreciated, " discharging the compound of PUG " but the coupled product color development to increase the optical density of photosensitive material.But rolling up optical density is not preferred for the printing of colour paper.The optical density of the photosensitive material that is produced by the coupled product color development of " discharge PUG compound " is preferably 0.5 or lower, and more preferably 0.3 or lower, most preferably be 0.1 or lower.

Variation for the minimum density values that causes owing to colour development particularly preferably is " compound that discharges PUG " and does not make the coupled product color development.Most preferably, coupled product is by flowing out in the photosensitive material.

Silver halide photographic sensitive material of the present invention only needs at least one to be formed on photographic layer on the carrier.Its typical example is a silver halide photographic sensitive material, and this photosensitive material has at least one by the photographic layer that a plurality of silver halide emulsion layers constitute on its carrier, and described silver halide emulsion layer has substantially the same color sensitivity, but has different light sensitivity.This photographic layer comprises a unit photographic layer, and it is to any sensitivity of blue light, green light and red light.In the multilayer silver halide colour photographic sensitive material, these unit photographic layers are provided with by the carrier side order according to red, green and blue look sensitive layer usually.But according to desirable application, this is provided with order also can be opposite, order perhaps is set different photographic layers is embedded between the layer of same hue sensitivity.Non-photographic layer can be formed between the light-sensitive silver halide layer, and as the superiors and the bottom.They can comprise for example the DIR compound and the mixed color inhibitor of colour coupler, the following stated.As a plurality of silver halide emulsion layers that constitute each unit photographic layer, the double-layer structure that high speed and low speed emulsion layer constitute preferably is set, so that descend in proper order to the carrier direction as the 1st, 121, No. 470 Deutsche Bundespatents or the 923rd, No. 045 described light sensitivity that makes of BrP.Equally, described in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541 and JP-A-62-206543, also each layer can followingly be set:

The low speed emulsion layer is formed on away from carrier one side, and the high-speed emulsion layer is formed near on carrier one side.

Particularly, according to the order of order, BH/BL/GL/GH/RH/RL or the BH/BL/GH/GL/RL/RH of the green photographic layer (GL) of the blue photographic layer (BL) of the low speed/blue photographic layer of high speed (BH)/green photographic layer of high speed (GH)/low speed/red photographic layer of the red photographic layer of high speed (RH)/low speed (RL) each layer is set by distance carrier farthest side.

In addition, as described in JP-B-55-34932, according to the order of blue photographic layer/GH/RH/GL/RL each layer is set by distance carrier farthest side.Moreover, as described in JP-A-56-25738 and JP-A-62-63936, according to the order of blue photographic layer/GL/RL/GH/RH each layer is set by distance carrier farthest side.

As described in JP-B-49-15495, three layers can followingly be set, silver halide emulsion layer with top high photographic sensitivity is the upper strata, and the silver halide emulsion layer that light sensitivity is lower than the upper strata light sensitivity is set to the middle layer, is set to lower floor and light sensitivity is lower than the silver halide emulsion layer of the light sensitivity in middle layer; That is to say that the order that three layers with different light sensitivity descend according to the light sensitivity order is towards the carrier setting.Even when the structure of layer by above-mentioned three layers when constituting with different light sensitivity, as described in JP-A-59-202464, these layers can by distance carrier farthest side according to middling speed emulsion layer/high-speed emulsion layer/low speed emulsion layer be set in sequence in to a color sensitivity the layer in.

In addition, also can adopt the order of high-speed emulsion layer/low speed emulsion layer/middling speed emulsion layer or low speed emulsion layer/middling speed emulsion layer/high-speed emulsion layer.Moreover, when forming four or more a plurality of layers, can change as mentioned above that also order being set.

For improving color reprodubility, as the 4th, 663,271,4,705,744,4,707, No. 436 United States Patent (USP), JP-A-62-160448 and JP-A-63-89850 are described, at donor layer (CL) contiguous or have the middle layer effect of the spectral sensitivity distribution different with RL with main photographic layer BL, GL near main photographic layer setting.

The silver halide that also preferably uses except that above-mentioned silver emulsion among the present invention is iodine silver bromide, silver iodochloride or iodine chlorine silver bromide, wherein comprises about 30mol% or lower silver iodide.Particularly preferred silver halide is iodine silver bromide or the iodine chlorine silver bromide that comprises about 2-10mol% silver iodide.

The silver halide particle that is included in the used photographic emulsion of the present invention's photographic material can be that those have conventional crystal person, as cube, octahedra or tetrakaidecahedron crystal, has unconventional crystal person, as ball or flat crystal, the person that perhaps has the crystal defect, as at least one twin plane, perhaps their complex form.

For particle diameter, silver halide can be that the bulky grain that about 0.2 μ m or littler fine grained or area diameter projected are about 10 μ m to the maximum is formed by particle diameter, and emulsion can be polydispersion or single emulsion that disperses.

The silver halide photographic emulsions that can be used among the present invention can be in order to the method preparation in the following document, for example " I.Emulsion preparation and types ", research open (below be abbreviated as RD) No. 17643 (in Dec, 1978), the the 22nd and 23 page, " I.Emulsion preparation and types "; And No. the 18716th, RD (in November, 1979), the 648th page; No. the 307105th, RD (in November, 1989), the 863-865 page or leaf; P.Glafkides, " Chemie et PhisiquePhotographiques ", Paul Montel, 1967; G.F.Duffin, " Photographic EmulsionChemistry ", Focal Press, 1966; And people such as V.L.Zelikman, " Making andCoating Photographic Emulsion ", Focal Press, 1964.

For example be described in the 3rd, 574,628 and 3,655, it also is preferred that single in No. 394 United States Patent (USP)s and the 1st, 413, No. 748 BrPs disperses emulsion.

Equally, length breadth ratio be about 3 or bigger platy shaped particle can be used among the present invention.

Platy shaped particle can be easily by the method preparation of describing in the following document: Gutoff, " PhotographicScience and Engineering ", the 14th volume, 248-257 page or leaf (1970); The 4th, 434,226,4,414,310,4,433,048 and 4,439, No. 520 United States Patent (USP)s and the 2nd, 112, No. 157 BrPs.

Equally, length breadth ratio be about 3 or bigger platy shaped particle be particularly preferred among the present invention.The interarea of platy shaped particle is (100) face or (111) face.Interarea is that the particle of (100) can be with the 5th, 320,938,5,264,337 and 5,292, and the method described in No. 632 United States Patent (USP)s prepares.Interarea can prepare with the method for describing among the JP-A-10-221827 (45 page of 20 row of the 38th page of 14 row-Di) for the particle of (111)." interarea is (100) " be meant its outside surface 50% or mostly be by the silver halide particle that (100) constitute account for the total projection area 50% or more.Equally, " interarea is (111) " be meant its outside surface 50% or mostly be by the silver halide particle that (111) constitute account for the total projection area 50% or more.

Crystal structure is uniformly, can have halogenic ingredient, and this composition is different between inside and outside, perhaps can be layer structure.Perhaps, silver halide can lump together by the orientation johning knot with the silver halide with different compositions, for example can combine with the compound of non-halogenated silver such as rhodanide silver or massicot.Also can use the potpourri of particle with various crystal forms.

Above-mentioned emulsion can be mainly at the surface latent image type emulsion that forms latent image on the surface of particle, form the internal latent image type emulsion of latent image and any in the surface of particle and the inner other types emulsion that forms latent image in the inside of particle.But emulsion must be egative film type emulsion.Internal latent image type emulsion can be core/shell internal latent image type emulsion of describing among the JP-A-63-264740.The method for preparing this core/shell internal latent image type emulsion is described among the JP-A-59-133542.Though the thickness of the shell of this emulsion depends on for example development conditions, it is preferably 3-40nm, more preferably 5-20nm.

Silver emulsion passes through physical ripening, chemical ripening and spectral sensitization usually before use.The adjuvant that uses in these steps is listed among No. the 17463rd, 18716 and 307105, the RD, and its relevant portion will be summarised in the following table.

In photosensitive material of the present invention, can be mixed together and use in simple layer at the mutual different two or more photosensitive silver halide emulsions of at least one properties, described character for example is particle diameter, size distribution, halogen composition, particle shape and light sensitivity thereof.

As the 4th, 082, No. 553 United States Patent (USP)s are described to have the silver halide particle on ashing surface, as the 4th, 626, No. 498 United States Patent (USP)s and described silver halide particle and the collargol with ashing interior section of JP-A-59-214852 are preferred in photosensitive silver halide emulsion layer and/or the non-basically sensitization hydrophilic colloid floor.Silver halide particle inner or surperficial ashing is meant that the exposure of photosensitive material or unexposed portion all can be by the silver halide particles of evenly develop (in the askiatic mode).The method that produces this effect is described in the 4th, 626, among No. 498 United States Patent (USP)s and the JP-A-59-214852.Form inside and can be had different halogen compositions by the silver halide of the kernel of the core of ashing/shell mould silver halide particle.Its granule interior or surface can be any in silver chloride, chlorine silver bromide, iodine silver bromide and the chlorine iodine silver bromide by the silver halide of ashing.The mean grain size of the silver halide particle of these ashing is preferably 0.01-0.75 μ m, more preferably 0.05-0.6 μ m.For the morphology of particle, can use conventional granulates and continuous polydispersion emulsion.But, the preferred single emulsion that disperses, promptly, the general assembly (TW) of silver halide particle or total number of particles at least 95% ± mean grain size 40% in.

In the present invention, preferably use non-sensitization fine grained silver halide.Non-sensitization fine grained silver halide preferably is made up of the silver halide fine grained, and this particle is insensitive during image exposure, obtaining dye image, and is not developed basically during the development step.These silver halide particles are not preferably in advance by ashing.In the fine grained silver halide, the content of silver bromide is 0-100mol%, and can comprise silver chloride and/or silver iodide if desired.The fine grained silver halide preferably comprises the silver iodide of 0.5-10mol%.The fine grain mean grain size of silver halide promptly, be equivalent to the mean value of the round diameter of projected area, is preferably 0.01-0.5 μ m, more preferably 0.02-0.2 μ m.

The fine grained silver halide can be used the method preparation identical with conventional Photoactive silver-halide.

Optical sensibilization or spectral sensitization must not carried out in the surface of silver halide particle.But, in coating solution, add before the silver halide particle, preferably to wherein adding known stabilizing agent usually, as triazole compounds, azepine indene compound, benzothiazole father-in-law compound, sulfhydryl compound or zinc compound.Can in comprising the layer of this fine grained silver halide, mix collargol.

The silver-colored coating weight of photosensitive material of the present invention is preferably 6.0g/m ²Or lower, most preferably be 4.5g/m ²Or it is lower.

The photograph adjuvant that can be used among the present invention also is described among the RD, and relevant description partly is summarised in the following table.

Additive types	RD17643	RD18716	RD307105
				1, chemical sensitizer	The 23rd page	The 648th page of right hurdle	The 866th page
2, sensitizer		The 648th page of right hurdle
				3, spectral sensitizer, the telegraphy agent	The 23-24 page or leaf	Page right hurdle, the 648th page of right hurdle-649	The 866-868 page or leaf
4, whitening agent	The 24th page	The 647th page of right hurdle	The 868th page
				5, light absorber, filter dye, ultraviolet absorber	The 25-26 page or leaf	Page left hurdle, the 649th page of right hurdle-650	The 873rd page
6, bonding agent	The 26th page	The 651st page of left hurdle	The 873-874 page or leaf

7, plastifier, lubricant	The 27th page	The 650th page of right hurdle	The 876th page
				8, coating additive, surfactant	The 26-27 page or leaf	The 650th page of right hurdle	The 875-876 page or leaf
9, antistatic agent	The 27th page	The 650th page of right hurdle	The 876-877 page or leaf
				10, opacifier			The 878-879 page or leaf

In photosensitive material of the present invention, can use various dye forming couplers, and following colour coupler is particularly preferred.

Yellow colour former: EP No.502,424A Chinese style (I) and the colour coupler of (II) representing; EP No.513, the colour coupler of 496A Chinese style (1) and (2) expression (particularly the 18th page on Y-28); EP No.568, the colour coupler of claim 1 Chinese style (I) expression of 037A; The colour coupler of the 5th, 066, No. 576 United States Patent (USP) capable formula ofs of the 1st hurdle 45-55 (I) expression; The colour coupler of the 0008th section formula of (I) expression of JP-A-4-274425; EP No.498, the colour coupler of describing in the 40th page of claim 1 of 381A1 (particularly the 18th page on D-35); EP No.447, the colour coupler of the 4th page of following formula (Y) of 969A1 expression (the particularly Y-54 on the 17th page Y-1 and the 41st page); And B4, the colour coupler (particularly II-17 and the II-19 in 17 hurdles, and the II-24 in the 19th hurdle) of the capable Chinese style of the 7th hurdle 36-58 (II)-(IV) expression of 476, No. 219 United States Patent (USP)s.

Magenta colour coupler: JP-A-3-39737L57 (the 11st page, the hurdle, bottom right), L-68 (the 12nd page, the hurdle, bottom right) and L-77 (the 13rd page, the hurdle, bottom right); EP No.456, [A-4]-63 (the 134th page) in 257 and [A-4]-73 and [A-4]-75 (the 139th page); EP No.486, M-4 and M-6 (the 26th page) and M-7 (the 27th page) in 965; EP No.571, the M-45 (the 19th page) in 959; (M-1) among the JP-A-5-204106 (the 6th page); And the M-22 in the 0237th section of JP-A-4-362631.

Cyan colour coupler: the CX-1 among the JP-A-4-204843, CX-3, CX-4, CX-5, CX-11, CX-12, CX-14 and CX-15 (14-16 page or leaf); C-7 among the JP-A-4-43345 and C-10 (the 35th page), C-34 and C-35 (the 37th page) and (I-1) and (I-17) (the 42nd and 43 page); And the claim 1 of JP-A-6-67385 formula of (Ia) and (Ib) expression colour coupler.

Polymkeric substance colour coupler: P-1 among the JP-A-2-44345 and P-5 (the 11st page).

Be used to form and have suitably the colour coupler of diffusible coloured dyestuff and preferably be described in the 4th, 366, No. 237 United States Patent (USP)s, GB No.2,125,570, EP No.96,873 B and DE No.3, those in 234,533.

Be used to proofread and correct coloured dyestuff unnecessary absorption colour coupler preferably: EP No.456, the formula of describing in the 5th page of 257A1 (CI), (CII), (CIII) and (CIV) cyan colour coupler that has yellow of expression; EP No.456, magenta colour coupler ExM-7 (the 202nd page), the Ex-1 (the 249th page) and the Ex-7 (the 251st page) that have yellow that describe among the 257A1; That describes in the 4th, 833, No. 069 United States Patent (USP) has pinkish red cyan colour coupler CC-9 (hurdle 8) and a CC-13 (hurdle 10); (2) of the 4th, 837, No. 136 United States Patent (USP)s (hurdle 8); And the colourless covering colour coupler (the particularly examples of compounds on the 36-45 page or leaf) of claim 1 Chinese style (A) of WO No.92/11575 expression.

The example of compound (comprising colour coupler) that discharges the useful compound residue of taking a picture with the reaction of the developer of oxidised form thus is as follows.Development restrainer discharges compound: EP No.378, the 11st page of following formula (I) of 236A1, (II), (III) and the compound (IV) represented (the particularly T-158 on the T-144 on the T-131 on the T-113 on the T-104 on the T-101 on the 30th page, the 31st page, the 36th page, the 45th page, the 51st page and the 58th page); EP No.436, the compound of the 7th page of following formula (I) of 938A2 expression (particularly the 51st page on D-49); EP No.568, the compound of 037 A Chinese style (1) expression (particularly the 11st page on (23)); And EP No.440, the 5th and 6 page of following formula (I) of 195A2, (II) and (III) compound of expression (particularly the 29th page on I-(1)).Bleach boosters discharges compound: EP No.310, the compound that the 5th page of following formula (I) of 125A2 and (I ') represent (particularly the 61st page on (60) and (61)); And the compound of the claim 1 of JP-A-6-59411 Chinese style (I) expression (particularly the 7th page on (7)).Aglucon discharges compound: the compound that LIG-X represents in the claim 1 of the 4th, 555, No. 478 United States Patent (USP)s (the particularly compound of hurdle 12 21-41 in capable).Leuco dye discharges compound: the compound 1-6 in the 3-8 hurdle of the 4th, 749, No. 641 United States Patent (USP)s.Fluorescent dye discharges compound: the compound that COUP-DYE represents in the claim 1 of the 4th, 774, No. 181 United States Patent (USP)s (the particularly compound 1-11 in the 7-10 hurdle).Image promoter or fogging agent discharge compound: the compound (particularly (I-22) in the 25th hurdle) of the 3rd hurdle Chinese style (1) of the 4th, 656, No. 123 United States Patent (USP)s, (2) and (3) expression; And EP No.450, the ExZK-2 during the 75th page of 36-38 of 637A2 is capable.Discharge the compound that only when division, just plays the group of dyestuff effect: the compound (the particularly Y-1 to Y-19 in the 25-36 hurdle) of claim 1 Chinese style (I) expression of the 4th, 857, No. 447 United States Patent (USP)s.

The preferred example of the adjuvant except that colour coupler is as follows.

The dispersion medium of oil-soluble organic compound: the P-3 among the JP-A-62-215272, P-5, P-16, P-19, P-25, P-30, P-42, P-49, P-54, P-55, P-66, P-81, P-85, P-86 and P-93 (140-144 page or leaf).The dipping latex of oil-soluble organic compound: the latex of describing in the 4th, 199, No. 363 United States Patent (USP)s.Developer oxidation product scavenger: the 4th, 978, the compound (the particularly I-(1) in the 4th and 5 hurdles, I-(2), I-(6) and I-(12)) of the capable Chinese style of the 2nd hurdle 54-62 (I) of No. 606 United States Patent (USP)s expression; And the capable compound (particularly compound 1 in the 3rd hurdle) of the 2nd hurdle 5-10 in the 4th, 923, No. 787 United States Patent (USP)s.Pollution inhibitor: the 4th page of capable Chinese style of 30-33 (I)-(III), particularly I-47, I-72, III-1 and the III-27 (24-48 page or leaf) of EP No.298321A.Fade inhibitor: EP No.298, A-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 (69-118 page or leaf) among the 321A1; II-1 to III-23, particularly III-10 in the 5th, 112, No. 444 United States Patent (USP) 25-38 hurdles; EP No.471,8-12 page or leaf I-1 to III-4, particularly II-2 among the 347A1; And A-1 to A-48, particularly A-39 and A-42 in the 32-40 hurdle of the 5th, 139, No. 931 United States Patent (USP)s.Reduce the material of the use amount of color reinforcing agent or mixed color inhibitor: EP No.411, I-1 to II-15 in the 5-24 page or leaf of 324A, particularly I-46.Formalin scavenger: EP No.477, SCV-1 to SCV-28 in the 24-29 page or leaf of 932A, particularly SCV-8.H-1, H-4, H-6, H-8 and H-14 in the 17th page of film rigidizer: JP-A-1-214845; The compound (H-1 to H-54) of 13-23 hurdle Chinese style (VII)-(XII) expression of the 4th, 618, No. 573 United States Patent (USP)s; The compound (H-1 to H-76), particularly H-14 of the 8th page of hurdle, bottom right Chinese style (6) expression of JP-A-2-214852; And the compound of describing in the claim 1 of the 3rd, 325, No. 287 United States Patent (USP)s.Development restrainer precursor: the P-24 among the JP-A-62-168139, P-37 and P-39 (the 6th and 7 page); And 28 and 29 in the compound, particularly the 7th hurdle of the description of the claim 1 of the 5th, 019, No. 492 United States Patent (USP)s.Antiseptic and mildewproof agent: I-1 to III-43, particularly II-1, II-9, II-10, II-18 and II-25 in the 3-15 hurdle of the 4th, 923, No. 790 United States Patent (USP)s.Stabilizing agent and antifoggant: in the 6-16 hurdle of the 4th, 923, No. 793 United States Patent (USP)s I-1 to (14), particularly I-1, I-60, (2) and (13); And compound 1-65 in the 25-32 hurdle of the 4th, 952, No. 483 United States Patent (USP)s, particularly compound 36.Chemical sensitizer: compound 50 among triphenylphosphine, selenide and the JP-A-5-40324.Dyestuff: the a-1 to b-20 among the JP-A-3-156450 on the 15-18 page or leaf, particularly a-1, a-12, a-18, a-27, a-35, a-36 and b-5, and the V-1 to V-23 on the 27-29 page or leaf, particularly V-1; EP No.445, F-I-1 to F-II-43 on the 33-55 page or leaf of 627A, particularly F-I-11 and F-II-18; EP No.457, III-1 to III-36 on the 17-28 page or leaf of 153A, particularly III-1 and III-3; Dyestuff-1 is to the crystallite dispersion of dyestuff-124 in the 8-26 page or leaf of WO No.88/04794; EP No.319, compound 1-22 on the 6-11 page or leaf of 999A, particularly compound 1; EP No.519, the Compound D-1 of 306A Chinese style (1)-(3) expression is to D-87 (3-28 page or leaf); The compound 1-22 (3-10 hurdle) of the 4th, 268, No. 622 United States Patent (USP) formula ofs (I) expression; And compound (1)-(31) (2-9 hurdle) of the 4th, 923, No. 788 United States Patent (USP) Chinese styles (I) expression.UV absorbing agent: the compound (18b)-(18r) and the 101-427 (6-9 page or leaf) of JP-A-46-3335 Chinese style (1) expression; EP No.520, the compound H BT-1 to HBT-10 (the 14th page) of compound (3)-(66) (10-44 page or leaf) of 938A Chinese style (I) expression and formula (III) expression; And EP No.521, compound (1)-(31) (2-9 hurdle) of 823A Chinese style (1) expression.

The useful compound of photograph of the present invention can be applied on the various color sensitive materials, as is used for the colour negative film of common purpose or film, the color reverse film that is used for magic lantern and TV, colour paper, colour positive and colour reversal photographic paper.In addition, photographic material of the present invention is suitable for having as JP-B-32615 and the described film unit that has camera lens of real fair 3-39784.

The carrier that can suitably be used for the present invention for example is described in the 28th page of No. the 17643rd, RD; Page left hurdle, No. 18716 the 647th page of right hurdle to 648 of RD; And among the 879th page of No. the 307105th, the RD.

In photosensitive material of the present invention, be preferably 28 μ m or lower at total film thickness with all the hydrophilic colloid layers on the emulsion layer side, 23 μ m or lower more preferably, 18 μ m or lower more preferably still, and most preferably be 16 μ m or lower.Film swelling speed T _1/2Be preferably 30 seconds or lower, more preferably 20 seconds or lower.Film swelling speed T _1/2As give a definition: when saturated thickness for flushing is reached after 3 minutes 15 seconds in colour developing solution under 30 ℃ maximum swelling thickness 90% the time, thickness reaches the needed time of 1/2 saturated thickness.Thickness is meant the value that records (2 days) under the wet condition of 25 ℃ and 55% relative humidity.Film swelling speed T _1/2Can measure by using swelling instrument people such as (, Photogr.Sci.Eng., the 19th volume, 124-129 page or leaf) A.Green.Film swelling speed T ₁₂Can be by in as the gelatin of bonding agent, adding the film rigidizer or regulating by the aging condition that changes after being coated with.The swelling rate is preferably 150-400%.The available maximum swelling thickness of measuring under these conditions of swelling rate calculates according to following formula:

(maximum swelling thickness-thickness)/thickness

In photosensitive material of the present invention, preferably on opposition side, form hydrophilic colloid layer (being called " black layer ") with emulsion layer one side, its total dry film thickness is 2-20 μ m.Bottom preferably comprises above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, film rigidizer, bonding agent, plastifier, lubricant, coating additive and surfactant.The swelling rate of bottom is preferably 150-500%.

Photosensitive material according to the present invention can be used on the conventional method of describing among the 880th and 881 page of No. the 307105th, the 28th and 29 page of No. the 17643rd, above-mentioned RD, No. 18716 the 651st page of L-R hurdle of RD and the RD and develops.

Below use description to the color negative film processing solution among the present invention.

Can walk to the 14th row listed compound in the 11st page of hurdle, lower-left on the 9th page of upper right hurdle the 1st that is used for colour developing solution use JP-A-4-121739 of the present invention.The preferred color developer that is used for getting express developed especially for example is 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.

The preferable amount of these color developers is every liter of (hereinafter referred to as " L ") colour developing solution 0.01-0.08mol, 0.015-0.06mol more preferably, and most preferably be 0.02-0.05mol.The additional liquid of colour developing solution preferably comprise be equivalent to above-mentioned concentration 1.1-3 doubly, more preferably 1.3-2.5 color developer doubly.

Azanol can be widely used as the antiseptic of colour developing solution.When the stronger antiseptic property of needs, the preferred hydroxylamine derivative that uses with substituting group such as alkyl, hydroxy alkyl, sulfo group alkyl and carboxyalkyl, its example comprises N, N-two (sulfo group ethyl) azanol, monomethyl azanol, dimethyl hydroxylamine, single ethyl azanol, diethyl hydroxylamine and N, N-two (carboxy ethyl) azanol.In these compounds, N most preferably, N-two (sulfo group ethyl) azanol.Though these compounds can be used in combination with azanol, preferably use a kind of or at least two kinds of above-claimed cpds replacement azanols.

The preferable amount of these antiseptics is every liter of colour developing solution 0.02-0.2mol, 0.03-0.15mol more preferably, and most preferably be 0.04-0.1mol.The amount of the antiseptic that additional liquid comprised of colour developing solution be equivalent to color developer mother liquor (can,douche solution) concentration 1.1-3 doubly.

Use sulphite to prevent agent as the tarring of the color developer of oxidised form in the colour developing solution.The preferable amount of each sulphite in colour developing solution is every liter of 0.01-0.05mol, 0.02-0.04mol more preferably, and the 1.1-3 that the consumption in replenishing liquid preferably is equivalent to above-mentioned concentration is doubly.

The pH value of colour developing solution is preferred in the scope of 9.8-11.0, more preferably 10.0-10.5.The pH value of replenishing liquid preferably sets and is exceeding 0.1-1.0 than above-mentioned value.For stablizing above-mentioned pH value, can use conventional damping fluid, as carbonate, phosphate, sulfosalicylate and borate.

Though the consumption of the additional liquid of colour developing solution is preferably every square metre of photosensitive material with 80-1300 milliliter (below be also referred to as " ml "), wishes that from the angle that reduces environmental pollution this amount is littler.Particularly, the amount of additional liquid is 80-600ml more preferably, most preferably is 80-400ml.

Though the bromide ion concentration of colour developing solution is usually at 0.01-0.06mol/L, preferred above-mentioned concentration is set at 0.015-0.03mol/L, to suppress ashing when keeping light sensitivity, improves resolution and better granularity thus.When the concentration of bromide ion was set in the above-mentioned scope, additional liquid preferably comprised the bromide ion of the concentration that calculates with following formula.But, when C when negative, preferably in replenishing liquid, do not comprise bromide ion.

C＝A-W/V

Wherein: C is the concentration (mol/L) that colour development replenishes bromide ion in the liquid,

A is the concentration (mol/L) that colour development replenishes target bromide ion in the liquid,

W is for having 1m when photosensitive material ²Colour development the time, leach into the amount (mol) of the bromide ion the colour developing solution from photosensitive material, and

V is every m ²The colour development that photosensitive material provides replenishes the amount (L) of liquid.

When the amount of replenishing liquid reduces or sets high bromide ion concentration, preferably use following development accelerant for strengthening light sensitivity: the pyrazolidone compounds, as 1-phenyl-3-pyrazolidone and 1-phenyl-2-methyl-2-methylol-3-pyrazolidone, and sulfide compound, as 3,6-two sulphur-1, the 8-ethohexadiol.

The 4th page of hurdle, lower-left the 16th of JP-A-4-125558 can be walked to the washing fluid that compound described in the 7th page of hurdle, lower-left the 6th row and washing condition are applied to the present invention with bleaching power.

The preferred bleaching agent that uses has the redox-potential of 150mV at least.Particularly, its suitable example is the description among JP-A-5-72694 and the JP-A-5-173312, and its specially suitable example is 1, the iron complex salt of embodiment 1 compound of listing on the 7th page of 3-diaminopropanetetraacetic acid and JP-A-5-173312.

For improving the biodegradability of bleaching agent, preferably use JP-A-4-251845, JP-A-4-268552, EP No.588,289, EP No.591,934 and JP-A-6-208213 in the iron complex salt of listed compound as bleaching agent.The concentration of above-mentioned bleaching agent is preferably every liter of solution 0.05-0.3mol with bleaching power, particularly preferably is design and makes every liter of 0.1-0.15mol, is used to reduce the pressure to environment.When the solution with bleaching power is bleaching liquid, preferably mix bromide therein, the amount of this bromide is 0.2-1mol, more preferably 0.3-0.8mol is every liter.

Be incorporated in each component calculating concentration as follows basically in the additional liquid of solution with bleaching power.This can make the concentration of mother liquor keep constant.

CR＝CT×(V1+V2)/V1+CP

Wherein: CR is each component concentrations in the additional liquid,

CT is a component concentrations in the mother liquor (can,douche solution),

The concentration of component that consumes between CP carboxyl flush period,

V1 is the amount (ml) of the additional liquid with bleaching power that provides of every square metre of photosensitive material, and

V2 is the amount (ml) of carrying out in the bathing in advance of 1 square metre of photosensitive material.

In addition, preferably in bleaching liquid, mix the pH buffering agent, particularly preferably be and mix a spot of carbon acid, succinic acid, maleic acid, malonic acid, glutaric acid and hexane diacid.Also preferably use the conventional bleaching promoter of in No. the 17129th, JP-A-53-95630, RD and the 3rd, 893, No. 858 United States Patent (USP)s, listing.

Every square metre of photosensitive material, the preferred addition amount of bleaching liquid are 50-1000ml, more preferably 80-500ml, and 100-300ml bleaching liquid most preferably.In addition, bleaching liquid is preferably through aeration.

The 7th page of hurdle, lower-left the 10th can using JP-A-4-125558 in the washing fluid with photographic fixing ability walks to the 8th page of hurdle, bottom right the 19th described compound of row and washing condition.

For strengthening fixation rate and keeping quality, particularly preferably in compound independent in the washing fluid with photographic fixing ability or that combination is mixed the general formula (I) of JP-A-6-301169 and (II) represented.In addition, from strengthen conservatory angle, preferably use list among the JP-A-1-224762 to toluenesulfinate and sulfinate.

Though say at solution or have that to mix ammonium ion the solution of photographic fixing ability be preferred from strengthening bleaching power, see preferably that from the angle of minimum contaminated environment amount with ammonium reduces or do not use with bleaching power.

In bleaching, bleaching-photographic fixing and photographic fixing step, especially preferably carry out the injection described in the JP-A-1-309059 and stir.

The amount of the additional liquid that provides in bleaching-photographic fixing or photographic fixing step is every square metre of photosensitive material 100-1000ml, preferred 150-700ml, more preferably 200-600ml.

Preferably any various silver recovery unit is set in bleaching-photographic fixing or photographic fixing step, thus cash register back and forth with online or offline mode.On-line equipment can make the silver concentration of rinse solution reduce, and makes and can reduce the amount of replenishing liquid.It also is suitable carrying out off-line silver recovery and again residual solution being used for replenishing liquid.

Bleaching-photographic fixing and photographic fixing step can be made of a plurality of can,douches respectively.Preferably, described jar has the pouring fluid catheter, and uses multistage convection system.From the angle that the size with developing machine balances each other, the cascade structure of 2 jars is normally effective.The ratio of the flush time in the flush time in the prime jar and the back level jar is preferably 0.5: 1-1: 0.5, more preferably 0.8: 1-1: 0.8.

From strengthening conservatory angle, preferably in bleaching-photographic fixing and stop bath, there is free sequestrant, it does not form any metal complex.Preferably use the biodegradable cheating agent relevant as described sequestrant with bleaching liquid.

Preferably in washing and stabilizing step, use the 12nd page of hurdle, bottom right the 6th of JP-A-4-125558 to walk to the 13rd page of hurdle, bottom right the 16th description in capable.Particularly; for stabilizing solution; angle from the protection working environment; preferably use EP No.504; 609 and 519; the N-methylol azole compounds of describing among pyrrole radicals methyl amine of describing in 190 and the JP-A-4-362943 replaces formaldehyde, and the magenta colour coupler dimerization is the surfactant solution that does not comprise image stabilizing agent such as formaldehyde.

In addition, the stabilizing solution of describing among the JP-A-6-289559 is preferred for reducing refuse to being applied in the bonding of the pinkish red recording layer on the photosensitive material.

From guaranteeing washing and stabilization function and reduce waste liquid amount and help point of view of environment protection that the magnitude of recruitment of washing and stabilizing solution is preferably every square metre of photosensitive material 80-1000ml, more preferably 100-500ml, and 150-300ml most preferably.When washing with above-mentioned magnitude of recruitment, for preventing the breeding of bacterium and mould, preferred known mildewproof agent such as the thiabenzazole, 1 of using, 2-benzisothiazole-3-ketone and 5-chloro-2-methyl isothiazoline-3-ketone, microbiotic such as gentamicin, and by for example using ion exchange resin and by the water of deionization.It is more effective than using separately to be used in combination deionized water, mildewproof agent and microbiotic.

For the solution that is placed in washing or the stable flow container, also preferably reduce magnitude of recruitment by carrying out handling as the described reverse osmotic membrane of JP-A-3-46652, JP-A-3-53246, JP-A-3-55542, JP-A-3-121448 and JP-A-3-126030.The preferred low pressure reverse osmotic membrane that uses in above-mentioned processing.

In flushing of the present invention, particularly preferably be, proofread and correct as the disclosed evaporation of carrying out washing fluid among JIII (Japan Institute of Inventionand Innovation) the Journal of Technical Disclosure No.94-4992.Particularly, preferable methods is to use according to the formula on its 2nd page 1 to use the information of the temperature and humidity of relevant developing machine device context to implement to proofread and correct.Be used for evaporating the water of correction preferably by additional jar of collection of washing.In the case, preferably use deionized water as the washing supplementing water.

Preferred the 3rd page of right hurdle the 15th of the open magazine of above-mentioned technology that use in the present invention walks to the 4th page of described irrigation of left hurdle the 32nd row.Preferred use wherein the 3rd page of capable described film developer of right hurdle 22-28 as used developing machine in the present invention's flushing.

Carry out the object lesson of the irrigation, automatic processing machine and the evaporation correcting scheme that preferably use when of the present invention and see that the 5th page of right hurdle the 11st of the open magazine of above-mentioned technology walks to the 7th page of right hurdle last column.

The irrigation that is used for the present invention's photographic material can provide in any form, liquid agent or concentrating agents, particle, powder, tablet, paste or the emulsion of same concentrations during for example with use.For example, JP-A-63-17453 discloses the liquid agent that is stored in the low oxygen permeability container, JP-A-4-19655 and JP-A-4-23078 disclose vacuum-packed powder, JP-A-4-221951 discloses the particle that comprises water-soluble polymers, JP-A-51-61837 and JP-A-6-102628 disclose tablet, and the open 57-5000485 of PCT country has disclosed paste.Though can suitably use above-mentioned any, from the easiness of using, the preferred liquid that has same concentrations when using that uses.

The container that is used for storing above-mentioned irrigation for example is made of any of tygon, polypropylene, Polyvinylchloride, polyethylene terephthalate and nylon or their potpourri.Can select according to needed oxygen permeability.The material of low oxygen permeability is preferably used as the liquid such as the colour developing solution of easy oxidation, and this material for example is the compound substance of polyethylene terephthalate or tygon and nylon.Preferably, these materials are used for container with the thickness of 500-1500 μ m respectively, make that whole oxygen permeability is 20ml/m ²24hrsatm or lower.

Below description is applicable to the washing fluid that is used for color reverse film of the present invention.

For the color reverse film flushing, the preferred use the following specifically describes: the PublicTechnology No.6 (on April 1st, 1991) that Aztek publishes, the 1st page the 5th is walked to the 10th page of the 5th row, and 24 page of the 2nd row of the 15th page of eighth row to the.In the color reverse film flushing, in regulating bath and final the bath, add the image stabilizing agent.The example of suitable image stabilizing agent comprises formalin, sodium formaldehydebisulfite and N-methylol azoles.From the angle of working environment, sodium formaldehydebisulfite and N-methylol azoles are preferred.In N-methylol azoles, N-methylol triazole is particularly preferred.Also preferably be applicable to the flushing of color reverse film about colour developing solution, bleaching liquid, stop bath and the washings of colour negative flushing.

Can use the irrigation E-6 that obtains by Eastman Kodak and by Fuji Photo Film Co., the irrigation CR-56 that Ltd. obtains is as the preferred color reverse film irrigation that comprises above-mentioned feature.

The used colour photographic sensitive material of the present invention is suitable as the negative film that is used for advanced photographic system (hereinafter referred to as " AP system ").For example, film is processed into the AP system format, and in the magazine with its specific use of packing into, as Fuji Photo Film Co., NEXIA A, NEXIA F that Ltd. (hereinafter referred to as " FujiFilm ") makes or NEXIA H (order is ISO200/100/400).This magazine film that is used for the AP system is put into the Epion series that the camera that is used for the AP system such as Fuji Film make, and for example Epion 300Z is used for actual use then.And colour photographic sensitive material of the present invention is suitable for being equipped with the film of camera lens, as the Fuji Color Uturundesu Super Slim of Fuji Film manufacturing.

Thus the film of Zhao Xianging in the microscale experiment chamber system by the following steps printing:

(1) accepts (accept exposed magazine film) by client;

(2) take (film being transferred to the middle magazine that is used for developing from above-mentioned magazine) apart;

(3) film development;

(4) back contact (negative film that develops is back in the original magazine);

(5) printing (on colour paper, printing three types of photos of C/H/P and index photo (the Super FA8 that preferred Fuji Film makes) continuously automatically); Then

(6) proofread and send (, sending photo then) with ID number check and correction magazine and index photo.

Said system is Fuji Film Minilabo Champion Super FA-298/FA-278/FA-258/FA-238 or Fuji Film Digital Labo System Frontier preferably.The film procnssing machine of MinilaboChampion for example is FP922AL/FP562B/FP562BL, AL/FP362B/FP3622B, AL, and the flushing chemicals of recommending is Fuji Color Just It CN-16L or CN-16Q.The printingout developing machine for example is PP3008AR/PP3008A/PP1828AR/PP1828A/PP1258AR/PP1258A/PP728 AR/PP728A, and the flushing chemicals of recommending is FujiColor Just It CP-47L or CP-40FAII.In the Frontier system, use scanning and image processor SP-1000 and laser printer and paper processor LP-1000P or laser printer L-1000W.Preferred Fuji Film DT200/DT100 and the AT200/AT100 of using is respectively as the back contactor in the dismounting machine of taking step apart and the back contact procedure.In addition, Aladdin 1000 can directly export numerical information to floppy disk, Zip dish or export on the CD by the CD read write line.

The AP system can appreciate with the fast music system (photo joy system) of taking a picture, and its central location is Fuji Film digitized video station Aladin 1000.For example, the AP system magazine film that has developed directly is placed among the Aladdin 1000, or, can easily process and edit resulting digital image data then with wherein 35mm Film scanner FE-550 or tack scanner PE-550 input negative film, positive or photo image information.The gained data can be exported in the mode of photo with present laboratory equipment, for example by based on the digital color printer NC-550AL of the hot color printing system of photo fixed or based on the Pictrography 3000 of laser explosure thermal development transfer system or pass through film unit.

On the other hand, if at home, photo player (photoplayer) AP-1 that the AP system magazine film that only will develop is put into Fuji Film manufacturing can appreciate photo at TV.Put it among the photo scanning instrument AS-1 that Fuji Film makes and also at full speed image information is imported in the personal computer serially.In addition, the Photovision FV-10/FV-5 of available Fuji Film manufacturing is with in film, photo or the stereo article input personal computer.Moreover, use FujiFilm Application Soft Photofactory on personal computer, to carry out various processing, appreciate the image information that is recorded in floppy disk, Zip dish, CD-R or the hard disk thus.The digital color printer NC-2/NC-2D based on the hot color printing system of photograph fixed that is made by Fuji Film is suitable for the photo by the personal computer outputting high quality.

The preferred storage of using Fuji Color Pocket Album AP-5 Pop L, Ap-1 Pop L or Ap-1Pop KG or Cartridge File16 to be used for the AP system film that develops.

Below will the present invention be described in more detail by embodiment.

Embodiment 1

In embodiment 1, be the situation of bleach boosters as the compound of the useful group of photograph with describing release.

Preparation sample 101

Make following photosensitive material.That notes is the following ashing emulsion Z that is manufactured in the ground floor.The manufacturing of ashing emulsion Z

Preparation emulsion Z

The 1% inertia aqueous gelatin solution of 2.0L is remained under 40 ℃, add the gold chloride of 0.1g then, and stirring and dissolving.Add 0.6mol potassium bromide, 0.006mol potassium iodide and 0.6mol silver nitrate by two gunitees flow velocity with same fixed in 4 minutes time.Add 0.1g gold chloride and 0.02mol NaOH, stir the gained material then.Afterwards, add the 0.1mol potassium bromide, obtain the particle that mean grain size is 0.08 μ m.After washing these particles with water, add 100g inertia gelatin, make emulsion Z thus with surperficial ashing nuclear with discrete particles.

The film carrier of bottom coating cellulose triacetate is with a plurality of layers of coating with following composition, to make the sample 101 as the multi layer colour photosensitive material.

The composition of photographic layer

The used following classification of main material in single layer:

ExC: cyan colour coupler UV: ultraviolet absorber

ExM: magenta colour coupler HBS: high boiling organic solvent

ExY: yellow colour former H: gelatin hardener

ExS: sensitizing dye

The numeral of corresponding each component is with g/m ²Coating weight for unit.The coating weight of silver halide is shown with the scale of silver.The coating weight of each sensitizing dye is unit representation with the mol number of every mol silver halide in the identical layer.

Sample 101

Ground floor (the first anti-halation layer)

The black collargol	Silver 0.155
		Ashing 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

The second layer (the second anti-halation layer)

The black collargol	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

The 3rd layer (middle layer)

Iodine silver bromide emulsion O	0.020
		ExC-2	0.022
Polyethyl acrylate latex	0.085
		Gelatin	0.294

The 4th layer (the low sensitive emulsion layer that rapidly becomes popular)

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

Layer 5 (in rapidly become popular sensitive emulsion layer)

Iodine silver bromide emulsion B	Silver 0.30
		Iodine silver bromide emulsion C	Silver 0.60
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

Layer 6 (height rapidly become popular sensitive 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

Layer 7 (middle layer)

Cpd-1	0.012
		Solid disperse dye ExF-4	0.030
HBS-1	0.050
		Polyethyl acrylate latex	0.83
Gelatin	0.84

The 8th layer (layer of intermediate imagery effect is provided to red photographic 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

The 9th layer (the green sensitive emulsion layer of low speed)

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

Iodine silver bromide emulsion H	Silver 0.38
		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

The tenth layer (the green sensitive emulsion layer of middling speed)

Iodine silver bromide emulsion I	Silver 0.60
		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 floor (the green sensitive emulsion layer of high speed)

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
		Polyethyl acrylate latex	0.099
Gelatin	1.11

Floor 12 (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 dyes ExF-7	0.010
HBS-1	0.082
		Gelatin	1.057

The 13 layer (the blue sensitive emulsion layer of low speed)

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

The 14 layer (the blue sensitive emulsion layer of high speed)

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 15 layer (first protective seam)

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

The 16 layer (second protective seam)

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

S-1	0.20
		Gelatin	0.75

Except that said components, for improving storage stability, handlability, resistance to pressure, antibiotic property and mildew resistance, antistatic behaviour and coating character, single layer can comprise W-1 to W-5, B-4 to B-6, F-1 to F-18, molysite, lead salt, golden salt, platinum salt, palladium salt, iridium salt, ruthenium salt and rhodium salt.In addition, with the score of every mole of silver halide not to the 8th and the coating solution of eleventh floor in add the calcium 8.5 * 10 of calcium nitrate aqueous solution form ^-3G to 7.9 * 10 ^-3G prepares sample thus.

Following table 1 shows AgI content, particle size, surperficial content of iodine of the emulsion of abridging among this embodiment etc.The surface content of iodine can be following by using XPS to check.In 1 * 10Torr or lower vacuum, each sample is cooled to-115 ℃, excites MgK α with the x-ray source voltage of 8kV and the X ray electric current of 20mA then, measure Ag3d5/2, Br3d and I3d5/2 electronics thus.Measure the global density at peak with the light sensitivity factor correction.Can calculate surperficial content of iodine by these density ratios.

Table 1

The emulsion title	Average iodine content (mol%)	The variation factor that iodine distributes between relevant particle	Mean grain size (being equivalent to spherical diameter μ m)	The variation factor (%) that is equivalent to spherical diameter	Area diameter projected (being equivalent to round diameter, μ m)	The diameter/thickness ratio	Surface content of iodine (mol%)	Particle shape
									A	3.9	20	0.37	19	0.40	2.7	2.3	Platy shaped particle
B	5.1	17	0.52	21	0.67	5.2	3.5	Platy shaped particle
									C	7.0	18	0.86	22	1.27	5.9	5.2	Platy shaped particle
D	4.2	17	1.00	18	1.53	6.5	2.8	Platy shaped particle
									E	7.2	22	0.87	22	1.27	5.7	5.3	Platy shaped particle
F	2.6	18	0.28	19	0.28	1.3	1.7	Platy shaped particle
									G	4.0	17	0.43	19	0.58	3.3	2.3	Platy shaped particle
H	5.3	18	0.52	17	0.79	6.5	4.7	Platy shaped particle
									I	5.5	16	0.73	15	1.03	5.5	3.1	Platy shaped particle
J	7.2	19	0.93	18	1.45	5.5	5.4	Platy shaped particle
									K	1.7	18	0.40	16	0.52	6.0	2.1	Platy shaped particle
L	8.7	22	0.64	18	0.86	6.3	5.8	Platy shaped particle
									M	7.0	20	0.51	19	0.82	5.0	4.9	Platy shaped particle
N	6.5	22	1.07	24	1.52	7.3	3.2	Platy shaped particle
									O	1.0	-	0.07	-	0.07	1.0	-	Homogeneous texture
P	0.9	-	0.07	-	0.07	1.0	-	Homogeneous texture

In table 1:

(1) emulsion L-O carries out reduction sensitization with thiourea dioxide and thiosulfonic acid according to the embodiment of JP-A-2-191938 during preparation of granules.

(2) emulsion A-O carries out golden sensitizing, sulphur sensitizing and selenium sensitizing according to the embodiment of JP-A-3-237450 in the presence of spectral sensitizing dye described in the single photographic layer and sodium thiocyanate.

(3) prepare platy shaped particle according to JP-A-1-158426 with low molecular weight gelatine.

(4) when using high-voltage electron microscope, in platy shaped particle, observe as the described dislocation line of JP-A-3-237450.

The preparation of the dispersion of organic solid disperse dyes

Disperse ExF-2 in order to following method.That is to say, in the pot mill of 700ml, put into the 5% pair of Octylphenoxy Ethoxyethane sulfonic acid soda water solution of water, 3ml of 21.7ml and 5% pair of Octylphenoxy polyoxyethylene ether (degree of polymerization 10) aqueous solution of 0.5g, in this mill, add dyestuff ExF-2 and the 500ml zirconia ball (diameter 1mm) of 5.0g then.Content disperseed 2 hours.This dispersion prepares by the BO type vibromill that uses Chuo Koki K.K. to make.From mill, take out dispersion, be added into then in 12.5% aqueous gelatin solution of 8g.Filter out zirconia ball, obtain the gelatin dispersion of dyestuff.The mean grain size of thin dye granule is 0.44 μ m.

According to above identical method, make solid dispersions ExF-3, ExF-4 and ExF-6.The mean grain size of these thin dye granules is respectively 0.24,0.45 and 0.52 μ m.With EP 549, the described microdeposit dispersion method of the embodiment of 489A is disperseed ExF-5.Its mean grain size is 0.06 μ m.

In order to following method dispersing solid dispersion ExF-8.

In the moist cake of ExF-8 that water and the W-2 of 70g is added on 1400g, this cake comprises 30% water, stirs the gained material then, forms concentration and be 30% ExF-8 slurries.Next, with the 1700ml mean grain size be the ULTRAVISO MILL (UVM-2) of the zirconia ball filling Imex K.K. manufacturing of 0.5mm.Make above-mentioned slurries by passing through in this mill, ground these slurries thus 8 hours, the circumferential speed of this mill is about 10m/sec, and loading is 0.5L/min.

The compound that is used to form each layer is as follows.

HBS-1 tricresyl phosphate cresyl ester

HBS-2 phthalic acid di-n-butyl ester

The HBS-4 tri-2-ethylhexyl phosphate

X/y=10/90 (weight ratio) mean molecular weight: about 35,000

X/y=40/60 (weight ratio) mean molecular weight: about 20,000

Mean molecular weight: about 750,000

X/y=70/30 (weight ratio) mean molecular weight: about 17,000

Mean molecular weight: about 10,000

The manufacturing of sample 102

According to the method perparation of specimen 102 identical, but replace ExC-1 and ExC-3 in the ground floor with equimolar compound (A-21) with sample 101 among the embodiment 1.

The manufacturing of sample 103-105

According to the method perparation of specimen 103-105 identical, but replace compound (A-21) with equimolar compound as shown in table 2 with sample 102.

The manufacturing of sample 106

According to the method perparation of specimen 106 identical, but compound in the ground floor (A-21) and ashing emulsion Z are moved on in the 4th layer with sample 102.

The manufacturing of sample 107

According to the method perparation of specimen 107 identical, but compound in the ground floor (A-21) and ashing emulsion Z are moved on in the 4th layer with sample 103.

The manufacturing of sample 108

According to the method perparation of specimen 108 identical, but the compound in the ground floor (A-21) is moved on in the second layer with sample 102.In this sample, " compound that discharges PUG " (A-21) coating of the contiguous layer that wherein adds the layer of ashing emulsion.

The assessment of desilverization characteristic

In this embodiment, use bleach boosters as the useful group of taking a picture.Therefore, assess release characteristics by the desilverization characteristic of assessment photosensitive material.

Above-mentioned sample is carried out the wedge exposure, use following developing programs (1) to develop then.Just carry out developing programs (2) when simultaneously, only in the blanching step of developing programs (1), using time solution.

After the development, carry out density measure.Density is under the exposure of minimum yellow density+1.8 o'clock in developing programs (1), assesses desilverization characteristic with the increase of yellow density in the developing programs (2).(optical density changes the residual silver under the inferior condition of assessment).

The results are shown in Table shown in 2.

The method of each sample that develops is below described.

Program (1)

Step	Time	Temperature (℃)
			Colour development	3 minutes 15 seconds	38
Bleaching	3 minutes 00 second	38
			Washing	30 seconds	24
Photographic fixing	3 minutes 00 second	38
			Washing (1)	30 seconds	24
Washing (2)	30 seconds	24
			Stable	30 seconds	38
Dry	4 minutes 20 seconds	55

In program (2), bleaching time is 2 minutes and 30 seconds.

Washing fluid composed as follows.

Color developer

Diethylene triamine pentacetic acid (DTPA)	1.0g
		1-hydroxy ethylene-1, the 1-di 2 ethylhexyl phosphonic acid	2.0g
Sodium sulphite	4.0g
		Sal tartari	30.0g
Potassium bromide	1.4g
		Potassium iodide	1.5mg
Hydroxylamine sulfate	2.4g
		4-[N-ethyl-N-(the beta-hydroxy ethylamino]-2-aminotoluene sulfate	4.5g
Add and add water to	1.0L
		PH (with potassium hydroxide and sulfuric acid control)	10.05

Bleaching-stop bath

The Ferric Sodium Edetate trihydrate	100.0g
		Disodium ethylene diamine tetraacetate	10.0g
3-sulfydryl-1,2, the 4-triazole	0.03g
		Ammonium bromide	140.0g
Ammonium nitrate	30.0g
		Ammoniacal liquor (27%)	6.5ml
Add and add water to	1.0L
		PH (with ammoniacal liquor and nitric acid control)	6.0

Fixer

Disodium ethylene diamine tetraacetate	0.5g
		Ammonium sulfite	20.0g
Thiosulfuric acid aqueous ammonium (700g/L)	295.0ml
		Acetate (90%)	3.3g
Add and add water to	1.0L
		PH (with ammoniacal liquor and acetate control)	6.7

Stabilizing agent

To Nonylphenoxy poly epihydric alcohol (diglycidyl average degree of polymerization 10)	0.2g
		Ethylenediamine tetraacetic acid	0.05g
1,2, the 4-triazole	1.3g
		1,4-two (1,2,4-triazol-1-yl methyl) piperazine	0.75g
Glycolic acid	0.02g
		Hydroxyethyl cellulose (DAISERU KAGAKU HEC SP-2000)	0.1g
1, the 2-benzisothiazole-3-ketone	0.05g
		Add and add water to	1.0L
pH	8.5

The storage stability of assessment photosensitive material

In the developing programs (1) of aforesaid assessment desilverization characteristic, before exposure, photosensitive material was placed 4 days under 50 ℃ and 55%RH condition, the sample that will obtain thus exposes simultaneously and develops then, assesses the variation of the light sensitivity of blue or green image between the storage life thus.Logarithm with the inverse of the blue or green density of minimum+1.2 exposures that provide obtains light sensitivity, checks that thus the light sensitivity between the storage life changes.

The result also is shown in Table 2.

The assessment of fluctuation is handled in colour development

In the developing programs (1) of aforesaid assessment desilverization characteristic, use color developer similarly to assess, the concentration change of potassium bromide is in above-mentioned color developer 90% in this developer.In this way, assess the value of ashing fluctuation in the blue or green image.

Handling fluctuation is that 1 relative value is represented with the density fluctuation of assumes samples 101.

The result also is shown in Table 2.

Table 2

Sample number	The interpolation layer of ashing emulsion	PUG discharges the type of compound and adds layer	Desilverization characteristic	Storage characteristics	Handle fluctuation
						101 Comparative Examples	The 1st layer	Do not have	+0.27	-0.03	(1.0 contrast)
102 the present invention	The 1st layer	The 1st layer of A-21	+0.03	-0.03	1.0
						103 the present invention	The 1st layer	The 1st layer of A-24	+0.03	-0.03	1.0
104 the present invention	The 1st layer	The 1st layer (46)	+0.02	-0.03	0.7
						105 the present invention	The 1st layer	The 1st layer (123)	+0.02	-0.03	0.7
106 Comparative Examples	The 4th layer	The 4th layer of A-21	+0.05	-0.23	1.3
						107 Comparative Examples	The 4th layer	The 4th layer of A-24	+0.05	-0.24	1.3
108 the present invention	The 1st layer	The 2nd layer of A-21	+0.09	-0.03	0.7

As shown in table 2, each sample of the present invention slightly increases density, even and still have a good desilverization characteristic when the bleaching liquid that uses time.

Table 2 shows that also when having ashing emulsion and " PUG discharges compound " in adjacent layer (sample 108), this effect is lowered.In this regard, ashing emulsion and " PUG discharges compound " are preferably in identical layer.Sample 102 and 103 comprises " PUG discharges compound " that produces cyan.Though desilverization characteristic and storage stability are good, the ashing fluctuation that causes owing to the colour development fluctuation is bigger.In this regard, more preferably, " PUG discharges compound " is the compound (not producing any colored dyestuff that forms in photosensitive material) of not developing color.

In sample 106 and 107, ashing emulsion is added in the photosensitive silver halide emulsion layer.These samples are in the scope of JP-A-63-175850.But, change (light sensitivity variation) greatly owing to store the photographic property that causes, making also needs further improvement for pushing these photosensitive materials to practical application.

Embodiment 2

In embodiment 2, the compound of released development inhibitor will be described below.

The manufacturing of sample 201-204

According to the step perparation of specimen 201-204 identical, but the compound in the ground floor (A-21) is become the compound shown in the table 3 with the sample 102 of embodiment 1.What note is, coating weight is 0.1 times (mol) of the coating weight of compound in the ground floor of sample 102.

The manufacturing of sample 205

In the sample 101 of embodiment 1, remove the iodine silver bromide emulsion O in the 3rd layer.The substitute is, use 0.1g/m for the 3rd layer ²The ashing emulsion Z coating that in embodiment 1, forms.Also use 0.01g/m for the 3rd layer ²Compound (12) coating.

The manufacturing of sample 206

In sample 205, remove ashing emulsion Z and compound (12) in the 3rd layer.The substitute is, add control compounds (a) with the molar weight identical with compound (12)

Control compounds (a)

(compound of describing among the JP-B-4-73573)

Because the minimum density that colour development causes fluctuation

Being similar among the embodiment 1 " assessment of colour development fluctuation " assesses.

In addition, repeatedly be coated with the amount of the middle Hydroxylamine sulfate of developing programs (1) of embodiment 1,0.7 times, similarly assess thus.

The assessment of storage stability

Being similar among the embodiment 1 " assessment of the storage stability of photosensitive material " assesses.

Table 3

Sample number	The interpolation layer of ashing emulsion	PUG discharges the type of compound and adds layer	The ashing fluctuation	The ashing fluctuation	Storage characteristics
						101 Comparative Examples	The 1st layer	Do not have	(1.0 reference)	(1.0 reference)	-0.03
201 the present invention	The 1st layer	The 1st layer (12)	0.50	0.8	-0.03
						202 the present invention	The 1st layer	The 1st layer (106)	0.52	0.8	-0.04
203 the present invention	The 1st layer	The 1st layer of A-4	0.6	0.8	-0.04
						204 Comparative Examples	The 1st layer	The control compounds of describing among the 1st layer of JP-B-4-73573 (a)	0.8	1.1	-0.25
205 the present invention	The 3rd layer	The 3rd layer (12)	0.7	0.8	-0.03
						206 Comparative Examples	Do not add	The control compounds of describing among the 3rd layer of JP-B-4-73573 (a)	0.9	1.1	-0.27

The result of embodiment 2 shows that each sample of the present invention has little ashing fluctuation and high storage stability.

On the contrary, though the compound of describing among the JP-B-4-73573 has effect (fluctuation of concentration of potassium bromide) to the ashing fluctuation, it is little to the dependent effect of density that it improves Hydroxylamine sulfate.Equally, this compound still needs to improve aspect storage stability.

Embodiment 3

Make the sample 301 and 302 (colour paper) of the following stated.

On the surface of the carrier that forms by two surfaces, carry out corona discharge with the polyvinyl resin coated paper.Afterwards, form the gelatin bottom that comprises neopelex.In addition, form first to the 7th photograph by coating squence and constitute layer, make sample (301) thus with the silver-halide color photoelement that is provided with lower floor.The coating solution that single photograph constitutes layer is prepared as follows.

The preparation of layer 5 coating solution

Cyan colour coupler (ExC-1), the chromatic image stabilizing agent (Cpd-1) of 250g, the chromatic image stabilizing agent (Cpd-10) of 10g, the chromatic image stabilizing agent (Cpd-12) of 20g, the ultraviolet absorber (UV-1) of 14g, the ultraviolet absorber (UV-2) of 50g, the ultraviolet absorber (UV-3) of 40g and the ultraviolet absorber (UV-4) of 60g of dissolving 300g in the solvent (Solv-6) of 230g and 350ml ethyl acetate.Gained solution is dispersed in by emulsion in 10% aqueous gelatin solution of 6500g, and this aqueous gelatin solution comprises the surfactant (Cpd-20) of 25g, with preparation emulsion dispersion C.

(cube, mean grain size are the large scale emulsion C of 0.40 μ m and 5: 5 potpourris of the small size emulsion C that mean grain size is 0.30 μ m (mol ratio of silver) to prepare chlorine silver bromide emulsion C individually; The size distribution variation factor of two kinds of emulsions is respectively 0.09 and 0.11; In these two kinds of emulsions, the silver bromide part of 0.5mol% is included in a part to have in the surface of silver halide as the particle of substrate).

Red sensitization sensitizing dye G as follows and H are respectively with every mol silver 9.0 * 10 ^-5Mol and 12.0 * 10 ^-5The amount of mol is added among large scale emulsion C and the small size emulsion C.Add sulphur sensitizer and golden sensitizer, carry out the chemical ripening of emulsion thus best.

Emulsion dispersion C and this chlorine silver bromide emulsion C mix, and dissolve then, have the layer 5 coating solution of following composition with preparation.According to first to fourth layer of the method identical preparation and the 6th and the coating solution of layer 7 with the layer 5 coating solution.Use H-1, H-2 and H-3 as the gelatin hardener in each layer.

In each layer, add 15.0,60.0,5.0 and 10.0mg/m equally, respectively ²Ab-1, Ab-2, Ab-3 and the Ab-4 of amount.

(H-1) rigidizer

(use amount is the 0.50wt% of gelatin)

(H-2) rigidizer

(use amount is the 1.20wt% of gelatin)

(H-3) rigidizer

(use amount is the 0.40wt% of gelatin)

(Ab-1) antiseptic (Ab-2) antiseptic (Ab-3) antiseptic

(Ab-4) antiseptic

R ₁ R ₂a -CH ₃ -NHCH ₃b -CH ₃ -NH ₂c -H -NH ₂d -H -NHCH ₃

A: b: c: d was with 1: 1: 1: the potpourri of 1 mol ratio

In the chlorine silver bromide emulsion of each sensitive emulsion layer, use spectral sensitizing dye and crystal controlling agent 1 mutually.

Blue sensitive emulsion layer

Sensitizing dye A

Sensitizing dye B

Sensitizing dye C

Crystal controlling agent 1

(sensitizing dye A and the C addition in large scale emulsion and small size emulsion is respectively every mole of silver halide 0.42 * 10 ^-4Mol and 0.05 * 10 ^-4Mol.The addition of sensitizing dye B in large scale emulsion and small size emulsion is respectively every mole of silver halide 3.4 * 10 ^-4Mol and 4.1 * 10 ^-4Mol.)

Green sensitive emulsion layer

Sensitizing dye D

Sensitizing dye E

Sensitizing dye F

(addition of sensitizing dye D in large scale emulsion and small size emulsion is respectively every mole of silver halide 3.0 * 10 ^-4Mol and 3.6 * 10 ^-4Mol.The addition of sensitizing dye E in large scale emulsion and small size emulsion is respectively every mole of silver halide 4.0 * 10 ^-5Mol and 7.0 * 10 ^-5Mol.The addition of sensitizing dye F in large scale emulsion and small size emulsion is respectively every mole of silver halide 2.0 * 10 ^-4Mol and 2.8 * 10 ^-4Mol.)

Red sensitive emulsion layer

Sensitizing dye G

Sensitizing dye H

(sensitizing dye G and the H addition in large scale emulsion and small size emulsion is respectively every mole of silver halide 8.0 * 10 ^-5Mol and 10.7 * 10 ^-5Mol.)

In addition, in red photographic layer with every mole of silver halide 3.0 * 10 ^-3The amount of mol is added following Compound I.

Compound I

Equally, in each indigo plant, green and red sensitive emulsion layer respectively with every mole of silver halide 3.3 * 10 ^-4Mol, 1.0 * 10 ^-3Mol and 5.9 * 10 ^-4The amount of mol is added 1-(3-methyl urea groups phenyl)-5-mercapto-tetrazole.

In addition, in second, four, six and seven layer, add 0.2,0.2,0.6 and 0.1mg/m respectively ²Same compound.

In blue and green sensitive emulsion layer, 4-hydroxyl-6-methyl isophthalic acid, 3,3a, the addition of the 7-purine is respectively every mole of silver halide 1 * 10 ^-4Mol and 2 * 10 ^-4Mol.

In red sensitive emulsion layer, add 0.05g/m ²Methacrylic acid and the copolymer emulsion (weight ratio is 1: 1, and mean molecular weight is 200000-400000) of butyl acrylate.

In second, four and six layer, add 6,6 and 18mg/m respectively ²The catechol-3 of amount, 5-disulfonic acid disodium.

For preventing radiation, add following dyestuff (the numeral coating weight in the bracket).

Layer is provided with

The composition of each layer below will be described.Digitized representation coating weight (g/m ²).The coating weight of each silver emulsion is represented with the coating weight of silver.

Carrier

{ polyvinyl resin is comprising Chinese white (titania, content 16wt% to the polyvinyl resin laminated paper, zinc paste, content 4wt%), whitening agent (4,4 ,-two-(5-methylbenzoxazole base) stilbenes, content 0.03wt%), and blue dyes (ultramarine)

Ground floor (blue sensitive emulsion layer)

(cube, mean grain size are the large scale emulsion A of 0.72 μ m and 5: 5 potpourris of the small size emulsion A that mean grain size is 0.06 μ m (mol ratio of silver) to chlorine silver bromide emulsion A; The size distribution variation factor of two kinds of emulsions is respectively 0.08 and 0.10; In these two kinds of emulsions, the silver bromide part of 0.3mol% is included in a part to have in the surface of silver halide as the particle of substrate)	0.24
		Gelatin	1.25
Yellow colour former (ExY)	0.57
		Chromatic image stabilizing agent (Cpd-1)	0.07
Chromatic image stabilizing agent (Cpd-2)	0.04
		Chromatic image stabilizing agent (Cpd-3)	0.07
Chromatic image stabilizing agent (Cpd-8)	0.02
		Solvent (Solv-1)	0.21

The second layer (colour mixture prevents layer)

Gelatin	0.99
		Colour mixture prevents agent (Cpd-4)	0.09
Chromatic image stabilizing agent (Cpd-5)	0.018
		Chromatic image stabilizing agent (Cpd-6)	0.13
Chromatic image stabilizing agent (Cpd-7)	0.01
		Solvent (Solv-1)	0.06
Solvent (Solv-2)	0.22

The 3rd layer (green sensitive emulsion layer)

(cube, mean grain size are the large scale emulsion B of 0.45 μ m and 1: 3 potpourri of the small size emulsion B that mean grain size is 0.35 μ m (mol ratio of silver) to chlorine silver bromide emulsion B; The size distribution variation factor of two kinds of emulsions is respectively 0.10 and 0.08; In these two kinds of emulsions, the silver bromide part of 0.4mol% is included in a part to have in the surface of silver halide as the particle of substrate)	0.14
		Gelatin	1.36
Magenta colour coupler (ExM)	0.15
		Ultraviolet absorber (UV-A)	0.14
Chromatic image stabilizing agent (Cpd-2)	0.02
		Chromatic image stabilizing agent (Cpd-4)	0.002
Chromatic image stabilizing agent (Cpd-6)	0.09
		Chromatic image stabilizing agent (Cpd-8)	0.02
Chromatic image stabilizing agent (Cpd-9)	0.03
		Chromatic image stabilizing agent (Cpd-10)	0.01

Chromatic image stabilizing agent (Cpd-11)	0.0001
		Solvent (Solv-3)	0.11
Solvent (Solv-4)	0.22
		Solvent (Solv-5)	0.20

The 4th layer (colour mixture prevents layer)

Gelatin	0.71
		Colour mixture prevents agent (Cpd-4)	0.06
Chromatic image stabilizing agent (Cpd-5)	0.013
		Chromatic image stabilizing agent (Cpd-6)	0.10
Chromatic image stabilizing agent (Cpd-7)	0.007
		Solvent (Solv-1)	0.04
Solvent (Solv-2)	0.16

Layer 5 (red sensitive emulsion layer)

(cube, mean grain size are the large scale emulsion C of 0.40 μ m and 5: 5 potpourris of the small size emulsion C that mean grain size is 0.30 μ m (mol ratio of silver) to chlorine silver bromide emulsion C; The size distribution variation factor of two kinds of emulsions is respectively 0.09 and 0.11; In these two kinds of emulsions, the silver bromide part of 0.5mol% is included in a part to have in the surface of silver halide as the particle of substrate)	0.20
		Gelatin	1.11
Cyan colour coupler (ExC-1)	0.30
		Ultraviolet absorber (UV-A)	0.29

Chromatic image stabilizing agent (Cpd-1)	0.25
		Chromatic image stabilizing agent (Cpd-9)	0.01
Chromatic image stabilizing agent (Cpd-10)	0.01
		Chromatic image stabilizing agent (Cpd-12)	0.02
Solvent (Solv-6)	0.23

Layer 6 (uv absorption layer)

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

Layer 7 (protective seam)

Gelatin	1.00
		Acryloyl group modified polyethylene alcohol copolymer (modification degree 17%)	0.04
Whiteruss	0.02
		Surfactant (Cpd-13)	0.01

The manufacturing of sample 302

The composition of the layer 5 of the above-mentioned silver-halide color photoelement of making 301 of replacing as follows prepares sample 302 thus.

Layer 5 (red sensitive emulsion layer)

(cube, mean grain size are the large scale emulsion C of 0.40 μ m and 5: 5 potpourris of the small size emulsion C that mean grain size is 0.30 μ m (mol ratio of silver) to chlorine silver bromide emulsion C; The size distribution variation factor of two kinds of emulsions is respectively 0.09 and 0.11; In these two kinds of emulsions, the silver bromide part of 0.8mol% is included in a part to have in the surface of silver halide as the particle of substrate)	0.12
		Gelatin	1.11
Cyan colour coupler (ExC-2)	0.13
		Cyan colour coupler (ExC-3)	0.03
Chromatic image stabilizing agent (Cpd-1)	0.05
		Chromatic image stabilizing agent (Cpd-6)	0.06
Chromatic image stabilizing agent (Cpd-7)	0.02
		Chromatic image stabilizing agent (Cpd-9)	0.04
Chromatic image stabilizing agent (Cpd-10)	0.01
		Chromatic image stabilizing agent (Cpd-14)	0.01
Chromatic image stabilizing agent (Cpd-15)	0.12
		Chromatic image stabilizing agent (Cpd-16)	0.03
Chromatic image stabilizing agent (Cpd-17)	0.09
		Chromatic image stabilizing agent (Cpd-18)	0.07
Solvent (Solv-5)	0.15
		Solvent (Solv-8)	0.05

The structure of the compound in sample 301 and 302 is as follows.

(ExY) yellow colour coupler: the potpourri of following material

With

Mol ratio is 70: 30.

(ExM) magenta colour coupler: the potpourri of following material:

With

Mol ratio is 40: 40: 20.

(ExC-1) cyan colour coupler: the potpourri of following material:

With

Mol ratio is 15: 85.

(ExC-2) cyan colour coupler

(ExC-3) cyan colour coupler: the potpourri of following material:

With

Mol ratio is 50: 25: 25.

(Cpd-1) chromatic image stabilizing agent (Cpd-2) chromatic image stabilizing agent

Number-average molecular weight is 60,000

(Cpd-3) chromatic image stabilizing agent

N=7-8 (on average)

(Cpd-4) mixed color inhibitor

(Cpd-5) colour mixture prevents agent (Cpd-6) stabilizing agent

Number-average molecular weight is 600 m/n=10/90

(Cpd-7) mixed color inhibitor (Cpd-8) chromatic image stabilizing agent

(Cpd-9) chromatic image stabilizing agent (Cpd-10) chromatic image stabilizing agent

(Cpd-12) chromatic image stabilizing agent

(Cpd-13) surfactant: 7: 3 potpourri of following material

With

(Cpd-19) mixed color inhibitor

(Cpd-20) surfactant: the potpourri of 1: 4 mol ratio of following material

(UV-1) UV absorbing agent (UV-2) UV absorbing agent

(UV-3) UV absorbing agent (UV-4) UV absorbing agent

(UV-5) UV absorbing agent (UV-6) UV absorbing agent

The potpourri of UV-A:UV-1/UV-2/UV-3/UV-4=4/2/2/3

UV-B：

The potpourri of UV-1/UV-2/UV-3/UV-4/UV-5/UV-6=9/3/3/4/5/3

The potpourri of UV-C:UV-2/UV-3/UV-6/UV-7=1/1/1/2

(Solv-6) mixing of 1: 1 mol ratio of following material

Thing

With

According to the step perparation of specimen 303 identical, comprise 0.6g/m but between carrier and ground floor, form with sample 301 ²Gelatin, 0.06g/m ²(in the silver amount) ashing emulsion Y and 0.01g/m ²The layer of compound (12) (PUG releasing unit).

According to the step perparation of specimen 304 identical, comprise 0.6g/m but between carrier and ground floor, form with sample 302 ²Gelatin, 0.06g/m ²(in the silver amount) ashing emulsion Y and 0.01g/m ²The layer of compound (12) (PUG releasing unit).Below the method for preparing ashing emulsion Y will be described.

According to the step perparation of specimen 305 identical, but in layer 7, add 0.06g/m with sample 301 ²(in the silver amount) ashing emulsion Y and 0.01g/m ²Compound (106).

According to the step perparation of specimen 306 identical, but in layer 7, add 0.06g/m with sample 302 ²(in the silver amount) ashing emulsion Y and 0.01g/m ²Compound (106).

As above these samples of Zhi Zaoing expose equably and develop, and wherein on purpose weaken stirring in the colour development step.Observe and assess the variation in this process.

Consequently, the fluctuation of the processing in the photosensitive material of the present invention is significantly little.

The preparation of emulsion Y

At 35 ℃ of 1% inertia gelatin solutions that stir and dissolve 2.0L down.In 4 minutes time, add the sodium chloride of 0.66mol and the nitrate of 0.6mol by two gunitees with identical fixed flow rate.Add the gold chloride of 0.1g and the NaOH of 0.02mol, stirred the gained material then 10 minutes.Afterwards, add the sodium chloride of 0.4mol, obtain the particle that mean grain size is 0.1 μ m.Wash these particles with water, add 100g inertia gelatin then to disperse described particle, to make thus to have the emulsion Y of surperficial ashing nuclear.

Handle A

Photosensitive material 305 is rolled into the wide reel of 127mm, uses then to be obtained from Fuji PhotoFilm Co., the PP1258AR small test chamber photo developing machine of Ltd. carries out image exposure.Afterwards, washing (running experiment) continuously with following rinsing step, is the twice of colour development tank volume until the additional liquid that replenishes.The flushing of using this additional liquid is for handling A.

Step	Temperature (℃)	Time (second)	Supplementary rate *
				Colour development	38.5	45	45ml
Bleaching-photographic fixing	38.0	45	35ml
				Rinsing (1)	38.0	20	-
Rinsing (2)	38.0	20	-
				Rinsing (3)	38.0 **	20	-
Rinsing (4)	38.0 **	30	121ml

^*The supplementary rate of every square metre of photosensitive material

^*Use Fuji Photo Film Co. in rinsing (3), the RC50D rinsing purging system that Ltd. makes is with extraction rinsing liquid from rinsing (3), and this solution is provided to inverse osmosis membrane module (RC50D) by pump.The transmission water that obtains in this jar provides to rinsing (4), and condensed water is back to rinsing (3).Regulate pump pressure, make the water yield that transmits to the inverse osmosis assembly remain on 5-300ml/min.Water is controlled temperature next day circulation 10 hours (carrying out rinsing by the jar convection system by (1) to (4)).

Each washing fluid composed as follows.

Color developer	Jar solution	Replenish liquid
			Water	800ml	800ml

Dimethylpolysiloxane--based surfactivity (chemical industry society of SILICONE KF351A/ SHIN-ETSU HANTOTAI system)	0.1g	0.1g
			Three (isopropyl alcohol) amine	8.8g	8.8g
Ethylenediamine tetraacetic acid	4.0g	4.0g
			Polyglycol (molecular weight 300)	10.0g	10.0g
4,5-dihydroxy benzenes-1,3-sodium disulfonate	0.5g	0.5g
			Potassium chloride	10.0g	-
Potassium iodide	0.040g	0.010g
			The amino stilbene radicals whitening agent (the clear and chemical society of HAKKOL FWA-SF/ system) of three azines	2.5g	5.0g
Sodium sulphite	0.1g	0.1g
			N, N-two (sulfonic group ester) azanol disodium	8.5g	11.1g
N-ethyl-N-(β-methane sulfo group amido-ethyl)-3-methyl-4-amino-4-amino aniline 3/2 sulfuric acid monohydrate	5.0g	15.7g
			Sal tartari	26.3g	26.3g
Add and add water to	1000ml	1000ml
			PH (25 ℃/regulate) with potassium hydroxide and sulfuric acid	10.15	12.50

Bleaching-stop bath	Jar solution	Replenish liquid
			Water	700ml	600ml
Ethylenediamine tetraacetic acid ammonium iron (III)	47.0g	94.0g
			Ethylenediamine tetraacetic acid	1.4g	2.8g
Adjacent carboxyl benzenesulfinic acid	8.3g	16.5g

Acetate (67%)	16.5	33.0g
			Imidazoles	14.6g	29.2g
ATS (Ammonium thiosulphate) (750g/L)	107.0ml	214.0ml
			Ammonium sulfite	16.0g	32.0g
Ammonium bisulfite	23.1g	46.2g
			Add and add water to	1000ml	1000ml
PH (25 ℃/regulate) with acetate and ammoniacal liquor	6.0	6.0

Rinsing liquid	Jar solution	Replenish liquid
			Sodium isocyanurate through chlorination	0.02g	0.02g
Deionized water	1000ml	1000ml
			pH	6.5	6.5

Embodiment 4

Apparatus is the carrier of tri cellulose acetate membrane by the following a plurality of layers of barrier coating of forming, to make the sample 401 as the multi layer colour photosensitive material.

The composition of photographic layer

Corresponding to the numeral of each component with g/m ²Coating weight for unit.The coating weight of silver halide is shown with the scale of silver.The coating weight of each sensitizing dye is shown with the mol numerical table of every mole of silver halide interpolation in the identical layer.

Sample 401

Ground floor (the first anti-halation layer)

Iodine silver bromide emulsion P	Silver 0.01
		The black collargol	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

The second layer (the second anti-halation layer)

The black collargol	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

The 3rd layer (middle layer)

Polyethyl acrylate latex	0.085
		Gelatin	0.294

The 4th layer (the low sensitive emulsion layer that rapidly becomes popular)

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

Layer 5 (in rapidly become popular sensitive emulsion layer)

Iodine silver bromide emulsion B	Silver 0.24
		Iodine silver bromide emulsion C	Silver 0.60
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

Layer 6 (height rapidly become popular sensitive 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

Layer 7 (middle layer)

Cpd-1	0.089
		Solid disperse dye ExF-4	0.030
HBS-1	0.050
		Polyethyl acrylate latex	0.83
Gelatin	0.84

The 8th layer (being used for providing the layer of middle layer effect) to red photographic 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

The 9th layer (the green sensitive emulsion layer of low speed)

Bromine chlorosulfonylation silver emulsion F	Silver 0.45
		Bromine chlorosulfonylation silver emulsion G	Silver 0.30
Bromine chlorosulfonylation silver emulsion H	Silver 0.38
		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

The tenth layer (the green sensitive emulsion layer of middling speed)

Bromine chlorosulfonylation silver emulsion 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 floor (the green sensitive emulsion layer of high speed)

Bromine chlorosulfonylation silver emulsion I	Silver 0.19
		Bromine chlorosulfonylation silver 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
Polyethyl acrylate latex	0.099
		Gelatin	1.11

Floor 12 (middle layer)

Cpd-1	0.16
		HBS-1	0.082
Gelatin	1.057

The 13 layer (the blue sensitive emulsion layer of low speed)

Bromine chlorosulfonylation silver emulsion K	Silver 0.28
		Bromine chlorosulfonylation silver emulsion L	Silver 0.30
Bromine chlorosulfonylation silver emulsion M	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

The 14 layer (the blue sensitive emulsion layer of high speed)

Bromine chlorosulfonylation silver emulsion 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 15 layer (first protective seam)

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

The 16 layer (second protective seam)

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

Gelatin

0.75

Except that mentioned component, for improving storage stability, handlability, resistance to pressure, antibiotic property and mildew resistance, antistatic behaviour and coating character, single layer can comprise W-1 to W-3, B-4 to B-6, F-1 to F-19, molysite, lead salt, golden salt, platinum salt, palladium salt, iridium salt, ruthenium salt, rhodium salt and calcium salt.

Following table 4 shows in the above description the Br content, I content, particle diameter of each emulsion of abbreviation expression etc.

Table 4

The emulsion title	The variation factor (mol%) that iodine distributes between relevant particle	Br content (mol%)	1 content (mol%)	Mean grain size (being equivalent to spherical diameter μ m)	The variation factor (%) that is equivalent to spherical diameter	Area diameter projected (being equivalent to round diameter, μ m)	Area diameter projected/thickness ratio	Particle shape
									A	20	3.0	0.02	0.40	19	0.55	4.0	Platy shaped particle
B	17	2.0	0.01	0.54	21	0.86	6.0	Platy shaped particle
									C	18	3.0	0.01	0.90	22	1.50	7.0	Platy shaped particle
D	17	2.0	0.03	1.10	18	2.07	10.0	Platy shaped particle
									E	22	2.0	0.03	0.90	22	1.50	7.0	Platy shaped particle
F	18	3.0	0.02	0.30	19	0.38	3.0	Platy shaped particle
									G	17	2.0	0.02	0.50	19	0.70	4.2	Platy shaped particle
H	18	1.0	0.02	0.60	17	1.00	7.0	Platy shaped particle
									I	16	3.0	0.02	0.78	15	1.30	7.0	Platy shaped particle
J	19	3.0	0.02	0.97	18	1.88	11.0	Platy shaped particle
									K	18	4.0	0.02	0.40	16	0.55	4.0	Platy shaped particle
L	22	4.0	0.03	0.60	18	1.05	8.0	Platy shaped particle
									M	20	5.0	0.02	0.80	19	1.34	7.0	Platy shaped particle
N	22	6.0	0.04	1.40	24	2.80	12.0	Platy shaped particle
									P	-	1.0	0	0.07	-	0.07	1.0	Homogeneous texture

In table 4:

(2), carry out golden sensitizing, sulphur sensitizing and selenium sensitizing best according to the embodiment 6 of JP-A-10-221827 for emulsion A-N.

(3) interarea of platy shaped particle is (111) face, and this platy shaped particle can wait and prepares by changing adding conditional, addition among the JP-A-10-221827.The spectral sensitizing dye that is added is at the compound described in each photographic layer.

(4) use high-voltage electron microscope in platy shaped particle, to observe the dislocation line of describing among the JP-A-3-237450.

The preparation of organic solid disperse dyes dispersion

Disperse ExF-2 with the following method.That is to say, in the pot mill of 700ml, put into the 5% pair of Octylphenoxy Ethoxyethane sulfonic acid soda water solution of water, 3ml of 21.7ml and 5% pair of Octylphenoxy polyoxyethylene ether (degree of polymerization 10) aqueous solution of 0.5g, in this mill, add dyestuff ExF-2 and the 500ml zirconia ball (diameter 1mm) of 5.0g then.Content disperseed 2 hours.This dispersion prepares by the BO type vibromill that uses Chuo Koki K.K. to make.From mill, take out dispersion, be added into then in 12.5% aqueous gelatin solution of 8g.Filter out zirconia ball, obtain the gelatin dispersion of dyestuff.The mean grain size of thin dye granule is 0.44 μ m.

According to above identical method, make solid dispersions ExF-4.The mean grain size of this thin dye granule is 0.45 μ m.

Compound used when above-mentioned each layer forms is as follows.

HBS-1 tricresyl phosphate cresyl ester

HBS-2 phthalic acid di-n-butyl ester

The HBS-4 tri-2-ethylhexyl phosphate

X/y=10/90 (weight ratio) mean molecular weight: about 35,000

X/y=40/60 (weight ratio) mean molecular weight: 20,000

Mean molecular weight: about 750,000

X/y=70/30 (weight ratio) mean molecular weight: about 17,000

Mean molecular weight: about 10,000

The perparation of specimen 402

According to the step perparation of specimen 402 identical, but in the 3rd layer, add 0.08g/m with sample 401 ²The emulsion Y and the 0.02g/m of the ashing in advance in embodiment 3 ²Compound (12).

Use high boiling organic solvent (HBS-1) and surfactant (W-4) with 0.5 times of amount to colour coupler, the compound (12) that adds sample 401 becomes the emulsion dispersion.

The manufacturing of sample 403-405

Prepare sample 403-405 according to the step identical, but the compound in the 3rd layer changes over the compound shown in the following table 5 with sample 402.

The assessment of the ashing density fluctuation that flushing causes

Make sample 401-405 under white light, carry out wedge exposure and development with following processing A and B.Assess the ashing density fluctuation (handle among the A in the ashing density and treatments B the difference of ashing density) of pinkish red image.

Treatments B is identical with processing A, but the time of colour development step and temperature are changed into 2 minutes 10 seconds and 44 ℃ respectively.

This value is more little, and it is just more little to handle the ashing fluctuation that causes, and is preferred.

The results are shown in shown in the following table 5.Table 5 shows, the sample with PUG releasing unit of the present invention has little ashing fluctuation and is preferred.

Table 5

Sample number	Colour coupler in the 3rd layer	The ashing fluctuation	Explanation
				401	Do not have	0.20	Comparative Examples
402	Compound (12)	0.07	The present invention
				403	Compound (13)	0.09	The present invention
404	Compound (10)	0.11	The present invention
				405	Compound (106)	0.12	The present invention
406	ExC-6	0.10	The present invention

Handle and washing fluid composed as follows shown in.

Handle A

Step	Time	Temperature (℃)	Supplementary rate	Tank volume
					Colour development	1 minute 30 seconds	41	10ml	10.3L
Bleaching	20 seconds	41	5ml	3.6L
					Photographic fixing (1)	20 seconds	41	-	3.6L
Photographic fixing (2)	20 seconds	41	7.5ml	3.6L
					Stable (1)	10 seconds	41	-	1.9L
Stable (2)	10 seconds	41	-	1.9L
					Stable (3)	10 seconds	41	30ml	1.9L
Dry	30 seconds	60

^*Supplementary rate is with respect to the wide photosensitive material of the 35mm of 1.1m (being equivalent to one 24 embodiment 1).

Order according to (3) to (2) to (1) flows stabilizing agent, and by conduit being made fixer be connected to (1) by (2).Equally, the jar solution of stabilizing agent (2) offers fixer (2) with the supplementary rate of 15ml.What note is that the amount of developer, bleaching liquid and fixer all remains 2.0ml respectively for the wide photosensitive material of the 35mm of 1.1m in blanching step, photographic fixing step and washing step.It is also noted that be 6 seconds each switching time, and be included in the flush time of each rinsing step this time.

Shown in washing fluid composed as follows.

Color developer	Jar solution	Replenish liquid
			Diethylene triamine pentacetic acid (DTPA)	3.0g	5.0g
4,5-dihydroxy benzenes-1,3-sodium disulfonate	0.5g	0.5g
			N, N-two (sulfonic group ethyl) azanol disodium	10.0g	15.0g
Sodium sulphite	4.0g	10.0g
			Hydroxylamine sulfate	1.5g	3.0g
Potassium chloride	2.0g	-
			Diethylene glycol	10.0g	10.0g
Ethyl urea	3.0g	3.0g
			2-ethyl-4-[N-ethyl-N-(beta-hydroxy ethyl) amino] aniline sulfate	6.0g	11.4g
Sal tartari	35g	35g
			Add and add water to	1.0L	1.0L
PH (regulating) with potassium hydroxide and sulfuric acid	10.10	10.60

Bleaching liquid	Jar solution	Replenish liquid
			1,2-diaminopropanetetraacetic acid ammonium iron monohydrate	140g	200g

Ammonium bromide	50g	70g
			Succinic acid	10g	15g
Maleic acid	40g	60g
			Imidazoles	60g	90g
Add and add water to	1.0L	1.0L
			PH (regulating) with nitric acid and ammoniacal liquor	4.2	3.8

Stop bath	Jar solution	Replenish liquid
			ATS (Ammonium thiosulphate) (750g/L)	280ml	750ml
Bisulfite aqueous ammonium (72%)	20g	80g
			Imidazoles	10g	45g
1-sulfydryl-2-(N, N-dimethyl aminoethyl-tetrazolium	1g	3g
			Ethylenediamine tetraacetic acid	3g	9g
Add and add water to	1.0L	1.0L
			PH (with ammoniacal liquor and nitric acid control)	7.0	7.0

Stabilizing agent: jar solution is the same with additional liquid
		SPTS	0.03g
To Nonylphenoxy poly epihydric alcohol (diglycidyl average degree of polymerization 10)	0.4g
		Disodium ethylene diamine tetraacetate	0.05g
1,2, the 4-triazole	1.3g
		1, (1,2,4-triazole-1-is different for 4-two	0.75g

Methyl) piperazine
		1, the 2-benzisothiazole-3-ketone	0.10g
Add and add water to	1.0L
		pH	8.5

Other advantage and variation are conspicuous for those skilled in the art.Therefore, the present invention is not limited to above-mentioned detail and representational embodiment in its wideer scope.And under situation without departing from the spirit and scope of the present invention, also can carry out various improvement, and scope of the present invention limits with appended claims and equivalent thereof.

Claims (9)

1, a kind of silver-halide color sensitive photographic material, it is included at least one photosensitive silver halide emulsion layer and at least one non-photographic layer on the carrier,

It is characterized in that, have at least a layer to comprise the silver emulsion of ashing in advance in the non-photographic layer, this emulsion comprises and has the particle on ashing surface in advance, and comprise the non-photographic layer of ashing emulsion in advance and comprise the colour coupler that can discharge the useful group of taking a picture by the coupling reaction with the developer of oxidised form, the useful group of described photograph is selected from development restrainer, bleach boosters, development assistant agent, development accelerant, reductive agent and whitening agent; And

The emulsion of ashing in advance is developed during colour development, and with the color developer of even formation oxidised form, and the useful group of described photograph is d/d in the askiatic mode by coupling reaction.

2, photosensitive material as claimed in claim 1 is characterized in that, described colour coupler does not form image basically when the developer with oxidised form carries out coupling reaction.

3, photosensitive material as claimed in claim 1 is characterized in that, described colour coupler is represented in order to following formula (II):

COUP1-B1 (II)

Wherein, COUP1 represents to have at least one and is selected from substituent colour coupler group in following group: R ₇₁OCO-, HOSO ₂-, HO-, R ₇₂NHCO-and R ₇₂NHSO ₂-, R wherein ₇₁Represent hydrogen atom, have 6 or the still less alkyl or the phenyl of carbon atom, R ₇₂Represent R ₇₁Represented group, R ₇₄CO-, R ₇₄N (R ₇₅) CO-, R ₇₃SO ₂-group or R ₇₄N (R ₇₅) SO ₂-, R ₇₃Representative has 6 or the alkyl or phenyl of carbon atom still less, and R ₇₄And R ₇₅Represent by R respectively ₇₁Represented group; And the B1 representative useful group of photograph as defined in claim 1.

4, photosensitive material as claimed in claim 3 is characterized in that, the compound of formula (II) expression is the compound with following formula (III) expression:

COUP2-A-E-B2 (III)

Wherein, COUP2 represents the colour coupler group; E representative is selected from-CO-,-CS-,-COCO-,-SO-,-SO ₂-,-P (=O) (R ₁₅₁)-or-P (=S) (R ₁₅₁)-electrophilic group, R wherein ₁₅₁Represent aliphatic group, aromatic group, aliphatic oxygen base, aryloxy group, aliphatic sulfenyl or arylthio; A represents with linking group shown in the following formula (IV):

Wherein, ^*The part that representative is connected with COUP2, and ^*The part that representative is connected with E, R ₁₄₁, R ₁₄₂, R ₁₄₃Represent hydrogen atom, aliphatic group, aromatic group or heterocyclic group respectively independently, i represents the integer of 0-3, and j represents the integer of 0-2; And the B2 representative is as the useful group of the defined photograph of claim 1.

5, as the described photosensitive material of one of claim 1-4, it is characterized in that, comprise the non-photographic layer of silver emulsion of ashing in advance or the layer of contiguous this non-photographic layer and comprise the black collargol.

6, photosensitive material as claimed in claim 5 is characterized in that, the useful group of described photograph is a bleach boosters.

7, photosensitive material as claimed in claim 5 is characterized in that, the useful group of described photograph is a development restrainer.

8, photosensitive material as claimed in claim 5 is characterized in that, at least one that is included in the photosensitive silver halide emulsion at least one photosensitive silver halide emulsion layer is the emulsion that silver chloride content is at least 10mol%.

9, photosensitive material as claimed in claim 5 is characterized in that, at least one that is included in the silver emulsion of the ashing in advance at least one non-photographic layer is the emulsion that silver chloride content is at least 10mol%.