CN1326116A - Silver halide color photosensitive material - Google Patents

Abstract

A silver halide color negative photographic lightsentive material comprises at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one blue-sensitive silver halide emulsion layer on a support. The lightsensitive material has an ISO speed of 640 or more, the total silver content of 3.0 to 9.0 g/m<2>. Each of the red-sensitive emulsion layer, green-sensitive emulsion layer and blue-sensitive emulsion layer comprises two or more silver halide emulsion sub-layers having the same color sensitivity but different in speed to each other, and each of the red-sensitive sub-layer having the highest speed, green-sensitive sub-layer having the highest speed and blue-sensitive emulsion sub-layer having the highest speed has a silver content of 0.3 to 1.3 g/m<2>. At least two sub-layers selected from the red-sensitive sub-layer having the highest sensitivity, green-sensitive sub-layer having the highest sensitivity and blue-sensitive sub-layer having the highest speed contain silver halide grains in which tabular silver halide grains occupy 50% or more of the total projected area of all the silver halide grains in the sub-layer, and the tabular grains have an average aspect ratio of 8 or more.

Description

Silver-halide color photoelement

Present patent application based on and require the priority of following formerly Japanese patent application：No. 11-262187 filed in September in 1999 16 days, No. 2000-163294 filed in 31 days March in 2000, these patents are quoted in full herein as reference.

The present invention relates to fast colourful negative film photosensitive material.The present invention also relates to a kind of photographic product of built-in photosensitive material, the wherein product has exposure mechanism and built-in fast colourful negative film photosensitive material.More specifically, the present invention relates to a kind of fast colourful photosensitive material for being particularly suitable for photography, it has ISO, the colour reproduction saturation degree of excellent image quality and height, and improves photosensitive material and be deteriorated in the gray scale increase by production to this period of time of application, sensitivity reduction and graininess.The present invention also relates to a kind of photographic product of built-in photosensitive material, the wherein product has exposure mechanism and built-in above-mentioned colour negative photosensitive material.

With the progress of photographic light-sensitive material technology, quick photosensitive material is just delivered and arrives market in succession.Expand photographing region because of the raising of sensitivity of photographic material, photographed such as without using flash lamp in dark indoor scene or using long-distance photograph camera lens with no-delay gate photograph (such as sports photography) progressively become a reality.

A kind of photographic product (camera lens for being referred to as equipped with film) with exposure mechanism and built-in color negative film photosensitive material is widely used because of its easily characteristic.However, in order to provide the product at a low price, shutter speed and aperture are often fixed, or even when such as the product is equipped with flash lamp, its function is usually limited.To make up these problems, most built-in colour negative photosensitive materials are the colour negatives of ISO.

To improve sensitivity of photographic material, the conventional method of the field that the invention relates to is that the method and other technologies that increase silver halide emulsion grains degree is used in combination prepare quick photosensitive material.Although increase silver halide emulsion grains degree can improve sensitivity to a certain extent, serious defect is inevitably led to, such as：When silver halide level is fixed, as the reduction of silver halide emulsion grains number and development centre number is so as to cause serious graininess to be deteriorated.

For fast colourful negative film photosensitive material, as long as the performances such as blix desilver allow, the design that silver halide emulsion grains content is silver coating quantity is improved, has been used for the number for improving increased development centre synchronous with silver halide emulsion grains, that is afraid of simply slight raising.

However, the photosensitive material of the ISO and high image quality so produced is had been disclosed in Japanese patent application discloses (being hereinafter referred to as JP-A-) 63-226650 has following defect.

I.e. the defect is that photosensitive material product generation imaging performance during production is extremely using this is deteriorated, phenomenon that such as gray scale increase, sensitivity are reduced and graininess is deteriorated.The main cause that imaging performance is deteriorated is that photosensitive silver halide emulsion particle is exposed to the natural radiation discharged from building, ground etc., such as gamma-radiation or cosmic ray.It is well known that the performance of photosensitive material is deteriorated because being influenceed by X-ray and other high-energy radiations.However, with regard to ISO speed for 640 or higher fast colourful negative film photosensitive material for, it has been found that or even extremely weak natural radiation can result in imaging performance variation phenomenon it is unexpectedly serious.The method for resisting this imaging performance variation proposes that is, photosensitive material has used the high material of the radiation absorption factor as lead to separate in packaging or storage and radiated in such as Research Disclosure No.25610 (August 1985).However, unless heavy metal as such as lead reaches enough thickness, the purpose of this method can be fully achieved.So, think that the convenient ordinary consumer of supply at a low price is nearly impossible.The technology for reducing overall silver content or fast layer silver content in colour negative photosensitive material is disclosed in JP-A-63-226650, to tackle because imaging performance is deteriorated caused by natural radiation.However, JP-A-63-226650 invention does not propose any specific counter measure regarding to the issue above, that is, increase silver halide emulsion grains degree and serious defect is inevitably led to improve during sensitivity, but, such as：When silver halide level is fixed, with the reduction of silver halide emulsion grains number and development centre number, serious graininess is caused to be deteriorated.

Than that described above, it is well known by the technology for improving the quick photosensitive material graininess of silver halide particle aspect ratio improvement as disclosed in 434,226 such as U.S.P.4.

It is used as the result of study of invention persons, it has been found that, although producing following phenomenon reconciling in terms of ISO and graininess effectively using high aspect ratio silver halide particle：When the silver halide particle aspect ratio for colour negative photosensitive material reaches 8 or higher, development restrainer is discharged on DIR colour couplers because particle has large surface area compared with common silver halide particle and is excessively captured, so as to inhibit the performance of internal layer effect.Further find, the result is that seriously reducing color rendition saturation degree, this is for the problem of colour negative photosensitive material is one serious.

Increase the silver-colored coating weight of quick emulsion layer according to obtain more preferable graininess, and it is bigger for the particle size of quick emulsion layer, then aspect ratio is the bigger viewpoint of the increased degree in surface of 8 or more Gao Suozhi silver halide particle, invention person is it has also been found that when aspect ratio is used for quick emulsion coating for 8 or higher particle, above-mentioned color rendition saturation degree declines more serious.

Moreover, having recognized that to strengthen the sensitivity of silver emulsion selenium sensitizer and golden sensitizer and sulphur sensitizer is used in combination be preferred in recent years.The result studied as invention persons, it has been found that can be in the case where obtaining equal sensitivity using technique, the size of silver halide particle is reduced, so as to reduce the infringement that environmental radiation effect is caused, but color rendition saturation degree still occurs the problem of decline together.

The problem of above-mentioned color rendition saturation degree declines can be compensated for a large amount of DIR colour couplers.But so doing not only increases cost, and cause the development restrainer agent from DIR colour couplers in middling speed emulsion layer and emulsion layer development at a slow speed excessively to discharge, so that sensitivity declines, the problem of must being increased this creates the terminal the silver-colored coating weight of whole photosensitive material.

Therefore, for being deteriorated for improving caused by environmental radiation imaging performance, strengthening graininess immediately and make color rendition saturation degree increase after coating operation, it is absolutely not to produce a kind of excellent fast colourful negative film photosensitive material in all respects using routine techniques.

It is known that a kind of compound that bleaching accelerators can be disengaged with the reaction of oxidation state aromatic primary amine developer is introduced into sensitive photographic material can accelerate the desilver in developing process.But before invention persons have found, when this compound is introduced into ISO colour negative photosensitive material, using the sensitivity change and graininess change caused by this compound in colour negative photosensitive material, especially because the change exposed to environmental radiation graininess is still known little about it.

A kind of metal ion mixing thing that adulterates may be referred to so as to form the knowledge of electronics capture zone in silver halide particle, as Japanese patent application discloses (hereinafter referred to as JP-A-) 2-20854 and JP-1-7-72569.But, before invention persons have found, the sheet silver halide particle with electronics capture zone is applied still to be known little about it for the photosensitive property change caused by exposed to environmental radiation, the particularly effect produced when silver content changes in photosensitive material in the fast layer of ISO colour negative photosensitive material.

It is an object of the present invention to provide a kind of fast colourful negative film photosensitive material, its sensitivity is high and ensures to possess excellent graininess and higher color rendition saturation degree, while making Storage period internal cause is exposed to caused by environmental radiation after manufacture gray scale increase, sensitivity decline and graininess be deteriorated and reach minimum.

It is a further object to provide a kind of shooting product of built-in photosensitive material, wherein equipped with above-mentioned fast colourful negative film photosensitive material and with exposure mechanism.

As the result of extensive and careful research, invention persons, which have discovered that by following methods, can complete the task of the present invention.

A kind of (embodiment 1) silver-halide color negative film photosensitive material, wherein comprising at least one layer of red sensing coppering silver emulsion layer on a kind of carrier, at least one layer of green silver halide emulsion layer and the blue silver halide emulsion layer of at least one layer of sense,

Wherein photosensitive material ISO speed is 640 or higher；

The total silver content of the photosensitive material is 3.0 to 3.9g/m²；

Each red-sensitive emulsion layer, green-sensitive emulsion layer, blue-sensitive emulsion layer have same color susceptibility but each other different silver emulsion subgrade of speed comprising two layers or more layers；

Each magenta-sensitive emulsion subgrade of prestissimo, green-sensitive emulsion subgrade, blue-sensitive emulsion subgrade silver content are 0.3 to 1.3g/m²；

In magenta-sensitive emulsion subgrade, green-sensitive emulsion subgrade and blue-sensitive emulsion subgrade with prestissimo at least two layers, sheet silver halide particle accounts for 50% or more of all silver halide particle projected areas of whole subgrade in its contained silver halide particle；

And tabular grain average aspect ratio is 8 or bigger.

Photosensitive material described in (embodiment 2) embodiment 1, wherein magenta-sensitive emulsion subgrade, green-sensitive emulsion subgrade, blue-sensitive emulsion subgrade silver content with prestissimo respectively arrive 1.2g/m for 0.3²。

Photosensitive material described in (embodiment 3) embodiment 1 or 2, wherein in terms of every moles of silver, sheet-like particle accounts in the emulsion subgrade of total projection area 50% or more at least one layer and contains 2 × 10^-6To 5 × 10^-6Mol selenium sensitizers.

A kind of (embodiment 4) silver-halide color negative film photosensitive material, wherein comprising at least one layer of red sensing coppering silver emulsion layer on a kind of carrier, at least one layer of green silver halide emulsion layer and the blue silver halide emulsion layer of at least one layer of sense,

Wherein the ISO speed of photosensitive material is 640 or higher；

The total silver content of the photosensitive material is 3.0 to 9.0g/m²；

Each red-sensitive emulsion layer, green-sensitive emulsion layer, blue-sensitive emulsion layer have same color susceptibility but each other different silver emulsion subgrade of speed comprising two layers or more layers；

Total silver content of magenta-sensitive emulsion subgrade, green-sensitive emulsion subgrade, blue-sensitive emulsion subgrade with prestissimo is 1.5 to 3.5g/m²；

Sheet silver halide particle accounts for 50% or more of all silver halide particle projected areas of whole subgrade in contained silver halide particle at least two layers in magenta-sensitive emulsion subgrade, green-sensitive emulsion subgrade and blue-sensitive emulsion subgrade with prestissimo；

And tabular grain average aspect ratio is 8 or bigger.

Photosensitive material described in (embodiment 5) embodiment 4, wherein total silver content of magenta-sensitive emulsion subgrade, green-sensitive emulsion subgrade, blue-sensitive emulsion subgrade with prestissimo is 1.5 to 3.0g/m²；

Photosensitive material described in (embodiment 6) embodiment 4 or 5, wherein in terms of every moles of silver, sheet-like particle accounts in the emulsion subgrade of total projection area 50% or more at least one layer and contains 2 × 10^-6To 5 × 10^-6Mol selenium sensitizers.

Photosensitive material described in one of (embodiment 7) embodiment 1 to 6, wherein at least has one layer of emulsion subgrade to be reacted with oxidation state aromatic primary amine developer comprising a kind of and discharge the compound of bleaching accelerators.

Photosensitive material described in one of (embodiment 8) embodiment 1 to 7, wherein at least two layers emulsion subgrade with top high photographic sensitivity, at least one emulsion includes the sheet silver halide particle that aspect ratio is 8 or bigger, and each sheet-like particle has electronics capture zone.

(embodiment 9) a kind of photographic product of built-in photosensitive material, wherein built with photosensitive material and with exposure mechanism, wherein built-in photosensitive material is the photosensitive material described in one of embodiment 1 to 8.

The present invention described in detail below.

Increase silver halide emulsion grains consumption early to be known from gamma-radiation and X-ray sensitivity increase this case.For example, published in Viley-Interscience in 1969, write by R.H.Herz and " just describe this phenomenon in the texts of The Photographic Action of Ionizing Radiation " one.But, as previously described after silver halide level increases above certain limit, due to natural radiation during physical holding of the stock, the extremely weak gamma-rays occurred in such as our living environments so that fast colourful sensitive photographic material exposes.As a result fast colourful sensitive photographic material degradation is caused, such as gray scale increase and graininess are deteriorated, and this degradation is more serious than what is be expected.

The colour negative photosensitive material (being henceforth also referred to as " color sensitive material " or " photosensitive material ") of the present invention is the material that a kind of ISO speed is 640 or higher, one layer of red sensing coppering silver emulsion layer, one layer of green silver halide emulsion layer and the blue silver halide emulsion layer of one layer of sense wherein comprising a kind of carrier, on carrier, these silver halide emulsion layers include the multilayer different silver emulsion subgrade of speed each other.

In color sensitive material field, to obtain the color sensitive material of high image quality, common practice is to use to be so designed that, i.e. when the emulsion layer with same color susceptibility is made up of the different emulsion subgrade of multiple speed each other, in order to utilize so-called graininess disappearance effect, quick emulsion subgrade has high silver content.But, in the fast colourful photosensitive material that ISO speed is 640 or higher, compared with low speed emulsion subgrade silver content increase, the taking off of performance for having aggravated to elapse through the time after storage of quick emulsion subgrade silver content.Therefore, reduction is to the silver content of most quick emulsion subgrade in the emulsion subgrade with same color susceptibility, can by fast colourful photosensitive material when being stored caused by natural radiation influences taking off of performance, be reduced in a unchallenged level.

In one embodiment of the invention, the photosensitive material of the present invention includes a kind of magenta-sensitive emulsion elementary layer at least with two layers or more the layer different emulsion subgrade of speed each other, a kind of green-sensitive emulsion elementary layer at least with two layers or more the layer different emulsion subgrade of speed each other, a kind of blue-sensitive emulsion elementary layer at least with two layers or more the layer different emulsion subgrade of speed each other.Silver content is respectively 0.3g/m in magenta-sensitive emulsion subgrade with prestissimo, the green-sensitive emulsion subgrade with prestissimo, the blue-sensitive emulsion subgrade with prestissimo²To 1.3g/m², preferably 0.3g/m²To 1.2g/m²。

In another embodiment of the present invention, with the magenta-sensitive emulsion subgrade of prestissimo, the green-sensitive emulsion subgrade with prestissimo, in the blue-sensitive emulsion subgrade with prestissimo, the summation of silver content is 1.5g/m in color sensitive material of the present invention²To 3.5g/m², preferably 1.5g/m²To 3.0g/m²。

In the color sensitive material of the present invention, total silver content is 3.0g/m²To 9.0g/m², preferably 3.0g/m²To 8.0g/m²。

Term " silver content " used herein refers to the total amount of silver, including silver and argent as included in silver halide.The certain methods for analyzing silver content in photosensitive material are known.Although can optionally use, for example carry out elementary analysis using x-ray fluorescence technology and be then easy to carry out.

The ISO speed of the color sensitive material of the present invention is 640 or higher, preferably 800 or higher.

Emulsion available for photosensitive material of the present invention is related to the emulsion of silver iodobromide or chlorine silver iodobromide sheet-like particle.

The sheet silver halide particle that the present invention is used is the sheet silver halide particle with two or more twin planes that are parallel to each other.

For sheet silver halide particle (hereinafter referred to as " sheet-like particle "), term " aspect ratio " refers to the ratio of silver halide diameter and thickness.That is, it is the obtained quotient of diameter divided by thickness of each silver halide particle.Term " diameter " used herein refers to the diameter of a circle of the projected area area equation as obtained by microscope or electron microscope observation silver halide particle.

One layer red sensing coppering silver emulsion layer, one layer green silver halide emulsion layer, one layer sense blue silver halide emulsion layer of the color sensitive material of the present invention comprising a kind of carrier and on carrier, the silver emulsion subgrade that multiple speed each other are different is included in each silver halide emulsion layer, wherein at least two most quick emulsion subgrades, 50% or more of total projection area is occupied by sheet silver halide particle, the average aspect ratio of sheet silver halide particle is 8 or bigger, preferably 10 or bigger, more preferably 12 or bigger.The upper limit of aspect ratio is preferably 50.Feeling red, in the most quick emulsion subgrade that sense is green, sense is blue, at least two subgrades are preferably that sense is green and the blue subgrade of sense.

In the present invention, the gray scale increase caused by natural radiation is successfully inhibited by reducing the silver content in quick subgrade.Moreover, it is unrelated with quick subgrade silver content reduction, high aspect ratio is used in quick subgrade, such as average aspect ratio is 8 or higher sheet-like particle, successfully prevents graininess to be deteriorated.Meanwhile, silver content in the quick subgrade by reducing the sheet-like particle containing high aspect ratio is successfully solved the problem of the interior effect layer caused by using high aspect ratio sheet-like particle is too small.

In the present invention, term " average aspect ratio " refers to the average value of the aspect ratio of all sheet-like particles in emulsion.

Using transmission electron microscopy replica technique and determine each particle equivalent circular diameter and thickness, the method example that can be measured as aspect ratio.In the methods described above, thickness is calculated by the shadow length of replica.

The profile of sheet-like particle used of the invention is usually hexagon.Term " hexagon " refers to that the dominant plane of sheet-like particle is shaped as hexagonal shape, and its beside ratio (largest face length/minimal face length) is 2 or smaller.Beside ratio is preferably 1.6 or smaller, and more preferably 1.2 or smaller.Its minimum lower limit is 1.0 without carrying again.Especially, in the particle of high aspect ratio, the increase of sheet-like particle intermediate cam shape sheet-like particle.Triangle sheet-like particle is produced when Ostwald curings are excessive.For essentially hexagon sheet-like particle angle is obtained, it is preferable that the maturation period is as short as possible.For this purpose, must pass through nucleation improves sheet nucleus ratio.As described in the JP-A-63-11928 by Saito, when silver ion and bromide ion are added in reactant mixture using bi-injection method, it is preferred that gelatin is added in one or both of silver ionized water solution and the bromide ion aqueous solution, to increase the formation probability of hexagon sheet-like particle.

Hexagon sheet-like particle used of the invention can be cured by nucleation, Ostwald and grow up and be formed.Although all steps are all important to suppressing particle size distribution expansion, especially it should be noted that limiting the expansion of particle size distribution in above-mentioned nucleating step, because Size Distribution expansion will not narrow below in step caused by preceding step.It is important that relation between during reaction mixture temperature and nucleation in nucleation step, during this period including adding in reactant mixture and producing precipitation by silver ion and bromide ion using bi-injection method.Preferable case described in Saito JP-A-63-92942 is that, to promote the formation of monodisperse status, the temperature of reactant mixture is at 20~45 DEG C during nucleation.Moreover, the suitable temperature that nucleation is described in Zola et al. JP-A-2-222940 is 60 DEG C or less.

To obtain the monodisperse status sheet-like particle of high aspect ratio, gelatin can be added during particle formation.The gelatin added is preferably, as described in JP-A-10-148897,11-143002 containing gelatin (in this gelatin p- NH through being chemically modified₂Group chemical, which is improved, at least newly introduces two-COOH), these patents are quoted herein as reference.Although this gelatin being chemically modified is characterised by gelatin that contained amino, through being chemically modified at least two carboxyls of new introducing, preferably uses trimellitic acid gelatin.And succinated gelatin is also preferred.Gelatin is chemically modified it is preferred that being added before growth step, is more preferably added at once after nucleation.Total restatement of decentralized medium used is formed with granules, addition is preferably at least 60%, more preferably at least 80%, most preferably at least 90%.

Tabular grain emulsions include silver iodobromide or chlorine silver iodobromide.Although silver chlorate can be included, silver chloride content is preferably 8mol% or less, more preferably 3mol% or less, or 0mol%.Because the particle size distribution coefficient of variation of Tabular grain emulsions is preferably 30% or less, agi content is preferably 20mol% or less.The amount of reduction silver iodide helps to reduce the coefficient of variation of the equivalent circular diameter distribution of Tabular grain emulsions.The particle size distribution coefficient of variation of Tabular grain emulsions is more preferably 20% or less, and the amount of silver iodide is more preferably 10% or less.

Preferably silver iodide distribution Tabular grain emulsions have some particle inner structures.Silver iodide distribution may have two-layer structure, three-decker, four-layer structure or more Rotating fields.

In the present invention, sheet-like particle preferably has dislocation line.It can use, for example J.F.Hamilton, Phot.Sci.Eng., 11,57 (1967) and T.Shiozawa, J.Soc.Phot.Sci.Japan, 3, method described in 5,213 (1972), it directly observes the dislocation line of sheet-like particle using transmission electron microscope at low temperature.I.e., silver halide particle is carefully taken out from emulsion, it is to avoid the power pressurization that particle produces dislocation line can be made thereon, particle is placed on grid and carries out electron microscope observation, frozen samples are in order to avoid sample damages (such as printout) by electron beam, and is observed with transmission method.The thickness of above-mentioned particle is bigger, then electron beam is more difficult to pass through.Therefore high pressure (at least 200KV when grain thickness is 0.25 μm) electron microscope is preferably used to ensure clear observation.The particle photo obtained from perpendicular to the direction of major surfaces, can determine position and the number of each particle dislocation line.

The number of sheet-like particle dislocation line of the present invention is preferably averagely each particle at least ten, more preferably average each particle at least 20.When dislocation line is intensive or when observing that dislocation line intersects, is then unable to the dislocation line number of each particle of accurate metering.But, it can be classified in this case, for example, 10,20 or 30 rough calculation dislocation lines so that can clearly distinguish the particle of the presence of only a small number of dislocation lines.The average dislocation line number mesh of each particle is averagely obtained by counting the dislocation line of at least 100 particles.It is observed that the hundreds of situation of dislocation line.

Dislocation line can be introduced into, such as the vicinity of sheet-like particle outer edge area.In this case, dislocation line is basically perpendicular to outer rim and is being to be formed at x% of the sheet-like particle center with outer rim spacing away from outer rim distance.Numerical value x is preferably that 10 to less than 100, most preferably 30 to less than 99, and most preferably 50 to less than 98.In this case, although the shape obtained by connection dislocation line original position is substantially similar to grain shape, and resulting shape is not exclusively similar, but has deviateed.This dislocation line is can not see in granular center region.The orientation of dislocation line is about in (211) crystallization direction.But dislocation line often intersects for zigzag and sometimes.

The dislocation line that sheet-like particle has can substantially be uniformly distributed in whole outer edge area or the local location in outer edge area.That is, for hexagonal plate silver halide particle, dislocation line can be only located at the vicinity on six summits, can also be only located at the vicinity on one of six summits.In contrast, dislocation line can also be located at except on the face near six summits.

The dislocation line formed, which can also be passed through, includes the region of two parallel main centre of surfaces of sheet-like particle.When dislocation line passes through main surface whole region, the orientation of dislocation line is close to (211) direction perpendicular to main surface sometimes.But the formation orientation of dislocation line can be (110) direction or disorderly and unsystematic.The length of each dislocation line is also irregular：Dislocation line on main surface is sometimes short-term, is the long line for extending to border (outward flange) again sometimes.Although dislocation line is straight sometimes, they are often zigzag.As a rule, dislocation line intersects.

In the sheet-like particle of silver emulsion of the present invention, the position of dislocation line can be confined to simultaneously occur in outer edge, main surface or part, or these positions, i.e., there is dislocation line simultaneously at outer edge and main surface.

Dislocation line is introduced in sheet-like particle, can be accomplished by depositing a kind of special phase of high agi content in particle.In being introduced into of dislocation line, high agi content phase can be provided by the discontinuity zone of high agi content.In fact, the high agi content in particle mutually plus high agi content phase and can cover monoiod(in)ate silver content phase one layer mutually lower than high agi content outside it and obtain by preparing base particle first, and to them.The agi content of basic sheet-like particle is less than the content of silver iodide in high agi content phase, in terms of silver halide in base particle, and preferably 0 arrives 20mol%, and more preferably 0 arrives 15mol%.

Term " the high agi content phase in particle " refers to the silver halide solid solution comprising silver iodide.Silver halide in solid solution is preferably silver iodide, silver iodobromide or chlorine silver iodobromide, more preferably silver iodide and silver iodobromide (in terms of silver halide level in high agi content phase, the content of silver iodide is 10 to 40mol%).For the high agi content phase (being henceforth referred to as " internal high agi content phase ") being selectively generating in any place in side, angle and face of base particle in particle, preferable method is the formation condition, the formation condition of internal high agi content phase and the formation condition for covering its outside phase for controlling base particle.In terms of base particle formation condition, pAg values (the negative logarithm of concentration of silver ions), ag halide solvent presence or absence, type and quantity and temperature, are important factors.It is 8.5 or smaller that pAg is adjusted in basic iodine granular grows, it is proposed that 8 or smaller, and internal high silver iodide phase is formed selectively on the summit or face of basic silver iodide in the step of can subsequently forming internal high silver iodide phase.On the other hand, the pAg adjusted when base particle grows, which is at least in 8.5, preferably at least 9, the step of can subsequently forming internal high silver iodide phase on the summit or face of basic silver iodide, is formed selectively internal high silver iodide phase.The pAg threshold value changed up and down depends on temperature, ag halide solvent presence or absence, type and quantity.For example, when rhodanate is used as ag halide solvent, pAg threshold value will be skewed towards much higher value.

It is the pAg values that base particle grows latter stage in growth period most important pAg values.On the other hand, when or even when growth pAg values are unsatisfactory for above numerical value, the selectivity positioning of internal high silver iodide phase can be achieved after base particle growth by adjusting to above-mentioned pAg and curing.During this period, ammonia, aminated compounds, thiourea derivative or rhodanate are effective ag halide solvents.To form internal high agi content phase, using so-called method for transformation.These method for transformation include during particle formation, adding a kind of halide ion, and the dissolubility for the salt that it is formed with silver ion will be less than during particle formation, form the salt that the halogen ion in area near particle or particle surface is formed.In the present invention, form granule surface area according to during adding, the addition of relatively low deliquescent halogen ion is at least certain value (relative to halogen constituents).Such as preferred situation is, during particle formation, the amount of silver halide particle surface area when KI addition is not less than the formation of corresponding particle.Specifically, the addition of salt compounded of iodine is preferably at least 8.2 × 10^-5mol/m²。

Forming the method for optimizing of internal high silver iodide phase includes adding the aqueous solution of silver salt and the halogen saline solution containing salt compounded of iodine simultaneously.

For example, AgNO₃The aqueous solution is added simultaneously by bi-injection method and the KI aqueous solution.The KI aqueous solution and AgNO₃The initial time and deadline that the aqueous solution is added can be different, i.e. a kind of solution may early or late be added than another solution.AgNO₃The addition mol ratio of the aqueous solution and the KI aqueous solution is preferably at least 0.1, more preferably at least 0.5, most preferably at least 1.Relative to the halide ion in system and adding iodide ion, AgNO₃The aqueous solution, which always adds mole, can fall within silver-colored excess area.When halide solution and silver salt solution containing iodide ion are being added through double injection, pAg values preferably add the passage of time with double injection and reduced.When adding starting, pAg values are preferably 6.5 to 13, more preferably 7.0 to 11.PAg is preferably 6.5 to 10.0 after the completion of addition.

When carrying out aforesaid operations, preferably make mixture system dissolubility low as much as possible.Therefore in high silver iodide phase shaping age, the temperature of mixture system is preferably 30 to 80 DEG C, more preferably 30 to 70 DEG C.

Moreover, the formation of internal high silver iodide phase is preferably carried out by adding silver iodide fine grained, silver iodobromide fine grained, chlorosulfonylation silver fine grained or chlorine silver iodobromide fine grained.Particularly preferably carried out by adding silver iodide fine grained.Although these fine grain sizes are often 0.01 to 0.1 μm, 0.01 μm of undersize or the fine grained more than 0.1 μm can equally be used.On the fine grain preparation method of silver iodide, the description in JP-A-1-183417,2-44335,1-183644,1-183645,2-43534 and 2-43535 can refer to.By adding these fine particles of silver halide and curing, internal high silver iodide phase can be obtained.When fine grained dissolves through curing, above-mentioned ag halide solvent can be used.All fine graineds being added need not dissolve and disappear immediately.As long as they dissolve and disappeared when final particle is completed.

Hexagonal centre for example from particle projection formation is measured, in terms of the silver halide of whole particle, the position of internal high silver iodide phase preferably 5 to less than 100mol%, more preferably 20 to less than 95mol%, most preferably 50 at less than 90mol%.In terms of the silver halide of whole particle, the silver halide level for constituting internal high silver iodide phase is 50mol% or smaller, preferably 20mol% or smaller.For above-mentioned high silver iodide phase, mentioned herein is the formula value of silver emulsion production, rather than measures the numerical value obtained by the halogen constituents of final particle by using various analysis methods.Internal high silver iodide are mutually often wholly absent in final particle, such as are recrystallized in shell overwrite procedure.Above silver content is corresponding formula value.

Therefore, although easily can observe dislocation line in final particle by the above method, because border silver iodide component consecutive variations, the internal silver iodide introduced to introduce dislocation line is usually not determined as a clear and definite phase.For each particles sites halogen constituents measurement can be used in combination X-ray diffraction art, EPMA methods (also referred to as XMA methods, silver halide composition is wherein monitored using electron beam scanning silver halide particle), the method such as ESCA methods (also referred to as XPS methods, wherein being dispersed into spectrum using x-ray irradiation and by the photoelectron that particle surface is discharged) carries out.

The agi content in internal high silver iodide phase outer layer phase is covered in, relatively internal high silver iodide phase content is low.With silver halide gauge contained by outer layer phase, outer layer phase iodate content of iodine is preferably 0 to 30mol%, more preferably 0 to 20mol%, most preferably 0 to 10mol%.

Although the formation temperature and pAg of the outer layer phase of the internal high silver iodide phase of covering are arbitrarily selected, temperature is preferably 30 to 80 DEG C, more preferably 35 to 70 DEG C, and pAg is preferably 6.5 to 11.5.Sometimes above-mentioned silver halide solution is preferably used, most preferred silver halide solution is rhodanate.

The another method of dislocation line is introduced in sheet-like particle including the use of iodide ion releasing agent described in JP-A-6-11782, preferably using.

Meanwhile, the method for this introducing dislocation line can suitably be combined with the method for above-mentioned introducing dislocation line, introduce dislocation line.

The coefficient of variation that iodine is distributed in the particle of silver halide particle in the present invention is preferably 20% or less, and more preferably 15% or less, it is further preferably 10% or less.When the coefficient of variation of each silver halide content of iodine distribution is more than 20%, it is impossible to realize high contrast, sensitivity is substantially reduced in the presence of pressure.

To produce the silver halide particle of iodine narrowly distributing in particle, any of method is may be used alone or in combination, the fine grain method of addition and the method in the use iodide ion releasing agent as described in JP-A-2-68538 as described in JP-A-1-183417.

Iodine distribution variation coefficient is preferably 20% or less in its particle of silver halide particle of the present invention.To make iodine distribution in this particle turn into monodisperse status, the method described in JP-A-3-213845 is optimal method.That is, iodine distribution can be realized by such as the method in monodispersed particle：The aqueous solution (containing at least 95mol% iodide ion) of the aqueous solution of water soluble silver salt and water-soluble halide is mixed together in blender outside crystalline growth reactor, agi content at least 95mol% thin silver halide particle is formed, is added at once in reactor after its formation.The nucleation of term " reactor " fingering row sheet silver halide particle used herein and/or the container of crystal growth.

Prepared for above-mentioned blender and then the method added and the preparing mechanism employed in it, can be using following three kinds of technologies described in JP-A-3-213845：

(1) it is transferred at once in reactor after fine grained is formed in a mixer；

(2) strength is carried out in a mixer and is effectively stirred；And

(3) aqueous solution of a protective colloid is injected into blender.

The protective colloid used in above technology (3) individually can be injected into blender, can also be first incorporated into the silver halide aqueous solution or silver nitrate aqueous solution being injected into before agitator.By weight, the concentration of protective colloid is at least 1%, preferably 2 to 5%.Playing the embodiment of the polymerizable compound of protective colloid effect to silver halide particle for the present invention includes：Polyacrylamide polymers, amino polymer, poly- polymer, polyvinyl alcohol, acrylate copolymer, the oxyquinoline with polymer, cellulose, starch, acetal, polyvinylpyrrolidone and the ter-polymers for having a sulfide group.The gelatin of low molecule amount is preferably used as above-mentioned polymer.The molal weight of low molecular weight gelatine is preferably 40,000 or less, more preferably 30,000 or less.

In fine particles of silver halide is prepared, particle formation temperature is preferably 35 DEG C or smaller, more preferably 25 DEG C or smaller.The temperature for being introduced into the reactor of fine particles of silver halide is at least 50 DEG C, more preferably at least preferably at least 60 DEG C, 70 DEG C.

The particle diameter of fine particles of silver halide used in the present invention can be measured by the way that particle to be placed on grid and directly be observed by transmission electron microscope.Fine particle size of the present invention is 0.3 μm or smaller, preferably 0.1 μm or smaller, more preferably 0.01 μm or smaller.Fine particles of silver halide can simultaneously be added with other halogen ions and silver ion, can also be individually added into.In terms of the total amount of silver halide, the combined amount of fine particles of silver halide arrives 10mol% for 0.005 to 20mol%, preferably 0.01.

Each individually composition of particle can be analyzed by X-ray microscopic analyzer and its agi content is determined.The value that term " iodine distribution variation coefficient in particle " value is defined by below equation：

The coefficient of variation=(standard deviation/average silver iodide content) × 100

The wherein standard deviation of standard deviation, particularly agi content, and the content of average silver iodide is preferably at least 200, more preferably at least 300 after measured obtained from the agi content of at least 100 emulsion grains.As being measured using method described in EP No.147,868 to the agi content of each independent particle.Have between the agi content Yi (mol%) of each particle and the spherical diameter (Xi) (μm) of equal value of each particle and there is a situation where correlation, also there is the situation in the absence of correlation.It is preferred that the situation of correlation is not present between the two.The structure being associated with the silver halide composition of particle of the present invention can be identified by the following method：As use in conjunction X-ray diffraction method, EPMA methods (are also referred to as XMA methods, silver halide composition is wherein monitored using electron beam scanning silver halide particle), the method such as ESCA methods (also referred to as XPS methods, wherein being dispersed into spectrum with x-ray irradiation and by the photoelectron that particle surface is discharged) and identify.In agi content of the present invention measure, the  of term " particle surface " span case depth about 50 region.And term " inside particle " refers to other regions in addition to above-mentioned surface.The halogen composition of such particle surface can be generally measured by ESCA methods.

The silver emulsion of the present invention preferentially uses selenium sensitizing.

Selenium compound so far disclosed in patent can be used as the selenium sensitizer of the present invention.In using unstable selenides and/or non-unstable selenium compound, generally add it in emulsion and stir a period of time under conditions of preferably 40 DEG C or higher of high temperature.Compound is used as unstable selenium compound as described in Japanese Patent (being hereinafter denoted as JP-B-) 44-15748, JP-B-43-13489, JP-A-4-25832 and 4-109240.

The embodiment of unstable selenium compound is different selenocyanates (such as different fatty base ester of selenocyanic acid, such as different selenocyanic acid allyl ester), seleno urea, seleno ketone, selenium substituted acid amide, seleno carboxylic acid (such as 2- selenos propionic acid and 2- selenos butyric acid), seleno ester, diacyl selenides (such as double (3- chloro- 2,6- dimethoxybenzoyls) selenides), selenophosphates, the selenides of phosphine and colloidal metal selenium.

Although the foregoing describing the preferred embodiment of unstable selenium compound, the present invention is not limited merely to these embodiments.Those skilled in the art think that the structure of the unstable selenium compound as emulsion sensitizer is not particularly significant, as long as selenium is unstable, and the organic moiety of selenium sensitizer molecule does not have important function, and only it is to play a part of transhipment selenium and keep it to be unstable state in emulsion.In the present invention, it is more favourable using the unstable selenium compound of this broad sense.

The embodiment of non-unstable selenium compound of the present invention is described in JP-B-46-4553, JP-B-52-34492 and JP-B-52-34491.The specific embodiment of non-unstable selenium compound is selenous acid, selenocyanic acid potassium, seleno pyrroles, the level Four salt of seleno pyrroles, diaryl selenium, the selenium of diaryl two, selenium dialkyl, the selenium of dialkyl group two, 2- selenazolines alkanone, 2- selenazoline sulfane ketone and its derivative.

In these selenium compounds, the preferably compound of general formula (A) and formula (B).

In this molecular formula, Z₁And Z₂Can be identical, can also different from each other, respectively represent alkyl (such as methyl, ethyl, the tert-butyl group, adamantyl or t-octyl), alkenyl (such as vinyl or acrylic), aralkyl (such as benzyl or phenethyl), aryl (such as phenyl, pentafluorophenyl group, 4- chlorphenyls, 3- nitrobenzophenones, 4- octylames sulfonyl-phenyl or Alpha-Naphthyl), heterocyclic group (such as 2- pyridine radicals, 3- thienyls, 2- furyls or 2- imidazole radicals) ,-NR₁(R₂)、-OR₃Or-SR₄。

R₁、R₂、R₃And R₄May be identical, it is also possible to different from each other, respectively represent hydrogen atom, alkyl, aralkyl, aryl, heterocyclic radical or acyl group.Alkyl, aralkyl, aryl, the embodiment of heterocyclic radical and above-mentioned Z₁It is identical.As long as R₁And R₂Respectively represent hydrogen atom or acyl group (such as acetyl group, propiono, benzoyl, seven fluorine bytyries, difluoro acetyl group, 4- nitro benzoyls, α-naphthoyl or 4- TRIFLUOROMETHYLBENZOYLs).

In formula (A), Z₁It is preferred that representing alkyl, aryl or-NR₁(R₂), Z₂Representative-NR₅(R₆)。R₁、R₂、R₅And R₆Can be with identical, can also be different from each other, respectively represent hydrogen atom, alkyl, aryl or acyl group.

It is highly preferred that formula (A) represents N, N- dialkyl group selenourea, N, N, N '-trialkyl-N ' Acylselenoureas, tetraalkyl selenourea, N, N- di alkylaryls selenium substituted acid amide and N- alkyl-N-aryl phenyl or m-tolyl selenoamides.

In this molecular formula, Z₃, Z₄And Z₅Can be with identical, can also be different from each other, respectively represent alkyl, alkenyl, alkynyl group, aralkyl, aryl, heterocyclic group ,-OR₇、-NR₈(R₉)、-SR₁₀、SeR₁₁, X or hydrogen atom.

R₇、R₁₀And R₁₁Respectively represent alkyl, alkenyl, alkynyl group, aryl, heterocyclic group, hydrogen atom or cation.R₈And R₉Respectively represent alkyl, alkenyl, alkynyl group, aralkyl, aryl, heterocyclic group or hydrogen atom.X represents halogen atom.

In formula (B), by Z₃、Z₄、Z₅、R₇、R₈、R₉、R₁₀And R₁₁Alkyl, alkenyl, alkynyl group, the aralkyl of representative are respectively straight chain, side chain or ring-type alkyl, alkenyl, alkynyl group, aralkyl (such as methyl, ethyl, n-propyl, isopropyl, the tert-butyl group, normal-butyl, n-octyl, positive decyl, n-hexadecyl, pentamethylene base, cyclohexyl, pi-allyl, 2- cyclobutenyls, 3- pentenyls, propargyl, 3- propinyls, benzyl and phenethyl).

In formula (B), Z₃, Z₄, Z₅, R₇, R₈, R₉, R₁₀And R₁₁The aryl of representative can be monocyclic or condensed ring (such as phenyl, pentafluorophenyl group, 4-chlorphenyl, 3-sulfophenyl, α-naphthyl or 4-aminomethyl phenyl).

In formula (B), Z₃、Z₄、Z₅、R₇、R₈、R₉、R₁₀And R₁₁The heterocyclic group of representative is containing three to the ten yuan of saturations or unsaturated heterocycle group (such as 2- pyridine radicals, 3- thienyls, 2- furyls, 2- thiazolyls, 2- imidazole radicals or 2- benzimidazolyls) at least one nitrogen-atoms, oxygen atom and sulphur atom.In addition, heterocyclic group can also have parallel cyclization.

In formula (B), R₇、R₁₀And R₁₁The cation of representative is alkali metal atom (such as potassium and sodium) or ammonium ion.Halogen atom representated by X is fluorine atom, chlorine atom, bromine atoms and iodine atom.

In formula (B), preferably Z₃、Z₄And Z₅Respectively represent alkyl, aryl or-OR₇、R₇Represent alkyl or aryl.

It is highly preferred that formula (B) represents trialkyl phosphine selenides, triaryl phosphine selenides, trialkyl phosphoroselenoate or triaryl phosphoroselenoate.

The embodiment of compound representated by formula (A) and (B) is listed below, but they are not used to define the present invention.

These selenium sensitizers are dissolved in single solvent or in the mixed solvent selected from water and organic solvent such as methanol and ethanol, and added in chemical sensitization.It is preferred that being added before chemical sensitization starts.Above selenium sensitizer may be used alone or in combination.It is preferred that unstable selenium compound and non-unstable selenium compound is used in combination.

The addition of selenium sensitizer used in the present invention, although changing with selenium sensitizer used activity, the type and size of silver halide, the factor such as curing temperature and time, in terms of every mol silver halide, its preferred scope is 2 × 10^-6To 5 × 10^-6mol.The use of the chemical sensitization temperature of selenium sensitizer it is preferably 40 DEG C to 80 DEG C.PAg and pH value are arbitrary.For example, for pH value, effect of the invention is even achieved in 4 to 9 wide scope.

Selenium sensitizing is carried out in the presence of ag halide solvent then more effective.

Embodiment available for ag halide solvent of the present invention is：(a) in the organic thioether as described in U.S.P.3,271,157,3,531,286 and 3,574,628 and JP-A-54-1019 and JP-A-54-158917；(b) in the thiourea derivative as described in JP-A-53-82408, JP-A-55-77737 and JP-A-55-2982；(c) ag halide solvent with the sandwich thiocarbonyl group in an oxygen or sulphur atom and a nitrogen-atoms described in JP-A-53-144319；(d) glyoxaline compound described in JP-A-54-100717；(e) sulphite；(f) rhodanate.

Particularly preferred ag halide solvent is rhodanate and tetramethyl thiourea.Although the consumption of ag halide solvent changes with type of solvent, in terms of every mol silver halide, the consumption of such as thiocarbamide solvent is preferably 1 × 10^-4To 1 × 10^-2mol。

The carry out sensitizing of golden sensitizing is preferably used in combination in emulsion for the present invention.Golden oxidation number is+1 or+3 in golden sensitizer used in golden sensitizing, and the gold compound for being conventionally used as golden sensitizer can be used.It, which represents embodiment, includes：The golden potassium of chloroaurate, potassium chloroaurate, gold trichloride, sulphur cyanogen, Potassium Tetraiodoaurate, four auric cyanide acids, the golden ammonium of sulphur cyanogen, pyridine radicals gold trichloride, aurosulfo and Auric selenide.The addition of golden sensitizer, although changing according to a variety of conditions, in terms of every mol silver halide, preferably 1 × 10^-7Mol to 5 × 10^-5Between mol.

For emulsion used in the present invention, it is preferable that sulphur sensitizing, which is used in combination, and carries out chemical sensitization.

Sulphur sensitizing is generally through adding sulphur sensitizer and under preferably 40 DEG C of high temperature or higher temperature, stirring the emulsion regular hour and carry out.

In above-mentioned sulphur sensitizing, known sulphur sensitizer can be used.For example, can be used thiosulfate, allyl sulfide for kappa amine thiocarbamide, allyl isothiocyanate salt, cystine, to toluene thiosulfonate and rhodanine.Other sulphur sensitizers as described in U.S.P.1,574,944,2,410,689,2,278,947,2,728,668,3,501,313 and 3,656,955 and DE No.1,422,869, JP-B-56-24937 and JP-A-55-45016 can also be used.As long as sulphur sensitizer can sufficiently effective increase the sensitivity of emulsion, its addition is exactly gratifying.The addition is although with such as pH value, and temperature is different with a variety of conditions such as silver halide particle size and changes to a considerable extent, and in terms of every mol silver halide, its preferred scope is 1 × 10^-7Mol to 5 × 10^-7mol。

Particle formation during or particle formed after but before chemical sensitization, during chemical sensitization or after chemical sensitization, to for the present invention silver emulsion carry out reduction sensitization.

Reduction sensitization can be used to be carried out selected from the method for adding reduction sensitization agent in emulsion below, the so-called silver-colored ageing method for being grown and being cured under pAg values as little as 1 to 7 environment, and the so-called high ph-values ageing method for being grown and being cured in the environment of pH value up to 8 to 11.At least two can be used in combination in these methods.

From the point of view of reduction sensitization degree can be finely adjusted, the method for above-mentioned addition reduction sensitization agent can be carried out preferred.

The embodiment of known reduction sensitization agent includes tin salt, ascorbic acid and its derivative, amine and polyamine, hydrazine derivate, FAS, silane compound and borane compound.The present invention use in reduction sensitization, it is preferred that is selected one kind from known reduction sensitization agent and use or is selected at least two and be used in combination.It is preferred that reduction sensitization agent be stannous chloride, thiourea dioxide, dimethylamino borine, ascorbic acid and its derivative.Although the addition of reduction sensitization agent must be chosen according to emulsion manufacturing condition, in terms of every mol silver halide, addition is preferably 10^-7To 10^-3mol。

By each reduction sensitization agent be dissolved in the organic solvent such as water or alcohol, dihydric alcohol, ketone, ester and acid amides it is any among and added during particles generation.Although reduction sensitization agent can be added in reactor in advance, the addition of appropriate suitable time preferably during granular grows.Reduction sensitization agent is added into the aqueous solution of water soluble silver salt or water miscible alkali halide in advance, and silver halide particle is settled out using obtained aqueous solution.Or, according to the growth of particle, reduction sensitization agent can be added repeatedly in batches, or be continuously added in one section of longer time.

Preferably use a kind of oxidant for being capable of silver oxide, the production for emulsion of the present invention.Silver-colored oxidant is with the compound that silver ion is acted on and be translated into argent.Particularly effective compound is a kind of compound that very fine Argent grain is converted into silver ion, and very fine Argent grain is the accessory substance to be formed in silver halide particle and chemical sensitization step.Produced silver ion can form such as silver halide, and silver sulfide or silver selenide etc. are insoluble in the silver salt of water, or form the silver salt soluble in water such as nitrate.Silver-colored oxidant can be inorganic or organic compound.The embodiment of suitable inorganic oxidizer includes ozone, hydrogen peroxide and its addition product (such as NaBO₂·H₂O₂·3H₂O、2Na₂CO₃·3H₂O₂、Na₄P₂O₇·2H₂O₂And 2Na₂SO₄·H₂O₂·2H₂O), peracid salt (such as K₂S₂O₈、K₂C₂O₆And K₂P₂O₃), peroxide complex (such as K₂[Ti(O₂)C₂O₄·3H₂O、2K₂SO₄·Ti(O₂)OH·SO₄·3H₂O and Na₃[VO(O₂)(C₂H₄)₂]·6H₂O), permanganate (such as KMnO₄), bichromate (such as K₂Cr₂O₇) and other oxysalts, halogen such as iodine and bromine, perhalide (such as potassium metaperiodate), high-valency metal salt (such as six cyanogen close iron (II) and change potassium) and thiosulfate.

The embodiment of suitable organic oxidizing agent includes quinones such as 1,4-benzoquinone, organic peroxide such as Peracetic acid and benzoyl hydroperoxide and reactive halogen release compound (such as N-bromosuccinimide, toluene-sodium-sulfonchloramide and chloramine B).

Currently preferred oxidant is selected from ozone, hydrogen peroxide and its adduct, inorganic oxidizer of halogen and rhodanate and the organic oxidizing agent selected from quinone.

It is preferred that silver-colored oxidant is used in combination with above-mentioned reduction sensitization.Being used in combination can be by using carrying out reduction sensitization or in contrast after oxidant, or uses oxidant and reduction sensitization simultaneously.These methods can be carried out in particle forming step or chemical sensitization step.

To obtain the effect of the present invention, it is preferred to use methine dyes etc. carries out spectral sensitization to emulsion used in the present invention.Workable dyestuff includes cyanine dye, merocyanine dyes, compound cyanine dye, complex merocyanine dyes, holopolar form cyanine dye, half cyanine dye, styryl dye and half oxa- mountain valley with clumps of trees and bamboo dyestuff (hemioxonole).Most useful dyestuff is cyanine dye, merocyanine dyes and complex merocyanine dyes.Any parent nucleus that basic heterocycle parent nucleus is typically used in cyanine dye can be applied to these dyestuffs.Workable parent nucleus embodiment includes pyrrolin core, oxazoline core, thiazoline core, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazoline core, imidazole nucleus, tetrazolium core and pyridine nucleus；The core that aliphatic acyclic hydrocarbon a pair of horses going side by side is constituted together in above-mentioned parent nucleus；Aromatic hydrocarbon ring a pair of horses going side by side closes the core for stating parent nucleus composition, such as indoline core, benzindole quinoline core, indole nucleus, benzoxazole nucleus, aphthoxazoles core, benzothiazole nucleus, aphthothiazoles core, benzo selenazole nucleus, benzimidazole nucleus and quinoline nuclei.These parent nucleus can replace on a carbon atom.

It is possible in a kind of merocyanine dyes or complex merocyanine dyes introduce the 5 or 6 element heterocycle parent nucleus with ketone methylene based structures parent nucleus.Embodiment has pyrrolidines -5- ketone core, thio hydantoin core, the thio oxazolines -2 of 2-, 4- diketone core, thiazoline -2,4- diketone core, rhodanine core and thiobarbituricacidα- core.

Although these sensitizing dyes can be used alone, they can also be used in combination.The purpose for being usually used in supersensitization is used in combination in sensitizing dye.This embodiment being used in combination is in U.S.P2,688,545,2,977,229,3,397,060th, 3,522,052,3,527,641,3,617,293rd, 3,628,964,3,666,480,3,672,898th, 3,679,428,3,703,377,3,769,301st, 3,814,609,3,837,862 and 4,026,707th, it is described in British Patents 1,344,281 and 1,507,803, JP-B-43-4936, JP-B-53-12375, JP-A-52-110618 and JP-A-52-109925.

In addition to sensitizing dye, it substantially can not absorb containing the dyestuff without spectrum sensibilization or visible ray in emulsion and the material of supersensitization is presented.

The random time that sensitizing dye can be manufactured in emulsion is added in emulsion, it is known that this practice is typically all effective.More generally, it is added after the completion of chemical sensitization and before film.But such as U.S.P3,628,969 and 4, described in 225,666, can also be added in chemical sensitization same time so that the quick and chemical quick progress simultaneously of spectrum.Also it can be added as described in JP-A-58-113928 before chemical sensitization, or start spectral sensitization before silver halide particle precipitates and to form completion.Or these compounds are added portionwise as disclosed in U.S.P4,225,666：A part of compound is added before chemical sensitization, and remainder is added after chemical sensitization.According to U.S.P 4, the other methods of method disclosed in 183,756, spectral sensitizing dye can be added in any time of silver halide particle formation.

In terms of every mol silver halide, although spectral sensitizing dye consumption can be 4 × 10^-6To 8 × 10^-3Mol, when silver halide particle size is in 0.2 to 1.2 μm of preferred scope, in terms of every mol silver halide, its consumption is 5 × 10^-5To 2 × 10^-3mol。

The preferred twin plane distance of silver halide particle used is 0.017 μm or smaller, particularly preferably more preferably 0.007 to 0.017 μm, 0.007 to 0.015 μm in the present invention.

The gray scale of silver emulsion aging period used of the invention can be improved by being added in chemical sensitization and dissolving iodine silver bromide emulsion made above.Although the time added is arbitrary, as long as being added in chemical sensitization effect stage, preferably silver iodobromide is first added to and dissolved, and afterwards adds sensitizing dye and chemical sensitizer order.Content of iodine is less than the surface content of iodine of host grain, preferably pure silver bromide emulsion in the iodine silver bromide emulsion used.This silver iodobromide, although can be completely dissolved as long as its size is not limited, preferred size is spherical a diameter of 0.1 μm or smaller, more preferably 0.05 μm or smaller of equal value.Although the addition of iodine silver bromide emulsion depends on used host grain, in terms of every mol silver halide, its consumption is preferably 0.005 to 5mol%, more preferably 0.1 to 1mol%.

Bleaching accelerators used release compound will be described below in the present invention.

Bleaching accelerators release compound is preferably represented with following general molecular formula (I)：

            A—(L)_k—Z    (I)

Wherein A is represented to react to be broken (L) with oxidation states and developer_k- Z group；L represents a kind of group, when with being broken out Z after the fracture of A key；K is 0 or 1；And Z represents bleaching accelerators.

The compound of logical formula (I) described in detail below.

In logical formula (I), especially, A represents colour coupler residue or oxidizing reducing group.

Colour coupler residue representated by A can be, for example, any yellow colour former residue (such as open chain carbonyl methylene fundamental mode colour coupler residue, such as acetyl acetonitrile compound and malonyl diethyl nitrile compound), magenta colour coupler residue (such as 5- pyrrolones type and pyrroles's triazole type colour coupler residue), cyan coupler residue (such as phenol type and naphthol type colour coupler residue) and the colour coupler (such as 1,2- dihydroindene type and acetophenone type colour coupler residue) for forming leuco-compounds.Moreover, the colour coupler residue representated by A can be, and such as U.S.P.Nos.4,315,070 and 4, any heterocyclic coupler agent residue described in 183,752 quotes these patents as reference herein.

When A represents redox gene, the oxidizing reducing group is oxidized the developer institute cross-over oxidation of state, it can be any of quinhydrones, catechol, burnt palmitic acid phenol, Isosorbide-5-Nitrae-naphthalene quinhydrones, 1,2- naphthalenes quinhydrones, sulfonamide aldehyde phenol, hydrazine and sulfonamide naphthol compound.The specific embodiment of these groups is in JP-A-61-230135,62-251746 and 61-278852, U.S.P.3,364,022,3,379,529th, 3,639,419 and 4,648, addressed in 605 and J.Org.Chem., 29,588 (1964), these patents are quoted herein as reference.

The L of logical formula (I) preferably following any groups.

(1) group of hemiacetal cleavage reaction is utilized：

That is, such as U.S.P.No.4,146,396 and JP-A-60-249148,60-249149 described in group, these patents are quoted herein as reference, molecular formula that can be following is represented, in this molecular formula, mark^*The position being bonded with the left side in logical formula (I), and mark^**Represent the position being bonded with the right.

     (T-1)

In molecular formula (T-1), W represents oxygen atom, sulphur atom or molecular formula-NR₆₇- the group represented, R₆₅And R₆₆Respectively represent oxygen atom or a kind of substituent, R₆₇A kind of substituent is represented, and t is 1 or 2.When t is 2, two-W-CR₆₅R₆₆- group represents one species or species different from each other.Work as R₆₅And R₆₆When representing substituent, same to R₆₇Respective exemplary embodiments include R together₆₉、R₆₉CO-、R₆₉SO₂-、R₆₉R₇₀NCO- and R₆₉R₇₀NSO₂-.In these molecular formula, R₆₉Represent aliphatic group, aromatic radical or heterocyclic group.R₇₀Represent aliphatic group, aromatic radical or heterocyclic group or hydrogen atom.The present invention also includes the R of two valencys₆₅、R₆₆And R₆₇, they are connected with each other composition cyclic structure.

(2) group of intramolecular nucleophilic substitution reaction inductive cleavage reaction is utilized：

For example, can be U.S.P.No.4, group described in 248,962 be quoted this patent as reference, can represented with lower molecular formula herein：

            -Nu-Link-E-^**   (T—2)

In this molecular formula (T-2), mark^*The position of molecule formula (I) left side bonding is represented, and is marked^**Represent the position of bonding on the right of molecule formula (I).Nu represents a nucleophilic group, and for example it can be oxygen atom or sulphur atom.E represents an electrophilic group, and it runs into is broken mark from Nu nucleophillic attack^**The key of expression.Link represents a linking group, and the group can contact to provide solid by the intramolecular nucleophilic displacement of fluorine of Nu and E realizations.

(3) using the group along the electron transfer reaction inductive cleavage reaction in conjugated system：

These groups such as U.S..P.Nos.4,409,323 and 4, described in 421,845, these patents are quoted herein as reference, can be represented with molecular formula the following：  (T-3)

In this molecular formula (T-3), mark^*, mark^**, W, R₆₅, R₆₆There are the same specific meanings in molecular formula (T-1) with t.

(4) group of ester hydrolysis cleavage reaction is utilized：

These linking groups disclose 2, described in 626,315 such as Germany, and this patent is quoted herein as reference, can be represented with lower molecular formula

In these molecular formula, mark^*And mark^**With the same specific meanings in molecular formula (T-1).

(T-4),  (T-5)

(5) group of imines ketal cleavage reaction is utilized：

Can be that the linking group described in 456,073 quotes this patent as reference herein such as U.S.P.No.4, it can be represented with lower molecular formula：

  (T-6)

In these molecular formula, mark^*And mark^**With the same specific meanings in molecular formula (T-1).R₆₈With R₆₇With identical meanings.

It is exemplified below the embodiment for playing colour coupler or the group of oxidizing reducing group effect representated by L.

Colour coupler, such as phenol type colour coupler, they are bonded by the oxygen atom of hydroxyl with the A phases in logical formula (I), thus have eliminated a hydrogen atom.On the other hand, 5- pyrrolones type colour coupler is bonded with the A phases in logical formula (I) using the oxygen atom on dynamic isomer 5- hydroxypyrrole hydroxyls and has eliminated a hydrogen atom.

Fracture and discharge the quality position that Z is bonded as colour coupler, on these groups only A with the reaction of the developer of oxidation state and can show its function.

As the L of colour coupler, preferred embodiment includes following molecular formula (C-1) to the group representated by (C-4)：  (C-1)

  (C-2)  (C-3)   (C-4)

In molecular formula, V₁And V₂Represent substituent, and V₃、V₄、V₅And V₆Each represents nitrogen-atoms or a substituted or non-substituted methine.V₇A substituent is represented, its x is the integer of one 0 to 4.When x is two or more, group V₇It can be same to each other or different to each other, and two group V₇Also it can be connected with each other to form a cyclic structure.V₈Represent group-CO-, group-SO₂-, oxygen atom or substituted amino.V₉A non-metal atom group is represented, 5 to 8 yuan of rings can be constituted with halogen in combination shown in lower molecular formula：V₁₀Represent a halogen atom or a substituent.

In molecule formula (I), when L represents an oxidizing reducing group, the group represented by preferably following formula (R -1)：

^*- P- (Y=)_k-Q-B

P and Q each represent an oxygen atom or a substituent or unsubstituted imido grpup by oneself.At least one in k Ys and k Zs is represented containing methines of the Z as substituent, and other Ys and Zs represent replacing or non-substituted methin groups or a nitrogen-atoms.K is the integer from 1 to 3 (k Ys and Zs each other can be with identical or different).B represents halogen atom or a group that can be removed by alkali.In P, Y, Z, Q and B that the present invention is included, any two can be divalent substituents and be connected with each other and be consequently formed a cyclic structure.For example, passing through contained (Y=Z)_kForm phenyl ring or pyridine ring.

When P and Q represent substituted or non-substituted imido grpup, the imido grpup that they are preferably replaced with sulfonyl or acyl group.

In that case, P and Q can use following general formula：

  (N-1)     (N-2)

In these molecular formula, mark^*The position being bonded with B is represented, and is marked^**Represent and-(Y=Z)_k- in a free bonding end bonding position.

In these molecular formula, the group representated by G ' is aliphatic group, aromatic group and heterocyclic group.

With in the group of (R-1) representative more than, particularly preferably with following molecular formula (R-2) or the group of (R-3) representative. (R-2 )

 (R-3)

In these molecular formula, mark^*Representative and the position that A is bonded in molecule formula (I), and mark^**Represent the position being bonded with its Z.

R₆₄A substituent is represented, and q is 0 and 1 to 3 integer.When q is two or more, two or more R₆₄Group each other can be with identical or different.Work as R₆₄When being the substituent of neighbouring two carbon atoms, they can be divalent groups and be connected with each other to form cyclic structure.These groups are also contained in the present invention.

Specifically, in general molecular formula (I), the group representated by Z can be chosen from known bleaching accelerators group.For example, it can be any one in the group obtained in following compound：U.S.P.No.3,893,858, GB No.1, the various sulfhydryl compounds described in 138,842 and JP-A-53-141623, these are found in this and incorporated into own forces as reference；The compound for having disulfide bond described in JP-A-53-93630, this is found in this and incorporated into own forces as reference；Thiazoline derivative described in JP-B-53-9854, this is found in this and incorporated into own forces as reference, the isothiourea derivatives described in JP-A-53-94927, and this is found in this and incorporated into own forces as reference；Thiourea derivative described in JP-B-45-8506 and JP-B-49-26586, this is found in this and incorporated into own forces as reference；Sulfonyl amines described in JP-A-49-42349, the aminodithioformic acid compound described in JP-A-55-26506, this is found in this and incorporated into own forces as reference；U.S.P.No.4, the arlydene diamine compound described in 552,384, this is found in this and incorporated into own forces as reference；In situations where it is preferred, these compounds by a commutable hetero atom with the A- (L) in molecule formula (I)_k- be connected.

Group representated by Z is preferably following molecule formula (V), the group representated by (VI) and (VII).

In these molecular formula, mark^*Represent and A- (L)_kThe position of-bonding, and R₃₁Represent the aliphatic divalent group with 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms.R₃₂The same R of group of representative₃₁Representative is identical, aromatic group or 3 to 8 yuan preferably 5 or 6 yuan of double bond heterocyclic group with 6 to 10 carbon atoms.X₃Representative-O- ,-S- ,-COO- ,-SO₂-、-NR₃₃-、-NR₃₃-CO-、-NR₃₃-SO₂-、-S-CO-、-CO-、NR₃₃- COO- ,-N=CR₃₃-、-NR₃₃CO-NR₃₄- or-NR₃₃SO₄NR₃₄-。X₄Representing has the divalent aromatics of 6 to 10 carbon atoms, and X₅For 3 to 8 yuan preferably 5 or 6 yuan of divalent heterocyclic group, and its at least one carbon atom is bonded with the S-phase in ring.Y₁Represent carboxylic group and its salt, sulfonyl group and its salt, oh group, phosphate group and its salt, amino group (having the unsubstituted of 1 to 4 carbon atoms or the aliphatic group replaced) ,-NHSO₂-R₃₅- or-SO₂NH-R₃₅(these salt are such as sodium, potassium and ammonium salt).Y₂Represent and Y₁Representative compound identical group or a halogen atom.R be 0 or 1, i be 0 to 4 integer, j is 1 to 4 integer, and k is 0 to 4 integer.And the jY provided₁' s and R₃₁-{(X₃)r-R₃₂}_iAnd X₄-{(X₃)r-R₃₂}_iCommutable position is mutually bonded.And k Y₁' s and X₅-{(X₃)r-R₃₂}_iCommutable position is mutually bonded.When i and j is 2 or more, i and j ((X₃)r-R₃₂) ' s is each separately represents identical or different group.In these molecular formula, R₃₃、R₃₄And R₃₅In each represent halogen atom or the aliphatic substitution with especially 1 to 5 carbon atoms of 1 to 8 carbon atoms.

Work as R₃₁To R₃₅In each when representing aliphatic group, this aliphatic group can be chain or ring-type, straight or branched, saturation or undersaturated and substitution and unsubstituted.Although it is preferred that unsubstituted aliphatic group, this aliphatic group can also use the aliphatic group replaced such as halogen atom, alkoxy grp (such as methoxy or ethoxy) or alkylthio (such as sulphomethyl or thio-ethyl) as substituent.

X₄Aromatic group is represented, and works as R₃₂During for an aromatic group, then representing has a substituent.This substituent can be such as any one in aliphatic group is previously mentioned above group.

X₅Heterocyclic group is represented, and works as R₃₂During for a heterocyclic group, then represent a saturation or it is unsaturated, substituted or unsubstituted, include oxygen atom, sulphur atom or nitrogen-atoms as heteroatomic heterocyclic group.For example, it can be any of pyridine, imidazoles, piperidines, alkylene oxide, epithio alkane, imidazoline, thiazolidine and piperazine oxazolidine group.Substituent can be such as any one in aliphatic group is previously mentioned above group.

The particular example for the group that molecule formula (V) is represented includes following group：-SCH₂CH₂CO₂H ,-SCH₂CO₂H, -SCH₂CH₂NH₂,

-SCH₂CH₂NHCOCH₃,-S (CH₂)₄CO₂H,-SCH₂CH₂OH ,-SCH₂CONHCH₂CH₂OH ,-SCH₂CONHCH₂CH₂OH,

-SCH₂CONHCH₂CH₂Example representated by COOH molecule formula (VI)s can enumerate as follows：

Example representated by molecule formula (VII) can enumerate as follows：

Be preferred for the present invention the particular example for the compound representated by general molecular formula (I) can enumerate it is as follows, still, now invent be not limited to that.

In addition to above compound, other compounds are addressed Research Disclosure Item Nos.24241 and 11449 and JP-A-61-201247,63-106749,63-121843,63-121844,63-214752 and 2-93454's, these are found in this and incorporated into own forces as reference, similarly act on similar applications.

The compound represented in the present invention with logical formula (I) can be easily synthesized according to the method for above-mentioned patent specification.

The compound represented in the present invention with logical formula (I) can be added into the present invention in any one layer of photosensitive material, but is preferably added in photosensitive silver halide emulsion layer or its adjacent layer.

The compound represented because bleaching the result formula of of the present invention (I) of acceleration effect can improve desilver, thus improve color rendition degree.In the photosensitive silver halide emulsion coating away from carrier, i.e., as in the blue layer of sense of exposure side or adjacent silver halide emulsion layer, add and be less than the compound that the present invention that can play desilverization improvement consumption leads to formula (I) representative, stability image quality change simultaneously just can be provided for photosensitive material small during colour development operating process.

The addition of compound of the invention as representated by molecule formula (I) changes according to compound structure, but the amount of being usually added into is 5 × 10^-4To 1.0g/m², preferably 1 × 10^-3To 5 × 10^-1g/m², most preferably 2 × 10^-3To 2 × 10^-1g/m²。

The sheet-like particle of the present invention preferably has electronics capture zone.Sheet-like particle is preferably contained in contained tabular grain average aspect than in the emulsion for two or more, being contained at least two layers emulsion subgrade with prestissimo.

Electronics capture zone is such part, in terms of every mole of local silver, is 1 × 10 as the concentration of the electronics trap center compound (hereafter referred to as " electronics trap center ") of electronics trap center^-5To 1 × 10^-3Mol, accounts for the 5% to 30% of whole particle volume.In terms of every mole of local silver, electronics trap center concentration is more preferably 5 × 10^-5To 5 × 10^-4mol.Refer to by " in terms of the every mole of local silver " for defining electronics capture zone concentration relative to the silver-colored gauge added with electronics trap center compound, the concentration of electronics trap center simultaneously.

The concentration at electron capture center must be uniform in electronics capture zone.The uniform electronics trap center for meaning to introduce fixed amount into particle with the silver-colored gauge of per unit, and electronics trap center is for granuloplastic AgNO₃It is added into while being added into granuloplastic reactor.Halogen solutions can be also added into simultaneously.It can be added as an aqueous solution as the compound at electron capture center.Or, doping can be prepared or be adsorbed with the fine grained as electron capture central compound and be added.

Any part that electronics capture zone may be present in particle.Also two or more electronics capture zones may be present in particle.

The electronics trap center for forming electronics capture zone can be used to lower molecular formula to represent：

Molecular formula I：[M(CN)_x1L (6-x1)]ⁿ⁺

Molecular formula II：[M(CN)_x2L (4-x2)ⁿ⁺

Molecular formula III：[ML1_x3X (6-2x3)]ⁿ⁺

Molecular formula IV：[ML1 (6-3i) × 1/3L2iX (6-3i) × 1/3)]ⁿ⁺

Wherein, M represents any metal or metal ion, and L is represented with chain or cyclic hydrocarbon as the compound that parent compound or wherein some hydrogen atoms or carbon atom of precursor structure are other atoms or atomic group substitution.L can be identical compound or different compounds.L1 represents the organic compound with metal or metal ion double coordination, and L2 represents the organic compound with metal or metal ion tridentate ligand.X represents any chemical group.

X1 represents the integer from 0 to 6, and x2 represents the integer from 0 to 4, and x3 represents 1,2 or 3, and i represents 1 or 2.

When adulterated in silver halide particle the hexa-coordinate Octahedral Complexes as dopant when, thus it is speculated that a part for silver halide particle is with [the AgX in particle₆]^5-(X^-=halogen ion) agent displacement is doped for unit, this is in such as J.Phy.：It is mentioned in many bibliography such as Condes.Matter 9 (1997) 3227-3240 and patent.Therefore, if the complex molecule being doped is oversized, the complex may be not suitable as dopant.Equally, when the electric charge for the complex being such as doped not is -5, thus it is speculated that the displacement of complex will be changed into unfavorable.Considered by molecular model, when doped complexes have 5 or 6 membered ring compounds as part, thus it is speculated that this complex has exceeded the size that unit is replaced in silver halide particle.But it is believed that this complex is possible to be doped into silver bromide grain, because slight strain only occurs in lattice and complex molecule.

The preferred embodiment of part is that pyrroles, pyrazoles, imidazoles, triazole and tetrazole so can be by removing H⁺And the compound with negative electrical charge.Be also using the derivative of such compound also, it is preferred that.Preferred substituent is in derivative：Halogen atom,Substituted or unsubstituted alkyl group (such as methyl,Ethyl,N-propyl,Isopropyl,Normal-butyl,The tert-butyl group,Hexyl,Octyl,2- ethyl hexyl alkyl,Dodecyl,Cetyl,Special octyl,Isodecyl,Isooctadecane base,Dodecane oxygen propyl group,Trifluoromethyl and Methanesulfomide methyl),Alkenyl,Alkynyl group,Aralkyl,Cycloalkyl (such as hexamethylene and 4- t-butylcyclohexanes),Substitution and unsubstituted aryl (phenyl,P-methylphenyl,To anisyl,Rubigan,4- tert-butyl-phenyls and 2,4- phenylenediamines base),Halogen (fluorine,Chlorine,Bromine and iodine),Cyano group,Nitro,Sulfydryl,Hydroxyl,Alkoxy (such as methoxyl group,Butoxy,Methoxyethoxy,Dodecyloxy and 2- ethyl hexanes epoxide),Fragrant epoxide (such as phenoxy group,To toloxyl,P-chlorophenyl and 4- tert-butyl benzenes epoxide),Alkylthio,Thioaryl,Acyloxy,Sulfonyloxy,Substituted or unsubstituted amino (such as amino,Methylamino,Dimethylamino,Anilino- and methylphenylamine base),Ammonium,Carbonamido,Sulfoamido,Oxygen carbonyl amido,The thio carbonyl amido of oxygen,Substituted urea groups (such as 3- methyl urea groups,3- phenylcarbamidos,3,3- dibutyl urea groups),Ghiourea group,Acyl group (such as formoxyl and acetyl group),Oxygen carbonyl,Substitution and unsubstituted carbamyl (such as ethyl amine formyl,Dibutylamine formoxyl,Dodecane oxygen propylamine formoxyl,3-(2,- t- amine benzene the oxygen of 4- bis-) propylamine methyl,Piperidines acyl group and morpholine acyl group),Thiocarbonyl,Thiocarbamoyl,Sulfonyl,Sulfinyl,Oxygen sulfonyl,Formyl sulfide base,Sulfino,Sulfo group (sulfano),Carboxylic acid and its salt,Sulfonic acid and its salt and phosphoric acid and its salt.

The central metal and without concrete restriction of electronics trap center in the present invention.It is preferable, however, that metallic perimeter coordination structure is the metal of four-coordination structure or hexa-coordinate structure.Also, it is preferred that being each filled with the metal of electronics for the metal or metal ion without unpaired electron and when d tracks are split timesharing, its all stable orbit by ligand.In all other metal ion, preferably positive divalence (+2) metal ion.The use of the metal ion of alkaline-earth metal, iron (II), ruthenium (II), osmium (II), zinc, cadmium and mercury is preferred.The use of the metal ion of magnesium, iron (II), ruthenium (II) and zinc is most preferred.

It is listed below being used as in the present invention specific embodiment of electronics trap center compound.But the compound of the present invention is not limited merely to these embodiments：

[Fe(CN)₆]^3-       [Fe(CN)₅F]^3-

[Fe(CN)₄F₂]^3-    [Fe(CN)₅Cl]^3-

[Fe(CN)₄Cl₂]^3-   [Fe(CN)₅Br]^3-

[Fe(CN)₄Br₂]^3-      [Fe(CN)₅(SCN)]^3-

[Fe(CN)₅(SCN)]^3-     [Fe(CN)₅(NO)]^3-

[Fe(CN)₅(H₂O)]^2-    [Fe(CN)₆]^4-

[Fe(CN)₅F]^4-         [Fe(CN)₄F₂]^4-

[Fe(CN)₅Cl]^4-        [Fe(CN)₄Cl₂]^4-

[Fe(CN)₅Br]^4-        [Fe(CN)₄Br₂]^4-

[Fe(CN)₅(SCN)]^4-     [Fe(CN)₅(SCN)]^4-

[Fe(CN)₅(NO)]^4-      [Fe(CN)₅(H₂O)]^3-

[Fe(CN)₅(PZ)]^3-      [Fe(CN)₄(PZ)₂]^2-

[Fe(CN)₅(Im)]^3-      [Fe(CN)₄(Im)₂]^2-

[Fe(CN)₅(trz)]^3-     [Fe(CN)₄(trz)₂]^2-

[Ru(CN)₆]^4-          [Ru(CN)₅F]^4-

[Ru(CN)₄F₂]^4-       [Ru(CN)₅Cl]^4-

[Ru(CN)₄Cl₂]^4-      [Ru(CN)₅Br]^4-

[Ru(CN)₄Br₂]^4-      [Ru(CN)₅I]^4-

[Ru(CN)₄I₂]^4-       [Ru(CN)₅(SCN)]^4-

[Ru(CN)₅(SCN)]^4-     [Ru(CN)₅(NO)]_4-

[Ru(CN)₅(H₂O)]^3-    [Ru(CN)₄(PZ)₂]^2-

[Ru(CN)₅(PZ)]^3-      [Ru(CN)₄(Im)₂]^2-

[Ru(CN)₅(Im)₂]^3-    [Ru(CN)₄(trz)₂]^2-

[Ru(CN)₅(trz)]^3-

[Re(CN)₅F]^4-         [Re(CN)₆]^4-

[Re(CN)₅Cl]^4-        [Re(CN)₄F₂]^4-

[Re(CN)₅Br]^4-        [Re(CN)₄Cl₂]^4-

[Re(CN)₅I]^4-         [Re(CN)₄Br₂]^4-

[Re(CN)₄I₂]^4-

[Os(CN)₆]^4-          [Os(CN)₅F]^4-

[Os(CN)₄F₂]u         [Os(CN)₅Cl]^4-

[Os(CN)₄Cl₂]^4-      [Os(CN)₅Br]^4-

[Os(CN)₄Br₂]^4-      [Os(CN)₅I]^4-

[Os(CN)₄I₂]^4-       [Os(CN)₅(SCN)]^4-

[Os(CN)₅(SCN)]^4-     [Os(CN)₅(NO)]^4-

[Os(CN)₅(H₂O)]^3-    [Os(CN)₄(PZ)₂]^2-

[Os(CN)₅(PZ)]^3-      [Os(CN)₄(Im)₂]^3-

[Os(CN)₅(Im)]^3-      [Os(CN)₄(trz)]^2-

[Os(CN)₅(trz)]^3-

[Ir(CN)₅Cl]^3-        [Ir(CN)₆]^3-

[Ir(CN)₅Br]^3-        [Ir(CN)₄Cl₂]^3-

[Ir(CN)₅I]^3-         [Ir(CN)₄Br₂]^3-

[Ir(CN)₅(NO)]^3-      [Ir(CN)₄I₂]^3-

[Ir(CN)₅(H₂O)]^2-

[Pt(CN)₄]^2-          [Pt(CN)₄Cl₂]^2-

[Pt(CN)₄Br₂]^2-      [Pt(CN)₄I₂]^2-

[Au(CN)₄]^-           [Au(CN)₂Cl₂]^2-In above metal complex, Pz=pyrroles, Im=imidazoles, and trz=triazoles.(M=Mg²⁺, Mn²⁺, Fe²⁺, Ru²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺)

(M=Mg²⁺, Mn²⁺, Fe²⁺, Ru²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺)

(M=Mg²⁺, Mn²⁺, Fe²⁺, Ru²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺)

(M=Mg²⁺, Mn²⁺, Fe²⁺, Ru²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺)

(M=Mg²⁺, Mn²⁺, Fe²⁺, Ru²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺)

(M=Mg²⁺, Mn²⁺, Fe²⁺, Ru²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺)

(M=Mg²⁺, Mn²⁺, Fe²⁺, Ru²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺)

(M=Mg²⁺, Mn²⁺, Fe²⁺, Ru²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺)

(M=Mg²⁺, Mn²⁺, Fe²⁺, Ru²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺)

(M=Mg²⁺, Mn²⁺, Fe²⁺, Ru²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺)

(M=Mg²⁺, Mn²⁺, Fe²⁺, Ru²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺)

(M=Mg²⁺, Mn²⁺, Fe²⁺, Ru²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺)

(M=Mg²⁺, Mn²⁺, Fe²⁺, Ru²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺)(M=Mg²⁺, Mn²⁺, Fe²⁺, Ru²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺)

(M=Mg²⁺, Mn²⁺, Fe²⁺, Ru²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺)

(M=Mg²⁺, Mn²⁺, Fe²⁺, Ru²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺)

[M(bpy)₃]²⁺                                      [M(phen)₃]²⁺M=Fe²⁺, Ru²⁺, Co²⁺M=Fe²⁺, Ru²⁺, Co²⁺Bpy=2,2 '-bipyridyl phen=1,10- phenanthroline [M (py)₆]²⁺                                      [M(trpy)₂]²⁺M=Fe²⁺, Ru²⁺, Co²⁺M=Fe²⁺, Ru²⁺, Co²⁺Py=pyridines trpy=2,2 '：5 ', 2- terpyridyl [M (bpy)₂L₂]ⁿ⁺                                  [M(bpy)₂LL]ⁿ⁺M=Fe²⁺, Ru²⁺, Co²⁺M=Fe²⁺, Ru²⁺, Co²⁺Bpy=2,2 '-bipyridyl bpy=2,2 '-bipyridyl

N=2,1,0 n=2,1,0L=Cl^-, CN^-, NH₃, H₂O, CO, H₂, CH₃CN,

L, L '=Cl^-,

Methyl-diphenyl-phosphine, butylamine [M (bpy)₂L]²⁺M=Fe²⁺, Ru²⁺, Co²⁺Bpy=2,2 '-bipyridyl

[ML₂]²⁺M=Fe²⁺, Ru²⁺, Co²⁺ [M(bpy)(phen)₂]²⁺      [M(bpy)(phen)(py)]²⁺M=Fe²⁺, Ru²⁺, Co²⁺M=Fe²⁺, Ru²⁺, Co²⁺Bpy=2,2 '-bipyridine bpy=2,2 '-bipyridinephen=1,10- phenanthroline phen=1,10- phenanthroline

Py=pyridines [M (bpy) (py) (en)]²⁺        [M(bpy)(py)(NH₃)]²⁺M=Fe²⁺, Ru²⁺, Co²⁺M=Fe²⁺, Ru²⁺, Co²⁺Bpy=2,2 '-bipyridyl bpy=2,2 '-bipyridyl

Py=pyridine py=pyridine en=ethylenediamines [M (bpy) (trpy) L]²⁺M=Fe²⁺, Ru²⁺, Co²⁺Bpy=2,2 '-bipyridyl trpy=2,2 '：5 ' 2 "-terpyridyl L=Cl^-, CN^-, NH₃

In the present invention, present invention preferably uses part in can introduce H⁺Add or remove H⁺。

In the present invention, complex molecule is dissociated with counter ion completely in aqueous, and is existed with anion or cationic form.Therefore counter ion is unimportant to image quality.When complex molecule be changed into anion and with a cation into salt when, the counter cation is preferably alkali metal ion such as sodium ion, potassium ion, rubidium ion or cesium ion or the alkyl phosphate ion represented by following molecular formula V, and above ion is easy to be dissolved in water and is adapted to the precipitation of silver emulsion.

Molecular formula V：[NR₁R₂R₃R₄]⁺

Wherein R₁、R₂、R₃And R₄Respectively the substituent in methyl, ethyl, propyl group, isopropyl and normal-butyl is represented respectively.In particular it is preferred to be tetramethyl amine ion, tetraethyl amine ion, tetrapropyl amine ion and four primary butylamine ions, wherein R₁、R₂、R₃And R₄The ion of preferably identical substituent.H is introduced on the noncoordinating nitrogen-atoms of part⁺It is also preferred that ion, which obtains pyrazoles cation or glyoxaline cation as counter cation,.

When complex be changed into cation and with anion into salt when, the preferred halide ion of counter ion, nitrate ion, perchlorate, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, tetraphenyl borate radical ion, hexafluorosilicic acid ion or trifluoromethanesulfonic acid radical ion, above ion are easy to be dissolved in water and are suitable for the precipitation of silver emulsion.If strong coordinating anion is when for example cyanide ion, Thiocyanate ion, nitrite ion or oxalate denominationby are as counter ion, counter ion as the halogen ion of part very likely with occurring ligand exchange reaction, so that the Nomenclature Composition and Structure of Complexes of complex of the present invention can not possibly be controlled.Therefore, the use of these anion is not preferred.

Metal complex used in the present invention can be synthesized by several method.For example, containing magnesium complex, iron complex and Zn complex that pyrazoles or imidazoles are part, can be by will be formed in a kind of anhydrous solvent as the pyrazoles or imidazoles of part with the perchlorate or tetrafluoro boric acid reactant salt of various metals.The specific synthetic example of these complexs is that its synthetic method is addressed in Rec.Trav.Chim.1969,88.1451.Equally, ruthenium -1,2,4-triazole complex can refer to the reaction for the ruthenium -1,2,4-triazole complex addressed in Inorg.Chrm.Acta1983,71,155 and be synthesized.

The compound represented by below formula (VI) also is used as forming the electronics trap center of electronics capture zone：

Molecular formula VI：[L′_nM(L(ML′_m)_i)k]^p

Wherein, M represents any one metal or metal ion.M can be that same metal may also be not same metal.L is crosslinking ligand and represents and can be crosslinked the organic compound of two or more metal and metal ion.It is H that L ', which represents a uncharged small molecule,₂O、NH₃、CO、N₂NO₂、CO₂、SO₂、SO₃、N₂H₄、O₂Or PH₃, any organic compound or any inorganic anion, it is all these be identical chemical species or different chemical species.Each of n and m represent the integer from 1 to 5, and j represents positive integer, and k represents the integer from 1 to 5, and p represents positive or negative arbitrary integer or 0.

For example, as in Bulgarran Chem.Commun., 20 (1993) 350-368, Radiat.Eff.Deffects Solids 135 (1995) 101-104 and J.Phys：As indicated in Condens Matter, 9 (1997) 3327-3240, the 6- cyano group complex that can adulterate introduces a shallow electron trap by Coulomb in silver halide particle.Particularly such as in ICPS, described in 1998, Final Program andProceedings, Vol.1, p89, ICPS, 1998 Final Program and Proceedings, Vol.1, p92 and JP-A-8-286306, as use divalence d⁶Low spin metal ion such as Fe²⁺Or Ru²⁺During as central metal, electric charge is crossed by introducing+1 in the particle environments being made up of Ag+ and halogen anion, the photoelectron trap of appropriate depth is introduced due to Coulomb.As a result the period for causing exposed caused photoelectron to produce to inactivation is extended, so as to significantly increase sensitivity.During this period, cyanide ion is used as the part with strong ligand field-effect.π-key is formed by supplying (feedback) electronics to part from metal.This π-key makes t_2g- track is more stable, and effective positive charge of Distance Shortened and metal ion increases between metal/part, thus presents and increases considerably the effect that metallic d-orbital splits point.By means of this effect, the e of doped complexes_gThe energy that-track (being used as complex lowest unoccupied molecular orbital) has is higher than the energy of silver halide conduction band bottom, so as to show a kind of not level related to electronics capture.In this case, the shallow electron trap using Coulomb can be produced near doping body first.It is well known that heterocyclic compound, particularly 1,10- phenanthrolenes and 2,2 '-bipyridyl ligand-field effect introduced in complex synthesis is more close than cyano group complex.Thus it can be assumed that it is complex doped using these complexs such as 6- cyano group, the e being made up of metal ion track can be made_gThe energy level of-track is higher than the bottom of silver halide conduction band.And in these heterocyclic compounds in use, although it is possible to the π of part occur^*Orbital energy is less than metal e_gTrack and the situation as lowest unoccupied molecular orbital, this energy level is also higher than the bottom of silver halide conduction band by inference.

It is similar with the impurity band in semiconductor for the formation of galactic nucleus in silver halide particle, it can be assumed that the more free movement of photo-excited electron causes efficiently silver-colored nucleation in a wide range.In fact in J.Phys.：Condens.Matter, described in 9 (1997) 3227-3240 ENDOR experiment in, for adulterate potassium ferrocyanide emulsion, it is observed that wherein electronic signal, the rich miscellaneous band of potassium ferrocyanide doping through assuming to be captured by impurity band is related to the abundance zone promoted with obvious sensitivity.This state of the shallow capture of electronics can be described by effectively estimating, hydrogen atom can be counted as a kind of model.It is therefore contemplated that the increase (the hydrogen atom model radius effectively described in estimation) of the bound field radius of electronics will make sensitivity increase more.Based on this viewpoint, it is preferred that the size as the complex of dopant will increase.In this regard, it can speculate that the use of binuclear complex is better than mononuclear complex, the use of the complex of more multinuclear is then more highly preferred to.

When complex molecule is incorporated into silver halide particle, such as J.Phys.：Described in Condens.Matter, 9 (1997) 3227-3240 and other documents and patent, it is believed that [the AgX of silver halide particle₆]^5-The part components of (X=halide ions) are replaced by complex molecule, so as to cause its central metal to occupy Ag⁺The dot matrix of ion.This imagination is extended, then it is contemplated that the complex of double-core or more core will replace silver halide unit such as [Ag₂X₁₁]^9-, [Ag₃X₁₆]^13-Deng.And the research based on molecular model shows, it is assumed that U.S.P.No.5, the iron complex [(NC) described in 360,712₅Fe (m-4,4 '-bipyridyl) Fe (CN)₅]^6-[the X in silver halide particle will be replaced₅Ag-X-Ag-X-AgX₅]^9-.It is therefore expected that when complex molecule enters in silver halide, will appear from the displacement with some flexibilities.Certainly from the perspective of displacement, very big complex molecule is used as dopant and is not beneficial to.Therefore speculate that it is not preferred.Therefore, be preferred for doping in polynuclear complex is double-core or trinuclear complex.

In the present invention, term " organic compound " refers to the compound as main body by chain or cyclic hydrocarbon, or agent structure the compound that is replaced by other atoms or atomic group of carbon or hydrogen.The part for connecting metal and metal is preferably organic compound, particularly with the compound of the double coordinations of metal, or its coordination atom pu tracks are subjected to the compound of metal d electronics, its coordination atom is constitutes (may be constructed feedback bonding) such as the N atoms of double or triple bonds, or N atoms, P atoms, S atoms in aromatic ring.I.e. crosslinking ligand be preferably can be with metal ion strong bonding compound, the compound of strong ligand effector ligand is more preferably showed in coordination.

And other parts are preferably made up of the identical compound for constituting crosslinking ligand, it is particularly the compounds being coordinated with metal pair or the compound of feedback bonding can be constituted with metal.And these parts preferably have negative electrical charge.The reason is that in the hypothesis that complex enters silver halide particle, having replaced itself as the organic compound of part has the halide ion of negative electrical charge, thus realizes in terms of electric charge a kind of result to the close displacement of silver halide unit.The use of the part for not possessing opposite charges is also preferred in very wide scope in the hypothesis of above-mentioned electronics capture.To obtain appropriate shallow electron trap by dopant, it is preferred that the distribution of charges of the molecule as dopant is limited, and is confined to so as to avoid electronics in electron trap.When also existing in part in addition to central metal donor site as hetero atom or the donor site of substituent form, the possibility polarized in part is high, thus speculates that it may not be suitable for the electronics capture with homogeneous loose bonding force.Moreover, halide ion position is not only replaced when the molecular size of part increases to ligand moiety, and when replacing adjacent silver ion, dopant part is also preferred without electronics.Although using negative electrical charge organic compound now as part and being used without electric organic compound as part, considerably increase sensitivity, both can not being said, who is more superior, and aromatic compound or heterocyclic compound can only be said, more specifically with ligand field-effect, can be coordinated with metal ion two or three-fold coordination compound preferably as the dopant for promoting quick luminosity.

In the present invention, crosslinking ligand is preferably constituted by containing saturation or unsaturated hydrocarbons as the compound of basic framework, such as oxalic acid, malonic acid, amber are arrived, glutaric acid, adipic acid, tartaric acid, meso -2,3- dimercaptosuccinic acids, 1,2,3,4- cyclobutane tetrabasic carboxylic acid, oxamides, oxamic acid, malonamide, succinamide, caproamide, dimercapto oxamides, 1,1,3,3- four cyanos pentamethylene, TCNE, the dicyan of diaminourea third, 1,2,4, the aniline of 5- tetra- and 1,2,4,5- tetracarboxylic benzene.Its small molecular such as oxalic acid, malonic acid, oxamides and oxamic acid are more highly preferred to.By H in hydroxyl in alcohol or phenol⁺Eliminate composition-O^-Situation with two metals or metal ion crosslinked is also preferred.

On the other hand, it is preferably pyrazoles, imidazoles, triazole, tetrazolium, oxazole, isoxazole, thiazole, thiadiazole, the nitrogen of thiophene three, four dithioles, 4 as the heterocyclic compound of crosslinking ligand, 4 '-bipyridyl, 4- pyridones, isonicotinic acid, 4- cyanopyridines, pyridazine, pyrimidine, pyrazine, 2,3- bis- (2- pyridine radicals) pyrazine, 2,5- bis- (2- pyridine radicals) pyrazine, triazine, 2,2 '-connection pyrimidine, 2,2 '-imidazoles, 2,2 '-bibenzimidaz sigmale and the derivative containing these skeletons.In these heterocyclic compounds, pyrazoles, 4,4'-Bipyridine, pyrazine, 2,3- bis- (2- pyridine radicals) pyrazine, 2,5- bis- (2- pyridine radicals) pyrazine, 2,2 '-connection pyrimidine, 2,2 '-imidazoles and 2,2 '-bibenzimidaz sigmale is preferred.

From the viewpoint of the degree of above-mentioned ligand field-effect, other parts being made up of aromatic compound or heterocyclic compound are also preferred.Aromatic compound has two substituents for playing coordination preferably on adjacent two carbon atom.Specifically, aromatic compound can be black false hellebore phenol (veratrol), catechol, (+/-)-hydrobenzoin, 1,2- thioresorcins, Ortho-Aminophenol, o-anisidine, 1,2- phenylenediamines, 2- nitronaphthols, 2- nitroanilines and 1,2- dinitro benzene.In addition to having the aromatic compound of two substituents for playing coordination on above-mentioned adjacent two carbon atom, it is also preferred that two of which, which plays the location of substituent of coordination pair aromatic compound of coordination can occur with a metal,.For example, this aromatic compound can be benzyl, 1,8- dinitros naphthyl and 1,8- naphthyl glycol.

Preferably comprised in heterocyclic compound for single coordination can be carried out, part as heteroatomic oxygen atom, sulphur atom, selenium atom, tellurium atom or nitrogen-atoms.It is also preferred that phosphorus atoms, which are included in part,.For example, single ligand is preferably furans, thiophenine, 2H- pyrroles, pyrans, pyridine and its derivatives.Can be preferably multi-ring heterocyclic compound with the heterocyclic compound of a metal or the double coordinations of metal ion or three-fold coordination, they are interconnected to constitute by that can carry out the heterocyclic compound of single coordination.For instance, it may be preferable to for through connecting the compound that above-mentioned preferred single ligand is constituted.Especially, bidentate ligand is preferably 2,2 '-bithiophene, 2,2 '-bipyridyl and its derivative.Tridentate ligand is preferably 2,2 '：5,2 "-terthienyl, 2,2 '：5,2 "-terpyridyl or derivatives thereof.And it has the skeleton that above-mentioned bidentate ligand is connected by commissural arch.Preferably use 2,2 '-diquinoline, 1,10- phenanthroline or derivatives thereof.And the compound that can be bonded with metal ion by more than three co-ordination positions is it is also preferred that as non-crosslinked part.For example, it is preferable to use crown ether such as 18- crown ethers -6 and Isosorbide-5-Nitrae, 8,11- tetraazacyclododecane tetradecanes.

The substituent of these derivatives is preferably hydrogen atom,Substituted or non-substituted alkyl (such as methyl,Ethyl,N-propyl,Isopropyl,Normal-butyl,The tert-butyl group,Hexyl,Octyl group,2- ethylhexyls,Dodecyl,Cetyl,T-octyl,Isodecyl,Iso stearyl,Dodecane oxygen propyl group,Trifluoromethyl or Methanesulfomide ylmethyl),Alkenyl,Alkynyl,Aralkyl,Cycloalkyl (such as cyclohexyl or 4- tert-butylcyclohexyls),Substituted or non-substituted fragrance (such as phenyl,P-methylphenyl,P-aminophenyl,Rubigan,4- tert-butyl-phenyls or 2,4-t- phenylenediamines base),Halogen (fluorine,Chlorine,Bromine or iodine),Cyano group,Nitro,Sulfydryl,Hydroxyl,Alkoxy (such as methoxyl group,Butoxy,Methoxy ethoxy,Ten alkoxies or 2- ethyl hexyl oxies),Aryloxy group (such as phenoxy group,To toloxyl,P-chlorophenyl or 4- tert-butyl benzenes epoxide),Alkylthio group,Arylthio,Acyloxy,Sulfonyloxy,Substituted or non-substituted amino (such as amino,Methylamino,Dimethylamino,Anilino- or methylphenylamine base),The molten base of ammonia (ammonio),Amide groups,Sulfoamido,Oxygen carboxylic amino,Oxygen thion amino,Replace urea groups (such as 3- methyl urea groups,3- phenyl urea groups or 3,3- dibutyl urea groups),Ghiourea group,Acyl group (such as formoxyl or acetyl group),Oxygen carbonyl,Substituted or non-substituted carbamoyl (such as ethylaminocarbonyl,Dibutylamino formoxyl,Dodecane oxygen propyl carbamic acid base,3—(2,4-t- phenylenediamine epoxides,Propvlcarbamovl)),Send pyridine carbonyl or morpholine carbonyl,Thiocarbonyl group,Thiocarbamoyl,Sulfonyl,Sulfinyl,Hydroxysufonyl (oxysulfonyl),Sulfamoyl,Sulfino,Sulfo group (sulfano),Carboxylic acid and its salt,Sulfonic acid and its salt and phosphoric acid and its salt.R2 and R3 cyclisation constitutes carbocyclic ring, and aromatic rings or hetero-aromatic ring are also preferred.

Although there is no particular restriction for central metal in the present invention, such as J.Phys.：Described in Condens.Matter, 9 (1997) 3227-3240 and many other files and patent, from hexa-coordinate Octahedral Complexes enter silver halide particle as dopant, to [AgX in silver halide particle₆]^5-(X^-=halide ion) component units enter from the viewpoint of line replacement, and it is preferred to constitute the central metal that metal ligand structure is plane four-coordination structure or hexa-coordinate structure.With unpaired electron or after metallic d-orbital is split point by ligand field, the metal that all stabilisation tracks are filled with electronics is more highly preferred to as central ion.For example, it is preferred that central atom be alkaline-earth metal, iron, ruthenium, manganese, cobalt, rhodium, iridium, copper, nickel, palladium, platinum, metal, zinc, titanium, chromium, osmium, the ion of cadmium and mercury, preferred central atom is iron, ruthenium, manganese, cobalt, rhodium, iridium, titanium, chromium, osmium.Most preferred central atom has the ion of iron, ruthenium and cobalt.

The specific embodiment of complex of the present invention is as follows, but they are not intended to define the compound of the present invention.

            -112-

         -113-

         -114-

         -115-

M ', M "=Ru, Ru Os, Os Ru, Os

M=Ru²⁺, Os²⁺ M=Fe²⁺, Ru²⁺；P=P (OMe)₃, P (OEt)₃

        -116-

The complex of the present invention can be synthesized by several method.For example, proposing good summary to ruthenium complex in Coord.Chem.Rev.84,85-277 (1988), many complexs can be synthesized based on wherein listed bibliography.Other complexs are synthesized using the Coord.Chem.Rev synthetic methods for summarizing each metal in cited several years.

The complex of the present invention is preferably directly added into the reaction solution for forming silver halide particle and entered in silver halide particle, or be added to complex in the halide solution to form silver halide particle or other solution, and solution is added in the particle reaction liquid to be formed and complex is incorporated into silver halide particle.

When the present invention is complex doped to be entered in silver halide particle, complex uniformly can be in particle.Or as disclosed in JP-A-4-208936,2-125245 and 3-188437 by complex doped in particle surface, these patents are quoted herein as reference, or only to particle inside doping without being adulterated to its top layer.In the present invention, it is preferred in particle top layer doped complexes.Such as U.S.PatentNos.5,252,451 and 5, as disclosed in 256,530, the fine grained doped with complex is cured by physics, particle surface can be improved, these patents are quoted herein as reference.Prepare doped with complex fine grained and by fine grained carry out physics curing, be also by it is complex doped enter silver halide particle in method for optimizing.

In terms of every mol silver halide, applicable complex doped amount is 1 × 10^-9To 1 × 10^-2Mol, preferably 1 × 10^-7To 1 × 10^-3mol.Distribution of the complex inside particle is preferably narrow.

Emulsion for the present invention preferably closes iron (II) complex by six cyanogen or six cyanogen close ruthenium complex (hereinafter referred to as " metal complex ") and adulterated.In terms of every mol silver halide, the addition of metal complex is preferably 10^-7To 10^-3Mol, more preferably 1.0 × 10^-5To 5 × 10^-4mol。

The either step addition that can be prepared in the silver halide particle before or after nucleation, growth, physics curing, chemical sensitization and introducing metal complex.Meanwhile, addition and introducing can also be conducted batch-wise.At least the 50% of total metal complex content that preferably silver halide particle is included is in away from the layer under silver halide particle outmost surface, there is the silver content for accounting for surface 1/2 or less in this layer.Layer comprising metal complex can be covered by the layer not comprising metal complex.

It is preferred that metal complex is dissolved in water or appropriate solvent and the solution is added directly into the reactant mixture during silver halide particle formation, or be added to metal complex solution in the halide solution for preparing silver halide particle, silver salt solution or other solution, then grow particle.Or the silver halide particle of previously-introduced metal complex can be added, dissolved and be deposited on other silver halide particles and introduce metal complex.

The hydrogen ion concentration in reactant mixture for adding metal complex, pH is preferably 1 to 10, and more preferably 3 to 7.

In the silver-halide color negative film photosensitive material of the present invention, at least one layer of red sensing coppering silver emulsion layer on a kind of carrier, at least one layer of green silver halide emulsion layer and the blue silver halide emulsion layer of at least one layer of sense are included.Each photosensitive layer includes the photosensitive unit layer that one has essentially identical color sensitivity by multilayer but the different silver emulsion subgrade of speed is constituted each other.In silver-halide color photoelement of the present invention, from carrier, these unit photosensitive layers are typically by sense red, green and blue layer arrangement.But it can be overturned according to this order of presentation of designed use, or the sense chromatograph with same color susceptibility can sandwich the sense chromatograph to another Color-sensitive.Non-photo-sensing layer such as intermediate layer can also be used as the superiors and orlop in the centre of light-sensitive silver halide layer.These intermediate layers can include colour coupler as hereinafter described and DIR compounds.Constitute the multilayer silver emulsion subgrade of photosensitive unit layer, it is preferred to use the arrangement of the double-decker with high, low speed emulsion subgrade so that such as DE No.1,121,470 or GB No.923, described in 045, decline by the direction sensitivity order towards carrier, these patents are quoted herein as reference.Simultaneously as described in JP-A-57-112751,62-200350,62-206541 and 62-206543, arrangement, which can be carried out, to subgrade causes low speed emulsion subgrade to be formed away from carrier side, and high-speed emulsion subgrade is formed close to carrier side, these patents are quoted herein as reference.

Specifically, from carrier distalmost end, can be according to the blue subgrade (BL) of low speed sense/feel blue subgrade (BH) at a high speed/to feel green subgrade (GH)/the green subgrade of low speed sense (GL)/at a high speed and feel red subgrade (the RH)/red subgrade of low speed sense (RL) arrangement at a high speed, or arrange by BH/BL/GL/GH/RH/RL or BH/BL/GH/GL/RL/RH order.

In addition, as described in JP-B-35-34923, being started at from carrier distalmost end, each layer can be arranged according to sense indigo plant subgrade/GH/RH/GL/RL order, this patent is quoted herein as reference.Moreover, as described in JP-A-56-25738 and 62-63936, from carrier distalmost end, can be arranged according to sense indigo plant subgrade/GL/RL/GH/RH order, these patents are quoted herein as reference.

As described in JP-B-49-15495, three subgrades can be arranged, so that the silver-colored emulsion subgrade of the emulsification of top high photographic sensitivity is used as upper strata, the silver-colored emulsion subgrade of emulsification of the sense height less than upper strata is used as intermediate layer, and the silver-colored emulsion subgrade of emulsification of the sensitivity less than intermediate layer is used as lower floor, and three subgrades with different sensitivity can be carried out to arrange the direction sensitivity order decline caused by towards carrier, these patents are quoted herein as reference.Even as described above, when a unit Rotating fields are made up of three subgrades with different sensitivity, in a kind of elementary layer sensitive to solid color as described by JP-A-59-202464, started at from carrier distalmost end, these subgrades can be arranged by the order of middling speed emulsion subgrade/high-speed emulsion subgrade/low speed emulsion subgrade, and this patent is quoted herein as reference.

In addition, putting in order for high-speed emulsion subgrade/low speed emulsion subgrade/middling speed emulsion subgrade or low speed emulsion subgrade/middling speed emulsion subgrade/high-speed emulsion subgrade can be taken.When unit Rotating fields are made up of four layers or more layers, the arrangement of each layer can also be arranged as described above.

When photosensitive silve halide material of the present invention includes the red sensing coppering silver emulsion layer of the green silver halide emulsion layer and at least one layer of the blue silver halide emulsion layer of at least one layer of sense containing yellow colour former being on carrier, at least one layer of colour coupler containing magenta containing cyan coupler, the ISO speed of material is 640 or higher, the sensitivity S of red sensing coppering silver emulsion layer on wavelength 580nm_R(580)It is preferred that with sense red beds sensitivity maximum wavelength on sensitivity S_R(max)With following relation：

            0.6≤S_R(max)-S_R(580)≤0.9

In 500nm between 600nm, the average sensitive wave length (λ of sensitivity distribution of weights of the interlayer effect occurred between red sensing coppering silver emulsion layer and other silver halide emulsion layers_-R) meet following relation：500nm ＜ λ_-R＜ 560nm；Weighted average sensitive wave length (the λ of the spectral sensitivity distribution of green silver halide emulsion layer_G) meet following relation：520nm≤λ_G≤580nm；λ_GAnd λ_-RMeet relational expression：λ_G- λ_-R≥5nm.When feeling red elementary layer comprising two layers or more layer subgrade, whole elementary layer meets λ_-RRelational expression.When feeling green elementary layer comprising two layers or more layer subgrade, whole elementary layer meets λ_GRelational expression.

This patent can be introduced herein as reference using the spectral sensitizer and solid disperse dye described in JP-A-11-305396.Above-mentioned ISO speed and red sensitive silver halide grain emulsion layer and the sensitivity distribution of weights mean wavelength of the interlayer effect of other layers of appearance can be obtained using method described in JP-A-11-305396.

The sensitivity S of red beds is felt in silver halide photosensitive materials of the present invention_R(580)With the sensitivity S of green layer_G(586)It is preferably in following scope：

        0.6≤S_R(max)-S_R(580)≤0.9

        0.6≤S_R(max)-S_G(580)≤1.1

Wherein, S_G(580)It is sensitivity, it is the negative logarithm that required light exposure during pinkish red color density+1.0 is obtained under this wavelength；S_R(580)It is sensitivity, it is the negative logarithm that required light exposure during cyan density+1.0 is obtained under this wavelength；

Moreover, the wavelength of sense red beds sensitivity maximum in 610nm between 640nm, preferably 620nm to 635nm.In addition, feeling the sensitivity S of red beds at wavelength 650nm_R(650)Preferably conform to relationship below：

S_R(650)≤S_R(max)-0.7

Wherein the definition of sensitivity with it is upper identical.

Moreover, the wavelength of green layer sensitivity maximum in 520nm between 580nm, preferably 540nm to 565nm.In addition, feeling the sensitivity S of red beds at wavelength 525nm_G(525)Preferably conform to relationship below：

0.1≤S_G(max)- S_G(525)≤0.3

Preferably by method of the interlayer depression effect as improvement color rendition degree.Particularly preferred situation is the weighted average wavelength photoreceptor (λ of the sensitivity distribution of green silver halide emulsion layer_G) meet following relation：520nm ＜ λ_G≤580nm；At 500nm to 600nm, red sensing coppering silver emulsion occurs the average weight wavelength photoreceptor (λ of the sensitivity distribution of interlayer effect with other silver halide emulsion layers_-R) meet following relation：500nm ＜ λ_-R≤560nm；And λ_G- λ_-RAt least 5nm, preferably at least 10nm.

To make sense red beds that there is above-mentioned interlayer effect in particular range of wavelengths, a single layer containing silver halide particle is preferably provided with, the interlayer effect donor layer of spectral sensitization is used as.For the spectral response needed for realizing the present invention, the interlayer sensitive wave length of interlayer effect donor layer is set to 510 to 540nm.

By the method described in JP-A-11-305396, in 500 to 600nm wave-length coverages, obtain red-sensitive emulsion layer and occur the weighted average sensitive wave length (λ of the spectral response distribution of interlayer effect with other layers_-R).Meanwhile, work as λ_-BBy λ_-RWhen similarity method is obtained, the interlayer effect assigned by interlayer effect donor layer has to comply with the condition equation (2) described in JP-A-11-305396, and this patent is quoted herein as reference.

It can be reacted with the oxidation states developer obtained by development and discharge development restrainer or the compound of its precursor, be used as assigning the material of interlayer effect.For example, the colour coupler of DIR (development restrainer release) colour coupler, DIR quinhydrones and releasable DIR quinhydrones and its precursor can be used.When development restrainer has high diffusibility, the position that development inhibition effect can be independent of donor layer in sandwich construction.But also there is development inhibition effect on some non-required directions.Therefore, it is correction this case, preferred pair donor layer dyeing (for example, the same color for the layer for undesirable development restrainer effect occur can be dyed).From this viewpoint, photosensitive material of the present invention achieves preferable spectral response, it is preferred that magenta is presented in the donor layer that interlayer effect can be achieved.

Although the size and shape of the silver halide particle of the layer to interlayer effect can be achieved in sense red beds are not particularly limited, the so-called sheet-like particle with high aspect ratio, the single dispersing emulsion with uniform grading or the silver iodobromide with iodine Rotating fields are preferably used.And be increase exposure latitude, preferably mix the mutually different a variety of emulsions of its particle diameter.

Although the donor layer of effect layer is coatable on any position of carrier being produced sense red beds, the coating position ratio of preferred donor layer feels blue layer closer to carrier, but more farther apart from carrier than sense red beds.It is also preferred that donor layer than Yellow filter layer closer to carrier.

It is further preferred that can sense red beds produce effect layer donor layer coating position than green layer closer to carrier, but than feel red beds it is farther apart from carrier.The most preferably set location of donor layer is neighbouring green layer on the side of carrier.Term " neighbouring " as used herein refers to intermediate layer or any other thing being disposed therein.

Can have it is multiple can sense red beds produce effect layer layer.The setting of these layers can be mutually adjacent or be located remotely from each other.

Emulsion for photosensitive material of the present invention can be the main surface latent image type emulsion that latent image is formed on the surface of particle, in the internal latent image type emulsion for being internally formed latent image of particle and on any one of the surface of particle and the internal other types emulsion for all forming latent image.But, emulsion must be egative film type emulsion.Internal latent image type emulsion can be core/shell internal latent image type emulsion described in JP-A-63-264740 (content of the document is herein incorporated by reference).The method for preparing the core/shell internal latent image type emulsion is described in JP-A-59-133542.Although the thickness of the shell of the emulsion depends on such as development treatment Conditions Condition, it is preferably 3-40nm, more preferably 5-20nm.

Silver emulsion is generally passing through physical ripening, chemical ripening and spectral sensitization using preceding.The additive used in those steps is listed in RD the 17643rd, in 18716 and No. 307105, and its relevant portion will be summarized in the following table.

In the photosensitive material of the present invention, it can be mixed together and be used in simple layer in the mutually different two or more photosensitive silver halide emulsions of at least one properties, the property is, for example, particle diameter, particle diameter distribution, halogen composition, particle shape and its sensitivity.

Such as the 4th, 082, silver halide particle with ashed surfaces, the such as the 4th described in No. 553 United States Patent (USP)s, No. 626,498 United States Patent (USP)s and JP-A-59-214852 (content of these documents is herein incorporated by reference) silver halide particles and collargol with ashing interior section are used for photosensitive silver halide emulsion layer and/or substantially in non-photo-sensing hydrophilic colloid floor.Term " silver halide particle of internal or surface ashing " refers to that the exposure of photosensitive material or unexposed portion all can be by the silver halide particles of uniform development (in askiatic mode).The method for producing the effect is described in No. 4,626,498 United States Patent (USP) and JP-A-59-214852.Forming the silver halide of the kernel of the internal core/shell mould silver halide particle being ashed can have different halogens to constitute.The silver halide that its particle inside or surface are ashed can be any one of silver chlorate, chlorine silver bromide, silver iodobromide and chlorine silver iodobromide.The average grain diameter of the silver halide particle of these ashing is preferably 0.01-0.75 μm, more preferably 0.05-0.6 μm.For the morphology of particle, conventional granulates and polydispersion emulsion can be used, it is preferred that single dispersing emulsion (gross weight of silver halide particle or at least the 95% of total number of particles are within ± 40% scope of average grain diameter).

In the present invention, it is preferred to use non-photo-sensing fine grained silver halide.Term " non-photo-sensing fine grained silver halide " refers to following fine particles of silver halide：The particle is insensitive during image exposure, with substantially not developed during obtaining dye image, and development treatment.These silver halide particles are not preferably ashed in advance.In fine grained silver halide, the content of silver bromide is 0-100mol%, and can include silver chlorate and/or silver iodide if desired.Fine grained silver halide preferably comprises 0.5-10mol% silver iodide.The average grain diameter (equivalent to the average value of the round diameter of projected area) of fine particles of silver halide is preferably 0.01-0.5 μm, more preferably 0.02-0.2 μm.

Fine grained silver halide is available to be prepared with Conventional photosensitive silver halide identical method.The surface of silver halide particle necessarily carries out optical sensibilization.In addition, what spectral sensitization nor is it necessary that.But, added in coating solution before silver halide particle, commonly known stabilizer, such as triazole compounds, azepine indene compound, benzothiazole father-in-law compound, sulfhydryl compound or zinc compound are preferably added thereto.Collargol can be mixed in the layer comprising the fine grained silver halide.

Above-mentioned various additives can be used in the photosensitive material according to the technology of the present invention, and can also add other various additives according to specific purpose within this material.

These additives are specifically described in Research discosure Item 17643 (in December, 1978), Item 18716 (in November, 1979) and Item 308119 (in December, 1989), and related description section is summarized in the following table.

Additive types	RD17643	RD18716	RD308119
				1st, chemical sensitizer	Page 23	The right column of page 648	Page 996
2nd, sensitizer		The right column of page 648
				3rd, spectral sensitizer, telegraphy agent	Page 23-24	Right column -649 page the right column of page 648	Right column -998 page the right column of page 996
4th, brightening agent	Page 24		The right column of page 998
				5th, anti-fogging agent and stabilizer	Page 24-25	The right column of page 649	Right column -1000 page the right column of page 998
6th, light absorber, filter dye, ultraviolet absorber	Page 25-26	Right column -650 page the left column of page 649	Left column -1003 page the right column of page 1003
				7th, anti-stain agent	The right column of page 25	A left side-the right column of page 650	The right column of page 1002
8th, dye image stabilizer	Page 25		The right column of page 1002
				9th, film curing agent	Page 26	The left column of page 651	Right column -1005 page the left column of page 1004
10th, adhesive	Page 26	The left column of page 651	Right column -1004 page the right column of page 1003
				11st, plasticizer, lubricant	Page 27	The right column of page 650	A left side-the right column of page 1006
12nd, coating additive, surfactant	Page 26-27	The right column of page 650	Left column -1006 page the left column of page 1005
				13rd, antistatic additive	Page 27	The right column of page 650	Right column -1007 page the left column of page 1006

10th, delustering agent

Left column -1009 page the left column of page 1008

Set for the layer that can be used in the sensitive photographic material of the present invention and the emulsion being suitable in the photosensitive material and correlation technique, silver emulsion, dye forming coupler, DIR colour couplers and other function colour coupler, various additives and development treatments, EP 0565096A1 (being disclosed on October 13rd, 1993) are referred to, the content of the document is herein incorporated by reference.The each details and position of description are as follows.

1st, layer is set：Page 61 23-35 rows, the row of row-62 page 14 of page 61 41,

2nd, intermediate layer：36-40 rows of page 61,

3rd, the layer of interbed effect is produced：15-18 rows of page 62,

4th, silver halide halogen is constituted：21-25 rows of page 62,

5th, silver halide particle crystal habit：26-30 rows of page 62,

6th, silver halide particle size：31-34 rows of page 62,

7th, emulsion manufacture method：35-40 rows of page 62,

8th, silver halide particle diameter distribution：41-42 rows of page 62,

9th, sheet-like particle：43-46 rows of page 62,

10th, the internal structure of particle：47-53 rows of page 62,

11st, the emulsion of latent image formation type：The row of 54 rows -63rd page 5 of page 62,

12nd, the physical ripening and chemical sensitization of emulsion：6-9 rows of page 63,

13rd, emulsion is mixed：10-13 rows of page 63,

14th, it is ashed emulsion：14-31 rows of page 63,

15th, non-photo-sensing emulsion：32-43 rows of page 63,

16th, silver-colored coating amount：49-50 rows of page 63,

17th, formaldehyde scavenger：54-57 rows of page 64,

18th, the anti-fogging agent of sulfydryl：1-2 rows of page 65,

19th, fogging agent ,-releasing agent：3-7 rows of page 65,

20th, dyestuff：7-10 rows of page 65,

21st, colour former agent brief summary：11-13 rows of page 65,

22nd, yellow, pinkish red and cyan colour coupler：14-25 rows of page 65,

23rd, polymeric couplers：26-28 rows of page 65,

24th, dye forming coupler is spread：29-31 rows of page 65,

25th, colour coupler is coloured：23-28 rows of page 65,

26th, function colour coupler brief summary：39-44 rows of page 65,

27th, bleach accelerator releasing coupler：45-48 rows of page 65,

28th, development accelerant release colour coupler：49-53 rows of page 65,

29th, other DIR colour couplers：The row of 54 row -66 page 4 of page 65,

30th, the method for colour coupler is disperseed：5-28 rows of page 66,

31st, antiseptic and mould inhibitor：29-33 rows of page 66,

32nd, the type of intensifying material：34-36 rows of page 66,

33rd, the thickness of photosensitive layer and swelling speed：1 rows of page 40-67 of page 66,

34th, backing layer：3-8 rows of page 67,

35th, development treatment brief summary：9-11 rows of page 67,

36th, developer solution and developer：12-30 rows of page 67,

37th, develop additive：31-44 rows of page 67,

38th, reverse developing：45-56 rows of page 67,

39th, flushing liquor opens ratio：The row of 57 row -68 page 12 of page 67,

40th, developing time：13-15 rows of page 68,

41st, bleach-be fixed, bleach and be fixing：The row of 16 row -69 page 31 of page 68,

42nd, automatic film developer：32-40 rows of page 69,

43rd, wash, elute and stably：The row of 41 row -70 page 18 of page 69,

44th, flushing liquor supplement and circulation：19-23 rows of page 70,

45th, the photosensitive material of interior shape developer：24-33 rows of page 70,

46th, development treatment temperature：34-38 rows of page 70, and

47th, the application of the film with camera lens：39-41 rows of page 70.

Furthermore, preferably use comprising 2-picolinic acid or 2,6-pyridinedicarboxylic acid, molysite such as ferric nitrate and EP 602, the liquid lime chloride of the persulfate described in 600, the content of the document is herein incorporated by reference.When using liquid lime chloride, stopped preferably between colour development and blanching step and water-washing step.It is preferred that using organic acid such as acetic acid, butanedioic acid or maleic acid in solution is stopped.Ashing is adjusted and bleached for pH, and preferably bleaching liquid includes organic acid such as acetic acid, butanedioic acid, maleic acid, glutaric acid or adipic acid, and their consumption is 0.1-2mol/L.

The magnetic recording layer explained below being used in the present invention.

Suitable magnetic recording layer can be made up of any ferromagnetism iron oxide, such as γ Fe₂O₃, the coated γ Fe of cobalt₂O₃, coated magnetic iron ore, the magnetic iron ore comprising cobalt, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, the barium ferrite of hexahedron system, strontium ferrite, ferrous acid lead and the calcium ferrite of cobalt.Wherein, the preferably γ Fe of the ferromagnetism iron oxide of cobalt coating such as cobalt coating₂O₃.Its configuration can be any one of needle-like, the grain of rice, spherical, cube and sheet.Specific surface area is with S_BETMeter is more preferably at least 20m²/ g, more preferably at least 30m²/g。

The saturation magnetization (σ S) of ferrimagnet is preferably 3.0 × 10⁴To 3.0 × 10⁴A/m, more preferably 4.0 × 10⁴To 2.5 × 10⁵A/m.The surface of ferromagnetic particle can be surface-treated with silica and/or aluminum oxide or organic material.In addition, the surface of particles of magnetic material can be handled with the silane coupler or titanium coupling agent described in JP-A-6-161032.Furthermore, the magnetic material that can be applied as described in JP-A-4-259911 and 5-81652 using surface with inorganic or organic material.

Can be by any natural polymer (such as cellulose derivative and sugar derivatives) described in JP-A-4-219569 for the adhesive in particles of magnetic material, acid-, alkali-or Biodegradable polymeric, reaction resin, any one of radiation curing resin, thermosetting resin and thermoplastic resin and their mixture are constituted.The Tg of above-mentioned resin is respectively-40 to 300 DEG C, and weight average molecular weight range is 2000-1000000.For example, ethylenic copolymer can be used as suitable adhesive resin, cellulose derivative such as cellulose diacetate, cellulose triacetate, cellulose-acetate propionate, cellulose acetate-butyrate and three cellulose propionates, acrylic resin and acetals resin.Gelatin is also suitable adhesive resin.Wherein, particularly preferably two (three) cellulose acetates.It can be solidified by adding epoxy radicals, acridine or isocyanate crosslinking.Suitable isocyanate crosslinking includes such as isocyanates such as inferior cresyl vulcabond, 4,4 '-methyl diphenylene diisocyanate, 1,6-ethylidene diisocyanate and eylylene diisocyanate, the reaction product (reaction product of such as 3mol inferior cresyl vulcabonds and 1mol trimethylolpropanes) of these isocyanates and polyalcohol, and by being condensed PIC prepared by these isocyanates, these materials are for example described in JP-A-6-59537.

The method of dispersed magnetic material includes kneader, post (pin) type mill, ring ball mill are used alone or in combination as described in JP-A-6-35092 in above-mentioned adhesive.It may be used at dispersant and other conventional dispersants described in JP-A-5-088283.The thickness range of magnetic recording layer is 0.1-10 μm, preferably 0.2-5 μm, more preferably 0.3-3 μm.The weight ratio of particles of magnetic material and adhesive is preferably in the range of 0.5: 100-60: 100, and more preferably 1: 100-30: 100.The coating amount of particles of magnetic material is 0.005-3g/m², preferably 0.01-2g/m², and more preferably 0.02-0.5g/m².The transmission yellow density of the magnetic recording layer is preferably 0.01-0.50, more preferably 0.03-0.20, and most preferably 0.04-0.15.Magnetic recording layer can be whole or applied with candy strip by applying or being printed on the dorsal part of photograph carrier.Such as gas scraper, scraper plate, air knife coaters, extruding, dipping, reverse roller, transferring roller, intaglio printing, kiss painting, curtain coating, spraying, dip-coating, drawdown rod or squeezing and coating can be used to apply magnetic recording layer.It is preferred that the coating liquid described in JP-A-5-341436.

Magnetic recording layer, which can be also provided with, for example lubricity enhancing, curling regulation, antistatic, anti-sticking and magnetic head cleaning function layer, or sets other functional layers, to assign these functions.It is preferred that at least one part of abrasive particles is Mohs hardness be at least 5 aspherical inorganic particle.Aspherical inorganic particle is preferably by following material composition：Oxide such as aluminum oxide, chromium oxide, silica and titanium dioxide, carbide such as carborundum and titanium carbide, and diamond.The surface of these grinding agents can be handled with silane coupler or titanium coupling agent.Above-mentioned particle can be added in magnetic recording layer, or magnetic recording layer is with particle coated (such as protective layer or lubricating layer).Adhesive for this purpose with it is above-described identical, it is preferably identical with magnetic recording layer.Photosensitive material with magnetic recording layer is described in USP 5,336,589,5,250,404,5,229,259 and 5,215,874 and EP 466,130.

The polyester support explained below being used in the present invention.Its details and photosensitive material as described below, processing, magazine and working Examples are all specifically described (being published by Japan Institute of Invention and Innovation, on March 15th, 1994) in JIII Journal of TechnicalDisclosure No.94-6023.It is made up for the polyester in the present invention of glycol and aromatic dicarboxylic acids as basis.Suitable aromatic dicarboxylic acids include 2,6-, 1,5-, Isosorbide-5-Nitrae-and 2,7-naphthalenedicarboxylic acid, terephthalic acid (TPA), M-phthalic acid and phthalic acid, and the example of suitable glycol includes diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol-A and other bisphenol compounds.Resulting polymers include homopolymer, the sour glycol ester of such as polyethylene terephthalate, poly- naphthalenedicarboxylic acid and poly- cyclohexanedimethanol terephthalate.Particularly preferred 2,6-naphthalenedicarboxylic acid content is 50-100mol% polyester.Most preferably poly- 2,6-(ethylene naphthalate).Their mean molecule quantity is about 5000-200000.The Tg of polyester of the present invention is at least 50 DEG C, more preferably at least 90 DEG C.

To suppress curling, polyester support needs to be heat-treated, and temperature is 40 DEG C-be less than Tg, is preferably (Tg -20 DEG C) to being less than Tg.The heat treatment can be carried out under the steady temperature being held within above range, or can be carried out under cooling.The time range of heat treatment is 0.1-1500 hours, preferably 0.5-200 hours.Carrier can be heat-treated as rolls, or be carried out in the form of piece.The format surface of carrier to be improved (can for example use SnO by making surface in irregular₂、Sb₂O₅Deng the coating of Conductive inorganic fine grained).Additionally, it is desirable that the edge of carrier is twisted so that only edge is slightly higher, the photograph of core segment is thus prevented.Above-mentioned heat treatment can be carried out in any stage after carrier film is formed, after surface treatment, after application backing layer (such as using antistatic additive or lubricant) and after coating priming coat.Heat treatment is preferably carried out after antistatic additive is applied.

Ultraviolet absorber can be ground in polyester.Photoconductive tube (light piping) can be prevented by grinding in the polyester into commercially available as the dyestuff and pigment of polyester additives, the dyestuff and pigment are, for example, Mitsubishi Chemical Industries, Ltd. the Kayaset of Diaresin and NIPPONKAYAKU CO., the LTD. manufactures manufactured.

In the present invention, it is preferred to be surface-treated, carrier and photosensitive material composition layer are together with each other.The surface treatment is, for example, surface activation process such as chemical treatment, mechanical treatment, halation discharge process, flame treatment, ultraviolet processing, high-frequency therapeutic treatment, glow discharge process, activating plasma processing, laser treatment, mixing acid treatment or ozone Oxidation Treatment.

The method of coating bottom explained below.The bottom can be made up of single layer or two or more layers.It is used as the adhesive of the bottom, it can be not only the copolymer being made up of monomer as starting material, can also be polycyclic propylamine, epoxy resin, grafted gelatin, NC Nitroncellulose and gelatin, wherein described monomer is selected from vinylidene chloride, 1,2-dichloroethylene, butadiene, methacrylic acid, acrylic acid, itaconic acid and maleic anhydride.Carrier swelling compound is used as using resorcinol and parachlorophenol.Gelatin hardener such as chromic salts (such as chrome alum chromalum), aldehyde (such as formaldehyde or glutaraldehyde), isocyanates, active halogen compound (such as 2,4-dichloro-6-hydroxyl-S-triazole), epichlorohydrin resins are utilized within the bottom.Equally, silica, titanium dioxide, fine inorganic particles or polymethyl methacrylate copolymer fine grained (0.01-10 μm) can be also mixed wherein as delustering agent.

Additionally, it is preferred that using antistatic additive in the present invention.Suitable antistatic additive includes containing carboxylic acid and carboxylate, the polymer of sulfonate, cationic polymer and anion surfactant.

Most preferred antistatic additive be in the following group at least-fine grained of kind of crystalline metal oxide：ZnO、TiO₂、SnO₂、Al₂O₃、In₂O₃、SiO₂、MgO、BaO、MoO₃And V₂O₅, their specific insulation is 10⁷Ω cm or lower, preferably 10⁵Ω cm or lower, and particle diameter is 0.001-1.0 μm, or their composite oxides (Sb, P, B, In, S, Si, C etc.), and the metal oxide fine particles of aerosol form or its composite oxides.

Its they content in photosensitive material is preferably 5-500mg/m², more preferably 10-350mg/m².The ratio of electric conductivity crystalline oxide or its composite oxides and adhesive is preferably 1/300-100/1, and more preferably 1/100-100/5.

It is preferred that the photosensitive material of the present invention has lubricity.Layer comprising lubricant is preferably provided on both photosensitive layer side and dorsal part.In terms of the coefficient of kinetic friction, lubricity is preferably 0.25-0.01.Lubricity is by being measured (25 DEG C, 60%RH) in a diameter of 5mm enterprising line slip of stainless steel ball with 60cm/min speed.In the assessment, even if opposite material is replaced with photosensitive material side, the value of almost identical level still can obtain.

Can lubricant used in this invention be, for example, polysiloxane, higher fatty acid amides, higher fatty acid metal salt or higher fatty acids and higher alcohol ester.The example of suitable polysiloxane includes dimethyl silicone polymer, polydiethylsiloxane, polystyrylmethyl siloxanes and PSI.Lubricant is preferably added in the outermost layer of backing layer or emulsion layer.Particularly preferred dimethyl silicone polymer and the ester with chain alkyl.

Delustering agent is preferably used in the photosensitive material of the present invention.Although delustering agent can be separately employed on emulsion side or dorsal part, particularly preferably by delustering agent addition on the outermost layer of emulsion side.Delustering agent may be dissolved in flushing liquor or insoluble in flushing liquor, and preferably use the combination of soluble and insolubility delustering agent.For example, it is preferable to polymethyl methacrylate, poly- (methyl methacrylate/methacrylic acid) (9/1 or 5/5 mol ratio) and granules of polystyrene.Its particle size range is preferably 0.8-10 μm.It is preferred that it has a narrow particle diameter distribution, and it is desirable that at least 90% it is included in amounts of particles in the range of 0.9-1.1 times of average grain diameters.In addition, being enhancing extinction, the fine grained of 0.8 μm or smaller particle is preferably added simultaneously, it is for example including following particle：Polymethyl methacrylate (0.2 μm), poly- (methyl methacrylate/methacrylic acid) (9/1 mol ratio, 0.3 μm), polystyrene (0.25 μm) and cataloid (0.03 μm).

The film cassette explained below being used in the present invention.The main material for constituting film cassette in the present invention is metal or synthetic plastic.

The preferred example of plastics includes polystyrene, polyethylene, polypropylene and polyphenyl ether.Various types of antistatic additive can be included for the film cassette in the present invention, and preferably for example comprising carbon black, metal oxide particle, nonionic surfactant, anion surfactant, cationic surfactant or betaine type amphoteric surfactant and polymer.These anlistatig film cassette descriptions are in JP-A-1-312537 and 1-312538.Resistance under 25 DEG C, 25%RH is preferably 10¹²Ω or lower.Plastic film magazine is generally by plastic, and grinding adds carbon black or pigment in the plastics, to make it have shading performance.Magazine size can be identical with common 135 size, or in miniature camera, and the 25mm magazine diameters of current 135 size advantageously can be reduced to 22mm or smaller.The volume of cassette shell is preferably 30cm³Or smaller, more preferably 25cm³Or it is smaller.The weight of plastics used is preferably 5-15g in magazine or cassette shell.

Magazine used can be sent out film with rotary shaft in the present invention.In addition, the structure of magazine should be such that film leading edge is in magazine main frame, and film leading edge is sent by rotary shaft by the exit portion of magazine according to film transport direction.These are all disclosed in USP 4,834,306 and 5,226,613.Still undeveloped raw material or development photographic film are referred to as the photographic film in the present invention.Raw material and developed photographic film can be placed in the new magazine of identical or in different magazines.

The colour photographic sensitive material of the present invention is suitable as the negative film for Advanced Photo System (hereinafter referred to as " AP systems ").For example, film is processed into AP system formats, and be loaded into the magazine of specific use, such as NEXIA A, the NEXIA F or NEXIA H (being sequentially ISO 200/100/400) of Fuji Photo Film Co., Ltd.s (hereinafter referred to as " Fuji Film ") manufacture.The magazine film for being used for AP systems is put into the Epion series manufactured in the camera for AP systems such as Fuji Film, such as Epion 300Z are subsequently used in actual use.Moreover, the colour photographic sensitive material of the present invention is suitable for the film equipped with camera lens, the Fuji ColorUturundesu Super Slim (Quick Snap) of such as Fuji Film manufactures.

Thus the film taken a picture is printed in microscale experiment chamber system by following steps：

(1) accept (the magazine film for receiving oneself exposure by customer)；

(2) take apart and (film is transferred to from above-mentioned magazine in the middle magazine for development)；

(3) film development；   

(4) (negative film of development is back in original magazine) is contacted afterwards；

(5) printing (continuous automatic printing C/H/P three types photo and index photo (the Super FA8 of preferably Fuji Film manufactures) on colour paper)；Then

(6) proofread and send out and (proofread magazine and index photo with ID numbers, then send out photo).

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

AP systems can be appreciated with fast music system (photo joy system) is taken a picture, and its central location is Fuji Film digitized video stations Aladin 1000.For example, developed AP systems magazine film is directly placed into Aladdin 1000, negative film, positive or Photograph image information either are inputted with 35mm Film scanners FE -550 therein or tack scanner PE -550, resulting digital image data then easily can be processed and edit.The data obtained can use current laboratory equipment to be exported in the way of photo, such as by digital color printer NC -550AL based on the hot color printing system of photo fixed or the Pictrography 3000 based on laser explosure heat development transfer system or pass through film unit.In addition, Aladdin 1000 directly can export digital information to floppy disk or Zip disks, or it is exported to CD-R by CD read write lines.

On the other hand, if at home, only developed AP systems magazine film, which is put into photo player (photoplayer) AP -1 of Fuji Film manufactures, can appreciate photo on television.Putting it into photograph scanner AS -1 of Fuji Film manufactures continuously at full speed can also input image information in personal computer.In addition, the Photovision FV-10/FV-5 that can be manufactured with Fuji Film input film, photo or stereo article in personal computer.Furthermore, various processing are carried out on a personal computer using Fuji FilmApplication Soft Photofactory, thus appreciate image information of the record in floppy disk, Zip disks, CD-R or hard disk.It is suitable for by the Fuji Film digital color printer NC-2/NC-2D based on the photograph hot color printing system of fixed manufactured by the photo of personal computer outputting high quality.

Fuji Color Pocket Album AP-5 Pop L, Ap-1 Pop L or Ap-1Pop KG or Cartridge File16 are preferably used for the storage of the AP system films developed.

The embodiment present invention described in more detail will be passed through below.Embodiment

Embodiments of the invention explained below, but these embodiments are not limited the scope of the present invention.The preparation of the sample 001 (present invention) of embodiment 1

Emulsion Em-A to Em-O is prepared using the following method.Em-A preparation

The aqueous solution 1200ml comprising 1.0g low molecular weight gelatines and 1.0g KBrs is stirred vigorously while being kept for 35 DEG C, the molecular weight of the gelatin is 15000.With double gunite the addition aqueous solution 30ml comprising 1.9g silver nitrates and the aqueous solution 30ml comprising 1.5g KBrs and 0.7g low molecular weight gelatines within the time of 30 seconds, to carry out nucleation, the molecular weight of the gelatin is 15000.During this period, the excessive concentrations of KBr are consistently kept.6g KBrs are added, 75 DEG C are then heated to, and make mixture ripe.After the completion of maturation, 35g succinated gelatin is added.PH is adjusted to 5.5.Pass through double gunitees addition kbr aqueous solution and the aqueous solution 150ml comprising 30g silver nitrates within the time of 16 minutes.During this period, silver-colored potential is maintained at -25mV relative to calomel electrode.In addition, adding the aqueous solution and kbr aqueous solution that include 110g silver nitrates by double gunitees within the time of 15 minutes, while increasing flow velocity, it is 1.2 times of initial flow rate to make final flow rate.During this period, while adding particle diameter is 0.03 μm of silver iodide fine particle emulsion, and increase flow velocity so that agi content is 3.8mol%, and silver-colored potential is maintained at -25mV.

Next, adding kbr aqueous solution by double gunitees within the time of 7 minutes and including the aqueous solution of 35g silver nitrates.Adjust the addition of kbr aqueous solution so that adding potential when completing for -20mV.40 DEG C are adjusted the temperature to, 5.6g following compound 1 is then added according to silver iodide.65ml 0.8M sodium sulfite aqueous solutions are added again.Then, sodium hydrate aqueous solution is added, pH is thus increased to 9.0, and kept for interference-free 4 minutes so that quickly form iodide ion.PH comes back to 5.5, and temperature returns to 55 DEG C, then adds 1mg sodium benzenethiosulfonate.Then gelatin of the 13g through lime treatment is added, the wherein concentration of calcium ion is 1ppm.After the completion of addition, kbr aqueous solution and the aqueous solution 250ml comprising 70g silver nitrates are added within the time of 20 minutes, while making potential be maintained at 60mV.During this period, with every mol silver 1.0 × 10^-5Mol amount addition potassium ferrocyanide.Mixture is washed with water, gelatin of the 80g through lime treatment is then added, the concentration of its calcium ion is 1ppm.PH and pAg are adjusted to 5.8 and 8.7 respectively at 40 DEG C.Compound 1

Calcium, magnesium and the content of strontium in so obtained emulsion are measured with ICP emission spectro-chemical analysis.Their content is 15,2 and 1ppm respectively.

Emulsion is heated to 56 DEG C.First according to the pure silver bromide fine particle emulsion that silver addition 1g particle diameters are 0.05 μm, shell covering is thus carried out.Then, respectively with every mol silver 5.85 × 10^-4mol、3.06×10^-4Mol and 9.00 × 10^-6Mol amount adds the following sensitizing dye 1,2 and 3 of solid fine dispersions form.Under the preparation condition shown in table 1, inorganic salts are dissolved in ion exchange water, sensitizing dye is then added.With dissolvers blade under 2000rpm in 60 DEG C of dispersed with stirring sensitizing dyes 20 minutes.Thus the solid fine dispersions of sensitizing dye 1,2 and 3 are made.Add after sensitizing dye, when sensitizing dye adsorbs reach equilibrium state absorption 90%, add calcium nitrate, calcium concentration is changed into 250ppm.The adsorbance of sensitizing dye is determined as follows：Mixture is separated into solid layer and liquid level (supernatant) with centrifugal, the difference between the amount of sensitizing dye present in the amount and supernatant of the sensitizing dye initially added is then measured, thus calculates the amount of adsorbed sensitizing dye.Add after calcium nitrate, thus addition potassium rhodanide, gold chloride, sodium thiosulfate, N, N- dimethyl selenourea and compound 4 carry out optimal chemical sensitization.The addition of N, N- dimethyl selenourea is per mol silver 3.40 × 10^-6mol.After the completion of chemical sensitization, following compound 2 and 3 is added, emulsion Em-A is thus obtained.

Table 1

Sensitizing dye	1	2/3
			The amount (parts by weight) of sensitizing dye	3	4/0.12
Sodium nitrate/sodium sulphate (parts by weight)	0.8/3.2	0.6/2.4
			Water (parts by weight)	43	42.8
Jitter time	20 minutes	20 minutes
			Dispersion temperature	60℃	60℃

Sensitizing dye 1Sensitizing dye 2Sensitizing dye 3Compound 2

Compound 3Compound 4Em-B preparation

Emulsion Em-B is prepared according to emulsion Em-A identical methods, but the KBr quantitative change added after nucleation is 5g, succinated gelatin is changed into trimellitic acid gelatin, wherein trimellitic acid rate is 98%, methionine and molecular weight of the gelatin per g comprising 35 μm of ol are 100000, compound 1 is changed into following compound 6, and its addition is 8.0g according to KI, and the amount of the sensitizing dye 1,2 and 3 added before chemical sensitization is changed into 6.50 × 10 respectively^-4mol、3.40×10^-4Mol and 1.00 × 10^-5Mol, and addition of N, N- the dimethyl selenourea in chemical sensitization changes into 4.00 × 10^-6mol.Compound 6

Em-C preparation

Emulsion Em-B is prepared according to emulsion Em-A identical methods, but the KBr quantitative change added after nucleation is 1.5g, succinated gelatin is changed into phthalated gelatin, wherein phthalic acid rate is 97%, methionine and molecular weight of the gelatin per g comprising 35 μm of ol are 100000, compound 1 is changed into following compound 7, and its addition is 7.1g according to KI, and the amount of the sensitizing dye 1,2 and 3 added before chemical sensitization is respectively 7.80 × 10^-4mol、4.08×10^-4Mol and 1.20 × 10^-5Mol, and addition of N, N- the dimethyl selenourea in chemical sensitization is changed into 5.00 × 10^-6mol.Compound 7

Em-E preparation

The aqueous solution 1200ml comprising 1.0g low molecular weight gelatines and 1.0g KBrs is stirred vigorously while being kept for 35 DEG C, the molecular weight of the gelatin is 15000.With double gunite the addition aqueous solution 30ml comprising 1.9g silver nitrates and the aqueous solution 30ml comprising 1.5g KBrs and 0.7g low molecular weight gelatines within the time of 30 seconds, to carry out nucleation, the molecular weight of the gelatin is 15000.During this period, the excessive concentrations of KBr are consistently kept.6g KBrs are added, 75 DEG C are then heated to, and make mixture ripe.After the completion of maturation, 15g succinated gelatin and 20g above-mentioned trimellitic acid gelatin are added.PH is adjusted to 5.5.Pass through double gunitees addition kbr aqueous solution and the aqueous solution 150ml comprising 30g silver nitrates within the time of 16 minutes.During this period, silver-colored potential is maintained at -25mV relative to saturated calomel electrode.In addition, adding the aqueous solution and kbr aqueous solution that include 110g silver nitrates by double gunitees within the time of 15 minutes, while increasing flow velocity, it is 1.2 times of initial flow rate to make final flow rate.During this period, while adding particle diameter is 0.03 μm of silver iodide fine particle emulsion, and increase flow velocity so that agi content is 3.8mol%, and silver-colored potential is maintained at -25mV.

Next, passing through double gunitees addition kbr aqueous solution and the aqueous solution 132ml comprising 35g silver nitrates within the time of 7 minutes.Adjust the addition of kbr aqueous solution so that adding potential when completing for -20mV.KBr is added, potential is changed into -60mV.Then the 1mg gelatin of sodium benzenethiosulfonate and 13g through lime treatment is added, the wherein concentration of calcium ion is 1ppm.After the completion of addition, kbr aqueous solution and the aqueous solution 250ml comprising 70g silver nitrates are added within the time of 20 minutes, and potential is maintained at 60mV, continuously added according to KI simultaneously silver iodide fine particle emulsion that 8.0g particle diameters are 0.008 μm (waiting bulb diameter) (assembling just like JP-A-10-43570 described in magnetic coupling induction type agitator independent chamber in the aqueous solution, silver nitrate aqueous solution and the potassium iodide aqueous solution of mixing low molecular weight gelatine prepare, thus carry out preparing the emulsion only before addition, wherein 15000) molecular weight of the gelatin is.During this period, with every mol silver 1.0 × 10^-5Mol amount addition potassium ferrocyanide.Mixture is washed with water, gelatin of the 80g through lime treatment is then added, the concentration of its calcium ion is 1ppm.PH and pAg are adjusted to 5.8 and 8.7 respectively at 40 DEG C.

Calcium, magnesium and the content of strontium in so obtained emulsion are measured with ICP emission spectro-chemical analysis.Their content is 15,2 and 1ppm respectively.

Identical method, which is entered, during according to preparing emulsion Em-A is about to chemical sensitization, but sensitizing dye 1,2 and 3 is changed into following sensitizing dye 4,5 and 6 respectively, and their addition is respectively 7.73 × 10^-4mol、1.65×10^-4Mol and 6.20 × 10^-5mol.Thus emulsion Em-E is obtained.Sensitizing dye 4

Sensitizing dye 5

Sensitizing dye 6Em-F preparation

The aqueous solution 1200ml comprising 1.0g low molecular weight gelatines and 1.0g KBrs is stirred vigorously while being kept for 35 DEG C, the molecular weight of the gelatin is 15000.With double gunite the addition aqueous solution 30ml comprising 1.9g silver nitrates and the aqueous solution 30ml comprising 1.5g KBrs and 0.7g low molecular weight gelatines within the time of 30 seconds, to carry out nucleation, the molecular weight of the gelatin is 15000.During this period, the excessive concentrations of KBr are consistently kept.5g KBrs are added, 75 DEG C are then heated to, and make mixture ripe.After the completion of maturation, 20g succinated gelatin and 15g phthalated gelatin are added.PH is adjusted to 5.5.Pass through double gunitees addition kbr aqueous solution and the aqueous solution 150ml comprising 30g silver nitrates within the time of 16 minutes.During this period, silver-colored potential is maintained at -25mV relative to saturated calomel electrode.In addition, adding the aqueous solution and kbr aqueous solution that include 110g silver nitrates by double gunitees within the time of 15 minutes, while increasing flow velocity, it is 1.2 times of initial flow rate to make final flow rate.During this period, while adding particle diameter is 0.03 μm of silver iodide fine particle emulsion, and increase flow velocity so that agi content is 3.8mol%, and silver-colored potential is maintained at -25mV.

Next, passing through double gunitees addition kbr aqueous solution and the aqueous solution 132ml comprising 35g silver nitrates within the time of 7 minutes.KBr is added, potential is changed into -60mV.Afterwards, the silver iodide fine particle emulsion that 9.2g particle diameters are 0.008 μm is added according to KI.Then the 1mg gelatin of sodium benzenethiosulfonate and 13g through lime treatment is added, the wherein concentration of calcium ion is 1ppm.After the completion of addition, kbr aqueous solution and the aqueous solution 250ml comprising 70g silver nitrates are added within the time of 20 minutes, and potential is maintained at 60mV.During this period, with every mol silver 1.0 × 10^-5Mol amount addition potassium ferrocyanide.Mixture is washed with water, gelatin of the 80g through lime treatment is then added, the concentration of its calcium ion is 1ppm.PH and pAg are adjusted to 5.8 and 8.7 respectively at 40 DEG C.

Calcium, magnesium and the content of strontium in so obtained emulsion are measured with ICP emission spectro-chemical analysis.Their content is 15,2 and 1ppm respectively.

Identical method, which is entered, during according to preparing emulsion Em-A is about to chemical sensitization, but sensitizing dye 1,2 and 3 is changed into sensitizing dye 4,5 and 6 respectively, and their addition is respectively 8.50 × 10^-4mol、1.82×10^-4Mol and 6.82 × 10^-5mol.Thus emulsion Em-F is obtained.Em-G preparation

The aqueous solution 1200ml comprising 1.0g low molecular weight gelatines and 1.0g KBrs is stirred vigorously while being kept for 35 DEG C, the molecular weight of the gelatin is 15000.With double gunite the addition aqueous solution 30ml comprising 1.9g silver nitrates and the aqueous solution 30ml comprising 1.5g KBrs and 0.7g low molecular weight gelatines within the time of 30 seconds, to carry out nucleation, the molecular weight of the gelatin is 15000.During this period, the excessive concentrations of KBr are consistently kept.1.5g KBrs are added, 75 DEG C are then heated to, and make mixture ripe.After the completion of maturation, 15g above-mentioned trimellitic acid gelatin and 15g above-mentioned phthalated gelatin are added.PH is adjusted to 5.5.Pass through double gunitees addition kbr aqueous solution and the aqueous solution 150ml comprising 30g silver nitrates within the time of 16 minutes.During this period, silver-colored potential is maintained at -25mV relative to saturated calomel electrode.In addition, adding the aqueous solution and kbr aqueous solution that include 110g silver nitrates by double gunitees within the time of 15 minutes, while increasing flow velocity, it is 1.2 times of initial flow rate to make final flow rate.During this period, while adding particle diameter is 0.03 μm of silver iodide fine particle emulsion, and increase flow velocity so that agi content is 3.8mol%, and silver-colored potential is maintained at -25mV.

Next, passing through double gunitees addition kbr aqueous solution and the aqueous solution 132ml comprising 35g silver nitrates within the time of 7 minutes.KBr is added, potential is changed into -60mV.Afterwards, the silver iodide fine particle emulsion that 7.1g particle diameters are 0.03 μm is added according to KI.Then the 1mg gelatin of sodium benzenethiosulfonate and 13g through lime treatment is added, the wherein concentration of calcium ion is 1ppm.After the completion of addition, kbr aqueous solution and the aqueous solution 250ml comprising 70g silver nitrates are added within the time of 20 minutes, and potential is maintained at 60mV.During this period, with every mol silver 1.0 × 10^-5Mol amount addition potassium ferrocyanide.Mixture is washed with water, gelatin of the 80g through lime treatment is then added, the concentration of its calcium ion is 1ppm.PH and pAg are adjusted to 5.8 and 8.7 respectively at 40 DEG C.

Calcium, magnesium and the content of strontium in so obtained emulsion are measured with ICP emission spectro-chemical analysis.Their content is 15,2 and 1ppm respectively.

Identical method, which is entered, during according to preparing emulsion Em-C is about to chemical sensitization, but sensitizing dye 1,2 and 3 is changed into sensitizing dye 4,5 and 6 respectively, and their addition is respectively 1.00 × 10^-3mol、2.15×10^-4Mol and 8.06 × 10^-5mol.Thus emulsion Em-G is obtained.Em-J preparation

Emulsion Em-J is prepared according to emulsion Em-B identical methods, but the sensitizing dye added before chemical sensitization is changed into following sensitizing dye 7 and 8, and their addition is 7.65 × 10 respectively^-4Mol and 2.74 × 10^-4mol.Sensitizing dye 7Sensitizing dye 8Em-L preparation prepares silver bromide crystal seed emulsion

Prepare the silver bromide sheet emulsion with following characteristics：Averagely bulb diameter is waited to be 0.6 μm, aspect ratio is 9.0, the silver comprising 1.16mol and 66g gelatin per kg emulsions.Growth step 1

It is 98% that the succinated ratio in 0.3g modified silicon oil, the succinated gelatin is added in the aqueous solution of the 1250g comprising 1.2g KBrs and succinated gelatin.Above-mentioned silver bromide sheet emulsion is added with the amount comprising 0.086mol silver, while keeping temperature is 78 DEG C, then stirred.Add the aqueous solution comprising 18.1g silver nitrates and relative to above-mentioned 0.037 μm silver iodide fine grained of the silver added in an amount of from 5.4mol.During this period, kbr aqueous solution also is added by double gunitees, while adjusting the addition, it is 8.1 to make pAg.Growth step 2

2mg sodium benzenethiosulfonate is added, then the 3 of addition 0.45g, the disodium salt of 5-disulfo catechol and 2.5mg thiourea dioxide.

Then the aqueous solution and kbr aqueous solution that include 95.7g silver nitrates are added by double gunitees within the time of 66 minutes, while increasing flow velocity.During this period, 7.0mol% above-mentioned 0.037 μm of silver iodide fine grained is added relative to the silver added.The amount for the KBr that regulation is added by double gunitees, it is 8.1 to make pAg.After the completion of addition, 2mg sodium benzenethiosulfonate is added.Growth step 3

The aqueous solution and kbr aqueous solution that include 19.5g silver nitrates are added by double gunitees within the time of 16 minutes, the addition of KBr is added, it is 7.9 to make pAg.Add almost insoluble silver emulsion 4

It is 9.3 that above-mentioned host grain is adjusted into pAg with kbr aqueous solution.Afterwards, the quick above-mentioned 0.037 μm of silver iodide fine particle emulsion for adding 25g within the time of 20 seconds.The formation 5 of outermost shell

Addition includes the aqueous solution of 34.9g silver nitrates within the time of 22 minutes.

Gained emulsion is made up of sheet-like particle, and the average aspect ratio of the particle is 9.8, averagely waits bulb diameter to be 1.4 μm, and wherein average silver iodide content is 5.5mol%.Chemical sensitization

Emulsion is washed, succinated gelatin and calcium nitrate is then added, wherein succinated ratio is 98%.At 40 DEG C, pH and pAg are adjusted to 5.8 and 8.7 respectively.Temperature is increased to 60 DEG C, 5 × 10 are then added^-3Mol 0.07 μm of silver bromide fine particle emulsion.After 20 minutes, following sensitizing dye 9,10 and 11 is added.Then addition potassium rhodanide, gold chloride, sodium thiosulfate, N, N-dimethyl selenourea and compound 4, thus carry out optimal chemical sensitization.Compound 3 is completed to add for first 20 minutes in chemical sensitization, and compound 5 is added when chemical sensitization is completed.Term " optimum chemical sensitizing " as used herein refers to every mol silver 10^-1To 10^-8Mol amount addition chemical sensitization dyestuff and compound so that when the speed when 1/100 is exposed is maximum.Sensitizing dye 9

Sensitizing dye 10Sensitizing dye 11

Compound 4Compound 5Em-O preparation

Aqueous gelatin solution (1250ml distilled water, 48g deionized gelatins and 0.75g KBrs) is put into the reaction vessel for be equipped with agitator.The temperature of the aqueous solution is set to be maintained at 70 DEG C.276ml silver nitrate aqueous solution (silver nitrate for including 12.0g) and the kbr aqueous solution of equimolar concentration are added within the time of 7 minutes by controlled double injection additive process, while making pAg remain 7.26.Mixture is cooled to 68 DEG C, 7.6ml thiourea dioxide (0.05 weight %) is then added.

Then, 592.9ml silver nitrate aqueous solution (including 108.0g silver nitrates) and the KBr and the aqueous solution (2.0mol% KIs) of KI mixture of equimolar concentration are added within 18 points of times of 30 seconds by controlled double injection additive process, while making pAg be maintained at 7.30.Complete first 5 minutes addition 18.0ml of addition thiosulfonic acid (0.1 weight %).

Gained particle is by waiting cubic granules that bulb diameter is 0.19 μm and average silver iodide content is 1.8mol% to constitute.

Gained emulsion Em-O desalinations, and washed with conventional flocculence, then disperse again.At 40 DEG C, pH and pAg are adjusted to 6.2 and 7.6 respectively.

Gained emulsion Em-following spectral sensitization of O progress and chemical sensitization.

In terms of silver, 3.37 × 10 are added^-4Mol/mol each sensitizing dye 10, sensitizing dye 11 and sensitizing dye 12,8.82 × 10^-4Mol/mol KBr, 8.83 × 10^-5Mol/mol sodium thiosulfate, 5.95 × 10^-4Mol/mol water-soluble potassium rhodanide and 3.07 × 1^0-5Mol/mol potassium chloroaurate.Carried out at 68 DEG C initially, the speed that its time should be adjusted to when 1/100 exposes is maximum.Sensitizing dye 12Em—D、H、I、K、M、N

When preparing sheet-like particle, macromolecule gelatin is as one man used with JP-A-1-158462.Golden sensitizing, sulphur sensitizing and selenium sensitizing are as one man carried out with JP-A-3-237450 in the presence of having the spectral sensitizing dye and sodium sulfocyanate listed by table 2.Emulsion D, H, I and K include the Ir and Fe of optimised quantity.For emulsion M and N, reduction sensitization is carried out according to JP-A-2-191938 embodiment in particle preparation using thiourea dioxide and thiosulfonic acid.

Table 2

Emulsion	Sensitizing dye	Addition (mol/mol silver)
			Em-D	Sensitizing dye 1	5.44×10-4
Sensitizing dye 2	2.35×10-4
		Sensitizing dye 3		7.26×10-6
Em-H	Sensitizing dye 8				6.52×10-4
		Sensitizing dye 13	1.35×10-4
	Sensitizing dye 6			2.48×10-5
		Em-I	Sensitizing dye 8		6.09×10-4
Sensitizing dye 13	1.26×10-4
			Sensitizing dye 6	2.32×10-5
Em-K	Sensitizing dye 7				6.27×10-4
		Sensitizing dye 8	2.24×10-4
	Em-M			Sensitizing dye 9	2.43×10-4
Sensitizing dye 10		2.43×10-4
			Sensitizing dye 11	2.43×10-4
Em-N		Sensitizing dye 9			3.28×10-4
	Sensitizing dye 10		3.28×10-4
		Sensitizing dye 11		3.28×10-4

Sensitizing dye 13

Table 3

Emulsion	Average iodine content (mol%)	Deng bulb diameter (μm)	Aspect ratio	Equal circle diameter (μm)	Grain thickness (μm)	Shape
							A	4	0.92	14	2	0.14	Sheet
B	5	0.8	12	1.6	0.13	Sheet
							C	4.7	0.51	7	0.85	0.12	Sheet
D	3.9	0.37	2.7	0.4	0.15	Sheet
							E	5	0.92	14	2	0.14	Sheet
F	5.5	0.8	12	1.6	0.13	Sheet
							G	4.7	0.51	7	0.85	0.12	Sheet
H	3.7	0.49	3.2	0.58	0.18	Sheet
							I	2.8	0.29	1.2	0.27	0.23	Sheet
J	5	0.8	12	1.6	0.13	Sheet
							K	3.7	0.47	3	0.53	0.18	Sheet
L	5.5	1.4	9.8	2.62	0.27	Sheet
							M	8.8	0.64	5.2	0.85	0.16	Sheet
N	3.7	0.37	4.6	0.55	0.12	Sheet
							O	1.8	0.19	-	-	-	Cube

Reference table 3, when being observed with high-voltage electron microscope, observed the dislocation line as described in JP-A-3-237450 in sheet-like particle.Carrier

Carrier used in the present embodiment is prepared using the following method.1st, first layer and bottom

With two main surfaces of the μ m-thick PEN carrier of glow discharge process 90, its treatment conditions is as follows：Processing environment pressure is 0.2Torr, and the water partial pressure of environmental gas is 75%, and discharge frequency is 30kHz, and power is 2500W, and processing intensity is 0.5kVAmin/m².The coating liquid of rod coating process consisting of according to JP-B-58-4589 (USP 4,263,870) is with 5ml/m²Amount apply the carrier, form first layer.

(concentration is 19% SnO to conductive particulate dispersion2/Sb2O5Pellet moisture granular media, two grades of agglomerates of 0.005 μm of host grain, its average grain diameter is 0.05 μm)	50 parts by weight
		Gelatin	0.5 parts by weight
Water	49 parts by weight
		Polyglycereol polyglycidyl ether	0.16 parts by weight
Polyoxyethylene sorbitan monolaurate (degree of polymerization is 20)	0.1 parts by weight

It is coated with the carrier of first layer to be wrapped on a diameter of 20cm stainless steel core, then (the Tg of PEN carriers at 110 DEG C：119 DEG C) heat 48 hours, thus implement thermal annealing.Carrier relative to first layer opposite side according to the coating liquid of rod coating process consisting of with 10ml/m²Amount be coated, formed emulsion bottom.

Gelatin	1.01 parts by weight
		Salicylic acid	0.30 parts by weight
M-cresol	0.40 parts by weight
		Ethylene nonyl phenyl ether (degree of polymerization is 10)	0.11 parts by weight
Water	3.53 parts by weight
		Methanol	84.57 parts by weight
Normal propyl alcohol	10.08 parts by weight

On the first layer by applying the following second layer of laminated structure and third layer.Finally, the colour negative photosensitive material of multilayer coated consisting of on the opposite side.Therefore, the transparent magnetic recording medium with silver halide emulsion layer is obtained.2nd, the dispersion of the second layer (transparent magnetic recording layer) (1) magnetisable material

Cobalt coating γ-Fe of 1100 parts by weight is sent into open kneader₂O₃Magnetisable material (average major-axis length：0.25 μm, S_BET：39m²/ g, Hc：831, Oe, σ s：77.1emu/g, σ r：37.4emu/g), the water of 220 parts by weight and the silane coupler of the 165 parts by weight (3-(poly- (degree of polymerization：10) oxygen ethene) epoxide propyl trimethoxy silicane), then mix 3 hours.Then coarse dispersion viscous liquid obtained by continuously being dried at 70 DEG C is heated 1 hour with removing water at 110 DEG C.Thus magnetic-particle of the surface through processing is obtained.

In addition, carrying out mixing 4 hours by open kneader according to formula as below and preparing composition again.

Magnetic-particle of the surface of gained through processing	855g
		Diacetyl cellulose	25.3g
Methyl ethyl ketone	136.3g
		Cyclohexanone	136.3g

Then it is finely divided according to formula as below with (1/4G sand millings) is sanded under 2000rpm scattered 4 hours, thus prepares composition.A diameter of 1mm bead is wherein used as medium.

The mixing liquid of gained	45g
		Diacetyl cellulose	23.7g
Methyl ethyl ketone	127.7g
		Cyclohexanone	127.7g

The intermediate liquid for including magnetisable material is prepared according further to formula as below.(2) intermediate liquid for including magnetisable material, is prepared

The magnetisable material fine dispersions of gained	674g
		Diacetyl cellulose (solid content：4.34%, solvent：Methyl ethyl ketone/cyclohexanone=1/1)	24280g
Cyclohexanone	46g

These material mixings are stirred together and with disperser, obtain including the intermediate liquid of magnetisable material.

The Alpha-alumina grinding distribution body of the present invention is prepared according to formula as below.(a) Sumicorundum AA-1.5 (average main particle diameters：1.5 μm, specific surface area：1.3m²/ g) particle dispersion preparation

Sumicorundum AA-1.5	152g
		Silane coupler KBM903 (is manufactured) by Shin-Etsu Silicone	0.48g
Diacetyl cellulose solution (solid content：4.5%, solvent：Methyl ethyl ketone/cyclohexanone=1/1)	227.52g

It is finely divided at 800 rpm with the sand milling (1/4G sand millings) of ceramic coating according to above formula scattered.Zirconium oxide bead using a diameter of 1mm is used as medium.(b) colloidal silica particles dispersion (fine grained)

Using by Nissan Chemical the Industries, " MEK-ST " of Ltd. manufactures.

The dispersion is that averagely main particle diameter is the dispersion of 0.015 μm of cataloid in the methyl ethyl ketone as decentralized medium, and wherein solid content is 30%.(3) the coating liquid for the second layer is prepared

Gained includes the intermediate liquid of magnetisable material	19053g
		Diacetyl cellulose (solid content：4.5%, solvent：Methyl ethyl ketone/cyclohexanone=1/1)	264g
Colloidal silica dispersion " MET-ST " (dispersion b, solid content：30%)	128g
		AA-1.5 dispersions (dispersion a)	12g
Millionate MR-400 (are manufactured) diluent (solid content 20%, retarder thinner by Nippon Polyurethane：Methyl ethyl ketone/cyclohexanone=1/1)	203g
		Methyl ethyl ketone	170g
Cyclohexanone	170g

Coating liquid is with 29.3ml/m obtained from by mixing and stirring mentioned component²Amount be coated with wire winding rod.It is dried at 110 DEG C.Dried magnetospheric thickness is 1.0 μm.3rd, third layer (layer for including high-grade aliphatic ester antiseize paste) (1), prepare the coarse dispersion of antiseize paste

Liquid A is heated at 100 DEG C, is thus dissolved, is added in liquid B, it is then scattered with high pressure homogenisers, obtain the coarse dispersion of antiseize paste.Liquid A

Formula C6H13CH(OH)(CH2)10COOC50H101Compound	399 parts by weight
		Formula n-C50H101O(CH2CH2O)16H compound	171 parts by weight
Cyclohexanone	830 parts by weight

Liquid B

Cyclohexanone

8600 parts by weight

(2) prepare spherical inorganic particle dispersion and spherical inorganic particle dispersion (c1) is prepared according to formula as below.

Isopropanol	93.54 parts by weight
		Silane coupler KBM903 (is manufactured) compound 1-1 by Shin-Etsu Silicone：(CH3O)3Si-(CH2)3-NH2	5.53 parts by weight
Compound 2-1	2.93 parts by weight
		Seahostar KEP50 (amorphous preparing spherical SiO 2, average grain diameter is 0.5 μm, is manufactured by Nippon Shokubai KagakuKogyo)	88.00 parts by weight

Compound 2-1

Said composition is stirred 10 minutes, then adds the parts by weight of diacetone alcohol 252.93.

" Sonifier 450 " (being manufactured by Branson) is scattered 3 hours, while being cooled with ice and stirring, thus obtains spherical inorganic particle dispersion cl with ultrasonic homogenizer for gained liquid.(3) spherical organic polymer particles dispersion is prepared

Spherical organic polymer particles dispersion (c2) is prepared according to formula as below.

XC99-A8808 (is manufactured, spherical cross linking polysiloxane particle, average grain diameter is 0.9 μm) by Toshiba Silicone Co., Ltd.s	60 parts by weight
		Methyl ethyl ketone	120 parts by weight
Cyclohexanone	120 parts by weight

(solid content 20%, solvent：Methyl ethyl ketone/cyclohexanone=1/1)

" Sonifier 450 " (being manufactured by Branson) is scattered 2 hours, while being cooled with ice and stirring, thus obtains spherical organic polymer particles dispersion c2 with ultrasonic homogenizer for the mixture.(4) the coating liquid for third layer is prepared

Following components is added in 542g above-mentioned antiseize paste coarse dispersion, the coating liquid for third layer is thus prepared.

Diacetone alcohol	5950g
		Cyclohexanone	176g
Ethyl acetate	1700g
		Above-mentioned Seahostar KEP50 dispersions (cl)	53.1g
Above-mentioned spherical organic polymer particles dispersion (c2)	300g

FC431 (is manufactured, solid content 50%, solvent by 3M：Ethyl acetate)	2.65g
		BYK310 (is manufactured, solid content 25%) by BYK Chemi Japan	5.3g

With 10.35ml/m²Amount by above-mentioned third layer coating liquid be coated on the second layer, at 110 DEG C dry, then at 97 DEG C carry out after dry 3 minutes.4th, photosensitive layer is applied by coating

The layer of multiple consisting of is applied on the backing layer of the opposite side of carrier, colour negative is thus obtained.The composition of photosensitive layer

Main material used is classified as follows in single layer：ExC：Cyan colour coupler UV：Ultraviolet absorber ExM：Magenta colour coupler HBS：High boiling organic solvent ExY：Yellow colour former H：Gelatin hardener ExS：Sensitizing dye (in the following description, for individual specific compound, is represented, and its structural formula is represented afterwards) after letter with numeral.

The numeral of correspondence each component is represented with g/m²For the coating weight of unit.The coating weight of silver halide is represented with the amount of silver.The coating weight of each sensitizing dye is represented in units of in identical layer per the mol numbers of mol silver halides.1st layer (the first anti-halation layer)

Black collargol	Silver 0.122
		0.07 μm of iodine silver bromide emulsion	Silver 0.01
Gelatin	0.919
		ExC-1	0.002
ExC-3	0.002
		Cpd-2	0.001
HBS-1	0.005
		HBS-2	0.002

2nd layer (the second anti-halation layer)

Black collargol	Silver 0.055
		Gelatin	0.425
ExF-1	0.002
		Solid disperse dye ExF-9	0.120
HBS-1	0.074

3rd layer (low speed red-sensitive emulsion layer)

Em-D	Silver 0.577
		Em-C	Silver 0.347
ExC-1	0.188
		ExC-2	0.011
ExC-3	0.075
		ExC-4	0.121

ExC-5	0.010
		ExC-6	0.007
Cpd-2	0.025
		Cpd-4	0.025
Cpd-7	0.050
		Cpd-8	0.050
HBS-1	0.114
		HBS-5	0.038
Gelatin	1.474

4th layer (middling speed red-sensitive emulsion layer)

Em-B	Silver 0.431
		Em-C	Silver 0.432
ExC-1	0.154
		ExC-2	0.068
ExC-3	0.018
		ExC-4	0.103
ExC-5	0.023
		ExC-6	0.010
Cpd-2	0.036
		Cpd-4	0.028
Cpd-7	0.010
		Cpd-8	0.010
HBS-1	0.129
		Gelatin	1.086

5th layer (high speed red-sensitive emulsion layer)

Em-A	Silver 1.108
		ExC-1	0.180
ExC-3	0.035
		ExC-6	0.029
Cpd-2	0.064
		Cpd-4	0.077
Cpd-7	0.040
		Cpd-8	0.040
HBS-1	0.329
		HBS-2	0.120
Gelatin	1.245

6th layer (intermediate layer)

Cpd-1	0.094
		Cpd-6	0.369
Solid disperse dye ExF-4	0.030
		HBS-1	0.049
Polyethyl acrylate latex	0.088
		Gelatin	0.886

7th layer (layer of effect layer being produced sense red beds)

Em-J	Silver 0.293
		Em-K	Silver 0.293
Cpd-4	0.030

ExM-2	0.120
		ExM-3	0.016
ExY-1	0.016
		ExY-6	0.036
Cpd-6	0.011
		HBS-1	0.090
HBS-3	0.003
		HBS-5	0.030
Gelatin	0.610

8th layer (low speed green-sensitive emulsion layer)

Em-H	Silver 0.329
		Em-G	Silver 0.333
Em-I	Silver 0.088
		ExM-2	0.378
ExM-3	0.047
		ExY-1	0.017
HBS-1	0.098
		HBS-3	0.010
HBS-4	0.077
		HBS-5	0.548
Cpd-5	0.010
		Gelatin	1.470

9th layer (middling speed green-sensitive emulsion layer)

Em-F	Silver 0.457

ExM-2	0.032
		ExM-3	0.029
ExM-4	0.029
		ExY-1	0.007
ExC-6	0.010
		HBS-1	0.065
HBS-3	0.002
		HBS-5	0.020
Cpd-5	0.004
		Gelatin	0.446

10th layer (high speed green-sensitive emulsion layer)

Em-E	Silver 0.794
		ExC-6	0.002
ExM-1	0.013
		ExM-2	0.011
ExM-3	0.030
		ExM-4	0.017
ExY-5	0.003
		Cpd-3	0.004
Cpd-4	0.007
		Cpd-5	0.010
HBS-1	0.148
		HBS-5	0.037
Polyethyl acrylate latex	0.099
		Gelatin	0.939

11th layer (Yellow filter layer)

Cpd-1	0.094
		Solid disperse dye ExF-2	0.150
Solid disperse dye ExF-5	0.010
		Oil-soluble dyes ExF-7	0.010
HBS-1	0.049
		Gelatin	0.630

12nd layer (low speed blue-sensitive emulsion layer)

Em-O	Silver 0.112
		Em-M	Silver 0.320
Em-N	Silver 0.240
		ExC-1	0.027
ExY-1	0.027
		ExY-2	0.890
ExY-6	0.120
		Cpd-2	0.100
Cpd-3	0.004
		HBS-1	0.222
HBS-5	0.074
		Gelatin	2.058

13rd layer (high speed blue-sensitive emulsion layer)

Em-L	Silver 0.714
		ExY-2	0.211

Cpd-2	0.075
		Cpd-3	0.001
HBS-1	0.071
		Gelatin	0.678

14th layer (the first protective layer)

0.07 μm of iodine silver bromide emulsion	Silver 0.301
		UV—1	0.211
UV—2	0.132
		UV—3	0.198
UV—4	0.026
		F—18	0.009
S—1	0.086
		HBS—1	0.175
HBS—4	0.050
		Gelatin	1.984

15th layer (the second protective layer)

H—1	0.400
		B -1 (1.7 μm of diameter)	0.050
B -2 (1.7 μm of diameter)	0.150
		B—3	0.050
S—1	0.200
		Gelatin	0.750

In addition to the above components, to improve storage stability, handlability, resistance to pressure, antibiotic property and mildew resistance, antistatic behaviour and coating property, single layer can include W -1 to W -6, B -4 to B -6, F -1 to F -17, lead salt, palladium salt, iridium salt and ruthenium salt.The preparation of the dispersion of organic solid disperse dyes

Disperse ExF-2 in 11th layer according to following methods.Specifically：

ExF-2 wet cake (water for including 17.6wt%)	2.800kg
		Octyl phenyl diethoxymethane sodium sulfonate (the 31wt% aqueous solution)	0.376kg
F -15 (7% aqueous solution)	0.011kg
		Water	4.020kg
Amount to	7.210kg

(being 7.2 with sodium hydroxide regulation pH)

The slurries of above-mentioned composition are stirred with dissolvers (dissolver), it is pre-dispersed to carry out, then further disperseed with agitator mill LMK -4, its condition is：Circumferential speed, delivery rate and the packing ratio of a diameter of 0.3 μm of zirconium oxide bead are 10m/s, 0.6kg/min and 80% respectively, until the absorptivity of dispersion is 0.29.Thus solid particulate dispersion is obtained, the wherein average grain diameter of dye granule is 0.29 μm.

ExF-4 and ExF-9 solid dispersions are obtained in the same fashion.The particle diameter of these dye granules is 0.28 μm and 0.49 μm respectively.Microdeposit dispersion method described in embodiment 1 with EP 549,489A disperses ExF-5.Its average grain diameter is 0.06 μm.

Compound used therefor is as follows in layers.

B-1

X/y=10/90 (Weight ratio) Average mol.wt.：about 35,000B-2

X/y=40/60 (Weight ratio) Average mol.wt.：about 20,000B-3

HBS-1 Tricresyl phosphateHBS-2 Di-n-butyl phthalateHBS-3

H8S-4 Tri(2-ethylhexyl)phosphate

W-1  C₈F₁₇SO₂NHCH₂CH₂CH₂OCH₂CH₂N(CH₃)₃

W-2   N=2~4

B-4    Average mol.wt.：about 750,000B-5                          Average mol.wt.：about 17,000B-6   Average mol.wt.：about 10,000

So obtained colour negative photosensitive material is referred to as sample 001.Prepare sample 002 (present invention)

Sample 002 is prepared according to the identical method of sample 001, but has following change.Emulsion Em-A '

Em-A ' is prepared according to emulsion Em-A identicals method, but the silver nitrate and KBr addition during nucleation are 0.7 times when preparing emulsion Em-A, all spectral sensitizing dyes added before chemical sensitization are all 0.9 times when preparing emulsion Em-A, N during chemical sensitization, the addition of N-dimethyl selenourea is 0, and the addition of other compounds is also changed, to obtain optimum chemical sensibilization.The aspect ratio of so obtained emulsion is 15.Emulsion Em-E '

Em-E ' is prepared according to emulsion Em-E identicals method, but the silver nitrate and KBr addition during nucleation are 0.7 times when preparing emulsion Em-E, all spectral sensitizing dyes added before chemical sensitization are all 0.9 times when preparing emulsion Em-E, N during chemical sensitization, the addition of N-dimethyl selenourea is 0, and the addition of other compounds is also changed, to obtain optimum chemical sensibilization.The aspect ratio of so obtained emulsion is 15.Emulsion Em-L '

Em-L ' is prepared according to emulsion Em-L identicals method, but the nitrate and KBr addition during nucleation are 0.7 times when preparing emulsion Em-L, all spectral sensitizing dyes added before chemical sensitization are all 0.9 times when preparing emulsion Em-L, N during chemical sensitization, the addition of N-dimethyl selenourea is 0, and the addition of other compounds is also changed, to obtain optimum chemical sensibilization.

Sample 002 is prepared according to the identical method of sample 001, but replaces emulsion Em-A, Em-E and Em-L with emulsion Em-A ', Em-E ' and Em-L ' respectively.Prepare sample 101 (comparative example)

Sample 101 is prepared according to the identical method of sample 001, but iodine silver bromide emulsion (non-sheet-like particles of the Em-A in JP-A-63-226650 embodiment part included in the 5th layer (the 3rd red-sensitive emulsion layer) of sample 001, its particle diameter is 2.0 μm, average silver iodide content is 10mol%) replace, and iodine silver bromide emulsion (non-sheet-like particles of the Em-E in JP-A-63-226650 embodiment part included in the 9th layer (the 3rd green-sensitive emulsion layer) of sample 001, its particle diameter is 2.0 μm, average silver iodide content is 10mol%) replace.Prepare sample 102 (comparative example), 103 (comparative examples) and 104 (comparative examples)

Sample 102 (comparative example) is prepared according to the identical method of sample 001, but the silver content of each of which layer is changed as shown in table 4.Sample 103 (comparative example) is prepared according to the identical method of sample 002, but the silver content of each of which layer is changed as shown in table 4.Sample 104 (comparative example) is prepared according to the identical method of sample 101, but the silver content of each of which layer is changed as shown in table 4.

Table 4

Explanation	The present invention	The present invention	Contrast	Contrast	Contrast	Contrast
							Sample	001	002	101	102	103	104
Silver-colored coating amount (the g/m of high speed blue-sensitive emulsion layer2)	0.71	0.71	0.71	0.80	1.03	1.31
							Silver-colored coating amount (the g/m of high speed green-sensitive emulsion layer (aspect ratio)2)	Em-E(14)0.79	Em-E′ (15) 0.79	Non- sheet 0.79	Em-E(14) 0.81	Em-E′(15) 1.29	Non- sheet 1.44
High speed red-sensitive emulsion layer (aspect ratio) silver coating amount (g/m2)	Em-A(14)1.11	Em-A′ (15) 1.11	Non- sheet 1.11	Em-A(14) 1.73	Em-A′(15) 1.89	Non- sheet 1.73
							Total silver amount (g/m in high-speed emulsion layer2)	2.61	2.61	2.61	3.34	4.21	4.48
Total silver amount (g/m in photosensitive material3)	7.36	7.36	7.36	8.09	8.96	9.23

Above-mentioned sample 001-002 and 101-104 is placed 2 weeks under conditions of 30 ± 1 DEG C, 60 ± 5% relative humidity, reacts gelatin hardener, is then stored under different conditions in two kinds shown in table 5 below.

Table 5：Condition of storage A：B is rinsed immediately：Stored 1 year in Fuji Photo Film Co., Ltd. Ashigara Laborato, MinamiAshigara City, Kanagawa Prefecture natural environment before flushing.

Condition of storage B is represented to store 1 year under natural environment, and the irradiation dose in laboratory is about 40mR/, and it is determined with TLD (thermoluminescence detector).

Gelatin filter SC -39 and continuous wedge that the sample stored under different condition as shown in table 5 is manufactured by Fuji Photo Film Co., Ltd.s expose 1/100 second.

Development is proceeded as described below using the Fuji Photo Film FP -360B automatic film developers manufactured.The developing machine is reconfigured so that the overflow solution of bleaching bath will not be carried into next bath, but all these are all emitted into waste liquid tank.FP -360B is equipped with the evaporation means for correcting described in JIII (JapanInstitute of Invention and Innovation) Journal of Technical Disclosure No.94-4992.

Rinsing step and flushing liquor composition explained below.Purging method

Step	Time	Temperature	Magnitude of recruitment*	Tank volume
					Colour development	3 points 5 seconds	37.8℃	20ml	11.5L
Bleaching	50 seconds	38.0℃	5ml	5L
					Fixing (1)	50 seconds	38.0℃	-	5L
Fixing (2)	50 seconds	38.0℃	8ml	5L
					Washing	30 seconds	38.0℃	17ml	3L
Stable (1)	20 seconds	38.0℃	-	3L
					Stable (2)	20 seconds	38.0℃	15ml	3L
Dry	1 point 30 seconds	60℃

^*Magnitude of recruitment is represented with the value of the wide samples of 1.1m 35mm (equivalent to the effect of 24 Ex. films).

Stabilizer and fixing solution are according to the order convection current of (2) to (1), and all washings overflows are all introduced into fixing bath (2).It is noted that the amount for carrying the bleaching liquid and the fixer carried into washing step of the developer into blanching step, carrying into fix steps is 2.5ml, 2.0ml and 2.0ml respectively for the 1.1m wide photosensitive materials of 35mm.

Open area for color developer and the above-mentioned developing machine of bleaching liquid is 100cm respectively²And 120cm², and the open area for being used for other solution is about 100cm²。

The composition of flushing liquor is as follows.Color developer

Composition	Tank solution (g)	Replenisher (g)
			Diethylene triamine pentacetic acid (DTPA)	3.0	3.0
Catechol-3,5-disulfonate	0.3	0.3
			Sodium sulfite	3.9	5.3
Potassium carbonate	39.0	39.0
			Disodium-N, N-bis- (2-sulfonic group ethyl) azanol	1.5	2.0
KBr	1.3	0.3
			KI	1.3mg	-
4-hydroxyl-6-methyl-1,3,3a, 7-purine	0.05	-
			HAS	2.4	3.3
2-methyl-4-[N-ethyl-N-(β-hydroxyethyl) amino]-aniline sulfate	4.5	6.5

Add and add water to	1.0L
			PH (is adjusted) with potassium hydroxide and sulfuric acid	10.05	10.18

Bleaching liquid

Composition	Tank solution (g)	Replenisher (g)
			EDTA-Fe (III) ammonium dihydrate	113	170
Ammonium bromide	70	105
			Ammonium nitrate	14	21
Butanedioic acid	34	51
			Maleic acid	28	42
Add and add water to	1.0L
			PH (is adjusted) with ammoniacal liquor	4.6	4.0

The 5 of the above-mentioned bleaching tank solution of fixer (1) tank solution and following fixing tank solution：95 (V/V) mixtures, pH is 6.8. fixer (2)

Composition	Tank solution (g)	Replenisher (g)
			Thiosulfuric acid aqueous ammonium (750g/L)	240ml	720ml
Imidazoles	7	21
			First thiosulfonic acid ammonium	5	15
The thio sulfinic acid ammonium of first	10	30
			Ethylenediamine tetra-acetic acid	13	39
Add and add water to	1.0L

PH (is adjusted) with ammoniacal liquor and acetic acid

7.4

7.45

Washings

Running water is delivered in mixed bed column, the post is filled with H types strong-acid cation-exchange resin (Amberlite IR-120B：Can be obtained from Rohm ＆ Haas Co.) and OH type alkali anion exchange resin (Amberlite IR-400), the concentration of calcium and magnesium is set as 3mg/l or lower.Then, addition 20mg/l isocyanuric acid dichloride sodium 0.15g/l sodium sulphate.The pH scopes of solution are 6.5-7.5.Stabilizer

Composition	Tank solution is identical (g) with replenisher
		SPTS	0.03
Polyoxyethylene p-mono- nonylplenyl ether (average degree of polymerization 10)	0.2
		1,2-benzisothiazole-3-ketone sodium	0.10
Disodium ethylene diamine tetraacetate	0.05
		1,2,4-triazole	1.3
Isosorbide-5-Nitrae-bis- (1,2,4-triazole-1-ylmethyl) piperazine	0.75
		Add and add water to	1.0L
PH	8.5

Measurement carries out sensitivity, ashing and the graininess of each sample of above-mentioned processing.Conventional RMS (root mean-square value) method measurement of graininess.

The measurement result of sensitivity, ashing and graininess is shown in Table 6.RMS value is, and measuring when by light exposure being 0.0005lux second obtains.

Table 6

Explanation		The present invention	The present invention	Contrast	Contrast	Contrast	Contrast
								Sample		001	002	101	102	103	104
Silver-colored coating amount (the g/m of high speed blue-sensitive emulsion layer2)		0.71	0.71	0.71	0.80	1.03	1.31
								Silver-colored coating amount (the g/m of high speed green-sensitive emulsion layer (aspect ratio)2)		Em-E    (14)    0.79	Em-E′    (15)    0.79	Non- sheet 0.79	Em-E    (14)    0.81	Em-E′      (15)    1.29	non-    tabular    1.44
High speed red-sensitive emulsion layer (aspect ratio) silver overlay (g/m2)		Em-A    (14)    1.11	Em-A′      (15)    1.11	non-    tabular    1.11	Em-A    (14)    1.73	Em-A′    (15)    1.89	non-    tabular    1.73
								Total silver amount (g/m in high-speed emulsion layer2)		2.61	2.61	2.61	3.34	4.21	4.48
Total silver amount (g/m in photosensitive material2)		7.36	7.36	7.36	8.09	8.96	9.23
								Sensitivity		800	798	796	800	799	781
Sensitivity after storage		782	775	771	620	574	563
								The forward and backward ashing value difference of storage is different (Δ fog)	B	0.03	0.03	0.03	0.04	0.05	0.07
G	0.02	0.02	0.04	0.02	0.05	0.08
							R		0.01	0.02	0.04	0.04	0.06	0.07
RMS	B	0.052	0.051	0.052	0.051	0.049									0.048
							G	0.036	0.035	0.043	0.036	0.034	0.041
	R	0.028	0.028	0.038	0.026	0.026								0.035
							RMS after storage	B	0.055	0.057	0.057	0.056	0.060		0.063
G	0.039	0.041	0.050	0.039	0.048	0.058
								R	0.034	0.036	0.049	0.044	0.050	0.055

From table 6 this it appears that, compared with the sample 102 and 103 with high silver content in high-speed layer, the sample 001 and 002 of the present invention has low silver content in high-speed layer, and the emulsion with high aspect ratio is used in two high-speed layers, they show excellent performance after being stored 1 year under natural environment, wherein sensitivity declines and ashing increases RMS after all small and only small storage.It is also apparent that, sample of the invention has used the sheet-like particle with high aspect ratio in high-speed layer, compared with using the comparative sample 101 of non-sheet-like particle in high-speed layer, shows more preferable graininess.Comparative sample 104 has used the non-sheet-like particle being commonly used in the prior art, and has high silver-colored coating amount in high-speed layer, and it shows big ashing increase after storage, and with RMS after big storage.On the contrary, the advantage that inventive samples 001 and 002 are reached is very big, this is highly useful.

The color compensation chart manufactured by Macbeth Co. is taken a picture with sample, is then printed upon with developed sample on commercially available colour paper.As a result, the sample of the present invention has substantially excellent color saturation compared with each sample for contrast.Embodiment 2 prepares sample 221 (comparative example)

Sample 221 is prepared by sample 001 by following change.

Sample 221 is prepared according to the identical mode of sample 001, but the Em-A and Em-E used in sample 001 is replaced with Em-A2 and Em-E2 respectively.Em-A2 and Em-E2 preparation method is as described below.Prepare Em-A2

Em-A2 is prepared according to Em-A identicals method, but the gelatin added during particle formation after the completion of 75 DEG C of maturations is from " succinated gelatin 35g " is changed into " the gelatin 35g " of lime treatment, the addition of all spectral sensitizing dyes added before chemical sensitization is changed into 0.7 times in Em-A, and they are the optimised quantities for producing sensitivity；And the addition of other compounds suitably changes, to reach optimum chemical sensitizing.Therefore, Em-A2 is prepared according to Em-A identicals method, but has above-mentioned difference.Em-A particle volume is identical with Em-A's, but Em-A2 aspect ratio is 7.3.Prepare Em-E2

Em-E2 is prepared according to Em-E identicals method, but the gelatin added during particle formation after the completion of 75 DEG C of maturations is from " succinated gelatin 15g and trimellitic acid gelatin and 20g " are changed into " the gelatin 35g " of lime treatment, the addition of all spectral sensitizing dyes added before chemical sensitization is changed into 0.7 times in Em-E, and they are the optimised quantities for producing sensitivity；And the addition of other compounds suitably changes, to reach optimum chemical sensitizing.Therefore, Em-E2 is prepared according to Em-E identicals method, but has above-mentioned difference.Em-E2 particle volume is identical with Em-E's, but Em-E2 aspect ratio is 7.3.Prepare sample 202,203,222 and 223

Change the silver-colored coating amount of the 6th layer (high speed red-sensitive emulsion layer) and 11th layer (high speed green-sensitive emulsion layer) in sample 001 or 221 as shown in table 7, thus prepare sample 202,203,222 and 223.Carry out assessment same as Example 1.It the results are shown in Table shown in 7.

Table 7

Explanation		The present invention	Contrast	The present invention	Contrast	Contrast	Contrast
								Sample		001	221	202	222	203	223
Silver-colored coating amount (the g/m of high speed blue-sensitive emulsion layer2)		0.71	0.71	0.90	0.90	1.10	1.10
								Silver-colored coating amount (the g/m of high speed green-sensitive emulsion layer (aspect ratio)2)		Em-E    (14)    0.79	Em-E2    (7.3)    0.79	Em-E    (14)    1.00	Em-E2    (7.3)    1.00	Em-E    (14)    1.40	Em-E2    (7.3)    1.40
High speed red-sensitive emulsion layer (aspect ratio) silver overlay (g/m2)		Em-A    (14)    1.11	Em-A2    (7.3)    1.11	Em-A    (14)    1.30	Em-A2    (7.3)    1.30	Em-A    (14)    1.75	Em-A2    (7.3)    1.75
								Total silver amount (g/m in high-speed emulsion layer2)		2.61	2.61	3.20	3.20	4.25	4.25
Total silver amount (g/m in photosensitive material2)		7.36	7.36	7.95	7.95	9.00	9.00
								Sensitivity		800	635	857	713	828	764
Sensitivity after storage		782	621	814	670	729	672
								The forward and backward ashing value difference of storage is different (Δ fog)	B	0.03	0.03	0.04	0.04	0.05	0.05
G	0.02	0.02	0.03	0.04	0.05	0.06
							R		0.01	0.01	0.02	0.03	0.04	0.05
RMS	B	0.052	0.052	0.050	0.050	0.049									0.049
							G	0.036	0.038	0.034	0.037	0.034	0.037
	R	0.028	0.030	0.026	0.028	0.026								0.028
							RMS after storage	B	0.055	0.055	0.057	0.057	0.060		0.060
G	0.039	0.041	0.040	0.044	0.047	0.050
								R	0.034	0.036	0.038	0.041	0.044	0.046

As can be seen from Table 7, the sample 001 and 202 of the present invention uses emulsion Em-A and Em-E with high aspect ratio, the silver amount that these emulsions are included within the scope of the invention, very excellent result is shown in terms of their sensitivity and Δ ashing after sensitivity, RMS, storage.

Contrasted with above-mentioned sample, sample 221 and 222 shows sensitivity and poor RMS after low sensitivity, low storage using aspect ratio relatively low emulsion Em-A2 and Em-E2, these samples.

The sample 223 of the emulsion of silver coating using low aspect ratio and comprising incrementss, wherein silver-colored coating amount is not within the scope of the present invention, it shows the sensitivity closer to inventive samples, but, sensitivity after particularly storing is still low, and the ashing increase after storage is larger, and graininess is significantly deteriorated after storage.

The silver-colored coating amount of sample 203 is not within the scope of the present invention, it still shows sensitivity after relatively low storage, and increase is ashed after big storage --- Δ is ashed, and the graininess after storage is significantly deteriorated, even if therefore sample 203 has used the emulsion of wide aspect ratio, its sample still than the present invention is poor.

In sample 001 and 202, sample 001 is than sample 202 more preferably, the silver-colored coating amount in the former each high-speed layer is 1.2g/m²Or it is lower, and total silver coating amount in high-speed layer is 2.61g/m², and total silver coating amount of the latter in high-speed layer is 3.20g/m², because sensitivity change is smaller after the storage of sample 001, increase is ashed after storage --- Δ ashing is smaller, and the RMS deteriorations after storage are smaller, and RMS is also smaller after storage.Embodiment 3 prepares sample 441 (present invention)

The following preparation method for changing sample 001, is thus made sample 441.

That is, being replaced respectively with Em-A5 and Em-E5 according to the Em-A used in sample 441, but sample 001 and Em-E is prepared with the identical method of sample 001.The preparation method is as described below.Prepare Em-A5

Em-A5 is prepared according to Em-A identicals method, but the addition of N, N-dimethyl selenourea is changed into every mol silver 0.800 × 10^-6Mol, the addition of other compounds suitably changes, to reach optimum chemical sensitizing.

In this regard, if the addition of N, N-dimethyl selenourea is changed into every mo1 silver 6.0 × 10^-6Mol, and suitably change the addition of other compounds, then only reach high ashing or low contrast.Prepare Em-E5

Em-E5 is prepared according to Em-E identicals method, but the addition of N, N-dimethyl selenourea is changed into every mol silver 0.80 × 10^-6Mol, the addition of other compounds suitably changes, to reach optimum chemical sensitizing.

In this regard, if the addition of N, N-dimethyl selenourea is changed into every mol silver 6.0 × 10^-6Mol, and suitably change the addition of other compounds, then only reach high ashing or low contrast.Prepare sample 202,203,442 and 443

Change the silver-colored coating amount of the 6th layer (high speed red-sensitive emulsion layer) and 11th layer (high speed green-sensitive emulsion layer) in sample 001 or 441 as shown in table 8, thus prepare sample 202,203,442 and 443.Carry out assessment same as Example 1.It the results are shown in Table shown in 8.

Table 8

Explanation		The present invention	The present invention	The present invention	The present invention	Contrast	Contrast
								Sample		001	441	202	442	203	443
Silver-colored coating amount (the g/m of high speed blue-sensitive emulsion layer2)		0.71	0.71	0.90	0.90	1.10	1.10
								High speed green-sensitive emulsion layer Se sensitizers/silver (× 10-6) silver-colored coating amount (g/m2)		Em-E    3.4    0.79	Em-E5    0.8    0.79	Em-E    3.4    1.00	Em-E5    0.8    1.00	Em-E    3.4    1.40	Em-E5    0.8    1.40
High speed red-sensitive emulsion layer se sensitizers/silver 1 × 10-6) silver-colored coating amount (g/m2)		Em-A    3.4    1.11	Em-A4    0.8    1.11	Em-A    3.4    1.30	Em-A4    0.8    1.30	Em-A    3.4    1.75	Em-A4    0.8    1.75
								Total silver amount (g/m in high-speed emulsion layer2)		2.61	2.61	3.20	3.20	4.25	4.25
Total silver amount (g/m in photosensitive material2)		7.36	7.36	7.95	7.95	9.00	9.00
								Sensitivity		800	713	857	764	828	800
Sensitivity after storage		782	703	814	740	729	696
								The forward and backward ashing value difference of storage is different (Δ fog)	B	0.03	0.03	0.04	0.04	0.05	0.05
G	0.02	0.015	0.03	0.025	0.05	0.04
							R		0.01	0.01	0.02	0.015	0.04	0.03
RMS	B	0.052	0.052	0.050	0.050	0.049									0.049
							G	0.036	0.035	0.034	0.034	0.034	0.034
	R	0.028	0.027	0.026	0.026	0.026								0.026
							RMS after storage	B	0.055	0.055	0.057	0.057	0.060		0.060
G	0.039	0.037	0.040	0.039	0.047	0.045
								R	0.034	0.033	0.038	0.037	0.044	0.043

As can be seen from Table 7, sample 001 and 202 of the invention is included by the emulsion Em-A and Em-E of selenium sensitizing so that the quantitative change of selenium sensitizer is 3.4 × 10^-6Mol/mol silver, and silver amount is within the scope of the invention, and very excellent result is shown in terms of their sensitivity and Δ ashing after sensitivity, RMS, storage.

On the contrary, sample 441 and 442 is included by the emulsion Em-A2 and Em-E2 of selenium sensitizing, the wherein amount of sensitizer is 0.8 × 10^-6Mol/mol silver, although sensitivity is very low, but these samples realize advantages of the present invention, not showing sensitivity after big storage is reduced, and increase is ashed after preferably small storage --- and Δ is ashed, and the RMS after RMS and storage is small.The use of by selenium sensitizing to selenium sensitizer is 3.4 × 10 from the point of view of more ISO^-6The sample of the emulsion of mol/mol silver shows the result being more highly preferred to.

Sample 443 has used selenium sensitizing emulsion, and wherein selenium sensitizer is changed into 0.8 × 10^-6Mol/mol silver, but the coating amount of silver increased to beyond the scope of the invention, it shows sensitivity after especially low storage, and increase is ashed after big storage --- Δ is ashed, and graininess significantly deteriorates after storage, although sensitivity of its sensitivity close to the present invention.Embodiment 4 prepares sample 551 (present invention)

The following preparation method for changing sample 001, thus prepares sample 551.

That is, addition is bleach boosters release compound when the 3rd layer, the 4th layer or the 5th layer of compound Cpd -7 and Cpd -8 of sample 001 are being reacted with oxidation state aromatic primary amine type color developer.Prepare sample 551 according to the identical method of sample 001, but all compound Cpd -7 and Cpd -8 all by with similar color but do not discharge bleach boosters etc. weight compound replace.Prepare sample 202,203,552 and 553

Sample 202 and 203 and sample 552 and 553 are prepared according to the identical method of sample 001 and 551 respectively, but changes the silver-colored coating amount of the 6th layer (high speed red-sensitive emulsion layer) and 11th layer (high speed green-sensitive emulsion layer) as shown in table 9.Carry out assessment same as Example 2.It the results are shown in Table shown in 9.

Table 9

Explanation		The present invention	The present invention	The present invention	The present invention	Contrast	Contrast
								Sample		001	551	202	552	203	553
Silver-colored coating amount (the g/m of high speed blue-sensitive emulsion layer2)		0.71	0.71	0.90	0.90	1.10	1.10
								Silver-colored coating amount (the g/m of high speed green-sensitive emulsion layer2)		Em-E    0.79	Em-E    0.79	Em-E    1.00	Em-E    1.00	Em-E    1.40	Em-E    1.40
High speed red-sensitive emulsion layer silver coating amount (g/m2)		Em-A    1.11	Em-A    1.11	Em-A    1.30	Em-A    1.30	Em-A    1.75	Em-A    1.75
								Bleach boosters discharge compound		In the presence of	Nothing	In the presence of	Nothing	In the presence of	Nothing
Total silver amount (g/m in high-speed emulsion layer2)		2.61	2.61	3.20	3.20	4.25	4.25
								Total silver amount (g/m in photosensitive material2)		7.36	7.36	7.95	7.95	9.00	9.00
Sensitivity		800	800	857	857	828	828
								Sensitivity after storage		782	782	814	814	729	738
Ashing value difference before storage is different (Δ fog)	B	0.03	0.03	0.04	0.04	0.05	0.05
								G	0.02	0.02	0.03	0.03	0.05	0.05
	R	0.01	0.01	0.02	0.02	0.04	0.03
								RMS	B	0.052	0.052	0.050	0.050	0.049	0.049
G	0.036	0.036	0.034	0.034	0.034	0.034
							R		0.028	0.030	0.026	0.028	0.026	0.028
RMS after storage	B	0.055	0.055	0.057	0.057	0.060									0.060
							G	0.039	0.039	0.040	0.040	0.047	0.047
	R	0.034	0.034	0.038	0.038	0.044								0.042

The sample of the present invention comprising can discharge the compound of bleach boosters, and when silver amount within the scope of the invention, show very excellent result in terms of its sensitivity and Δ ashing after sensitivity, RMS, storage.

Contrasted with above-mentioned sample, sample 551 and 552, which does not include, can discharge the compound of bleach boosters, also achieve advantages of the present invention, show that sensitivity declines after little storage, increase is ashed after small storage --- Δ is ashed, RMS after small RMS and storage, but the RMS value of red-sensitive emulsion layer is still larger.Therefore, from the point of view of smaller sense red beds RMS value, the sample comprising the compound that can discharge bleach boosters is preferred.

Compared with the sample 553 increased to not comprising the compound that can discharge bleach boosters and silver-colored coating amount beyond the scope of the invention, sample 203, which is included, can discharge the compound of bleach boosters, and its silver-colored coating amount is increased to beyond the scope of the invention, it, which shows, is ashed increase after big storage --- and Δ is ashed, and graininess is deteriorated after storage.That is, in the system comprising the compound that can discharge bleach boosters, it is especially big by the advantage for reducing the coating amount in ISO layer and reaching.Embodiment 5 prepares sample 331 and 332 (present invention)

The preparation method as described below for changing sample 001, is thus made sample 331 and 332.

Sample 331 and 332 is prepared according to the identical method of sample 001, but Em-A wherein used and Em-E are replaced by emulsion Em-A3 and Em-A4 and emulsion Em-E3 and Em-E4 respectively.The preparation method of these emulsions is as described below.Prepare Em-A3 and Em-A4

Em-A3 is prepared according to Em-A identicals method, but without potassium ferrocyanide, and suitably change the addition of other compounds, to reach optimal chemical sensitization.As above change and prepare Em-A3 in the same manner.

Em-A4 is prepared according to Em-A identicals method, but uses [Ru (bpy)₃]Cl₂Instead of potassium ferrocyanide, the silver-colored potential during adding herein is adjusted, and suitably changes the addition of other compounds, to reach optimal chemical sensitization.Emulsion Em-A4 is prepared according to Em-A identical methods, but has above difference.The volume and aspect ratio of particle are identical with Em-A particle.Prepare Em-E3 and Em-E4

Em-E3 is prepared according to Em-E identicals method, but without potassium ferrocyanide, and suitably change the addition of other compounds, to reach optimal chemical sensitization.As above change and prepare Em-E3 in the same manner.

Em-E4 is prepared according to Em-E identicals method, but uses [Ru (bpy)₃]Cl₂Instead of potassium ferrocyanide, the silver-colored potential during adding herein is adjusted, and suitably changes the addition of other compounds, to reach optimal chemical sensitization.Emulsion Em-E4 is prepared according to Em-E identical methods, but has above difference.The volume and aspect ratio of particle are identical with Em-E particle.Prepare sample 202,203,333,334,335 and 336

Sample 202 and 203, sample 333 and 334 and sample 335 and 336 are prepared according to sample 001,331 and 332 identical methods respectively, but changes the silver-colored coating amount of the 6th layer (high speed red-sensitive emulsion layer) and 11th layer (high speed green-sensitive emulsion layer) in sample 001,331 and 332 as shown in table 10.Carry out assessment same as Example 2.It the results are shown in Table shown in 10.

Table 10

Explanation		The present invention	The present invention	The present invention	The present invention	The present invention	The present invention	Contrast	Contrast	Contrast
											Sample		001	331	332	202	333	334	203	335	336
Silver-colored coating amount (the g/m of high speed blue-sensitive emulsion layer2)		0.71	0.71	0.71	0.90	0.90	0.90	1.10	1.10	1.10
											Silver-colored coating amount (the g/m in center is electronically activated in high speed green-sensitive emulsion layer2)		Em-E potassium ferrocyanides 0.79	Em-E3 is without 0.79	Em-E4    *1    0.79	Em-E potassium ferrocyanides 1.00	Em-E3 is without 1.00	Em-E4 *1 1.00	Em-E potassium ferrocyanides 1.40	Em-E3 is without 1.40	Em-E4    *1    1.40
Silver-colored coating amount (the g/m in center is electronically activated in high speed red-sensitive emulsion layer2)		Em-A potassium ferrocyanides 1.11	Em-A3 is without 1.11	Em-A4    *1    1.11	Em-A potassium ferrocyanides 1.30	Em-A3 is without 1.30	Em-A4 *1 1.30	Em-A potassium ferrocyanides 1.75	Em-A3 is without 1.75	Em-A4    *1    1.75
											Total silver amount (g/m in high-speed emulsion layer2)		2.61	2.61	2.6	3.20	3.20	3.20	4.25	4.25	4.25
Total silver amount (g/m in photosensitive material2)		7.36	7.36	7.36	7.95	7.95	7.95	9.00	9.00	9.00
											Sensitivity		800	755	781	857	809	836	828	781	808
Sensitivity after storage		782	742	766	814	780	802	729	695	711
											Ashing value difference before storage is different (Δ fog)	B	0.03	0.03	0.03	0.04	0.04	0.04	0.05	0.05	0.05
G	0.02	0.02	0.02	0.03	0.025	0.03	0.05	0.04	0.05
										R		0.01	0.01	0.01	0.02	0.02	0.02	0.04	0.03	0.04
RMS	B	0.052	0.052	0.052	0.050	0.050	0.050	0.049	0.049												0.049
										G	0.036	0.037	0.037	0.034	0.035	0.034	0.034	0.035	0.034
	R	0.028	0.029	0.028	0.026	0.027	0.026	0.026	0.027											0.026
										RMS after storage	B	0.055	0.055	0.055	0.057	0.057	0.057	0.060	0.060		0.060
G	0.039	0.039	0.039	0.040	0.039	0.040	0.047	0.048	0.047
											R	0.034	0.034	0.034	0.038	0.034	0.037	0.044	0.045	0.044

*1…[Ru(bpy)₃]Cl₂

The sample 001 and 202 of the present invention uses the emulsion Em-A and Em-E of high aspect ratio, with electronics trapping region, potassium ferrocyanide is wherein used as electronics trap center, and silver amount is within the scope of the invention, it shows to be ashed increase after high sensitivity, high storage after sensitivity, small storage --- and Δ is ashed, and RMS value is all small after RMS and storage.

Sample 331 and 333 has been used without electronics trapping region --- the Em-A3 and Em-E3 of potassium ferrocyanide, realize advantages of the present invention, sensitivity after preferably little storage is shown to decline, increase is ashed after small storage --- Δ is ashed, and the RMS after RMS and storage is small, but sensitivity is smaller.Using with electronics trapping region --- the sample 335 that the emulsion of potassium ferrocyanide and its silver-colored coating amount are increased to beyond the scope of the invention, show sensitivity after substantially low storage, increase is ashed after big storage --- Δ is ashed, and RMS is significantly deteriorated after storage, although its sensitivity is close to sample 001.

Sample 332 and 334 within the scope of the invention, using the emulsion with electronics trapping region, wherein with [Ru (bpy)₃]Cl₂Potassium ferrocyanide is substituted, it is preferred, shows the result close to sample 001 and 202.But, the silver-colored coating amount of sample 336 is increased to beyond the scope of the invention, and it shows sensitivity after especially low storage less than the sample of the present invention, and increase is ashed after big storage --- and Δ is ashed, and RMS is significantly deteriorated after storage, as sample 203.Embodiment 6

Illustrate the excellent results of advantage of the present invention using the above-mentioned sample of the present invention with the form of the product built with photographic material below, in the product equipped with exposure mechanism.

That is, by the present invention sample treatment into the 35mm cassettes for 24 exposed plates product, then by the sample mounted in Fuji Photo Film Co., Ltd.s manufacture " in 800 27-SHOT " of UTSURUNDESU SUPER (its trade name QuickSnap Super Flash 27) in the U.S..By the sample treatment of the present invention into after the product for the APS magazines of 25 exposed plates, by the sample in " SHOT of UTSURUNDESUSUPER STAR 25 " of Fuji Photo Film Co., Ltd.s.

The storage experimental result of above-mentioned form sample is, compared with comparative sample, and sample of the invention shows the excellent results as above-described embodiment.

The sample and comparative sample of the present invention is after the product of above-mentioned form is processed into, mounted in " in 800 27-SHOT " of UTSURUNDESU SUPER, then making to pass through in baggage check of the sample using X-ray in Narita airports, to be contrasted.Compared with comparative sample, sample of the invention shows very excellent result.

The reason for inventive samples have especially excellent result is that the sample receives stronger X-ray influence than the conventionally form that sample is mounted in metal film cassette, because " film cassette of UTSURUNDESUSUPER 800 27-SHOT " forms is made up of synthetic resin.

As described above, the photographic material of the present invention is showing especially excellent result built with photographic material and in the image products provided with exposure mechanism.

Other advantages and improvements are easy for those skilled in the art.Therefore, the present invention is not limited to details and representative embodiment as implied above in its broader scope.So, without departing from the spirit and scope of the present invention, various improvement and change can be also carried out, and the scope of the present invention should be limited by appended claims and its equivalent.

Claims (20)

1st, a kind of silver-halide color negative photographic photosensitive material, wherein comprising at least one layer of red sensing coppering silver emulsion layer on carrier, at least one layer of green silver halide emulsion layer and the blue silver halide emulsion layer of at least one layer of sense,

Wherein photosensitive material ISO speed is 640 or higher；

The total silver content of the photosensitive material is 3.0 to 3.9g/m²；

Each red-sensitive emulsion layer, green-sensitive emulsion layer, blue-sensitive emulsion layer are comprising two layers or more layers are sensitive to same color but the different silver emulsion subgrade of speed each other；

The magenta-sensitive emulsion subgrade of prestissimo, the green-sensitive emulsion subgrade of prestissimo, the silver content of the blue-sensitive emulsion subgrade of prestissimo are respectively 0.3 to 1.3g/m²；

At least two layers in the magenta-sensitive emulsion subgrade with top high photographic sensitivity, the green-sensitive emulsion subgrade with top high photographic sensitivity and the blue-sensitive emulsion subgrade with top high photographic sensitivity, sheet silver halide particle accounts for 50% or more of all silver halide particle projected areas of whole subgrade in the silver halide particle that they are included；

And the average aspect ratio of sheet-like particle is 8 or bigger.

2nd, photosensitive material as claimed in claim 1, wherein, the green-sensitive emulsion subgrade of magenta-sensitive emulsion subgrade, prestissimo with prestissimo, the silver content of the blue-sensitive emulsion subgrade of prestissimo are respectively 0.3 to 1.2g/m²。

3rd, photosensitive material as claimed in claim 1, wherein, in terms of every mol silver, wherein sheet-like particle accounts in the emulsion subgrade of total projection area 50% or more at least one layer and contains 2 × 10^-6To 5 × 10^-6Mol selenium sensitizers.

4th, a kind of silver-halide color negative film photosensitive material, it includes at least one layer of red sensing coppering silver emulsion layer, at least one layer of green silver halide emulsion layer and the blue silver halide emulsion layer of at least one layer of sense on carrier,

Wherein the ISO speed of photosensitive material is 640 or higher；

The total silver content of the photosensitive material is 3.0 to 9.0g/m²；

Each red-sensitive emulsion layer, green-sensitive emulsion layer, blue-sensitive emulsion layer are comprising two layers or more layers are sensitive to same color but the different silver emulsion subgrade of speed each other；

Magenta-sensitive emulsion subgrade with prestissimo, the green-sensitive emulsion subgrade with prestissimo, total silver content of blue-sensitive emulsion subgrade with prestissimo are 1.5-3.5g/m²

At least two layers in the magenta-sensitive emulsion subgrade with top high photographic sensitivity, the green-sensitive emulsion subgrade with top high photographic sensitivity and the blue-sensitive emulsion subgrade with top high photographic sensitivity, sheet silver halide particle accounts for 50% or more of all silver halide particle projected areas of whole subgrade in the silver halide particle that they are included；And

The average aspect ratio of sheet-like particle is 8 or bigger.

5th, photosensitive material as claimed in claim 4, wherein, the magenta-sensitive emulsion subgrade with prestissimo, the green-sensitive emulsion subgrade with prestissimo, total silver content of blue-sensitive emulsion subgrade with prestissimo are 1.5-3.0g/m²。

6th, photosensitive material as claimed in claim 4, wherein, in terms of every mol silver, wherein sheet-like particle accounts in the emulsion subgrade of total projection area 50% or more at least one layer and contains 2 × 10^-6—5×10^-6Mol selenium sensitizers.

7th, photosensitive material as claimed in claim 1, wherein, at least one layer of emulsion subgrade discharges the compound of bleach boosters comprising that can be reacted with oxidation state aromatic primary amine developer.

8th, photosensitive material as claimed in claim 3, wherein, at least one layer of emulsion subgrade discharges the compound of bleach boosters comprising that can be reacted with oxidation state aromatic primary amine developer.

9th, photosensitive material as claimed in claim 4, wherein, at least one layer of emulsion subgrade discharges the compound of bleach boosters comprising that can be reacted with oxidation state aromatic primary amine developer.

10th, photosensitive material as claimed in claim 6, wherein, at least one layer of emulsion subgrade can disengage the compound of bleaching accelerators comprising a kind of with the reaction of oxidation state aromatic primary amine developer.

11st, photosensitive material as claimed in claim 1 comprising at least two layers have top high photographic sensitivity emulsion subgrade in, containing aspect ratio for 8 or bigger sheet silver halide particle at least one emulsion include with electronics capture zone sheet-like particle.

12nd, photosensitive material as claimed in claim 3 comprising at least two layers have top high photographic sensitivity emulsion subgrade in, include aspect ratio for 8 or bigger sheet silver halide particle at least one emulsion include with electronics capture zone sheet-like particle.

13rd, photosensitive material as claimed in claim 4 comprising at least two layers have top high photographic sensitivity emulsion subgrade in, include aspect ratio for 8 or bigger sheet silver halide particle at least one emulsion include with electronics capture zone sheet-like particle.

14th, photosensitive material as claimed in claim 6 comprising at least two layers have top high photographic sensitivity emulsion subgrade in, include aspect ratio for 8 or bigger sheet silver halide particle at least one emulsion include with electronics capture zone sheet-like particle.

15th, photosensitive material as claimed in claim 7 comprising at least two layers have top high photographic sensitivity emulsion subgrade in, include aspect ratio for 8 or bigger sheet silver halide particle at least one emulsion include with electronics capture zone sheet-like particle.

16th, photosensitive material as claimed in claim 8 comprising at least two layers have top high photographic sensitivity emulsion subgrade in, include aspect ratio for 8 or bigger sheet silver halide particle at least one emulsion include with electronics capture zone sheet-like particle.

17th, photosensitive material as claimed in claim 9 comprising at least two layers have top high photographic sensitivity emulsion subgrade in, include aspect ratio for 8 or bigger sheet silver halide particle at least one emulsion include with electronics capture zone sheet-like particle.

18th, photosensitive material as claimed in claim 10 comprising at least two layers have top high photographic sensitivity emulsion subgrade in, include aspect ratio for 8 or bigger sheet silver halide particle at least one emulsion include with electronics capture zone sheet-like particle.

19th, a kind of built-in photosensitive material and the photographic product with exposure mechanism, wherein, built-in photosensitive material is photosensitive material as claimed in claim 1.

20th, a kind of built-in photosensitive material and with exposure mechanism photographic product, wherein, built-in photosensitive material is photosensitive material as claimed in claim 4.