CN1028915C - Silver halide color photographic material - Google Patents

Abstract

A silver halide color photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer is disclosed, wherein said light-sensitive material contains a DIR coupler represented by formula (I), wherein A represents a coupler residue; R represents an alkyl group having from 1 to 4 carbon atoms or a pyridyl group; and n represents 1 when A represents a phenol type or naphthol type coupler residue, or n represents 0 when A represents other coupler residues, and said emulsion layer contains chemically sensitized silver halide grains which individually have a distinct layer comprising silver iodobromide containing from 7 to 45 mol % of silver iodide and which individually have an overall silver iodide content of more than 4 mol %. The photographic material is excellent in sensitivity, graininess, sharpness, color reproducibility, and preservability and is less liable to variation in photographic performance properties even when continuously processed under replenishment.

Description

Silver halide color photographic material

The present invention relates to silver-halide color photoelement, the silver-halide color photoelement (1) that particularly contains following composition substantially has the development inhibition type colour coupler (DIR Coupler) that emulsion that the silver halide particle of high agi content forms and (2) can discharge development restrainer by the part, after it is released into developing solution, can be transformed into the material that in fact photosensitive property is not had influence.

People need a kind of photosensitive material always, particularly can obtain ISO, ISO 400 light sensitivity (Super HG-400) for example, and can also show the good quality of image simultaneously, comprise granularity, sharpness and colour reproduction, can be equivalent to have these performances of the photosensitive material of ISO 100 light sensitivity.

As the meaning of JP-A-60-143331(" JP-A " speech used herein for " Japanese patent application is not examined open text) in disclosed; as the method for improving granularity, proposed to have the silver halide particle of the structure of layer clearly that contains 7 to 45mol% silver iodide and the silver halide particle that average silver iodide content is at least 7mol%.Owing to only use this silver halide particle still can have the problem of sharpness and colour reproduction, so proposed recently these emulsion grains and so-called DIR colour coupler are combined use, this colour coupler can be by the form released development inhibitor of image, as disclosed among JP-A-1-186938, JP-A-1-259359, JP-A-1-269935 and the JP-A-2-28637.These technology brought some progressive in sharpness and the colour reproduction, but the level that is reached still can not be satisfactory in granularity.In addition, add man-hour when the photosensitive material with above-mentioned composition is used in the photograph machining experiment chamber conventional method that generally adopts, promptly processed continuously when replenishing developing solution simultaneously, developing solution can have the activity that reduces or strengthen gradually as a result.

On the other hand, as in disclosed JP-A-57-151944, JP-A-58-205150, JP-A-1-280755 and U.S. Pat 4,782, as described in 012, proposed to use the hydrolyzable DIR colour coupler or the compound that can improve sharpness and colour reproduction, these colour couplers or compound can not cause the change on the developing solution activity.These DIR colour couplers or compound can discharge the development restrainer part, have lost the inhibition activity thereby they are hydrolyzed in developing solution.Use these compounds to suppress the variation of developing solution activity a little, but the effect that is produced not enough, particularly when using those can discharge development restrainer, and this inhibitor is when discharging the aryloxy group ion during deactivation in developing solution, the aryloxy group ion that discovery discharges is incorporated in the colour coupler oil droplet of photosensitive material, causes the variation of colour coupler coupling activity.Further, so-called timing type DIR colour coupler need be done some improvement on stability and synthetic cost.In addition, as in above-mentioned U.S. Pat 4,782, disclosed in 012, DIR colour coupler via wherein sulphur atom released development inhibitor has lower coupling activity, promptly have lower development restrainer rate of release, consequently make on colour reproduction and sharpness, can not obtain enough improvement effects.

An object of the present invention is to provide a kind of have satisfactory sensitivity, granularity, sharpness, colour reproduction and conservatory photosensitive material.

Even another object of the present invention provides a kind of photosensitive material that can fully desensitize and can change under the situation of continuous processing and additional developing solution.

Further aim of the present invention provides a kind of containing can be with short synthetic route, and lower cost synthesizes and have the photosensitive material of the DIR colour coupler of good stable and high coupling activity.

Above-mentioned purpose of the present invention realizes that by the photosensitive material that is made of a kind of support that at least a photosensitive silver halide emulsion layer arranged on it wherein said photosensitive material contains by the DIR colour coupler shown in the formula (I):

Wherein A is expressed as the toner residue; R represents to have the alkyl or the pyridine radicals of 1 to 4 carbon atom; N represents 1 when representing phenol type or naphthol type colour coupler residue as A, or n represents 0 when A represents other colour coupler residue, described emulsion layer contains the silver halide particle of chemical sensitization, and it has the layer clearly that is made of the bromo-iodide that contains 7 to 45mol% silver iodide and its separately and has total agi content greater than 4mol% separately.

In the formula (I), the colour coupler residue of being represented by A comprises yellow colour coupler residue (for example open chain ketone-methylene fundamental mode), magenta colour coupler residue (for example 5-pyrazolone-type, pyrazolo imidazole type, Pyrazolotriazole type), cyan coupler residue (for example phenol type, naphthol type) and colourless coupler residue (for example 2,3-bihydrogen-1-indenone type, acetophenone type).As in U.S. Pat 4,315, disclosed heterocyclic type colour coupler residue is also included within the colour coupler residue A in 070,4,183,752,3,961,959 and 4,171,223.

In these colour coupler residues, even more preferably as follows have formula (Cp-1), (Cp-2), (Cp-3), (Cp-4), (Cp-5), (Cp-6), (Cp-7), (Cp-8), (Cp-9) or (Cp-10) structure, and this is because they have high coupling speed.

In (Cp-10), each free key table shows the position of coupling in formula (Cp-1), is connected with releasable coupling group at this.R wherein ₅₁, R ₅₂, R ₅₃, R ₅₄, R ₅₅, R ₅₆, R ₅₇, R ₅₈, R ₅₉, R ₆₀, R ₆₁, R ₆₂Or R ₆₃Contain the non-proliferation group, select it so that total carbon atom number is 8 to 40, and even more preferably 10 to 30.Yet even more preferably total carbon atom number is not more than 15.Under the colour coupler situation of two compound forms, telomer form or polymer form, any of these group all represents to connect the divalent group of repetitive.In this case, R ₅₁To R ₆₃In the total carbon atom number of each group can exceed the above-mentioned scope of mentioning.

Below described be relevant symbol R ₅₁To R ₆₃, b, d and e definition, R wherein ₄₁Expression aliphatic group, aryl or heterocyclic radical; R ₄₂Expression aryl or heterocyclic radical and R ₄₃, R ₄₄And R ₄₅Represent hydrogen atom, aliphatic group, aryl or heterocyclic radical respectively.

R ₅₁And R ₄₁Identical implication is arranged, and b represents 0 or 1.R ₅₂And R ₅₃Respectively with R ₄₂Identical implication is arranged, R ₅₄With R ₄₁Identical implication or expression are arranged

,

, R ₄₁S-, R ₄₃O-, , or N ≡ C-R ₅₅With R ₄₁Has identical implication, R ₅₆And R ₅₇Respectively with R ₄₃Identical implication or expression R are arranged ₄₁S-, R ₄₃O-,

R ₅₈With R ₄₁Identical implication is arranged, R ₅₉With R ₄₁Identical implication or expression are arranged

, R ₄₁O-, R ₄₁The S-halogen atom or , d represents 0,1,2 or 3.When d is 2 or 3, the R of plural number ₅₉Can be identical or different, perhaps each in them can be represented divalent group and be connected to each other to form a ring structure.The representative instance of the divalent group of this ring formation is:

Wherein f represents 0 or 1 to 4 integer; Represent 0 or 1 to 2 integer with g.R ₆₀With R ₄₁Identical implication is arranged, R ₆₁With R ₄₁Identical implication is arranged.R ₆₂With R ₄₁Identical implication or expression R are arranged ₄₁OCONH-, R ₄₁SO ₂NH-,

, R ₄₃O-, R ₄₁S-, halogen atom or

R ₆₃With R ₄₁Identical meanings or expression are arranged

,

, R ₄₁SO ₂-, R ₄₃OCO-, R ₄₃OSO ₂-halogen atom, nitro, cyano group or R ₄₃CO-.E represents 0 or 1 to 4 integer.When e is 2 to 4, the R of repetition ₆₂Or R ₆₃Can be identical or different.

The implication of above-mentioned " aliphatic group " mentioned be saturated or undersaturated, acyclic or ring-type, straight or branched with replacement or unsubstitutedly have 1 to 32, be preferably the aliphatic hydrocarbyl of 1 to 22 carbon atom.The representative instance of these aliphatic hydrocarbyls is methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group, isobutyl, tertiary pentyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,1,3,3-tetramethyl butyl, decyl, dodecyl, cetyl and octadecyl.

The implication of above-mentioned " aryl " mentioned is the aryl of 6 to 20 carbon atoms to be arranged and more preferably comprise replacement or unsubstituted phenyl or naphthyl.

The implication of above-mentioned " heterocyclic radical " mentioned is for replacing or unsubstituted, and is preferably and contains 1 to 20, and even more preferably ternary to the eight yuan heterocyclic radical of 1 to 7 carbon atom, and heteroatoms is selected from nitrogen-atoms, oxygen atom and sulphur atom.The representative instance of this heterocyclic radical is 2-pyridine radicals, 2-thienyl, 2-furyl, 1,3,4-thiadiazoles-2-base, 2,4-two oxa-s-1,3-imidazolidine-5-base, 1,2,4-triazole-2-base and 1-pyrazolyl.

The typical substituting group of the aliphatic hydrocarbyl of the above-mentioned replacement of mentioning, aryl or heterocyclic radical or comprise halogen atom, R ₄₇O-, R ₄₆S-,

,

Cyano group and nitro, wherein R ₄₆Aliphatic series, aromatics or the heterocyclic group of expression; And R ₄₇, R ₄₈And R ₄₉Expression aliphatic series respectively, aromatics or heterocyclic group or hydrogen atom.The implication of the aliphatic group of Ying Yonging, aryl or heterocyclic radical and above-mentioned definition herein identical.

In formula (Cp-1), R ₅₁Preferably represent aliphatic group or aryl or in formula (Cp-2), preferably represent hydrogen atom or aliphatic group.

R ₅₂, R ₅₃And R ₅₅Preferably represent heterocyclic radical or aryl respectively.

R ₅₄Preferably represent R ₄₁CONH-or

R ₅₆And R ₅₇Preferably represent aliphatic group, aryl, R respectively ₄₁O-or R ₄₁S-.

R ₅₈Preferably represent aliphatic group or aryl.

In formula (Cp-6), R ₅₉Preferably represent the chlorine atom, aliphatic group or R ₄₁CONH-; D preferably represents 1 or 2.In formula (Cp-7), R ₅₉Preferably represent R ₄₁CONH-; D preferably represents 1.

R ₆₀Preferably represent aryl.

R ₆₁Preferably represent aliphatic group or aryl.

In formula (Cp-8), e preferably represents 0 or 1; R ₆₂Preferably represent R ₄₁OCONH-, R ₄₁CONH-or R ₄₁SO ₂NH-and even more preferably being connected on the 5-position of naphthols ring.

In formula (Cp-9), R ₆₃Preferably represent R ₄₁CONH-, R ₄₁SO ₂NH-,

, R ₄₁SO ₂-,

, nitro or cyano group.

In formula (Cp-10), R ₆₃Preferably expression

, R ₄₃OCO-or R ₄₃CO-.

In the formula (I), the pyridine radicals that R represents comprises and replacing or unsubstituted 2-, 3-or 4-pyridine radicals.

The alkyl that R represents comprise straight or branched with replacement or unsubstitutedly 1 to 4 carbon atom arranged and preferably be the alkyl of 1 to 3 carbon atom and the alkyl of replacement.The substituted alkyl suitable substituents comprise have 2 to 6 carbon atoms alkoxy carbonyl group (for example: methoxycarbonyl group; the third oxygen carbonyl; butoxy carbonyl; isobutyl boc; the different third oxygen carbonyl; penta oxygen carbonyl; isoamyl oxygen carbonyl; 2-methoxyl carbethoxyl group); the carbamyl that 6 carbon atoms of as many as are arranged (for example: N; N-diethylamino formoxyl; N-methyl-N-ethylamino formoxyl; the pyrrolidinyl carbonyl; the piperidino carbonyl); halogen atom (for example: the chlorine atom; fluorine atom); nitro; cyano group; the alkoxy that 1 to 4 carbon atom arranged (for example: methoxyl; ethoxy benzene; methoxy ethoxy); there is at the most the sulfamoyl of 6 carbon atoms (for example: N; N-diethyl amino sulfonyl; N-methyl-N-ethyl sulfamoyl); the aryloxy group that 6 to 10 carbon atoms are arranged (for example: the 4-chlorophenoxy); the acyl group that 2 to 6 carbon atoms are arranged (for example: acetyl group; benzoyl); the sulfonyl that carbon atom on 1 to 6 arranged (for example: mesyl; the fourth sulfonyl); 1 to 5 carbon atom is arranged and contain and be selected from nitrogen-atoms; heteroatomic 3 yuan to the 6 yuan heterocycles of oxygen atom and sulphur atom (for example: the 2-pyridine radicals; the 3-pyridine radicals) and the phosphoryl (for example: O, O-diethyl phosphoryl) of 2 to 5 carbon atoms arranged.Even more preferably alkoxy carbonyl group and carbamyl in them.

The pyridine radicals suitable substituents that R represents comprises the above-mentioned group of enumerating as alkyl substituent, and the aliphatic group (for example: methyl, ethyl) of 1 to 6 carbon atom is arranged in addition.

The particular example of R comprises-CH ₂COOC ₃H ₇,

-CH ₂COOC ₄H ₉，-CH ₂COOC ₃H ₇（i），-CH ₂COOC ₄H ₉（i），

-CH ₂COOC ₅H ₁₁，-CH ₂COOC ₅H ₁₁（i），-CH ₂COOC ₅H ₁₁（t），

-CH ₂CH ₂COOC ₃H ₇，-CH ₂CH ₂COOC ₃H ₇（t），-CH ₂CH ₂CH ₂COOCH ₃，

-CH ₂CONHC ₄H ₉，-CH ₂CONHC ₅H ₁₁，-CH ₂CONHC ₄H ₉（i），

-CH ₂CHCl ₂，-CH ₂CF ₃，-CH ₂CF ₂CF ₃，

The particular example of the DIR colour coupler of formula (I) expression illustrates as follows:

The compound of formula (I) expression can be synthetic by known open method, for example: describe in JP-A-57-151944, EP336411A and EP320939A.The following description of proof of some synthetic examples of formula (I) compound.

Synthetic embodiment 1

Synthesizing of compound (D-1)

13.5g compound (ⅱ) and 4.9g triethylamine are added to 200ml N, in the dinethylformamide, and with potpourri in stirring at room 15 minutes.In the solution that obtains, add 20g compound (ⅰ), subsequently in stirring at room 3 hours.In reaction mixture, add 500ml ethyl acetate, and transfer to potpourri in the separating funnel and wash with water.Tell oil phase and use watery hydrochloric acid and water continuous washing, oil phase is removed with distillating method under the decompression desolvate then.The mixed solvent that in residue, adds 100ml ethyl acetate and hexane, and, get 15.3g compound (D-1) by filtering the crystallization of collecting precipitation.

Synthetic embodiment 2

Synthesizing of compound (D-6)

Except the compound (ⅳ) with equivalent replaces compound (ⅱ) and compound (ⅲ) the replacement compound (ⅰ) with 14.8g, be used in method identical among the embodiment 1 and react.Reaction mixture gets 8.5g compound (D-6) by crystallization in the mixed solvent of isopropyl alcohol and hexane.

Synthetic embodiment 3

Synthesizing of compound (D-8)

Except the compound (V) with 16.5g replaces compound (ⅰ) and compound (ⅵ) the replacement compound (ⅱ) with 12.3g, finish reaction with method identical among the embodiment 1.Reaction product gets 9.8g compound (D-8) by crystallization in the mixed solvent of ethyl acetate and hexane.

Synthetic embodiment 4

Synthesizing of compound (D-9)

Except the compound (ⅶ) with 15.0g replaces finishing reaction with the same procedure of synthetic embodiment 1 compound (ⅲ), get 12.1g compound (D-9).

Synthetic embodiment 5

Synthesizing of compound (D-17)

In the 200ml N,N-dimethylacetamide, add the compound (ⅸ) of 17.1g and the triethylamine of 6.3g, stirred subsequently 15 minutes.Under room temperature, last 20 minutes, in gained solution, drip the solution that 20g compound (ⅷ) forms in the 100ml chloroform.Make reaction mixture in room temperature reaction 3 hours and again in 40 ℃ of reactions 30 minutes.Reaction afterreaction potpourri is handled with embodiment 1 identical method.By crystallization in the mixed solvent of ethyl acetate and hexane, get 15.3g compound (D-17).

Synthetic embodiment 6

Synthesizing of compound (D-23)

At 100ml N, dissolve the compound (ⅳ) of 25.5g in N-dimethyl-2-imidazolone, and the solution ice bath is cooled off.In solution, add 3.7g sodium hydride (60%), stirred subsequently 20 minutes.The compound (X) that adds 20g in solution makes potpourri in room temperature reaction 5 hours, is heated to 50 ℃ then, under this temperature it is stirred 1.5 hours.After the reaction, make reaction mixture be cooled to room temperature, and to wherein adding 200ml ethyl acetate and 200ml water.Reaction mixture is poured in the separating funnel, and oil phase water, watery hydrochloric acid and water continuous washing are told oil phase and are descended distillation except that desolvating in decompression.Residue is filtered and is collected crystal by crystallization in ethyl acetate and the hexane, gets 15.5g compound (D-23)

According to the present invention, formula (I) colour coupler can be attached in the layer of any composition photosensitive material, but preferably it is added in photosensitive silver halide emulsion layer and/or its adjacent layer, and further preferably is added in the photosensitive silver halide emulsion layer.By two layers or more have under the layer situation about being formed of different light sensitivity, the colour coupler shown in the formula (I) most preferably is to be added to not to be to have in the layer of top high photographic sensitivity at the photosensitive silver halide emulsion layer that contains special silver halide particle according to the present invention.

The total amount normally 3 * 10 that is used for formula (I) colour coupler of photosensitive material ^-7To 1 * 10 ^-3Mol/m ², preferably 3 * 10 ^-6To 5 * 10 ^-4Mol/m ²And most preferably be 1 * 10 ^-5To 2 * 10 ^-4Mol/m ²Formula (I) colour coupler can be admixed in the photosensitive material by following conventional method.

In fact, should contain the silver halide particle of chemical sensitization according to emulsion layer of the present invention, this particle has the clear layer that is made of the bromo-iodide that contains 7 to 45mol% silver iodide separately and each has total agi content greater than 4mol%.

" layer clearly " state of herein mentioning can be observed by X-line diffractometer.For example at HHirsch, Journal of Photographic Science, Vol.10, P.129 ff.(1962) in described the application x-ray diffractometer and analyzed silver halide particle.Composition, angle of diffraction that the judgement grating constant depends on halogen satisfy the diffraction peak that Bragg equation (2dsin θ=n λ) occurs.

The detail of x-ray diffractometer can reference example such as Kisobunseki Kagaku Koza 24, " X-Sen kaisetsu ", Kyoritsu Shuppan and X-Sen kaisetsu no Tebiki, Rigaku Denki K.k.By the method for standard, make anticathode and K with Cu _B-ray is made the diffraction pattern (tube voltage: 40KV that radiographic source can obtain silver halide particle (220) crystal face; Tube current 60mA).In order to improve the resolution of diffractometer, should select suitable slit width (emission slit, reception slit etc.), the time constant of instrument, the sweep velocity and the writing speed of clinometer rule, and the precision of measuring should confirm by using standard model, for example silicon.

The implication of term used herein " layer " clearly be analyze the diffracted intensity of the silver halide with at least two peaks (220) crystal face shown on the x-ray diffractometer to the curve of angle of diffraction (angle of diffraction (2 θ) between 38 ℃ and 42 ℃ the time with the K of Cu _BRay obtains), one corresponding is that to have agi content be 7.0 to 45mol% high iodine layer, another is corresponding to be the low iodine layer that agi content is lower than 7mol%, a minimum is arranged between two peaks, is 1/10 to 3/1 corresponding to the diffracted intensity of high iodine range upon range of mountains with ratio corresponding to the diffracted intensity of low iodine range upon range of mountains, preferably be 1/5 to 3/1 and further preferably 1/3 to 3/1.

Between two peaks minimum diffracted intensity preferably be no more than peak lower in two or more peaks diffracted intensity 90%, further preferably be no more than 80% and most preferably be to be no more than 60%.

The analytic technique of the diffraction curve that is made of two diffraction components as everyone knows and at for example Jikken Butsurigaku kozall, " Koshi Kekkan " has description among the kyoritsu Shuppan.

Assumed curve is Gauss equation or Lorenz equation, the curve analyzer analytic curve that also available E.I.du Pont company produces.

A kind ofly contain two kinds of emulsions that all do not have clear layer structure and halogen to form two kinds of silver halide particles that differ from one another and on sensitometric characteristic, can not produce the significant effect that obtains as the present invention., two peaks also appear in the X-ray diffraction curve of this emulsion.No matter silver emulsion is emulsion prepared in accordance with the present invention or the emulsion that contains two kinds of variety classes silver halide particles as mentioned above, all can be judged by combining with above-mentioned x-ray diffractometer method with the method (after this being abbreviated as the EPMA method) of electro robemicroanalyser.

In order to carry out the EPMA method, prepare a kind of emulsion sample, wherein silver halide particle all scatter well, so that do not contact to each other.And with electronics come to its irradiation, can do ultimate analysis with the electrons excited bundle to very little part by x-ray analysis.Like this, determine the halogen composition of each particle by the intensity that obtains by the characteristic X-ray of silver of launching in each lattice and iodine.Be enough to judge by at least 50 particles being carried out the EPMA analysis whether the emulsion sample is according to the prepared emulsion of the present invention.

Emulsion of the present invention preferably is that uniform content of iodine is arranged in particle.Particularly, even more preferably have relative standard deviation by content of iodine distribution in the particle of EPMA method mensuration and be not more than 50%, and more preferably be to be not more than 35%.

To distribute be that the logarithm of iodide content and particle size has positive relationship to iodide in preferred another particle.Promptly bigger particle has higher iodide content, and smaller particles has minimum iodide content.Emulsion with this correlationship can provide granularity result preferably.Related coefficient preferably is 40% or higher, and further preferably is 50% or higher.

In each particle, except that bromo-iodide, its core also contains or chlorine silver bromide and/or silver bromide, and even more preferably the ratio of silver bromide is higher.The content of silver iodide is by 7.0 to 45mol% in the core, and even more preferably 15 to 45mol%, further preferably is 25 to 45mol%.The halogenic ingredient of most preferred nuclear is the bromo-iodide with agi content 30 to 45mol%.

The outermost layer of each particle contains and has agi content and be not more than 7.0mol%, even more preferably is not more than the silver halide of 5.0mol%.

Silver halide in outermost layer except that silver iodide can be any component in silver chloride, chlorine silver bromide and the silver bromide, and even more preferably the ratio of silver bromide is higher.Most preferred halogenic ingredient is bromo-iodide or the silver bromide that contains 0.5 to 5.0mol% silver iodide in the outermost layer.

Total halogenic ingredient should have the agi content above 4.0mol% in each particle, and even more preferably 6.0 to 25mol%, and further preferably 8.0 to 20mol% and most preferably be 10 to 25mol%.

Thereby because lower the active high content of iodine raising light absorption that just can realize of developing, therefore the granularity that is used for silver emulsion of the present invention has obtained partly improving, it is believed that this improvement should mainly give the credit to the structure of layer clearly that the outermost layer of the core that contains periodide content layer and protiodide content layer constitutes, this has caused the raising of latent image formation efficiency.

Having the average particle size particle size that the silver halide particle of clear layer structure has is 0.05 to 3.0 μ m, 0.1 to 1.5 μ m even more preferably, further preferably 0.2 to 1.3 μ m and most preferably 0.3 to 1.2 μ m.

The implication of term used herein " average particle size particle size " is as at T.H.James etc., The Theory of the Photographic Process, the third edition, P.39, the geometric mean of the particle size of describing MacMillan(1966) well-known in the art, the implication of term used herein " particle size " is as at Arakawa Masafumi, Ryudo Sokutei Nyumon, Vol.17, PP.299-313, Funtai Kogakukai(1980) the middle spherical diameter of describing (Sphere-equivalent diameter) such as grade.Particle size can be measured by for example Coulter computing method, individual particle ray scattering method (SingleParticle ray scattering method), laser beam scattering method methods such as (Laser ray scattering method).

Silver halide particle with clear layer structure can well-regulated crystalline form, as hexahedron, and the octahedral bodily form, dodecahedron shape and tetrakaidecahedron shape or irregular crystalline form are as spherical, potato-like crystalline form and form of flake crystal.The flakiness ratio of sheet twin is 1.2 to 8, especially particularly preferred 1.5 to 5.

No matter crystal grain is rule or irregular form, and preferably being has 50% or especially preferentially being selected for use of more (111) crystal face.(111) the crystal face ratio of crystal face can pass through the method mensuration of the colorant surface adsorption of Kubelka-Munk.When carrying out colorant surface adsorption method, should select preferential adsorption in or (111) crystal face or (100) crystal face cause the dyestuff that between the association state on (111) crystal face and (100) crystal face, has SPECTRAL DIVERSITY.This dyestuff is added in the emulsion, and draw the graph of a relation of spectral signature, and carefully examine and determine this figure to determine the crystal face rate of (111) crystal face to the amount of adding dyestuff.

Emulsion of the present invention can be used for any light-sensitive silver halide layer of photosensitive material, but preferably is to be used in blue or the green quick emulsion layer.When blue or green quick emulsion layer are when being made of the different layer of two or more light sensitivity, emulsion of the present invention preferentially be used for except that having minimum light sensitivity layer layer.

Among the present invention, what especially preferentially select for use is the compound of formula as follows (A) expression, so that guarantee that ISO is arranged, and improved granularity and Preser Nation of Photographic Materials stability and the variation that reduces the photosensitive property of processing solution.

Q-SM ¹（A）

Wherein Q represents to have directly or indirectly that thereon at least one of bonding is selected from-SO ₃M ²,-COOM ²,-OH and-NR ¹R ²The heterocycle residue of group; M ¹And M ²Represent hydrogen atom, alkaline metal, quartemary ammonium or Si Jia Phosphonium respectively; R ¹And R ²Represent hydrogen atom respectively or the replacement of 1 to 4 carbon atom is arranged or substituted alkyl not.

The compound of formula (A) expression is considered to have under the PH condition in developing solution water-soluble or improved water-soluble, thereby may be dissolved in the developing solution.In other words, if formula (A) compound is admixed in the photosensitive material, can expects that then it dissolves in developing solution, thereby pollute developing solution.But surprisingly owing to lowered photographic fog, the variation of development processing characteristics is very little.The behavior that the reason that this beyond thought result occurs is compound (A) is in it is present in photosensitive material the time and its very big difference when dissolving into developing solution.In any case, the mechanism of compound (A) effect it be unclear that and will obtain explaining by further studying in the future.

In the formula (A), example Bao Kuo oxazole, thiazole, imidazoles, selenazoles, triazole, tetrazolium, thiadiazoles, oxadiazole, pentazole, pyrimidine, thiazoa, triazine and the thiadiazine ring of the heterocycle residue that Q is represented, each ring wherein can with other carbocyclic ring or heterocyclic fused formation benzothiazole, benzotriazole, benzimidazole, benzoxazole, benzo selenazoles, Nai Bing oxazole, three azaindole alkane, diaza indoles alkane or four azaindole alkane rings.

Particularly preferably be those formulas (B) and the compound (C) represented in the sulfhydryl heterocycle compound of formula (A) expression:

In the formula (B), Y and Z represent nitrogen-atoms or CR respectively ⁴, R wherein ⁴The expression hydrogen atom replaces or substituted alkyl not, or replacement or unsubstituting aromatic yl; R ³Represent organic residue, particularly have the alkyl (for example: methyl, ethyl, propyl group, hexyl, dodecyl, octadecyl) of 1 to 20 carbon atom or have the aryl (for example: phenyl, naphthyl) of 6 to 20 carbon atoms that these groups are selected from-SO ₃M ²,-COOM ²,-OH and-NR ¹R ²In at least one group replace;-L ¹-represent to be selected from-S-,-O-, ,-CO-,-SO-and-SO ²-the connection base; N represents 0 or 1; M ¹, M ², R ¹And R ²As above definition.

R ³In alkyl or aryl can also have other substituting group, as halogen atom (for example: F; Cl; Br); alkoxy (for example: methoxyl; methoxy ethoxy); aryloxy group (for example: phenoxy group); alkyl (for aryl); aryl (for alkyl); amide group (for example: acetylamino; benzamido (benzoylamino)); carbamyl (for example: unsubstituted carbamyl; the phenyl amino formoxyl; the methylamino formoxyl); sulfonamido (for example: methanesulfonamido; benzenesulfonamido-); sulfamoyl (for example: unsubstituted sulfamoyl; the first sulfamoyl; the phenylamino sulfonyl); sulfonyl (for example: mesyl; benzenesulfonyl); sulfinyl (for example: the first sulfinyl; the benzene sulfinyl); cyano group; alkoxy carbonyl group (for example: methoxycarbonyl group); aryloxy carbonyl (for example: carbobenzoxy); nitro or the like.

R wherein ³There are two or more substituting groups to be selected from-SO ₃M ²,-COOM ²,-OH and-NR ¹R ²Group, these substituting groups can be identical or different.

In the formula (c), X represent sulphur atom, oxygen atom or

; R ⁵Expression hydrogen atom, replacement or substituted alkyl not, or replacement or unsubstituting aromatic yl; L ²Expression-CONR ⁶,-NR ⁶CO-,-SO ₂NR ⁶-,-NR ⁶SO ₂-,-OCO-,-S-,-NR ⁶-,-CO-,-SO-,-OCOO-,-NR ⁶CONR ⁷-,-NR ⁶COO-,-OCONR ⁶-or-NR ⁶SO ₂NR ⁷; R ⁶And R ⁷Represent hydrogen atom, replacement or not substituted alkyl or replacement or unsubstituting aromatic yl respectively; R ³, M ¹, M ²As above define with n.

R ⁴, R ⁵, R ⁶Or R ⁷The alkyl or aryl of expression can be to be selected from above-mentioned relevant R ³Cited substituting group.

In formula (B) and the compound (C), R wherein ³Be can be by-SO ₃M ²Or-COOM ²Those compounds during the organic residue that replaces.

The preferred embodiment of the compound of formula (A) expression is shown in following so that explanation.

Formula (I) compound is known, and available known method is synthetic.The list of references of synthesis type (I) compound is listed below.

United States Patent (USP) 2,585,388 and 2,541,924, JP-B-42-21842(terminology used here " JP-B " expression " Japanese patent specification of authorization bulletin "), JP-A-53-50169, BrP 1,275,701, D.A.Berges, et al., Journal of the Heterocyclic Chemistry, No.15, p.981(1978), The Chemistry of Heterocyclic Chemistry, " Imidazole and Derivatives Part I ", pp.336-339, Chemical Abstract, Vol.58, No.7921, p.394(1963), E.Hoggarth, Journal of Chemical Society, pp.1160-1167(1949), S.R.Saudler ﹠amp; W.Karo, Orqanic Functional Group Preparation, pp.312-315, Academic Press(1968), M.Chamdon, et al., Bulletin de la Societe Chimique de France, p.723(1954), D.A.Shirley ﹠amp; D.W.Alley, J.Amer.Chem.Soc., Vol.79, p.4922(1954), A.Wohl ﹠amp; W.Marchwald, Ber.(Jounal of Chemical Society, German), Vol.22, p.568(1889), J.Amer.Chem.Soc., Vol.44, p.1502-1510, U.S. Patent 3,017,270, British Patent 940,169, JP-B-49-8334, JP-A-55-59463, Advanced in Heterocyclic Chemistry, Vol.9, pp.165-209(1968), West German Patent 2,716,707, The Chemistryof Heterocyclic Compounds Imidazole and Derivatives, Vol.l, p.384, Orq.Synth., the Vol. IV, p.569(1963), Ber., Vol.9, p.465(1976), J.Amer.Chem.Soc., Vol. 45, p.239(1923), JP-A-50-89034, JP-A-53-28426, JP-A-55-21007, JP-B-40-28496.

The compound of formula (A) is mixed in silver halide emulsion layer or the hydrophilic colloid layer (for example, middle layer, sealer, Yellow filter layer, anti-dizzy layer), preferably silver halide emulsion layer or its associated layers.

The consumption of formula (A) compound is from 1 * 10 ^-7To 1 * 10 ^-3Mol/m ², preferably from 5 * 10 ^-7To 1 * 10 ^-4Mol/m ², and more preferably from 1 * 10 ^-6To 3 * 10 ^-5Mol/m ²

According to the present invention, contain the preferably monodispersed emulsion of emulsion of special silver halide grain.The grain size of terminology used here " monodispersed emulsion " expression emulsion distributes to have and is not more than 0.25 variation factor (S/ r), and wherein r is the average crystal grain size, and S is the standard deviation of grain size.The grain size that is each crystal grain is as r _i, and the number of crystal grain is as n _i, the average crystal grain size defines in order to following equation:

r＝∑n _i·r _i/∑n _i

Correspondingly, standard deviation S defines with following formula:

Projected area equivalent diameter in terminology used here " grain size of single crystal grain " the expression microphoto, microphoto with known technology (normally electron microscopic photography) as at T.H.James, et.al, The Theory of the Photographic process, The 3rd Ed., pp.36-43, MacMillan(1966) technology described in is taken.Terminology used here " projected area equivalent diameter " is defined as the diameter of a circle that equates with the projected area of silver halide grain, as described in the above list of references.Although silver halide has spherical outer other shape (for example, cube, the octahedral bodily form, tetrakaidecahedron shape, sheet, potato-like), average brilliant material size r and its standard deviation S can obtain as mentioned above.

Silver halide grain has and is not more than 0.25 grain size variation factor, preferably is not more than 0.20, more preferably is to be not more than 0.15.

In the present invention, in order further to improve sharpness, the polymer of monomers colour coupler that will contain useful formula given below (PA) expression mixes being particularly preferred in the green layer.As if if a kind of photochromics processed processing when replenishing developing solution that contains common hydrolyzable DIR colour coupler then can be observed the increase of contrast, this should give the credit to polymkeric substance colour coupler recited above.On the contrary, according to the present invention, the photochromics of DIR colour coupler that contains useful formula (I) expression is not impaired because of this phenomenon.That is to say, because the use of formula (I) DIR colour coupler makes this polymkeric substance colour coupler freely to use.

R wherein ₁₂₁Represent hydrogen atom, have the alkyl of 1 to 4 carbon atom, or the chlorine atom;-D-representative-COO-,-CONR ₁₂₂-, or that replace or unsubstituted phenyl; Replace or the unsubstituted alkylidene of-E-representative, phenylene replacement or unsubstituted, or that replace or unsubstituted inferior aralkyl;-F-representative-CONR ₁₂₂-,-NR ₁₂₂CONR ₁₂₂-,-NR ₁₂₂COO-,-NR ₁₂₂CO-,-OCONR ₁₂₂-,-NR ₁₂₂-,-COO-,-OCO-,-CO-,-O-,-S-,-SO ₂-,-NR ₁₂₂SO ₂-, or-SO ₂NR ₁₂₂-; R ₁₂₂Represent hydrogen atom, replace unsubstituted fat-based, or replacement or unsubstituted aryl; If any, Fu Shuo R ₁₂₂Can be identical or different; P, q and r represent 0 or 1 respectively, but they can not represent 0 simultaneously; And T represents with magenta colour coupler residue given below or that (PB) represent, any segment Ar that it is described below, Z, and R ₁₃₃The position is connected-(D)-(E)-(F)-segment on.

Wherein Ar representative is known, in the 1-position of 2-pyrazolin-5-one colour coupler as substituent group; R ₁₃₃Representative replaces or unsubstituted anilino-, replacement or unsubstituted amide group are (for example, the alkyl carbonamido, the phenyl carbons amide group, alkoxy carbonyl amido, phenoxy group carbonamido), replacement or unsubstituted urea groups are (for example, the alkyl urea groups, the phenyl urea groups), or replacement or unsubstituted sulfoamido; And Z represents hydrogen atom, halogen atom (for example, chlorine, bromine) or by oxygen atom, nitrogen-atoms, or the coupling leaving group that connects of sulphur atom.

In formula (PB), the substituting group of representing with Ar comprises alkyl, and the alkyl of replacement (for example; haloalkyl (for example, fluoro-alkyl), cyanoalkyl; the benzyl alkyl), replace or or unsubstituted heterocyclic (for example, 4-pyridine radicals; the 2-thiazolyl); with replacement or unsubstituted aryl, the substituting group of heterocyclic radical or aryl comprises alkyl (for example, methyl; ethyl); alkoxy (for example, methoxyl, ethoxy); aryloxy group (for example; phenoxy group), alkoxy carbonyl group (for example, methoxycarbonyl group); amide group (for example; acetamido), carbamyl, alkyl-carbamoyl (methylamino formoxyl; the ethylamino formoxyl); the dialkyl amido formoxyl (for example; formyl-dimethylamino), aryl-amino-carbonyl (for example, phenyl amino formoxyl); alkyl sulphonyl (for example; methyl sulphonyl), aryl sulfonyl (for example, phenyl sulfonyl); alkylsulfonamido (for example; the methylsulfonyl amido), aryl-sulfonyl amino (for example, phenyl-sulfamide base); sulfamoyl; alkylsulfamoyl group (for example, the ethyl sulfamoyl), dialkyl sulfamine (for example dimethylamino sulfonyl); alkylthio group (for example; the methyl sulfenyl), artyl sulfo (for example, phenyl sulfenyl); cyano group; nitro, and halogen atom (for example, fluorine; chlorine, bromine).If any, two or more substituting groups can be identical or inequality.These substituting groups are halogen atom preferably, alkyl, alkoxy, alkoxy carbonyl group, and cyano group.

As R ₁₃₃Anilino-, amide group, the substituting group of urea groups or sulfoamido comprises that halogen atom (for example, fluorine, chlorine, bromine), straight or branched alkyl (for example, methyl, the tert-butyl group, octyl group, myristyl), alkoxy is (for example, methoxyl, ethoxy, 2-ethyl hexyl oxy, tetradecyloxyaniline), amide group (for example, acetamido, benzamido, amide-based small, decoyl amido, the myristoyl amido, α-(2,4-two-tertiary pentyl phenoxy group) acetamido, α-(2,4-two-tertiary pentyl phenoxy group) amide-based small, α-(3-pentadecyl phenoxy group) hexanoyl amido, α-(4-hydroxyl-3-tert-butyl group phenoxy group) myristoyl amido, 2-oxygen-pyrrolidine-1-base, 2-oxygen-5-myristyl pyrrolidine-1-base, N-methyl-myristoyl amido); Sulfoamido (for example; the methylsulfonyl amido; benzene sulfonamido; ethanesulfonamide group; the tolysulfonyl amido; hot sulfoamido; to the dodecyl benzene sulfonamido; N-methyl-tetradecane sulfoamido); sulfamoyl (for example; sulfamoyl; N-methyl sulfamoyl; N-ethyl sulfamoyl, NN-dimethylamino sulfonyl, NN-dihexyl sulfamoyl; N-cetyl sulfamoyl; N-(3-(dodecyloxy)-propyl group) sulfamoyl, N-(4-(2,4-two-tertiary pentyl-phenoxy group) butyl) sulfamoyl; N-methyl-N-myristyl sulfonamide); carbamyl (for example, N-methylamino formoxyl, N-butyl carbamyl; N-octadecyl carbamyl; N-(4-(2,4-two-tertiary pentyl phenoxy group) butyl) carbamyl, N-methyl-N-myristyl carbamyl); the diamides base (for example; N-succimide base, N phlhalimide base, 2; 5-dioxy-1-oxazole alkyl; 3-dodecyl-2,5-dioxy-1-glycolylurea base, 3-(N-acetyl group-N-dodecyl amino) the succimide base); alkoxy carbonyl group (for example; methoxycarbonyl group, tetradecane oxygen carbonyl, benzyloxycarbonyl group); the alkoxy sulfonyl (for example; the methoxyl sulfonyl, butoxy sulfonyl, octyloxy sulfonyl; the tetradecyloxyaniline sulfonyl); (phenoxy group sulfonyl for example is to methyl-phenoxy group sulfonyl, 2 for aryloxy sulfonyl; 4-two-uncle-amyl group phenoxy group sulfonyl); alkyl sulphonyl (for example, mesyl, ethylsulfonyl; hot sulfonyl; 2-ethylhexyl sulfonyl, the hexadecane sulfonyl), aryl sulfonyl is (for example; benzenesulfonyl; 4-nonyl benzene sulfonyl), alkylthio group (for example, methyl mercapto; ethylmercapto group; own sulfenyl, benzylthio, tetradecane sulfenyl; 2-(2; 4-two-tertiary pentyl phenoxy group), arylthio (for example, thiophenyl; to the toluene sulfenyl); alkoxycarbonyl amido (for example, methoxycarbonyl group amino, carbethoxyl group amino; benzyloxycarbonyl amino; hexadecane oxygen carbonylamino), alkyl urea groups (for example, N-methyl urea groups; N; N-dimethyl urea groups, N-methyl-N-dodecyl urea groups, N-cetyl urea groups; N; N-two-octadecyl urea groups), acyl group (for example, acetyl group; benzoyl; octadecanoyl is to dodecanoyl amido benzoyl), nitro; carboxyl; sulfo group, hydroxyl, and trichloromethyl.In these substituting groups, alkyl group or part have 1 to 36 carbon atom, and aryl moiety has 6 to 38 carbon atoms.

The example of the coupling leaving group of representing with Z comprises that those connect by oxygen atom, for example, and acetoxyl group, propionyloxy, benzoyloxy, ethoxy grass acyloxy, the acetone acyloxy, cinnamoyloxy group, phenoxy group, the 4-cyano-benzene oxygen, 4-ethyl sulfonamide phenoxyl, alpha-naphthoxy base, 4-cyanato-, 4-Methanesulfomide phenoxyl, 3-pentadecane phenoxy group, benzyloxycarbonyl group oxygen base, ethoxy, 2-cyano group ethoxy, benzyloxy, 2-phenyl ethoxy, 2-phenoxy group ethoxy, 5-phenyl-tetrazole radical oxygen base and 2-[4-morpholinodithio base oxygen base; Those connect by nitrogen-atoms, described at JP-A-59-99437, for example, benzene sulfonamido, N-ethyltoluene sulfoamido, seven fluorine amide-based smalls, 2,3,4,5,6-phenyl-pentafluoride formamido, hot sulfoamido, to benzonitrile base urea groups, N, N-diethyl amino sulfoamido, 1-piperidyl, 5,5-dimethyl-2,4-dioxy-3-oxazole alkyl, 1-benzyl-5-ethoxy-3-glycolylurea base, 2-oxygen-1,2-dihydro-1-pyridine radicals, imidazole radicals, pyrazolyl, 3,5-diethyl-1,2, the 4-triazol-1-yl, 5-or 6-bromobenzene and triazol-1-yl, 5-methyl isophthalic acid, 2,3,4-triazol-1-yl, and benzimidazolyl; And those connect by sulphur atom, for example, and thiophenyl, 2-carboxyl thiophenyl, 2-methoxyl-5-octyl group-thiophenyl; 4-mesyl thiophenyl, the hot sulfoamido phenyl of 4-sulphur, benzylthio, 2-cyano group ethylmercapto group, 5-phenyl-2; 3,4,5-tetrazole radical sulphur and 2-[4-morpholinodithio base.Preferably those connect by nitrogen-atoms these coupling leaving groups, particularly pyrazolyl.

In formula (PA) ,-E-representative replaces or unsubstituted alkylidene, replace or unsubstituted inferior aralkyl, or replacement or unsubstituted phenylene, they can have 10 carbon atoms separately at most.Alkylidene can have the structure of straight or branched.The example of alkylidene comprises methylene, methyl methylene, dimethylated methylene base, dimethylene, trimethylene, tetramethylene, pentamethylene, hexa-methylene, and decamethylene.The example of inferior aralkyl comprises benzal, and the example of phenylene comprises phenylene, metaphenylene and methylphenylene.As the alkylidene of E, the substituting group of inferior aralkyl or phenylene comprises aryl (as phenyl), nitro; hydroxyl, cyano group, sulfo group; alkoxy (as methoxyl); aryloxy group (as phenoxy group), acyloxy (as acetoxyl group), amide group (as acetamido); sulfoamido (as the methylsulfonyl amido); sulfamoyl (as the methyl sulfamoyl), halogen atom (as, fluorine; chlorine; bromine), carboxyl, carbamyl (as the methylamino formoxyl); alkoxy carbonyl group (as methoxycarbonyl group); and sulfonyl (as mesyl), if any, two or more substituting groups can be identical or different.

In the described in the above polymkeric substance colour coupler, can not be with the oxidation product coupling of aromatic primary amine developer, can be with colour coupler monomer (PA) copolymerization, the ethylenically unsaturated monomer that does not add lustre to comprises acrylate, methacrylate, butenoate, vinyl esters, maleic acid diester, dimethyl ester, methylene-succinic acid diester, acrylamide, Methacrylamide, vinyl ether and styrene or derivatives thereof.

The example of acrylate has methyl acrylate, ethyl acrylate, acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Hexyl 2-propenoate, 2-ethylhexyl acrylate, acrylic acid acetoxyl group ethyl ester, phenyl acrylate, 2-methoxy acrylate, 2-ethoxy propylene acid esters and 2-(2-methoxy ethoxy) acrylate of ethyl.The example of methacrylate has methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, n-BMA, metering system tert-butyl acrylate, cyclohexyl methacrylate, methacrylic acid 2-hydroxyethyl ester and methacrylic acid 2-ethoxyethyl group ester.The example of butenoate has butyl crotonate and the own ester of butenoic acid.The example of vinyl esters has vinyl-acetic ester, vinyl propionate base ester, butyric acid vinyl esters, methoxyacetic acid vinyl esters and benzoic acid vinyl esters.The example of maleic acid diester has diethyl maleate, dimethyl maleate, and dibutyl maleate.The example of dimethyl ester has DEF, dimethyl fumarate, and dibutyl fumarate.The example of methylene-succinic acid diester has the methylene-succinic acid diethylester, methylene-succinic acid dimethyl ester and methylene-succinic acid dibutyl ester.The example of acrylic amide has acrylamide, Methacrylamide, ethyl acrylamide, propyl group acrylamide, the normal-butyl acrylamide, tert-butyl group acrylamide, cyclohexyl acrylamide, 2-methoxy ethyl acrylamide, DMAA, diethyl acrylamide, and Phenyl Acrylamide.The example of Methacrylamide has the methyl acrylamide, ethyl-methyl acrylamide, normal-butyl Methacrylamide, tertiary butyl Methacrylamide, 2-methoxy acrylamide, dimethylmethacryl amide and diethylmethyl acrylamide.The example of vinyl ether has methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxy ethyl vinyl ether and dimethyl aminoethyl vinyl ether.The example of styrene derivative has methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, cumene ethene, butylstyrene, 1-chloro-4-methyl-benzene, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chlorostyrene, dichlorostyrene, bromstyrol, vinyl benzoic acid methyl esters, and 2-methyl styrene.

What further comprise in comonomer has an allyl compound (as allyl acetate), vinyl ketone (as methyl vinyl ketone), vinyl heterocyclic compound (as, vinylpyridine), glycidyl esters (as the acrylic acid glycidyl esters), unsaturated nitrile (for example, vinyl cyanide), acrylic acid, methacrylic acid, the methylene butenoic acid, maleic acid, methylene butenoic acid mono alkyl ester (for example, methylene butenoic acid monomethyl ester), maleic acid mono alkyl ester (with maleic acid monomethyl ester), citraconic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid (as the acryloyl-oxy pyrovinic acid), with acrylamide alkyl sulfonic acids (as, 2-acrylamido-2-methyl ethyl sulfonic acid).These acid can be with alkaline metal (as Na, K) or the form of the salt that forms of ammonium ion.

Comonomer above-mentioned is acrylate preferably, methacrylate, styrene or derivatives thereof, maleate, acrylamide, and Methacrylamide.

These comonomers can two or more mix use.For example, can use the potpourri of n-butyl acrylate and styrene or butylstyrene and the potpourri of metering system tert-butyl acrylate and n-butyl acrylate.

With respect to the monomer (PB) in the pinkish red polymkeric substance colour coupler, the ratio of the unit that adds lustre to is 5 to 80% weight normally.From colour reproduction, colored colour rendering and stability, preferred ratio is 30 to 70% weight ratios.In this case, not restriction, the scope about 250 to 4000 that equivalent weight (the gram number that contains the polymkeric substance of 1mol monomer colour coupler) is common.

The polymkeric substance colour coupler that can use in invention is added in silver halide emulsion layer or its adjacent courses.

In the time of in pinkish red polymkeric substance colour coupler being added to the layer that contains silver halide, to 0.5mol, preferably 0.03 to 0.25mol from every mol silver 0.005 for the amount of adding.When it is added to light in the insensitive layer, the amount that is added into from 0.01 to 1.0g/m ², and preferably 0.1 to 0.5g/m ²

The polymkeric substance colour coupler can prepare by the polymerization of above-mentioned monomer colour coupler, and the lipophilic polymer colour coupler that produces is dissolved in organic solvent, and organic solvent solution emulsification in aqueous gelatin solution is formed latex.The polymkeric substance colour coupler also can directly prepare by emulsion polymerization.

The emulsification in aqueous gelatin solution of lipophilic polymer colour coupler is had description with the method for disperseing to form latex in U.S. Pat 3451820, and method of emulsion polymerization is at U.S. Pat 4080211 and US 3370952 and European patent EP 341088A ₂In description is arranged.

The synthetic of pinkish red polymkeric substance colour coupler can be undertaken by using polymerization initiator and polymer solvent.This compound is seen and is set forth in JP-A-56-5543, JP-A-57-94752, JP-A-57-176038, JP-A-57-204038, JP-A-58-28745, JP-A-58-10738, JP-A-58-42044, and JP-A-58-145944.

Polymerization temperature will be looked the polymer molecular weight of generation, used initiator type and similar factor and decide.Be lower than 0 ℃, up to 100 ℃ or even higher temperature be acceptable, yet polymerization is carried out under 30 ℃ to 100 ℃ temperature usually.

The special example of the pinkish red polymkeric substance colour coupler that can use in the present invention provides below, and they only are used for illustrative purposes, rather than is used for limiting. and the copolymerization ratio of demonstration provides with mole.

According to the present invention, photochromics comprises a kind of support, has at least a kind of sense blue in the above, feels green, feels red silver halide emulsion layer.The quantity of silver halide emulsion layer and non-photosensitivity layer and order have no particular limits.Typical material comprises support, have a photosensitive layer of being made up of two or more silver halide emulsion layers thereon at least, they are for blue light, green glow, or ruddiness has essentially identical colour sensitivity, and different is light sensitivity (after this being called the unit photosensitive layer).The multilayer color silver halide photographic-material comprises support usually, has in order thereon red sensing unit layer, to green sensing unit layer with to blue sensing unit layer.According to final use, the order of above-mentioned each layer can change, and perhaps has the layer that has to have different colours sensitivity between same color sensitivity two-layer.

The non-photosensitivity layer that comprises various middle layers can be arranged between these silver halide photosensitive layers, perhaps as the outermost layer or the bottom.

As at JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, described in JP-A-61-20037 and the JP-A-61-20038 like that, this middle layer can contain colour coupler, the DIR compound, or the like, and also can contain the blend of colors inhibitor usually.

As described in Deutsches Reichs-Patent 1121470 and the BrP 923045, each unit photosensitive layer preferably has by a high sense emulsion layer and the double-decker that low sense emulsion layer is formed.The two-layer order that reduces with its light sensitivity usually of each unit photosensitive layer is arranged towards support.Between two silver halide emulsion layers, can arrange a non-photosensitivity layer.Also a low sense emulsion layer can settled away from the one side of support, and settling a high sense emulsion layer near the place of support, just as JP-A-57-112751, JP-A-62-200350, such described in JP-A-62-206541 and the JP-A-62-206543.

The specific examples of order comprises the order of sense red beds (RH)/low sense red beds (RL)/support of feeling of green layer (GL)/height sense of green layer (GH)/low sense of the blue layer of sense (BH)/high sense of the blue layer of sense (the BL)/high sense of low sense between actual layer, the order of BH/BL/GL/GH/RH/RL/ support, and BH/BL/GH/GL/RL/RH/ support.

As also using in the interlayer order of the blue layer/GH/RH/GL/RL/ support of the sense described in the JP-B-55-34932 with in the interlayer order of the blue layer/GL/RL/GH/RH/ support of the sense described in JP-A-56-25738 and the JP-A-62-63936.

Further, as proposing among the JP-B-49-15495, a unit photosensitive layer can be formed by three layers, its light sensitivity is by towards the descending order of the direction of support and difference, the silver halide emulsion layer that is top high photographic sensitivity is as the superiors, the silver halide emulsion layer of medium-contrast is as the middle layer, and the minimum silver halide emulsion layer of light sensitivity is as orlop.In each elementary layer, three layers of order with the emulsion layer of the emulsion layer/low speed of the emulsion layer/ISO of medium-contrast of different light sensitivity begin to arrange from the side away from support, as described in JP-A-59-202464.

Further, the order of the emulsion layer of high sense emulsion layer/low sense emulsion layer/medium-contrast, or the order of the emulsion layer of low sense emulsion layer/medium-contrast/height sense emulsion layer also can be used.

If elementary layer is by four layers or more multi-layered the composition, the arrangement of interlayer can be done similar change.

As mentioned above, the structure of photosensitive material layer or arrangement can be done suitable selection according to last application.

Except that above-described specific silver halide, can be used for other silver halide of the present invention and be explained as follows.

The silver halide that uses in the emulsion layer of taking pictures is the iodine silver bromide preferably, silver iodochloride or iodine chlorine silver bromide, they in every kind the content of silver iodide be no more than about 30mol%, and the agi content of preferred iodine silver bromide or iodine chlorine silver bromide is from about 2mol% to 10mol%.

The silver halide grain in the emulsion of taking pictures can have the crystalline form of rule, and as cube shaped, the octahedral bodily form and tetrakaidecahedron shape and irregular crystalline form are as sphere and tabular; Crystalline form with crystal defect is as twin plane; Or it mixes crystalline form.

Silver halide grain can have the grain size of wide region, comprise the fine grain of about 0.2 μ m or reach the crystal grain of about 10 μ m than area diameter projected little, the both monodispersed emulsion of silver emulsion, also polydisperse emulsion.

The silver halide of the Shi Yonging emulsion of taking pictures can prepare with the method described in the following document in the present invention: RD is made in abbreviation later on as Research Disclosure(), No.17643(Dec., 1978), pp.22-23, " I.Emulsion Preparation and Types ", ibid, No.18716(Nov., 1979), p.648, ibid, No.307105(Nov., 1989), pp.863-865, P.Glafkides, Chemic et Phisique Photoqraphique, Paul Montel(1967), G.F.Duffin, Photoqraphic Emulsion Chemistry, Focal Press(1966), and V.L.Zelikman et al., Making and Coating Photoqraphic Emulsion, Focal Press(1964).

U.S. Pat 3574628 and 3655394 and BrP 1413748 in single emulsion that disperses of describing preferably used.

Flakiness ratio be about 3 or bigger tabular crystal grain also be useful.Such tabular crystal grain can be used for example Gutoff, Photographic Science and Engineering, Vol.14, pp.248-257(1970), U.S. Pat 4434226,4414310,4433048, with 4439520, and the method described in the BrP 2112157 prepares at an easy rate.

Silver halide grain can be homogeneous phase crystal grain or the heterogeneous crystal grain that whole single crystal grain has uniform crystal structure; heterogeneous crystal grain comprises those, and portion and shell have different halogens and form within it; those form different at its each interlayer halogen; have different halogens with those by epitaxial growth and form, and the silver halide that fuses to the there.Also can use with outer other compound of silver halide such as the silver halide of silver thiocyanate or massicot fusion.The potpourri that comprises various different crystal forms crystal grain also can be used.

The emulsion of taking pictures both can be the surface latent image type that mainly forms latent image at grain surface, can be again the internal latent image type of latent image that mainly forms in the inside of crystal grain, but should be negativity.Internal latent image type emulsion can be the core/shell type described in JP-A-63-264740.This core/shell type internal latent image type emulsion can prepare with the method described in the JP-A-59-133542.The thickness preferred range of this type emulsion shell is 3 to 40nm, and particularly 5 to 20nm, although change with the method for developing.

Silver emulsion adopts physical ripening usually, chemical ripening, and spectral sensitization.The adjuvant that can use in these steps has to be listed in the back, as RD, and Nos, described in 17643,18716 and 307105.

In photochromics of the present invention, two or more are comprising grain size, and grain size distributes, and halogen is formed, and crystalline form can be used in one deck with the potpourri of photosensitive emulsion different at least a characteristic of light sensitivity.

The silver halide grain of the surperficial ashing of in U.S. Pat 4082553, describing, the silver halide grain of the inside ashing of describing in U.S. Pat 4626498 and JP-A-59-214852 and micelle silver can preferably be applied in photosensitive silver halide emulsion layer and/or the photosensitive basically hydrophilic glue-line.The terminology used here silver halide grain of surperficial ashing " inner or " meaning is exposure or unexposed, can be equably (not having imaging) development, as broad as long silver halide grain.The method of the silver halide grain of preparation inside or surperficial ashing is described in U.S. Pat 4626498 and JP-A-59-214852.

In the core/shell type silver halide grain of inner ashing, the halogen of nuclear and shell is formed both can be different, also can be identical.

Silver halide grain inner or surperficial ashing can have the silver chloride of being selected from, the chlorine silver bromide, and any halogen of iodine silver bromide and chlorine iodine silver bromide is formed.The grain size of the silver halide grain of these ashing has no particular limits, and preferred average crystal grain size is 0.01 to 0.75 μ m, particularly preferably is 0.05 to 0.6 μ m.The crystalline form of the silver halide grain of ashing is not particularly limited, both regular, also irregular.Can use polydispersion emulsion, but wherein the grain size of silver halide grain at least 95% general assembly (TW) or granule number drop on the average crystal grain size 40% within single to disperse emulsion be preferred.

In the present invention, the fine grain of non-photosensitivity silver halide preferentially uses.Terminology used here " the non-photosensitivity silver halide fine grain " meaning is for insensitive for the light that obtains chromatic image imaging exposure and therefore not have the silver halide particulate of development basically in developing process.Preferably non-photosensitivity silver halide fine grain is not ashing in advance.

Silver halide compact grained bromide sliver content is 0 to 100mol%, if necessary, can contain silver chloride and/or silver iodide, and silver iodide preferably, and its content is 0.5 to 10mol%.

The silver halide compact grained average crystal grain size mean value of equivalent diameter of projected area circle (etc.) is preferably 0.01 to 0.5 μ m, more preferably is 0.02 to 0.2 μ m.

The silver halide fine grain can be used the method preparation identical with common photosensitive silver halide grains.The neither light requirement chemical sensitization of formed silver halide compact grained surface, not light requirement spectrum sensitization again.Yet what wish to do is, resembles triazole compounds, the azepine indene compound, and benzo plug azole compounds, the such known stabilizers of sulfhydryl compound and zinc compound was added in this silver halide fine grain before the silver halide fine grain adds coating composition.Contain silver halide compact grained layer and preferably contain micelle silver.

The photochromics of the present invention preferably coating weight scope of silver is no more than 6.0g/m ², more preferably be to be no more than 4.5g/m ²

The known adjuvant of taking pictures that can use in the present invention is at RD, and Nos has description in 17643, the 18716 and 307105 aforesaid lists of references, as listing in the following table.

Adjuvant RD 17643 RD 18716 RD 307105

1, chemical sensitizer P.23 P.648, right is P.866

column（RC）

2, sensation degree dose do.

3, spectral sensitization agent, PP.23-24 P.648, RC PP.866-868

Super quick dose of to P.649, RC

4, whitening agent P.24 P.647, RC is P.868

5, anti-photographic fog agent, PP.24-25 P.649, RC PP.868-870

Stabilizing agent

6, light absorber, PP.25-26 P.649, RC to is P.873

Filter dye, P.650, left

Ultraviolet absorber column(LC)

7, the stain inhibitor P.25, RC P.650, LC is P.872

to RC

8, dyestuff video stabilizing agent P.25 P.650, LC do.

9, hardener P.26 P.651, LC PP.874-875

10, bonding agent do. PP.873-874 P.26

11, plasticiser, lubricant P.27 P.650, RC is P.876

12, coating additive PP.26-27 P.650, RC PP.875-876

Surfactant

13, antistatic agent do. PP.876-877 P.27

14, delusterant PP.878-879

Because the decline of the performance of taking pictures that causes of formaldehyde gas, as described in U.S. Pat 4411987 and the US4435503, the compound that can be fixed with formaldehyde reaction can preferably be added in the photochromics in order to prevent.

Photochromics of the present invention preferably contains at U.S. Pat 4740454 and US4788132, the sulfhydryl compound described in JP-A-62-18539 and the JP-A-1-283551.

Photochromics preferably contains can discharge fogging agent, and the compound of development accelerant, or ag halide solvent, or its precursor are irrelevant with the silver amount of having developed that produces in the developing process, as described in the JP-A-1-106052.

Photochromics preferably contains at dye dispersion or the EP317308A described in WO88/04794 and the JP-A-1-502912, the dyestuff described in U.S. Pat 4420555 and the JP-A-1-259358.

Various colour coupler can be used in the present invention.The specific example of useful colour coupler is at RD, NO.17643, and VII-C to G and RD, NO.307105 states in the patent of quoting among VII-C to G.

The example of suitable yellow colour former is narrated in following document: as U.S. Pat 3933501,4022620,4326024,4401752 and 4248961, JP-B-58-10739, BrP 1425020 and 1476760, U.S. Pat 3973968,4314023 and 4511649 and EP249473A.

The example of suitable magenta colour coupler comprises 5-pyrazolone colour coupler and pyrazolo pyrroles colour coupler.The example of particularly preferred magenta colour coupler is described in following document: U.S. Pat 4310619 and 4351897, European patent 73636, United States Patent (USP) 3061432 and 3725067, RD NO.24220(Jun., 1984), JP-A-60-33552, RD NO.24230(Jun, 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, U.S. Pat 4500630,4540654 and 4556630 and WO88/04795.

Cyan coupler comprises phenol colour coupler and naphthols colour coupler.The example of suitable colour coupler is described in following document: U.S. Pat 4052212,4146396,4228233,4296200,2369929,2801171,2772162,2895826,3772002,3758308,4334011 and 4327173, the open NO.3329729 of Deutsches Reichs-Patent, EP121365A, EP249453A, U.S. Pat 3446622,4333999,4775616,44515559,4427767,4690889,4254212 and 4296199 and JP-A-61-42658.

The typical example of the dye forming coupler of polymerization is in U.S. Pat 3451820,4080211, and 4367282,4409320 and 4576910, describe among BrP 2102137 and the EP341188A.

The example that produces the suitable colour coupler with medium diffusible dyestuff is in U.S. Pat 4366237, and BrP 2125570 is described among European patent 96570 and Deutsches Reichs-Patent (OLS) NO.3234533.

The example of suitable colour former agent of unnecessary absorption that can be used in the dyestuff that correction produces is at RD, NO.17643, VII-G, ditto, NO.307105, VII-G, U.S. Pat 4163670, JP-B-57-39413, U.S. Pat 4004929 and 4138258 and BrP 1146368 in describe.Further, can discharge fluorescent dye, in U.S. Pat 4774181, describe by the colour coupler that can proofread and correct the unnecessary absorption of the dyestuff that produces with its coupling, and as described in the U.S. Pat 4777120, but has a dyestuff former base as leaving group and should base can preferentially be used with the colour coupler that the developer reaction forms dyestuff.

The use that can discharge a colour coupler of useful residue on taking pictures when coupling also is favourable.Except that those can discharge with formula (I) representative, the example of the suitable DIR colour coupler of development restrainer is at RD, NO.17643, VII-F and the same, NO.307105, the patent of being quoted among VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350, and describe in the United States Patent (USP) 4248962 and 4782012.

The example of suitable colour coupler of press image form release nucleator or development accelerator when developing is described among JP-A-59-157638 and the JP-A-59-170840 in BrP 2097140 and 2131188.As at JP-A-60-107029, described in JP-A-60-252340 and the JP-A-1-44940, when carrying out oxidation-reduction reaction, can discharge fogging agent with the developer oxidation product, development accelerator, the compound of ag halide solvent etc. is preferentially used.

The further example that can be used for the colour coupler in the photochromics of the present invention comprises the competition colour coupler described in U.S. Pat 4130427, the many equivalent colour couplers described in U.S. Pat 4283472,4338393 and 4310618; Can discharge the colour coupler of DIR redox compound; Can discharge the colour coupler of DIR colour coupler, can discharge the redox compound of DIR colour coupler, maybe can discharge the redox compound of DIR redox compound, as described in JP-A-60-185950 and the JP-A-62-24252; Described in EP173302A and EP313308A, can be released in the colour coupler of the dyestuff that discharges its color of back recovery; As RD, Nos.11449 and 24241 and JP-A-61-201247 described in, can discharge the bleaching accelerator colour coupler; Described in U.S. Pat 4555477, can discharge the colour coupler of ligand; As described in the JP-A-63-75747, can discharge the colour coupler of leuco dye; Described in United States Patent (USP) 4774181, can discharge the colour coupler of fluorescent dye.

These colour couplers can be added in the material of taking pictures with various known process for dispersing.High boiling organic solvent useful in the process for dispersing of oil in water is described in as U.S. Pat 2322027.Under atmospheric pressure boiling point is that the specific examples of 175 ℃ or higher high boiling organic solvent has: phthalic acid ester (for example, dibatyl phithalate, dicyclo-hexyl phthlate, phthalic acid two-2-ethylhexyl, the phthalic acid decyl ester, two (2, the 4-di-tert-pentyl-phenyl) esters of phthalic acid, m-phthalic acid two (2, the 4-di-tert-pentyl-phenyl) ester, two (1, the 1-diethyl propyl group) esters of phthalic acid, the Phosphoric acid or phosphonic acid ester is (for example, triphenyl, the trimethylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, thricyclohexyl phosphate, three-ethylhexyl dihydrogen phosphate, the basic phosphate of three (dodecanes), three (butoxyethyl group) phosphate, trichlorine propyl phosphate, two (2-ethylhexyl) Phenylphosphine acid esters), benzoic ether (for example, benzoic acid 2-ethylhexyl, benzoic acid dodecyl ester, P-hydroxybenzoic acid 2-ethylhexyl), acid amides (for example, N, N-diethyl dodecane acid amides, N, the N-diethyl lauramide, N-myristyl pyrrolidone), alcohol or phenol are (for example, isooctadecane alcohol, 2, the 4-di-tert-pentyl phenol), the fat carboxylic ether is (for example, decanedioic acid two (2-ethylhexyl) ester, dioctyl azelate, tributyrin, lactic acid isooctadecane base ester, citric acid trioctylphosphine ester), anil (for example, N, N-dibutyl-2-butoxy-uncle's 5-octyl group aniline), and hydrocarbon (for example, paraffin wax, dodecyl benzene, diisopropyl naphthalane).Have and be not less than 30 ℃, preferably the form that the organic solvent from 50 ℃ to 160 ℃ of boiling points can potpourri is as secondary solvent.The exemplary of this class secondary solvent has ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, acetate 2-ethoxy ethyl ester, and dimethyl formamide.

About the latex process for dispersing, the step that comprises, but the specific examples of the latex of effect and load reaches among Deutsches Reichs-Patent (OLS) Nos.2541274 and 2541230 and describes in U.S. Pat 4199363.

Color photosensitive material of the present invention preferably contains various anti-corrosion additives or antifungal agent, as phenylethyl alcohol; With 1,2-benzisothiazole alkane-3-ketone, the positive butyl ester of P-hydroxybenzoic acid, phenol, 4-chloro-3.5-xylenol, 2-phenoxetol, the 2-(4-thiazolyl) benzimidazole etc., as JP-A-63-257747, described in JP-A-62-272248 and the JP-A-1-80941 like that.

The present invention can be widely used in the color photosensitive material, for example, and colour negative common use or that film is used, the colour reversal film that magic lantern or TV are used, color photographic paper, colour positive, and colour reversal photographic paper.

The example of the support that can be suitable in color sensitive material is at for example RD, and NO.17643 is P.28 the same, NO.18716, the right row of PP.647() to the 648(left column) and the same, NO.307105 describes in P.879.

In color sensitive material of the present invention, be no more than 28 μ m at the preferred total film thickness of hydrophilic gel granulosa of the side that sensitive emulsion layer is arranged, the preferred 23 μ m that are no more than, the most preferred 18 μ m that are no more than are no more than 16 μ m especially, and expansion rate T _1/2Be no more than 30 seconds, more preferably be no more than 20 seconds.Terminology used here " total film thickness " meaning is to place the thickness that recorded in 2 days under the condition of 25 ℃ and relative humidity 55%.Term " expansion rate T _1/2" expression color photosensitive material expand into 1/2 required time of saturated expanded thickness; saturated expanded thickness is defined as 90% of maximum swelling thickness; when color sensitive material contacts with colour development solution, reached maximum swelling thickness in 3 minutes 15 seconds 30 ℃ of expansions.Expansion rate can be measured with the known method that use this area, for example, and A.Green, et.al., Photogr aphic Science and Engineering, Vol.19, NO.2, the swellability measurement meter of type described in the PP.124-129.

Expansion rate T _1/2Can be by adding an amount of controlling at the hardener of gelatin adhesive or by changing coating maturation condition afterwards.

Further, photosensitive material preferably has 150 to 400% degree of expansion.Terminology used here " degree of expansion " expression is from the thickness of maximum swelling defined above and the value that obtains according to following formula: (thickness-thickness of maximum swelling)/thickness.

Photosensitive material of the present invention preferably has the back sheet of being called at the reverse side of sensitive emulsion layer, and total dry thickness is the hydrophilic colloid layer of 2 to 20 μ m.Back sheet preferably contains aforesaid adjuvant, for example, and light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, bonding agent, plastifier, lubricant, coating additive, surfactant.Back sheet preferably has 150 to 500% degree of expansion.

Aforesaid color photographic material can develop according to the described common method of following document: RD, NO.17643, PP.28-29, the same, NO.18716, P.615, the right row of left column and the same, NO.307105, PP.880-881.

Used colour developing solution preferably contains the alkaline aqueous solution of aromatic primary amine color developer in the development processing.Useful color developer comprises aminophenol compound and P-pHENYLENE dI AMINE compound preferably.The exemplary of P-pHENYLENE dI AMINE compound has 3-methyl-4-amino-N, the N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-beta-hydroxy ethylaniline, 3-methyl-4-amino-N-ethyl-N-Beta-methyl sulfoamido ethylaniline, 3-methyl-4-amino-N-ethyl-'beta '-methoxy ethylaniline, and salt is (for example, sulfate, hydrochloride, and tosilate), and 3-methyl-4-amino-N-ethyl-N-beta-hydroxy ethylaniline sulfate is particularly preferred.According to the difference of purpose, these developers can use separately, also can two or more potpourri use.

Colour developing solution contains the PH buffering agent usually, for example, alkali-metal carbonate, borate or phosphate and development restrainer or anti-photographic fog agent, for example, chloride, bromide, iodide, benzimidazole, benzothiazole, and sulfhydryl compound.If desired, colour developing solution can further contain various antiseptics, as azanol, and diethyl hydroxylamine, sulphite, hydrazine (as N, N-dicarboxyl methyl hydrazine), Carbaphen, triethanolamine and catechol sulfonic acid; Organic solvent, for example, the pure and mild diethylene glycol of ethylene, development accelerator, for example, phenmethylol, poly-ethylidene glycol, quaternary ammonium salt, and amine; Dye forming coupler; The competition colour coupler; Auxiliary developer (as 1-phenyl-3-pyrrolidone); The viscosity delivery agent; With various sequestrants, as the aminopolycanboxylic acid, aminopolyphosphonic acid, alkyl phosphonic acid; phosphono-carboxylic acids (for example, ethylene diaminetetraacetic acid, nitrilotriacetic acid(NTA), ethylidene pentaacetic acid; 1,2-diaminocyclohexane tetraacetic acid, hydroxyl ethyleneimine oxalic acid, 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid; nitrilo--N, N, N-trimethylene phosphonic; ethylene diamine-N, N, N; the N tetramethylene phosphonic acid, ethylene diamine-two o-hydroxy phenylacetic acid, and salt).

Add man-hour reversing, often carry out black and white (being abbreviated as B/W later on) before the colour development and develop.The black-and-white developer that is used for black-and-white development contains one or more known black-and-white development agent, as dihydroxy benzenes (as quinhydrones), and 3-pyrazolidone (as 1-phenyl-3-pyrazolidone), and amino-phenol (as the N-methyl-p-aminophenol).

The PH of colour or black-and-white developer is generally between 9 to 12.Although change along with the difference of the color photographic material category of processing, the speed of adding of these developer solutions is no more than every square metre of photochromics 3L usually.Add that speed can the concentration of bromide ion be reduced to 500ml/m in the additive by reducing ²Or it is littler.When adding of reducing of the processing of developing carried out under the speed, preferably by the contact area that reduces development working fluid and air as much as possible prevent from the to develop volatilization and the air oxidation of working fluid.

The contact area of taking pictures between liquid and air of developing can represent that than this term it is by the contact area (cm of developing solution and air with opening wide ²) divided by the volume (cm of developing solution ³) calculate.Unlimited ratio defined above preferably is not more than 0.1, and more preferably between 0,001 and 0.05.

The unlimited ratio of development working groove can use the removable cover described in JP-A-1-82033 to regulate by for example placing a barrier as covering on liquid level of floating, or the scalloping developing process of the application described in JP-A-63-216050.

Preferably open wide ratio reduce not only be applied to colour development and black-and-white development, and be used for all processes subsequently, as bleaching, blix, photographic fixing, rinsing, and stabilization.

Add reducing also and can reaching of speed by the long-pending means of richness that utilization suppresses bromide ion in the developing solution.

Be 2 to 5 minutes the process time of using colour developing solution.Process time can be by making developing process in the temperature that improves, and under the PH of increase, carries out in the color developer that increases concentration and shorten.

The emulsion layer of taking pictures will be bleached after colour development usually.Bleaching and photographic fixing not only can the whiles (blix) but also can have been carried out separately respectively.For rapid processing, then blix after the bleaching.Further, according to final use, go silver-colored mode to select arbitrarily.For example, use the groove of two connections to carry out blix effectively, or follow blix after the photographic fixing, or then bleaching after the blix.

Used bleaching agent comprises polyvalent metal compounds, as ferric iron, and peracid, quinone and nitroso compound.Typical bleaching agent comprises ferric organic complex salt, as, with the aminopolycanboxylic acid (as, ethylene diaminetetraacetic acid, diethylene-triamine pentaacetic acid, 1,2-diaminocyclohexane tetraacetic acid, methyliminodiacetic acid, 1,3-diamino-propanol tetraacethyl, glycoletherdiaminotetraacetic acid), the complex salt of form, citric acid, tartrate, or the complex salt of maleic acid.From process velocity and antipollution angle, the volt choosing is aminopolycanboxylic acid's ferric complex among them, as, ethylene diaminetetraacetic acid) iron (III) salt and (1, the 3-diaminopropanetetraacetic acid) iron (III) salt.Aminopolycanboxylic acid's ferric iron complex salt no matter be in bleaching bath or the blix mono bath in all particularly useful.Contain the bleaching bath of these aminopolycanboxylic acid's ferric iron complex salts or float and decide the common PH of bath between 4.0 to 8.0.Low PH also can be applicable to rapid processing.

If desired, fixing bath floats and decides bath or its pre-liquid can contain known bleaching accelerator.Useful bleaching accelerator comprises the compound with sulfydryl or disulfide group, as U.S. Pat 3893858, and Deutsche Bundespatent 1290812 and 2059988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426, and RD, NO.17129(Jul., 1978) described in; Tetrahydrothiazole derivates described in JP-A-50-140129; As JP-B-45-8506, JP-A-52-20832, the thiourea derivative described in JP-A-53-32735 and the U.S. Pat 3706561; Iodide described in Deutsches Reichs-Patent 1127715 and JP-A-58-16235; Polyoxy ethylidene compound described in Deutsche Bundespatent 966410 and 2748430; Polyamine compounds described in JP-B-45-8836; At JP-A-49-40943, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, the compound described in JP-A-55-26506 and the JP-A-58-163940; And bromide ion.Among them, the compound with sulfydryl or disulfide group is preferred, and this is because their high acceleration effect.In U.S. Pat 3893858, disclosed compound is particularly preferred among Deutsches Reichs-Patent 1290812 and the JP-A-53-95630.In addition, disclosed compound also is preferred in U.S. Pat 4552834.These bleaching accelerators can be incorporated in the photosensitive material.The bleaching accelerator is for fixed effective especially as floating of the color sensitive material of taking pictures.

Painted in order to prevent to bleach, bleach or float and decide preferably to contain in the bath organic acid.The particularly preferred organic acid that plays this effect be those to have acid dissociation constant (PKa) be 2 to 5 acid, for example acetate and propionic acid.

Can be used for photographic fixing or float the fixer of deciding in the bath comprising thiosulfate, thiocyanate, sulfide compound, thiocarbamide and a large amount of iodide, wherein thiosulfate is the most commonly used.Particularly the application of ATS (Ammonium thiosulphate) is very extensive.Thiosulfate and thiocyanate, sulfide compound, it also is preferred that the mixing of thiocarbamide etc. is used.Be used for photographic fixing or float the protective agent of deciding bath preferably including sulphite, hydrosulfite, carbonyl-bisulfite addition product, and hydrosulfide have description in EP294769A.

Photographic fixing or float and decide preferably to contain various aminopolycanboxylic acids in the bath or organic phospho acid is used for stabilization.

Again further, it is that 6.0 to 9.0 compound is used for PH and regulates that photographic fixing or float decides preferably to contain in the bath 0.1 to 10ml/l PKa, imidazoles preferably, for example, imidazoles, 1-methylimidazole, 1-ethyl imidazol(e), and glyoxal ethyline.

Go the T.T. of silver preferably short as much as possible, but will grow to insufficient being unlikely to of silver taken place.Preferably going the silver time is 1 to 3 minute, and is more preferably 1 to 2 minute.Removing Yin Wendu is 25 ℃ to 50 ℃, and is preferably 35 to 45 ℃.In preferred temperature range, go silver-colored speed to be modified, the formation that stain the processing back has been prevented effectively.

Best is that silver carries out under strong as far as possible brute force stirs.Reach powerful stirring method or means and comprise the method for the injection diffluence of the process solutions of formation described in JP-A-62-183460 towards the surface of penetrating sensitive emulsion layer; As at the utilization rotary means described in the JP-A-62-183461 to strengthen the method for mixing effect; Mobile photosensitive material also contacts the method that forms turbulent flow with the surface of its sensitive emulsion layer with wire-shaped blade in being placed on process solutions; With the method that increases cyclic process solution total flow.These mixer meanses are for any bleaching bath, float to decide bath and fixing bath all is effective.As if powerful the stirring quickened bleaching agent and fixer for the action of sensitive emulsion layer, consequently increased and gone silver-colored speed.

The above-mentioned powerful means that stir are more effective under the situation that the bleaching accelerator is employed, and increased acceleration effect significantly and eliminated the photographic fixing depression effect of bleaching accelerator.

The automatic processing machine that can be used to process photosensitive material preferably has the means of delivery photosensitive material, as JP-A-60-191257, described in JP-A-60-191258 and the JP-A-60-191259 like that.As mentioning among the top JP-A-60-191257, thereby the amount of the working fluid that this class delivery means is taken out of from the pre-body lotion process in succession of bathing for obvious minimizing prevents that the minimizing of work capacity is very effective.This means are for the minimizing of process time in each procedure of processing or to add the reduction of rate effective especially.

Go the silver-halide color photoelement behind the silver generally will wash and/or stabilization.

According to the characteristic of photosensitive material (for example, the raw-material kind of taking a picture, as colour coupler), the final application of photosensitive material, the temperature of wash water, the number of flushed channel (number of rinse stage), (for example add system, anti-fluid system or drag flow system) and other various conditions, wash water amount used in rinsing step can be selected in very wide scope.For example, in the multistage, anti-fluid was, the number of flushed channel and the relation of the water yield can be passed through Journal of the Society of Motion Picture and Television Engineers, Vol, 64, PP.248-253(May, 1955) method described in obtains.

According to anti-fluid system of disclosed multistage, the required water yield can significantly reduce.On the other hand, when water residence time in groove increases, the tendency that has bacterium to grow therein, the bacterial cell of suspension sticks on the photosensitive material.This problem can solve effectively by the method for calcium and magnesium ion in the minimizing wash water of employing described in JP-A-62-288838.Using germifuge also is that effectively as described isothiazolone compounds of JP-A-57-8542 or thiabendazole compound, the chlorine series bactericidal agent is as chlorinated isocyanuric acid sodium; With as Horiguchi Hiroshi, Bokin bobaizai no kagaku, Sankyo shuppan(1986), Eisei Gijutsukai(ed.), Biseibutsu no mekkin, sakkin, bobai gijutsu kogyo Gijutsukkai(1982), with Nippon Bokin Bobai Gakkai(ed.), Bokin bobaizai jiten(1986), described in other germifuge, as benzotriazole.

The PH of wash water is usually between 4 and 9, and preferably between 5 and 8.Although washing condition becomes with the characteristic or final the application with similar situation of photosensitive material, normally temperature is 15 to 45 ℃, and the time is 20 seconds to 10 minutes, and preferably temperature is 25 to 40 ℃, and the time is 30 seconds to 5 minutes.

Available stabilization procedure of processing follows closely or replaces rinsing step.When replacing flushing with stabilization, any known stabilization technology, JP-A-57-8543 for example, described in JP-A-58-14834 and the JP-A-60-220345, can be employed.When stabilization followed closely after the rinsing step, used stabilizer bath comprised the solution that contains dye stabilizers and surfactant, and it is to bathe as the last processing together of the color sensitive material of the usefulness of taking pictures.Suitable dye stabilizers comprises aldehyde, for example, and formalin and glutaraldehyde, N-methylol compound, hexamethylene tetramine, and aldehyde-sulphite adduct.If necessary, can contain various sequestrants and antifungal agent in the stabilizer bath.

Be used to wash and/or stabilization, follow the overflow technology of the process of adding can be in other procedure of processing, as go to reuse in the silver-colored step.

Because add man-hour in automatic processing machine, every kind of process solutions all concentrates owing to evaporation, thus best in the process solutions supplementing water with corrected concentrations.

In order to simplify and to quicken the processing of developing, can contain color developer in the silver-halide color photoelement, preferably its precursor forms.The example of color developer precursor comprises the indeno aniline compound described in the United States Patent (USP) 3342597, United States Patent (USP) 3342599 and RD, Schiff alkali cpd described in the Nos.14850 and 15159, RD, Nos, alditol compounds described in 13924, the urethane compound described in metallic complex salt described in the United States Patent (USP) 3719492 and the JP-A-53-135628.

If desired, can contain further in the silver-halide color photoelement that various (1-phenyl-3-pyrazolidone compound is to quicken colour development.The exemplary of these accelerators has description at JP-A-56-64339 among JP-A-57-144547 and the JP-A-58-115438.

Every kind of above-mentioned process solutions is all used under 10 ℃ to 50 ℃ temperature, and standard is 33 ℃ to 38 ℃.Available higher processing temperature shortens process time, or adopts lower temperature to improve the stability of picture element amount or process solutions.

The present invention also can use United States Patent (USP) 4500626, JP-A-60-133449, JP-A-59-218443, the photosensitive material of the heat-developable described in JP-A-61-238056 and the EP210660A2.

The present invention illustrates in further detail by the following examples now, but should be understood that the present invention can not think the restriction that is subjected to them. and except as otherwise noted, all number percent and ratio all are by weight.

Embodiment 1

The preparation of emulsion:

Dissolving 20g inertia gelatin in 800ml distilled water, 2.4g potassium bromide and 2.05g potassium iodide, this solution remain on 58 ℃ and stirring.In this solution, add the aqueous solution that 150cc contains the 5.0g silver nitrate in batches, add excessive potassium bromide again, then make its potpourri physical ripening 20 minutes.Adding concentration in the emulsion that produces is 0.2mol/l, 0.67mol/l, silver nitrate aqueous solution with 2mol/l, mixed aqueous solution with potassium bromide that contains 58mol% and 42mol% potassium iodide, the speed of every kind of adding all is 10cc/min, according to the method described in the United States Patent (USP) 4242445, making iodide content is the iodine silver bromide crystal grain growth of 42mol%.After washing was desalted, obtaining 900g average crystal grain size was the iodine silver bromide emulsion of 0.61 μ m.The emulsion that is produced is denoted as emulsion a.

With the method identical with preparing emulsion a, the agi content 42mol% that respectively does for oneself, and the average crystal grain size is respectively 0.59 μ m, and 0.56 μ m, the emulsion b of 0.52 μ m and 0.46 μ m, c, d and e are produced respectively.

The kbr aqueous solution that adds 850cc distilled water and 30cc10% in the 300g emulsion a, and solution is heated to 70 ℃.The compound (18) that under agitation adds 0.02g formula (A) in this solution, add 30cc inside simultaneously with 40 minutes times and contain the aqueous solution of 33g silver nitrate and the aqueous solution that 320cc contains the 25g potassium bromide, keep PAg 8.0 simultaneously, add inside in 60 minutes time then that 800cc contains the aqueous solution of 100g silver nitrate and aqueous solution that 860cc contains the 75g potassium bromide is that 14mol% and average grain size are the iodine silver bromide emulsion of 0.88 μ m with the preparation agi content.The emulsion that is produced is denoted as emulsion 1.Emulsion 1 be found comprise flakiness ratio be 2.0 and (111) crystal face than the twin that is 80%.

Agi content is that the emulsion 2 of 12mol% can be used the mode identical with emulsion 1, and the silver nitrate that uses total amount to reach 125g deposits shell and prepares on 300g emulsion b.Similarly, emulsion 3 to 5 can be respectively from emulsion c, d, e preparation.

Emulsion 6 to 9 can be used the method preparation identical with emulsion 1 to 4, and just changing the condition of shell deposition into temperature is 60 ℃, and PAg is 9.0, and without the compound of formula (18).

With the method identical the potpourri of 133g emulsion b and 167g emulsion d is carried out the shell deposition with preparation emulsion 10 with preparing emulsion 3.

With the method identical with preparing emulsion 3, with 50g emulsion a, the potpourri of 50g emulsion d and 200g emulsion c carries out the shell deposition with preparation emulsion 11.

Emulsion 12 and 13 is used respectively and is prepared emulsion 3 and 4 identical method preparations, is the compound without formula (18).

Provide in the characteristic table 1 below of Zhi Bei emulsion like this.

Table 1

Emulsion AgI content nuclear/shell is the average clearly big flakiness ratio formula of Jingjing grain (A) on average

The big slight change-compound of AgI stratiform knot grain of number nuclear shell Ag

The mol of---ratio content structure coefficient

（mol%） （mol%） - - - - - -

（mol%） （μm）

1 42 0 1/2 14.0 is 0.88 0.20 2.0 (18)

2 ″ ″ 1/2.5 12.0 ″ 0.86 0.19 1.9 ″

3 ″ ″ 1/3.2 10.0 ″ 0.86 0.19 1.9 ″

4 ″ ″ 1/4 8.4 ″ 0.88 0.18 1.8 ″

5 ″ ″ 1/6 6.0 ″ 0.87 0.18 1.6 ″

6 " " 1/2 14.0 are not 0.89 0.21 2.2 nothings

7 ″ ″ 1/2.5 12.0 ″ 0.87 0.20 2.0 ″

8 ″ ″ 1/3.2 10.0 ″ 0.86 0.20 2.0 ″

9 ″ ″ 1/4 8.4 ″ 0.87 0.19 1.9 ″

10 " " 1/3.2 10.0 is 0.87 0.22 2.0 (18)

11 ″ ″ 1/3.2 10.0 ″ 0.87 0.27 2.2 ″

" 0.87 0.20 1.9 does not have 12 " " 1/3.2 10.0

13 ″ ″ 1/4 8.4 ″ 0.87 0.20 1.9 ″

The preparation of photosensitive material:

Following each layer is applied on the cellulose triacetate sheet base, and this sheet base has the required bottom of preparation multi layer colour photosensitive material.The material that obtains is denoted as sample 101.

Ground floor (anti-halation layer):

Black micelle silver 0.18gAg/m ²

Gelatin 0.80g/m ²

The second layer (middle layer):

2.5-two uncle's pentadecyl quinhydrones 0.18g/m ²

EX-1 0.070g/m ²

EX-3 0.020g/m ²

EX-12 2.0×10 ^-3g/m ²

U-1 0.060g/m ²

U-2 0.080g/m ²

U-3 0.10g/m ²

HBS-1 0.10g/m ²

HBS-2 0.020g/m ²

Gelatin 0.70g/m ²

The 3rd layer (first magenta-sensitive emulsion layer):

Emulsion A 0.25g-Ag/m ²

Emulsion F 0.25g-Ag/m ²

Sensitizing dyestuff I 6.9 * 10 ^-5Mol/mol-AgX

(X: halogen)

Sensitizing dyestuff II 1.8 * 10 ^-5Mol/mol-AgX

Sensitizing dyestuff III 3.1 * 10 ^-4Mol/mol-AgX

EX-2 0.34g/m ²

EX-10 0.020g/m ²

U-1 0.070g/m ²

U-2 0.050g/m ²

U-3 0.070g/m ²

HBS-1 0.005g/m ²

Gelatin 0.70g/m ²

The 4th layer (second magenta-sensitive emulsion layer):

Emulsion G 1.00g-Ag/m ²

Sensitizing dyestuff I 5.1 * 10 ^-5Mol/mol-AgX

Sensitizing dyestuff II 1.4 * 10 ^-5Mol/mol-AgX

Sensitizing dyestuff III 2.3 * 10 ^-4Mol/mol-AgX

EX-2 0.40g/m ²

EX-3 0.050g/m ²

EX-10 0.015g/m ²

U-1 0.070g/m ²

U-2 0.050g/m ²

U-3 0.070g/m ²

Gelatin 0.95g/m ²

Layer 5 (the 3rd magenta-sensitive emulsion layer):

Emulsion I 1.60g-Ag/m ²

Sensitizing dyestuff I 5.4 * 10 ^-5Mol/mol-AgX

Sensitizing dyestuff II 1.4 * 10 ^-5Mol/mol-AgX

Sensitizing dyestuff III 2.4 * 10 ^-4Mol/mol-AgX

EX-2 0.097g/m ²

EX-3 0.010g/m ²

EX-4 0.080g/m ²

HBS-1 0.11g/m ²

HBS-2 0.05g/m ²

Gelatin 1.20g/m ²

Layer 6 (middle layer):

EX-5 0.040g/m ²

HBS-1 0.020g/m ²

Gelatin 0.60g/m ²

Layer 7 (first green-sensitive emulsion layer):

Emulsion A 0.15g-Ag/m ²

Emulsion F 0.15g-Ag/m ²

Sensitizing dyestuff IV 3.0 * 10 ^-5Mol/mol-AgX

Sensitizing dyestuff V 1.0 * 10 ^-4Mol/mol-AgX

Sensitizing dyestuff VI 3.8 * 10 ^-4Mol/mol-AgX

EX-1 0.021g/m ²

Polymkeric substance colour coupler (P-13) 0.26g/m ²

EX-7 0.030g/m ²

EX-8 0.025g/m ²

HBS-1 0.10g/m ²

HBS-3 0.010g/m ²

Gelatin 0.63g/m ²

The 8th layer (second green-sensitive emulsion layer):

Emulsion C 0.45g-Ag/m ²

Sensitizing dyestuff IV 2.1 * 10 ^-5Mol/mol-AgX

Sensitizing dyestuff V 7.0 * 10 ^-5Mol/mol-AgX

Sensitizing dyestuff VI 2.6 * 10 ^-4Mol/mol-AgX

Polymkeric substance colour coupler (P-13) 0.094g/m ²

EX-7 0.026g/m ²

EX-8 0.018g/m ²

HBS-1 0.16g/m ²

HBS-3 8.0×10 ^-3g/m ²

Gelatin 0.50g/m ²

The 9th layer (the 3rd green-sensitive emulsion layer):

Emulsion E 0.10g-Ag/m ²

Sensitizing dyestuff IV 3.5 * 10 ^-5Mol/mol-Ag

Sensitizing dyestuff V 8.0 * 10 ^-5Mol/mol-Ag

Sensitizing dyestuff VI 3.0 * 10 ^-4Mol/mol-Ag

EX-1 0.025g/m ²

EX-11 0.10g/m ²

EX-13 0.010g/m ²

EX-6 0.025g/m ²

EX-8 0.010g/m ²

HBS-1 0.05g/m ²

HBS-2 0.05g/m ²

Gelatin 1.05g/m ²

The tenth layer (Yellow filter layer):

Yellow micelle silver 0.050g-Ag/m ²

EX-5 0.080g/m ²

HBS-1 0.030g/m ²

Gelatin 0.75g/m ²

Eleventh floor (first blue-sensitive emulsion layer):

Emulsion A 0.080g-Ag/m ²

Emulsion B 0.070g-Ag/m ²

Emulsion F 0.070g-Ag/m ²

Sensitizing dyestuff VII 3.5 * 10 ^-4Mol/mol-AgX

EX-8 0.042g/m ²

EX-9 0.72g/m ²

HBS-1 0.28g/m ²

Gelatin 1.10g/m ²

Floor 12 (second blue-sensitive emulsion layer):

Emulsion C 0.45g-Ag/m ²

Sensitizing dyestuff VII 2.1 * 10 ^-4Mol/mol-AgX

EX-9 0.15g/m ²

EX-10 7.0×10 ^-3g/m ²

HBS-1 0.050g/m ²

Gelatin 0.60g/m ²

The 13 layer (the 3rd blue-sensitive emulsion layer):

Emulsion H 0.77g-Ag/m ²

Sensitizing dyestuff VII 2.2 * 10 ^-4Mol/mol-AgX

EX-9 0.20g/m ²

HBS-1 0.070g/m ²

Gelatin 0.69g/m ²

The 14 layer (first protective seam):

Emulsion I 0.20g-Ag/m ²

U-4 0.11g/m ²

U-5 0.17g/m ²

HBS-1 5.0×10 ^-2g/m ²

Gelatin 0.70g/m ²

The 15 layer (second protective seam):

H-1 0.30g/m ²

B-1(diameter: 1.7 μ m) 5.0 * 10 ^-2G/m ²

B-2(diameter: 0.10g/m 1.7 μ m) ²

B-3 0.10g/m ²

S-1 0.20g/m ²

Gelatin 0.80g/m ²

In order to improve protectiveness, development processability, anti-pressure ability, antimicrobial and antimycotic character, anti-static function; with coating character, each layer of the first to the 15 layer further contains W-1, W-2, W-3, B-4; B-5, F-1, F-2, F-3, F-4; F-5, F-6, F-7, F-8, F-9; F-10, F-11, F-12, F-13, and iron; lead, gold, platinum, iridium and rhodium salt.

The dry film thickness of the sample 101 that obtains like this is 17.5 μ m, and the expansion thickness is 24.0 μ m.

Provide in the used emulsion table 2 below in the sample 101.

Table 2

The big flakiness ratio crystal grain of the average Jingjing grain of emulsion AgI is tied formula (A) clearly

Big slight allosteric of number content grain and nuclear/stratiform knot compound

Average value coefficient shell Ag(or AgI) structure

(mol%) (μ m) (%) mol ratio

A 4.0 0.45 27 1 double-deckers are not have

1/3（13/1）

B 4.0 0.55 14 1 double-deckers " "

1/2（12/0）

C 4.0 0.60 30 2 double-deckers " "

1/1（8/0）

D 4.0 0.90 35 2 double-deckers " "

1/1（8/0）

E 4.0 0.90 35 3 double-deckers " "

2/1（6/0）

F 4.0 0.25 28 1 double-deckers " "

1/1（8/0）

G 4.0 0.60 25 2 double-deckers " "

1/2（12/0）

H 4.0 1.05 25 3 double-deckers " "

1/3（16/0）

I 1 0.07 15 1 homogeneous structurals " "

Used following the illustrating of adjuvant in the sample 101:

(49) of JP-A-57-151944, (D-14) of JP-A-1-269935 and (D-14) of JP-A-2-28637

(D-12) of EX-14 JP-A-1-259359

Compound 27 in the EX-15(United States Patent (USP) 4782012)

HBS-1 tricresyl phosphate (cresyl) ester

HBS-2 phthalic acid di-n-butyl ester

HBS-3

The method preparation that sample 102 to 114 usefulness are same with preparing sample 101, just the emulsion that the used emulsion 1 of layer 5 is listed by following table 3 in the sample 101 replaces.

Sample 115 to 128 can be used the method preparation same with preparing sample 101 to 114 respectively, and just used DIR colour coupler (EX-8) replaces with the DIR colour coupler of the present invention (D-6) of equivalent in the the 7th, the eight, the nine layer.

The preparation that uses the same method of sample 129 and sample 117, just the 7th and the 8th layer of used colour coupler (P-13) of sample 117 replaces with the colour coupler (P-14) of 1.25 times of weight, 1.2 times will be increased to the amount of the HBS-1 in one deck, 1.2 times will be increased to the amount of gelatin in one deck.

The method preparation that sample 130 usefulness and sample 117 are same, just the 7th and the 8th layer of used colour coupler (P-13) replaces with (EX-13) of 1.5 times of weight in the sample 117, will with layer in the amount of HBS-1 double, will with layer in the gelatin amount be increased to 1.4 times.

Washing processing and assessment:

When according to the colour development job operation flushing after this described, the relative sensitivity of sample 129 and 130 green layer is identical with sample 117.Further, these samples the time demonstrate in indifference in fact aspect the anti-wiping property in the sapphire stylus test that with diameter is 0.05mm, and proof is equal in fact with the aspect of performance of taking pictures in the intensity of film.

To after the green glow imaging exposure, each sample all exposes uniformly to ruddiness, and its exposure is such, promptly in the sample 101 to the unexposed zone of green glow carrying out the following man-hour that adds, can have 0.8 cyan density, and then the processing of developing.

Further, every kind of sample dialogue photoimaging exposure, and relative sensitivity determines that from the logarithm of exposure inverse this exposure provides and added 0.4 cyan density more than the photographic fog.

Further, the granularity of sample is by use common method, by being that the RMS value that adds acquisition in 0.4 o'clock more than the photographic fog is assessed in cyan density.

In addition, the sharpness of sample can be assessed with the mtf value that conventional method obtains.

The result of these assessments lists in table 3.

According to following conditions, the development processing that is used to assess is carried out at 38 ℃.

1, colour development 3 ' 15 "

2, bleaching 6 ' 30 "

3, washing 3 ' 15 "

4, photographic fixing 6 ' 30 "

5, washing 3 ' 15 "

6, stabilization 3 ' 15 "

The process solutions of using in these steps has following prescription:

The colour development formula of liquid:

Sodium nitrilo triacetate 1.0g

Sodium sulphite 4.0g

Sodium carbonate 30.0g

Potassium bromide 1.3g

Hydroxylamine sulfate 2.4g

4(-N-ethyl-N-beta-hydroxy ethylamino)-

2-aminotoluene sulfate 4.5g

Add water to 1l

The bleaching liquid prescription:

Ammonium bromide 160.0g

Ammoniacal liquor (28%) 25.0ml

(ethylene diaminetetraacetic acid) 130g

Ferrisodium salt

Glacial acetic acid 14ml

Add water to 1l

The stop bath prescription:

Sodium tetrapolyphosphate 2.0g

Sodium sulphite 4.0g

ATS (Ammonium thiosulphate) (70%) 175.0ml

Sodium bisulfite 4.6g

Add water to 1l

The stabilizing solutions prescription:

Formalin 2.0ml

Add water to 1l

Table 3

The colored turbidity cyan of sample layer 5 the 7th, eight relative RMS values shadow remarks

Light sensitivity (* 1000) in emulsion nine floor in number is as mtf value

DIR colour coupler (25c/mm)

101 1 EX-8,0.00 2.45+0.03 55 contrast

102 2 ″ 0.00 24.6 +0.03 55 ″

103 3 ″ 0.01 24.8 +0.03 55 ″

104 4 ″ 0.01 24.9 +0.03 55 ″

105 5 ″ 0.01 25.0 +0.02 55 ″

106 6 ″ -0.06 26.8 +0.05 53 ″

107 7 ″ -0.05 26.8 +0.05 54 ″

108 8 ″ -0.04 26.6 +0.05 54 ″

109 9 ″ -0.04 26.5 +0.04 54 ″

110 10 ″ 0.00 25.5 +0.03 55 ″

111 11 ″ 0.00 26.1 +0.04 54 ″

112 12 ″ -0.02 25.3 +0.03 55 ″

113 13 ″ -0.02 25.5 +0.03 55 ″

114 D ″ -0.01 26.6 +0.04 54 ″

115 1 D-6,0.00 24.0-0.01 58 invention

Table 3(is continuous)

Sample number layer 5 the 7th, eight is the colored turbid cyan video remarks of sense RMS value relatively

In nine layers of emulsions in luminosity (* 1000) degree mtf value (25c/

DIR colour coupler mm)

116 2 D-6,0.01 24.1-0.01 58 invention

117 3 ″ 0.01 24.3 -0.01 58 ″

118 4 ″ 0.01 24.5 -0.01 58 ″

119 5 ″ 0.01 24.6 -0.01 58 ″

120 6 " 0.06 26.4+0.01 56 contrast

121 7 ″ -0.05 26.3 +0.01 56 ″

122 8 ″ -0.04 26.1 +0.01 56 ″

123 9 ″ 0.04 25.1 +0.01 57 ″

124 10 " 0.01 25.2 0.01 58 invention

125 11 ″ 0.00 25.6 +0.01 58 ″

126 12 ″ 0.00 24.9 0.00 58 ″

127 13 ″ 0.00 25.1 0.00 58 ″

128 D " 0.01 26.1+0.01 57 contrast

129 3 " 0.01 24.3 0.00 56 invention

130 3 ″ 0.00 2.42 +0.01 54 ″

From the result of table 3 as can be seen, have only those to use the sample of specific emulsion of the present invention and DIR colour coupler just to demonstrate ISO, the superior grain size of weighing with the RMS value, superior sharpness of weighing with mtf value and the superior colour reproduction of weighing with colored turbidity.

In the sample 101 to 105,115 to 119,126 and 127 each is cut into the wide band of 35mm respectively, is assembled into 36 times the J135 film of can exposing, and the magazine of packing into.Under the condition of ISO400, be that 36 photologgings of hawk (gray chart) of 18% are in these films with reflectance.

Each sample that white light is carried out imaging exposure develops automatically with process solutions given below respectively, and the light sensitivity of pinkish red image and γ value are recorded.

The film of 36 exposures that prepare above develops continuously with identical process solutions when replenishing with each replenishers described below, develops altogether 10 days, and speed is volumes every days 40.After processing continuously, each sample of dialogue photoimaging exposure is used with above-mentioned same method and is developed automatically respectively, and the light sensitivity of pinkish red image and γ value are measured.

Gained the results are shown in the table 4.

Colour development is processed in automatic processing machine in 38 ℃ of following carrying out.

1, develops 3 ' 15 "

2, bleaching 1 '

3, blix 3 ' 15 "

4, washing (1) 40 "

5, washing (2) 1 '

6, stabilization 40 "

7, dry (50 ℃) 1 ' 15 "

Washing is being carried out in the anti-fluid system of groove (1) by groove (2).

Process solutions has following prescription.The additional speed of colour development is 1200ml/m ², the additional speed that comprises other step of washing is 800ml/m ², the amount that is brought into the pre-bath in the washing step is 50ml/m ²

The colour development formula of liquid:

The working solution replenishers

Diethylene-triamine pentaacetic acid 1.0g 1.1g

1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid 2.0g 2.2g

Sodium sulphite 4.0g 4.4g

Sal tartari 30.0g 30.0g

Potassium bromide 1.4g 0.7g

Potassium iodide 1.3mg-

Hydroxylamine sulfate 2.4g 2.6g

4-(N-ethyl-N-β-hydroxyl second

Base is amino)-2-aminotoluene sulfate 4.5g 5.0g

Add water to 1.0l 1.0l

PH 10.0 10.05

The liquid lime chloride prescription:

Working solution and replenishers have same composition.

(ethylene diaminetetraacetic acid) iron (II) ammonium salt 120.0g

Ethylene diaminetetraacetic acid disodium 10.0g

Ammonium nitrate 10.0g

Ammonium bromide 100.0g

Bleaching accelerator 5 * 10 ^-3Mol

Ammoniacal liquor is adjusted to PH 6.3

Add water to 1.0l

The blix solution formula:

Working solution and replenishers have same composition.

(ethylene diaminetetraacetic acid) iron (II) ammonium 50.0g

Ethylene diaminetetraacetic acid disodium 5.0g

Sodium sulphite 12.0g

Thiosulfuric acid aqueous ammonium (70%) 240ml

Ammoniacal liquor is adjusted to PH 7.3

Add water to 1l

Slurry:

Make and contain 32mg/l calcium ion and 7.3mg/l magnesium ion, pillar and the OH-type strong-base anion-exchange resin post of tap water by H-type storng-acid cation exchange resin is housed, calcium ion is reduced to 1.2mg/l, magnesium ion is reduced to 0.4mg/l, and toward adding the 20mg/l DCCNa in the treated water like this.

The stabilizing solutions prescription:

The solution and the replenishers of work have same composition.

Formalin (37w/v%) 2.0ml

The single nonyl of polyoxyethylene-P--

Phenyl ether (the degree of polymerization: 10) 0.3g

Ethylene diaminetetraacetic acid disodium 0.005g

Add water to 1l

PH 5.8

Baking temperature is 50 ℃.

Annotate: ^*: the relative value of the logarithm of the inverse of the exposure of generation fuchsin density (photographic fog+0.2).

^*: the slope of the straight line of the density points of connection (photographic fog+0.2) and the density points of (photographic fog+1.0).

As can be seen from Table 4, photosensitive material of the present invention is not to be subject to the mode variable effect of taking pictures, even to add man-hour in a continuous manner under the situation of replenishing developing solution also be like this.

Embodiment 2

Sample 201 to 207 can use the mode identical with sample 116 to prepare, and just (D-6) in the seven, eight, nine layers in the sample 116 is with the DIR colour coupler replacement of listing in the following table 5.Select the amount of DIR colour coupler to make it provide γ value with sample 116 essentially identical light sensitivity.

The method assessment identical with embodiment 1 of the sample of gained, the results are shown in Table 5 for gained.

As can be seen from Table 5, the sample of the present invention even changes of properties of taking pictures also seldom occurs man-hour adding continuously, and demonstrate superior image definition and color reducibility.

Embodiment 3

Prepare a kind of photosensitive material with the method identical, just use the DIR colour coupler of the present invention (D-6) of equimolar amounts respectively and (D-30) replace (EX-8) and (EX-10) with the sample 212 of JP-A-1-269935.The sample that produces uses the mode identical with embodiment 1 to assess.As a result, sample even very little variation is arranged adding the performance of also just taking pictures man-hour continuously, and demonstrate superior color reducibility and sharpness.

Because the present invention is described in detail, and with reference to its certain embodiments, the variations and modifications of not violating its spirit and scope are conspicuous for those of ordinary skill in the art.

Claims (12)

1, a kind of silver-halide color photoelement, this material contain a support, and one deck photosensitive silver halide emulsion layer is at least arranged on support, and wherein said photosensitive material contains the DIR colour coupler of formula (I) expression:

Wherein A is expressed as the toner residue, and R is the C that is replaced by alkoxy carbonyl group or alkane carbamyl _1-4Alkyl; N represents 1 when A represents phenol type or naphthol type colour coupler residue, or n represents 0 when A represents other colour coupler residue, described emulsion layer contains the silver halide grain of chemical sensitization, it has the layer clearly that is made of the bromo-iodide that contains 7 to 45mol% silver iodide separately, and it has the total agi content greater than 4mol% separately.

2, according to the silver-halide color photoelement of claim 1, wherein said photosensitive material also contains the compound of formula (A) expression:

Q-SM ¹（A）

Wherein Q represents to have directly or indirectly that thereon at least one of bonding is selected from-SO ₃M ²,-COOM ²,-OH and-NR ¹R ²The heterocyclic radical of group; M ¹And M ²Represent hydrogen atom respectively, alkaline metal, quartemary ammonium or Si Jia Phosphonium; And R ¹And R ²Represent hydrogen atom or replacement or substituted alkyl not respectively.

3, according to the silver-halide color photoelement of claim 1, the variation factor of the crystallite dimension that wherein said silver halide grain had is not more than 0.25

4, according to the silver-halide color photoelement of claim 2, the variation factor of the crystallite dimension that wherein said silver halide grain had is not more than 0.25

5, according to the silver-halide color photoelement of claim 1, wherein said photosensitive material has the red sensing coppering silver emulsion layer that one deck at least contains cyan coupler, at least one deck contains the green silver halide emulsion layer of magenta colour coupler, at least one deck contains the blue silver halide emulsion layer of sense of yellow colour former, and described green silver halide emulsion layer contains pinkish red polymkeric substance colour coupler.

6, according to the silver-halide color photoelement of claim 2, wherein said photosensitive material has the red sensing coppering silver emulsion layer that one deck at least contains cyan coupler, at least one deck contains the green silver halide emulsion layer of magenta colour coupler, at least one deck contains the blue silver halide emulsion layer of sense of yellow colour former, and described green silver halide emulsion layer contains pinkish red polymkeric substance colour coupler.

7, according to the silver-halide color photoelement of claim 3, wherein said photosensitive material has the red sensing coppering silver emulsion layer that one deck at least contains cyan coupler, at least one deck contains the green silver halide emulsion layer of magenta colour coupler, at least one deck contains the blue silver halide emulsion layer of sense of yellow colour former, and described green silver halide emulsion layer contains pinkish red polymkeric substance colour coupler.

8, according to the silver-halide color photoelement of claim 4, wherein said photosensitive material has the red sensing coppering silver emulsion layer that one deck at least contains cyan coupler, at least one deck contains the green silver halide emulsion layer of magenta colour coupler, at least one deck contains the blue silver halide emulsion layer of sense of yellow colour former, and described green silver halide emulsion layer contains pinkish red polymkeric substance colour coupler.

9, according to the silver-halide color photoelement of claim 5, wherein said magenta colour coupler is the polymer of monomers colour coupler that contains by formula (PA) expression:

R wherein ₁₂₁Represent hydrogen atom, have the alkyl of 1 to 4 carbon atom, or the chlorine atom;-D-represents-COO-,-CONR ₁₂₂-or replacement or unsubstituted phenyl;-E-represents to replace or unsubstituted alkylidene, replaces or unsubstituted phenylene, or replacement or unsubstituted inferior aralkyl;-F-represents-CONR ₁₂₂-,-NR ₁₂₂CONR ₁₂₂-,-NR ₁₂₂COO--NR ₁₂₂CO-,-OCONR ₁₂₂-,-NR ₁₂₂-,-COO-,-OCO-,-CO-,-O-,-S-,-SO ₂-,-NR ₁₂₂SO ₂-or-SO ₂NR ₁₂₂-; R ₁₂₂The expression hydrogen atom replaces or does not replace aliphatic group, or replacement or unsubstituting aromatic yl; The R of plural number ₁₂₂Base if in same molecular, then can be identical or different; P, q and r represent 0 or 1 respectively, just they do not represent 0 simultaneously; Be expressed as follows the magenta colour coupler residue of formula (PB) expression with T, it is at following Ar, Z, and R ₁₃₃On any position at position with-(D)-(E)-(F)-partly bonding:

Wherein Ar represents as the substituent group on 1 of the 2-pyrazolin-5-one colour coupler; R ₁₃₃Expression replaces or the unsubstituting phenenyl amido, replaces or do not replace acylamino-, replaces or do not replace urea groups, or replaces or do not replace sulfonamido; Represent hydrogen atom with Z, halogen atom, or by oxygen atom, nitrogen-atoms, the coupling of sulfur atom linkage discharges group.

10, according to the silver-halide color photoelement of claim 6, wherein said magenta colour coupler is the polymer of monomers colour coupler that contains by formula (PA) expression:

R wherein ₁₂₁Represent hydrogen atom, have the alkyl of 1 to 4 carbon atom, or the chlorine atom;-D-represents-COO-,-CONR ₁₂₂-or replacement or unsubstituted phenyl;-E-represents to replace or unsubstituted alkylidene, replaces or unsubstituted phenylene, or replacement or unsubstituted inferior aralkyl;-F-represents-CONR ₁₂₂-,-NR ₁₂₂CONR ₁₂₂-,-NR ₁₂₂COO--NR ₁₂₂CO-,-OCONR ₁₂₂-,-NR ₁₂₂-,-COO-,-OCO-,-CO-,-O-,-S-,-SO ₂-,-NR ₁₂₂SO ₂-or-SO ₂NR ₁₂₂-; R ₁₂₂The expression hydrogen atom replaces or does not replace aliphatic group, or replacement or unsubstituting aromatic yl; The R of plural number ₁₂₂Base if in same molecular, then can be identical or different; P, q and r represent 0 or 1 respectively, just they do not represent 0 simultaneously; Be expressed as follows the magenta colour coupler residue of formula (PB) expression with T, it is at following Ar, Z and R ₁₃₃On any position at position with-(D)-(E)-(F)-partly bonding:

Wherein Ar represents as the substituent group on 1 of the 2-pyrazolin-5-one colour coupler; R ₁₃₃Expression replaces or the unsubstituting phenenyl amido, replaces or do not replace acylamino-, replaces or do not replace urea groups, or replaces or do not replace sulfonamido; Represent hydrogen atom with Z, halogen atom, or by oxygen atom, nitrogen-atoms, the coupling of sulfur atom linkage discharges group.

11, according to the silver-halide color photoelement of claim 7, wherein said magenta colour coupler is the polymer of monomers colour coupler that contains by formula (PA) expression:

R wherein ₁₂₁Represent hydrogen atom, have the alkyl of 1 to 4 carbon atom, or the chlorine atom;-D-represents-COO-,-CONR ₁₂₂-or replacement or unsubstituted phenyl;-E-represents to replace or unsubstituted alkylidene, replaces or unsubstituted phenylene, or replacement or unsubstituted inferior aralkyl;-F-represents-CONR ₁₂₂-,-NR ₁₂₂CONR ₁₂₂-,-NR ₁₂₂COO--NR ₁₂₂CO-,-OCONR ₁₂₂-,-NR ₁₂₂-,-COO-,-OCO-,-CO-,-O-,-S-,-SO ₂-,-NR ₁₂₂SO ₂-or-SO ₂NR ₁₂₂-; R ₁₂₂The expression hydrogen atom replaces or does not replace aliphatic group, or replacement or unsubstituting aromatic yl; The R of plural number ₁₂₂Base if in same molecular, then can be identical or different; P, q and r represent 0 or 1 respectively, just they do not represent 0 simultaneously; Be expressed as follows the magenta colour coupler residue of formula (PB) expression with T, it is at following Ar, Z, and R ₁₃₃On any position at position with-(D)-(E)-(F)-partly bonding:

Wherein Ar represents as the substituent group on 1 of the 2-pyrazolin-5-one colour coupler; R ₁₃₃Expression replaces or the unsubstituting phenenyl amido, replaces or do not replace acylamino-, replaces or do not replace urea groups, or replaces or do not replace sulfonamido; Represent hydrogen atom with Z, halogen atom, or by oxygen atom, nitrogen-atoms, the coupling of sulfur atom linkage discharges group.

12, silver-halide color photoelement according to Claim 8, wherein said magenta colour coupler are the polymer of monomers colour couplers that contains by formula (PA) expression:

R wherein ₁₂₁Represent hydrogen atom, have the alkyl of 1 to 4 carbon atom, or the chlorine atom;-D-represents-COO-,-CONR ₁₂₂-or replacement or unsubstituted phenyl;-E-represents to replace or unsubstituted alkylidene, replaces or unsubstituted phenylene, or replacement or unsubstituted inferior aralkyl;-F-represents-CONR ₁₂₂-,-NR ₁₂₂CONR ₁₂₂-,-NR ₁₂₂COO--NR ₁₂₂CO-,-OCONR ₁₂₂-,-NR ₁₂₂-,-COO-,-OCO-,-CO-,-O-,-S-,-SO ₂-,-NR ₁₂₂SO ₂-or-SO ₂NR ₁₂₂-; R ₁₂₂The expression hydrogen atom replaces or does not replace aliphatic group, or replacement or unsubstituting aromatic yl; The R of plural number ₁₂₂Base if in same molecular, then can be identical or different; P, q and r represent 0 or 1 respectively, just they do not represent 0 simultaneously; Be expressed as follows the magenta colour coupler residue of formula (PB) expression with T, it is at following Ar, Z and R ₁₃₃On any position at position with-(D)-(E)-(F)-partly bonding:

Wherein Ar represents as the substituent group on 1 of the 2-pyrazolin-5-one colour coupler; R ₁₃₃Expression replaces or the unsubstituting phenenyl amido, replaces or do not replace acylamino-, replaces or do not replace urea groups, or replaces or do not replace sulfonamido; Represent hydrogen atom with Z, halogen atom, or by oxygen atom, nitrogen-atoms, the coupling of sulfur atom linkage discharges group.