CN1299162C - Silver halide emulsion and silver halide photography photosensitive material - Google Patents

Abstract

The invention provides a silver halide emulsion having low fog in spite of its high sensitivity, excellent in reciprocity law characteristics at high illuminance and ensuring a small sensitivity change and a small gradation change due to a fluctuation of the time from the end of exposure to processing. In the silver halide emulsion comprising silver halide grains having >=90 mol% silver chloride content, wherein the silver chloroiodide grains or silver chloroiodobromide grains have a laye rand the maximum silver iodide content of the corners of the silver halide grains is higher than the silver iodide content of the principal surfaces of the grains.

Description

Silver emulsion and silver halide photographic sensitive material

Technical field

The present invention relates to silver emulsion and silver halide photographic sensitive material, say in detail, relate to the silver emulsion and the silver halide photographic sensitive material that uses this silver emulsion that in as the digit explosure of laser scanning exposure, also can obtain the vigour gray scale with high sensitivity.Though and then relate to high sensitivity but sensitization is inexcessive, reciprocity law characteristic under high illumination is very good, and changes very little silver emulsion, its manufacture method in time and use its silver halide colour photographic sensitive material up to the sensitivity change and the gray scale change of post-exposure processes.

Background technology

In recent years, use in the colored printing field of clour-printing paper, digitized infiltration is surprising, for example, utilize the digit explosure mode of laser scanning exposure, directly carry out the analogue exposure mode of printing down with the machine of carrying out for many years that makes colored printing of the colored negative film by handling and compare, demonstrate the popularity rate of developing by leaps and bounds.The feature of this digit explosure mode is can obtain high-quality image in carrying out Flame Image Process, has played great effect qualitatively in the colored printing that improves the use clour-printing paper.Being accompanied by popularizing fast of digital camera, can simple and easy acquisition high-quality colour photograph be important elements from these electronical record media, thinks that these can bring popularizing of further leap.

On the other hand, as the colored printing mode, technology such as inkjet printing mode, subliming type mode, color static duplicating all in development, are just praised photographic quality etc. separately, are obtaining confirming as the colored printing mode.In these, adopt the digit explosure mode of clour-printing paper, it is characterized in that high-quality screen, high productivity, also have the high fastness of image equally, but also thirst for these further raisings are provided higher-quality in simpler more cheap mode and take pictures.

For the employed silver emulsion of clour-printing paper, mainly be the fast processing that requires aspect boosting productivity, thereby use the high silver emulsion of silver chloride containing ratio.The high silver emulsion of this silver chloride containing ratio generally because of the high illumination exposure of laser scanning exposure, is easy to cause low sense softization, so just improve this point, has developed various technology.

In order to improve silver chloride emulsion agaainst the law to high illumination, known admixture iridium.Yet the silver chloride emulsion of iridium of also having known admixture can produce sub-image sensitizing after the exposure at short notice, for example, in the fair 7-34103 of spy number, disclose a kind of method, promptly, solved the problem of sub-image sensitizing by being provided with very high local mutually and to admixture iridium wherein of silver bromide containing ratio.With the silver emulsion of this method modulation,, do not produce the problem of sub-image sensitizing even, can obtain high sensitivity, vigour with the higher illumination exposure of 1/100 second ratio yet.Until the superelevation illumination exposure of 1 μ second that the digit explosure mode of utilizing laser scanning exposure obtains, still want to keep high sensitivity, but the problem that is difficult to obtain the vigour gray scale also clearly.In No. the 5691119th, United States Patent (USP), the method that a kind of usefulness has the modulation emulsion of the very high local phase of silver bromide containing ratio is disclosed, make the method for high illumination gray scale vigourization.But still exist effect insufficient, repeat to modulate down the shortcoming of unstable properties.

In United States Patent (USP) No. 5783373 and No. 5783378, a kind of 3 kinds of adulterants that use are at least disclosed, it is agaainst the law to reduce high illumination, forms the method for vigourization.Yet, in order to obtain the gray scale of vigour, used to have the adulterant that the desensitization vigour turns usefulness into, this in principle, with high sensitivityization be inconsistent.

In United States Patent (USP) No. 5726005 and No. 5736310, disclose and utilized the emulsion that on the inferior surface of high silver chloride emulsion, contains very big concentration I, obtained the agaainst the law very little emulsion of high illumination under the high sensitivity.In view of the above as can be known, the exposure of high illumination can obtain high sensitivity more, but is soft as for gray scale, only is limited to the digit explosure of dynamic range for light quantity, is unfavorable.

The spy open clear 58-95736 number, with 58-108533 number, with 60-222844 number, with 60-222845 number, with 62-253143 number, with 62-253144 number, with 62-253166 number, with 62-254139 number, with 63-46440 number, with 63-46441 number, with 63-89840 number, United States Patent (USP) No. 4820624, No. 4865962, No. 5399475, No. 5284743 etc. in, be disclosed in the very high emulsion of silver chloride containing ratio, with various forms, the very high phase of silver bromide containing ratio is contained in the part, thereby has obtained high sensitivity.Yet, use and contain the silver bromide phase and contain silver iodide emulsion mutually, in the superelevation illumination exposure that resembles laser scanning exposure, have special vigour and turn usefulness into, but not open.

In No. the 5049485th, United States Patent (USP), disclose and used Au (I) compound to carry out chemical sensitization, thereby obtained high sense vigourization by the mesoionic coordination.No. the 5945270th, United States Patent (USP) discloses and has used Au (I) compound by the mesoionic coordination that contains water-soluble base to carry out chemical sensitization, thereby obtained high sense vigourization.Though knowing these as more stable Au (I) compounds,, use the emulsion that contains the silver bromide phase and contain silver iodide, in high illumination exposure, have special vigour and turn usefulness into, but not open.

On the other hand, in recent years, with regard to clour-printing paper, to high sensitivityization, handle stabilization, performance requirement such as image high quality, video picture treatment process are rapid, more significantly strong.For the high sensitivityization of silver chloride emulsion, up to the present, mainly studied the method that in emulsion particles, contains bromide ion.For example, disclosed method is the method that contains bromide ion in particle surface portion in No. 0295439 instructions of European patent, the method that excessively forms the local phase of at least 20 moles of % of bromide concentration with oriented growth at particle surface is disclosed in No. 5252454 instructions of United States Patent (USP), in No. 5252456 instructions of United States Patent (USP), disclose fine particle emulsion is cooperated with bigger high-silver chloride host particles emulsion, by Ostwald ripening, on particle surface, form the method for rich bromide phase.On the other hand, also can contain iodide ion on the silver chloride emulsion particle, producing sensitivity increases.Yet, up to the present, with high sensitivity turn into for the purpose example seldom, in above-mentioned referenced patents for representative contain the iodide ion example, generally allow low concentration, perhaps avoided this problem.

Enumerate the example that several ions that make high silver chloride emulsion contain iodide produce high sensitivityization.Disclosed technical characterictic is that { later stage of the dull and stereotyped particle of 100} makes particle inside contain banded iodide forming high-silver chloride in United States Patent (USP) No. 5264337, No. 5292632 and No. 5314798 instructions.The iodide ion combination that bromizates thing ion and low ratio has been shown in No. 5275930 instructions of United States Patent (USP), and epitaxy is at the example in the corner of tabular particle.Opening flat 8-220681 number, spy the spy opens flat 8-234340 number, spy and opens flat 8-220684 number, spy and open flat 8-240879 number, spy and open disclosed technical characterictic in the flat 8-234345 instructions, common ground is to work hard in that host's high silver chloride emulsion particle is contained on the method for iodide ion, on the inferior surface of emulsion particles, form the perchloride layer, this layer has the iodide ion of Cmax, but do not plan to contain iodide on the iodide layer containing.

When making iodide ion and silver chloride form mixed crystal, silver ion significantly increases between the particle internal crystal framework.Therefore, discovery has promoted the sensitivity speck that the silver ion increase causes between lattice to form by the high sensitivityization that iodide ion forms.In the above-mentioned patent of quoting, do not contain on the surface iodide layer or, owing to be limited to corner portions located, so can not cause the effect of high sensitivityization to greatest extent.On the other hand, when on particle the most surperficial, containing iodide ion, after particle forms, be adsorbed on the most lip-deep iodide ion, form unsettled composition in the processing such as chemical sensitization afterwards and enter into silver chloride layer, being easy to form image blurring, is unfavorable to high sensitivityization.

Summary of the invention

First problem to be solved by this invention provides a kind of silver emulsion and uses its silver halide photographic sensitive material, even in resembling the digit explosure of laser scanning exposure, does not also cause low sensitivityization and softization, and obtains the gray scale of vigour with high sensitivity.

Second problem to be solved by this invention provides the good silver emulsion of a kind of sub-image keeping quality, exposure humiture dependence and uses its silver halide photographic sensitive material.And then the 3rd problem of the present invention provides a kind of silver emulsion and manufacture method, and with its silver halide colour photographic sensitive material, though this silver emulsion is a high sensitivity, but clear picture, reciprocity law characteristic under high illumination is very good, and changes very little at any time because of the change of the caused sensitivity of post-exposure processes time fluctuation and gray scale change.

Solve the method for problem

For the method that solves above-mentioned problem is as follows, promptly

＜1〉a kind of silver emulsion, silver halide particle by 90 moles of above silver chloride containing ratios of % forms, it is characterized in that the maximum containing ratio of the silver iodide of the corner portions located of this silver halide particle is higher than the silver iodide containing ratio of this particle first type surface part, and state silver halide particle and contain 1 H to the major general ₂O, OH, O, OCN, thiazole or displacement thiazole are formed, are 6 ligand complex bodies of central metal with Ir by Cl, Br or I as dentate, all the other dentates.

(following above-mentioned silver halide particle is called " specific silver halide particle ")

＜2〉a kind of silver emulsion is characterized in that respectively forming with stratiform and contains silver bromide mutually and contain silver iodide mutually, and, contain the silver halide particle of 90 moles of above silver chloride containing ratios of %.

＜3〉above-mentioned＜2〉in the silver emulsion of record, it is characterized in that the above-mentioned silver bromide that contains compares the above-mentioned inboard that silver iodide are formed on mutually particle more that contains.

＜4〉above-mentioned＜2〉or＜3〉record silver emulsion, it is characterized in that above-mentioned contain silver bromide mutually with the above-mentioned silver iodide that contain to abut to form.

＜5〉above-mentioned＜1〉to＜4 in the silver emulsion of each record, it is characterized in that above-mentioned silver halide particle is the particle of cube or 14 bodies.

＜6〉above-mentioned＜1〉to＜5 in the silver emulsion of each record, the release electronic time that it is characterized in that above-mentioned silver halide particle is 10 ^-5Second was by 10 seconds.

＜7〉above-mentioned＜1〉to＜6 in the silver emulsion of each record, it is characterized in that above-mentioned silver halide particle contains Cl, Br or I as dentate, with the 6 ligand complex bodies of Ir as central metal.

＜8〉above-mentioned＜7〉in the silver emulsion of record, it is characterized in that above-mentioned 6 ligand complex bodies, contain in mutually containing silver bromide.

＜9〉above-mentioned＜1〉to＜8 in the silver emulsion of each record, it is characterized in that the sub-image oxidizing potential of above-mentioned silver emulsion is higher than 70mV.

＜10〉above-mentioned＜1〉to＜9 in the silver emulsion of each record, it is characterized in that above-mentioned silver emulsion is carried out golden sensitizing.

＜11〉above-mentioned＜10〉the middle silver emulsion of putting down in writing, it is characterized in that above-mentioned silver emulsion, by the complexing degree of stability constant logB of colloidal aurosulfo or gold ₂More than 21, golden sensitizer below 35 carries out golden sensitizing.

＜12〉a kind of silver halide photographic sensitive material is characterized in that containing above-mentioned＜1〉to＜11 in the silver emulsion of each record.

＜13〉a kind of silver emulsion is formed by 90 moles of silver halide particles more than the % of silver chloride containing ratio, and the maximum containing ratio of the silver iodide of this silver halide particle corner portions located of its feature is higher than the silver iodide containing ratio of this particle first type surface part.

＜14〉above-mentioned＜1〉to＜13 in the silver emulsion of each record, it is characterized in that the first type surface of above-mentioned silver halide particle is made of (100) face.

＜15〉above-mentioned＜13〉or＜14 in the silver emulsion of record, it is characterized in that total silver amount with respect to total emulsion particles, the containing ratio of iodide ion is at 0.06 mole more than the %.

＜16〉above-mentioned＜13〉to＜15 in the silver emulsion of each record, it is characterized in that total silver amount with respect to total emulsion particles, the containing ratio of iodide ion is at 0.1 mole more than the %.

＜17〉above-mentioned＜1〉to＜16 in the silver emulsion of each record, it is characterized in that carrying out beam split sensitizing by the trimethadione anthocyanidin.

＜18〉above-mentioned＜13〉to＜17 in the silver emulsion of each record, it is characterized in that above-mentioned silver halide particle contains transition metal complex body more than a kind.

＜19〉above-mentioned＜18〉the middle silver emulsion of putting down in writing, it is characterized in that above-mentioned the mistake in the plating complexing body, the central metal of at least a kind of transition metal complex body is ruthenium, rhodium or osmium.

＜20〉above-mentioned＜1〉to＜19 in the silver emulsion of each record, the described bromide ion concentration of silver bromide in mutually that contains that it is characterized in that stratiform has very big concentration in silver halide particle inside, and the described iodide ion of silver iodide in mutually that contain has very big concentration on the silver halide particle surface.

＜21〉a kind of silver halide colour photographic sensitive material, on supporter, have the blue perceptual silver halide emulsion layer of one deck, green perceptual silver halide emulsion layer and red perceptual silver halide emulsion layer respectively at least, it is characterized in that one deck at least of the perceptual silver halide emulsion layer of above-mentioned orchid, green perceptual silver halide emulsion layer and red perceptual silver halide emulsion layer, contain above-mentioned＜1〉to＜20 in the silver emulsion of each record.

Embodiment

Below the present invention is elaborated.

Silver emulsion of the present invention contains specific silver halide particle.The shape of particle of this particle does not have particular determination, preferably by actually have the crystalline particle of the cube of 100} face or 14 bodies (these particle summits dribbling shapes, also can have the more face of high order) or 8 body crystalline particles or by full projected area more than 50% by { 100} face or { it is that tabular particle more than 2 forms that the 111} face forms aspect ratio.So-called aspect ratio is the value that the diameter of a circle suitable with projected area removed by particle thickness.Among the present invention, be more preferably the particle of cube or 14 bodies.

As silver emulsion of the present invention, use the emulsion that contains specific silver halide particle.The silver chloride containing ratio must consider that from the fast processing aspect silver chloride containing ratio is preferably in 93 moles more than the % at 90 moles more than the %, better at 95 moles more than the %.

Specific silver halide particle in the silver emulsion of the present invention is following 1) and 2) in any.

1) contains silver bromide mutually and contain (below be called formation 1) that silver iodide form stratiform mutually respectively.

2) the maximum containing ratio of corner portions located silver iodide is higher than the silver iodide containing ratio (below be called constitute 2) of this particle first type surface part.

In above-mentioned, though can satisfy 1) or 2) in any one, also can two all satisfy.

Among the present invention, above-mentioned silver halide particle is called specific silver halide particle, the silver emulsion that will contain this silver halide particle is called silver emulsion of the present invention.When being any one, being called the silver halide particle of formation 1 or constituting 2 silver halide particle.

Below describe about constituting 1 silver halide particle.

Consider that from vigour, the good aspect of latent-image stability that the silver bromide containing ratio is good is 0.1-7 mole %, more preferably 0.5-5 mole %.From the exposure of high illumination, high sensitivity, and be that the vigour aspect considers that the silver iodide containing ratio is good is 0.02-1 mole %, 0.05-0.50 mole % more preferably, especially good 0.07-0.40 mole %.Below tell about the situation that constitutes 2 silver halide particle, the silver iodide containing ratio is good is 0.1 mole more than the %, 0.1-0.8 mole % more preferably, and especially good is 0.25-0.60 mole %.

What formation 1 silver halide particle of the present invention was good is iodine bromine silver chloride particle, is more preferably the iodine bromine silver chloride particle that above-mentioned halogen is formed.

Formation 1 silver halide particle of the present invention has the silver bromide of containing phase and contains silver iodide mutually.Said contain silver bromide mutually or contain the silver iodide phase herein, be meant than around silver bromide or the high position of silver iodide concentration.Contain silver bromide mutually or contain silver iodide and also can change continuously, also can sharply change with halogen composition around it.Containing the silver bromide phase or containing the silver iodide phase like this can certain part in particle form the concentration layer with certain amplitude, also can be the maximal point of not expanding.Contain silver bromide in mutually local silver bromide containing ratio good at 5 moles more than the %, 10～80 moles of % more preferably, especially good is 15～50 moles of %.Contain silver iodide good 0.3 mole of local silver iodide containing ratio more than the % in mutually, better 0.5～8 mole of %, especially 1～5 mole of %.Containing the silver bromide phase or containing the silver iodide phase like this can be several stratiforms in each particle, and each silver bromide or silver iodide containing ratio can be different, but must have the minimum phase that contains 1.

The present invention constitutes containing the silver bromide phase and containing silver iodide mutually in 1 silver halide particle, the most important thing is to have the stratiform around each particle.Form around the particle stratiform contain silver bromide mutually or contain the silver iodide phase, best form is to have uniform CONCENTRATION DISTRIBUTION along the particle peripheral direction at each in mutually.Yet, with exist around the particle stratiform contain silver bromide mutually or contain silver iodide mutually in, the maximal point of silver bromide or silver iodide concentration or minimal point are present on the particle peripheral direction, also can have CONCENTRATION DISTRIBUTION.For example, have near particle surface around the such stratiform silver bromide of particle mutually or contain the silver iodide phase time, the silver bromide at particle corner or edge or silver iodide concentration form the concentration different with first type surface sometimes.With contain silver bromide around the stratiform of particle mutually and to contain silver iodide mutually different, the isolated fully privileged site that is present in particle surface also can be not center on containing the silver bromide phase or containing the silver iodide phase of particle.

Containing the silver bromide phase or containing the silver iodide phase like this considers that from having improved local concentration with the amount that still less contains silver bromide or silver iodide the silver amount by 3～30% that particle volume is good constitutes, and better silver amount by 3～15% constitutes.

The present invention constitutes containing the silver bromide phase and containing silver iodide mutually of 1 silver halide particle, may reside in the same position of particle, also may reside in different positions, and calm formation particle this point easy to control is considered, preferably is present in different positions.Can contain silver iodide in mutually containing silver bromide, otherwise, contain silver iodide and also can contain silver bromide in mutually.Generally say, in the high-silver chloride particle forms, because the iodide that add are easy to form near particle surface so contain silver iodide than the easier particle surface that is penetrated into of bromide mutually.Therefore, contain silver bromide mutually and when containing silver iodide and being present in the interior different parts of particle mutually, preferably make to contain silver bromide and be formed on the inboard that contains the silver iodide phase mutually.Such situation, near also can be particle surface the more lateral that contains the silver iodide phase is provided with the other silver bromide phase that contains.

In order to realize effects such as high sensitivityization of the present invention and vigourization, form more in particle inside and to contain silver bromide mutually or contain the mutually needed bromide sliver content of silver iodide or agi content increases more, but have this danger, promptly, reducing needs above silver chloride content, can damage fast processing.Therefore, for these functions that make the control photographic effect concentrate near surface in the particle, preferably make to contain silver bromide mutually and to contain silver iodide adjacent.Consider from these aspects, measure from the inboard that good is in 50%～100% position of particle volume, and any position forms contains the silver bromide phase, any position forms and contains silver iodide from 85%～100% position of particle volume.Be more preferably from 70%～95% position of particle volume any position and form and contain the silver bromide phase, any position forms and contains the silver iodide phase from 90%～100% position of particle volume.

Formation 2 silver halide particles of the present invention are described.

The so-called corner portions located that constitutes regulation in 2 is meant the part of the polygonal taper that separates with 1/5th length of the length of side (connecting the crest line length between the summit) from the summit of particle and form.When particle summit band is circular, crest line is prolonged, from the summit of inferring, it is definite to extrapolate.

The containing ratio of contained iodide ion in the silver halide particle, good is every mole of total silver is 0.01 mole more than the %, better, best more than the % at 0.1 mole at 0.06 mole more than the %.Good contain 0.06～1.0 mole of %, better contain 0.1～0.8 mole of %, the particle of silver iodochloride phase that preferably contains 0.25～0.60 mole iodide ion can obtain high sensitivity, and high illumination exposure adaptability is very good.Chlorine iodine silver bromide particle of the present invention also can have core shell structure.At this moment, the ion containing ratio of iodate is 0.01～8.0 mole of % of every moles of silver in the shell portion in the shell part, 0.05～6.0 mole of % more preferably, be preferably 0.25～4.0 mole of %, iodide ion containing ratio in the core segment, good is, and shell partly is worth below 1/10th.On the silver halide particle surface, have every mole of total 0.2～5 mole of silver-colored %, the silver bromide part of better 0.5～3 mole of % and have phase, can obtain high sensitivity, and photographic property is very stable, so good especially.

The silver iodide containing ratio of corner portions located in the silver halide emulsion particles can utilize the electronic analysis microscope to study.Utilize the established part of this particle of electronic analysis microscopic analysis, can carry out luminous point, measure the silver iodide containing ratio through narrowing down to the point analysis below the 2nm.The known silver halide particle of containing ratio is done same mensuration, draw detection curve,, can obtain the silver iodide containing ratio according to the ratio of Ag intensity of obtaining in advance and I intensity.As the microscopical analysis line source of electronic analysis, be applicable to than with thermionic electron-dense radial pattern electron gun, luminous point is directly narrowed down to below the 2nm, can be easy to analyze the halogen composition of small part.The mensuration of the silver iodide containing ratio of corner portions located is the apparent test portion of electricity that tilts, and only carries out with established part contact electronics line.When making test portion, also can adopt this way, emulsion particles is poured on the copper screen cloth that opens support membrane.Show big silver iodide containing ratio in overall surveyed and drawn with analyzing electricity, dwindle in the maximum region in established part after, in the zone of regulation, carry out above-mentioned point analysis, measure several points to the dozens of point, obtain maximal value.

Utilize the ESCA method, the silver iodide containing ratio of obtaining silver halide emulsion particles first type surface part is as surperficial iodine amount.Among the present invention, with respect to the maximum containing ratio of the silver iodide of first type surface part, the maximum containing ratio of the silver iodide of corner portions located, good is 1～100 times, better 1.1～50 times, best 1.2～20 times.

The silver halide particle of formation 2 of the present invention contains the silver bromide part and has phase time, preferably bromizates the local existence of the above silver bromide of at least 10 moles of % of silver-colored containing ratio and carry out epitaxial growth on particle surface.The silver bromide part exist the silver bromide containing ratio of phase good be 10～60 moles of %, 20～50 moles of % more preferably.The local existence of silver bromide is to be made of the silver that constitutes total silver-colored 0.1～5 mole of % that measures of silver halide particle among the present invention mutually, and preferably the silver by 0.3～4 mole of % constitutes.In the local existence mutually of silver bromide, preferably contain protochloride iridium (III), protobromide iridium (III), iridium chloride (IV), the sour sodium of chlordene iridium (III), the sour potassium of chlordene iridium (IV), six ammonia iridium (IV) salt, three oxalic acid iridium (III) salt, three oxalic acid iridium (IV) salt grade in an imperial examination (VIII) family metal complex ions.The addition of these compounds can be selected in wide range according to purpose, but with respect to 1 mole of silver halide, is preferably 10 ^-9～10 ^-2Mole.These group VIII metal complex ions are told about afterwards in detail.

At modulation specific silver halide particle of the present invention (promptly, at least a kind silver halide particle in the satisfied formation 1 and 2) time, the bromide or the iodide that import in order to contain silver bromide or silver iodide, can add the solution of bromide salt or iodide salt separately, perhaps, add bromide salt or iodide salt solution with adding silver salt solution and perchloride salt solusion.In the latter's situation, bromide salt or iodide salt solution and perchloride salt solusion are added separately, perhaps, add as the mixed solution of bromide salt or iodide salt and perchloride salt.Bromide salt or iodide salt, can alkali or the form of the dissolubility salt of alkali earths bromide salt or iodide salt one class add.Perhaps as the record of No. 5389508 instructions of United States Patent (USP), import by divide the bromide ion or the iodide ion that by organic molecule.As other bromide or iodide ion source, also can use small silver bromide particle or small silver iodide particle.

Bromide salt or iodide salt solution can be concentrated in the moment that particle forms and add, and also can add in a certain period.In perchloride emulsion, import the position of iodide ion, limit from the emulsion aspect that obtains high sensitivity, low overexposure.At the more inner iodide ion that imports of emulsion particles, sensitivity increases very little more more.Therefore, iodide salt solution is added in good 50% more lateral from particle volume, better adds from 70% more lateral, preferably adds from 85% more lateral.Iodide salt solution is added in good 98% inside from particle volume, better finishes from 96% inside to add.The interpolation of iodide salt solution from particle surface, in inboard slightly end, can obtain higher sensitivity, the emulsion of low transition sensitization.

On the other hand, the interpolation of bromide salt solution, better carry out from 70% more lateral good 50% more lateral from particle volume.

Bromide or iodide ion be the CONCENTRATION DISTRIBUTION on the depth direction in particle, can utilize etch/TOF-SIMS (Time of Flight-Secondary lon Mass Spectrometry) method, for example, use the system TRIFT II of Phi Erans society type TOF-SIMS to measure.About the TOF-SIMS method, specifically be documented in Japanese Surface Science and can compile in kind Co., Ltd. of " surface analysis technique is selected secondary イ オ Application mass analysis " ball (distribution in 1999).When using etch/TOF-SIMS method to resolve emulsion particles, the interpolation of iodide salt solution even finish in the inboard of particle, also can analyze iodide ion and permeate to particle surface.Emulsion of the present invention utilizes etch/TOF-SIMS method to analyze, and preferably iodide ion has very big concentration at particle surface, and iodide ion concentration reduces gradually to the inside, and bromide ion is preferably in particle inside and has very big concentration.The local concentration of silver bromide, if bromide sliver content is high to certain degree, also available X line refraction process is measured.

The electronics release time of silver emulsion of the present invention is preferably from 10 ^-5Second～10 seconds between.Be when silver emulsion is given to expose said electronics release time this moment, and the photoelectron that produces in the silver halide crystal is captured the time of emitting once more by the electron trap that is present in the crystallization.Electronics is shorter than 10 release time ^-6During second, be difficult to obtain high illumination exposure, high sensitivity, vigour gray scale, when being longer than 10 seconds, during the short time processing of exposure back, can produce the problem of sub-image sensitizing.Electronics release time, better 10 ^-4Between～10 seconds, best 10 ^-3Between～1 second.

Electronics can be measured with dipulse light conduction method release time.Use microwave light conduction method or radiation glistening light of waves conduction method, give the short time exposure that triggers with 1 time.Behind certain certain hour, give the short time exposure that triggers with 2 times afterwards.Trigger in the exposure at the 1st time, the electron trap trapped electrons in the silver halide crystal is given when triggering exposure with the 2nd time subsequently, because electron trap stops up, the light conducted signal that triggers for the 2nd time becomes big.2 exposure intervals are arranged on ten minutes, trigger under the exposure at the 1st time, when the electronics that electron trap is caught had discharged, the light conducted signal of the 2nd triggering roughly returned to original size.As change exposure interval 2 times, gather the exposure interval dependence of the light conducted signal intensity that triggers for the 2nd time, the situation that the light conducted signal intensity that mensuration triggers for the 2nd time along with exposure interval reduces.This expression photoelectron is by the release time of electron trap.Electronics discharges, after exposure, carries out continuously in a certain period sometimes, but good 10 ^-5Observation discharges slowly between～10 seconds.Better 10 ^-4Observation discharges between～10 seconds, is preferably in 10 ^-3Observation discharges slowly between～1 second.

Specific silver halide particle in the silver emulsion of the present invention preferably contains iridium.As the compound of iridium, preferably having 6 dentates is 6 ligand complex bodies of central metal with iridium; Since evenly enter in the silver halide crystal, ideal.As a kind of optimal morphology of using iridium among the present invention, good is to have Cl, Br or I are made dentate, is 6 ligand complex bodies of central metal with Ir, be more preferably whole 6 dentates and form by Cl, Br or I, and with Ir 6 ligand complex bodies of central metal.At this moment in the 6 ligand complex bodies, Cl, Br or I can mix existence.Having Cl, Br or I are made dentate, is 6 ligand complex bodies of central metal with Ir, for obtain the exposure of high illumination, vigour gray scale, preferably be included in to contain silver bromide mutually in.

Below enumerate whole 6 dentates and form, be 6 ligand complex body examples of central metal with Ir that by Cl, Br or I the iridium among the present invention is not limited in these.

[IrCl ₆] ^2-

[IrCl ₆] ^3-

[IrBr ₆] ^2-

[IrBr ₆] ^3-

[IrI ₆] ^3-

As the different optimal morphology of using iridium among the present invention, good is to have to 1 non-halogen of major general to make dentate, is 6 ligand complex bodies of central metal with Ir, and good is to have H ₂O, OH, O, OCN, thiazole or displacement thiazole make dentate, be 6 ligand complex bodies of central metal with Ir, is more preferably to have 1 H to the major general ₂O, OH, O, OCN, thiazole or displacement thiazole are made dentate, all the other dentates are formed, are 6 ligand complex bodies of central metal with Ir by Cl, Br or I.Best is has 1 or 2 5-methylthiazols are made dentate, all the other dentates are formed with Ir by Cl, Br or I is 6 ligand complex bodies of central metal.

Below list and have 1 H to the major general ₂O, OH, O, OCN, thiazole or displacement thiazole are made dentate, and all the other dentates are formed, are 6 ligand complex body examples of central metal with Ir by Cl, Br or I, but the iridium among the present invention is not limited to these.

[Ir(H ₂O)Cl ₅] ^2-

[Ir(H ₂O) ₂Cl ₄] ^-

[Ir(H ₂O)Br ₅] ^2-

[Ir(H ₂O) ₂Br ₄] ^-

[Ir(OH)Cl ₅] ^3-

[Ir(OH) ₂Cl ₄] ^3-

[Ir(OH)Br ₅] ^3-

[Ir(OH) ₂Br ₄] ^3-

[Ir(O)Cl ₅] ^4-

[Ir(O) ₂Cl ₄] ^5-

[Ir(O)Br ₅] ^4-

[Ir(O) ₂Br ₄] ^3-

[Ir(OCN)Cl ₅] ^3-

[Ir(OCN)Br ₅] ^3-

[Ir (thiazole) Cl ₅] ^2-

[Ir (thiazole) ₂Cl ₄] ^-

[Ir (thiazole) Br ₅] ^2-

[Ir (thiazole) ₂Br ₄] ^-

[Ir (5-methylthiazol) Cl ₅] ^2-

[Ir (5-methylthiazol) ₂Cl ₄] ^-

[Ir (5-methylthiazol) Br ₅] ^2-

[Ir (5-methylthiazol) ₂Br ₄] ^-

As long as use separately any one in following, can finish problem of the present invention, that is, whole 6 dentates are by Cl, Br or I forms and be 6 ligand complex bodies of central metal with Ir or have 1 H to the major general ₂O, OH, O, OCN, thiazole or displacement thiazole are made dentate, all the other dentates by Cl, Br or I forms and be 6 ligand complex bodies of central metal with Ir.Yet, in order further to improve effect of the present invention, preferably and with whole 6 dentates by Cl, Br or I forms and be 6 ligand complex bodies of central metal with Ir and have 1 H to the major general ₂O, OH, O, OCN, thiazole or displacement thiazole are made dentate, all the other dentates by Cl, Br or I forms and be 6 ligand complex bodies of central metal with Ir.And then, have 1 H to the major general ₂O, OH, O, OCN, thiazole or displacement thiazole are made dentate, all the other dentates by Cl, Br or I forms and be 6 ligand complex bodies of central metal with Ir, and be the most handy by 2 kinds of dentate (H wherein ₂Among in O, OH, O, OCN, thiazole or the displacement thiazole a kind and Cl, Br or the I a kind) the complexing body that constitutes.

The metal complex body of more than enumerating is a negative ion, and is during with salt forming cation, preferably water-soluble easily to kation as it.Specifically, alkali metal ions such as sodion, potassium ion, rubidium ion, cesium ion and lithium ion preferably, ammonium ion, alkyl ammonium ion.To these metal complex bodies may be dissolved in dewater outside, use in the mixed solvent of the suitable organic solvent that mixes with water (for example, alcohols, ethers, glycols, ketone, ester class, amide-type etc.).These iridium complexing bodies, in particle forms, per 1 moles of silver, good interpolation 1 * 10 ^-10Mole～1 * 10 ^-3Mole preferably adds 1 * 10 ^-8Mole～1 * 10 ^-5Mole.

Among the present invention, above-mentioned iridium complex is when forming silver halide particle, directly add in the reaction solution, or add in the halide solution that forms silver halide particle, or add in other the solution, form in the reaction solution by adding particle to, can enter in the silver halide particle well.Carry out the physics maturation with the particulate that iridium complexing body is entered in the particle, also can enter in the silver halide particle well.And then the combination of these methods also can be included in the silver halide particle.

When making these complexing bodies enter in the silver halide particle, also can evenly be present in particle inside, but the spy opens flat 4-208936 number, spy and opens flat 2-125245 number, spy and open disclosed form flat 3-188437 number, can only there be the particle surface layer, only has the complexing body and to have added the layer that does not contain the complexing body on particle surface also passable in particle inside.Disclosed in No. the 5252451st, United States Patent (USP) and No. 5256530 instructions is to carry out the physics maturation so that the complexing body enters into the particulate of particle inside, upgrading particle surface phase.Also can make combination in this way, several complexing bodies can be combined in the silver halide particle.The halogen that contains above-mentioned complexing body position is formed, and does not have particular restriction, preferably makes whole 6 dentates by Cl, Br or I forms and be that 6 ligand complex bodies of central metal are present in the great position of silver bromide concentration with Ir.

Among the present invention, on the inside and/or the surface of silver halide particle, other metallic ions except that iridium can mix.As used metallic ion transition metal ion preferably.Wherein, good is iron, ruthenium, osmium, lead, cadmium or zinc.Better these metallic ions that use are accompanied by the 6 coordination octahedral build complexing bodies that ligand forms.When mineral compound is used as ligand, preferably use cyanide ion, halide ion, thiocyanogen, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion or sulfo-nitrosyl ion, preferably use any metallic ion in above-mentioned iron, ruthenium, osmium, lead, cadmium or the zinc to carry out coordination, also can in 1 complexing body molecule, use several ligands.Also can use organic compound as ligand, as good organic compound, the heterogeneous ring compound of main chain carbon number at the chain compound below 5 and/or 5 yuan of rings or 6 yuan of rings arranged, good organic compound is to have in the molecule nitrogen-atoms, phosphorus atoms, oxygen atom or sulphur atom as the compound to the coordination atom of metal, and good is furans, thiophene,  azoles, different  azoles, thiazole, isothiazole, imidazoles, pyrazoles, triazole, brazan, bilane, pyridine, pyridazine, pyrimidine, pyrazine.Be more preferably these compounds as skeleton, import substituent compound to them.

As the combination of good metallic ion and ligand, be the combination of ferric ion and ruthenium ion and cyanide ion.Among the present invention, also can and use iridium and these compounds.In these compounds, cyanide ion preferably occupies plurality in the coordination number to center metallic iron or ruthenium, all the other coordination parts, and good by thiocyanogen, ammonia, water, nitrosyl ion, dimethyl sulfoxide (DMSO), pyridine, pyrazine or 4,4 '-two pyridines occupy.Preferably 6 of central metal coordination parts are all occupied by prussiate, can form six cyanogen iron complexing bodies or six cyanogen ruthenium complexing bodies.These make the complexing body of ligand with cyanide ion, and in particle formed, good was that per 1 moles of silver adds 1 * 10 ^-8～1 * 10 ^-2Mole preferably adds 1 * 10 ^-6～5 * 10 ^-4Mole.When being central metal with ruthenium and osmium, good is that nitrosyl ion, sulfo-nitrosyl ion or hydrone and chloride ion are used jointly as ligand.Be more preferably and form pentachloro-nitrosyl complexing body, pentachloro-sulfo-nitrosyl complex or pentachloro-water complexing body, also can form the chlordene complex compound.These complex compounds, in particle forms, per 1 moles of silver, good interpolation 1 * 10 ^-10～1 * 10 ^-6The mole, better add 1 * 10 ^-9～1 * 10 ^-6Mole.

Silver emulsion of the present invention is used in combination several transition metal complex bodies, and can obtaining more, the gray scale of high sensitivity, low concentration part is the emulsion of the reciprocity law characteristic good under vigour, the high illumination.Used transition metal complex body, with height help to change, vigourization, when reciprocity law is improved to purpose, the good complexing body that is to use more than at least 3 kinds for obtaining the wideer good emulsion of reciprocity law characteristic, better uses the transition metal complex body more than 4 kinds.In order to make the gray scale vigourization of low concentration part, in the used complexing body at least a kind, preferably use with ruthenium or osmium transition metal complex body as central metal, optimum is used to constitute the situation of 2 silver halide particles.

That the average particle size of contained silver halide particle in the silver emulsion of the present invention (get and particle projecting plane diameter of a circle of equal value, as particle size, take the mean) is good is 0.1-2 μ m.These particle size distribution preferably coefficient of alteration (with average particle size divided by the standard deviation of particle size distribution) below 20%, good 15% below, better in the dispersion of the what is called below 10%.At this moment, be purpose to obtain wideer tolerance, with above-mentioned single emulsion fusion use in that disperses, also can carry out the double-layer coating with one deck.

In silver emulsion of the present invention,, also can contain other silver halide particles except containing outside the silver halide particle contained in the silver emulsion that defines among the present invention (that is, specific silver halide particle).Yet, contained silver halide particle in the silver emulsion that defines among the present invention, the projected area of total silver halide particle is good more than 50% in silver emulsion, and is better more than 80%.

The sub-image oxidizing potential of silver emulsion of the present invention, the good 70mV that is higher than better is higher than 100mV.So-called sub-image oxidizing potential is higher than 70mV, is meant that the oxidative resistance of sub-image is more intense.The oxidizing potential of sub-image can utilize the method for citing sb. for meritorious service in the known data such as 103 pages of photograph, photonasty (Photo graphic Sensitivity Oxford University Press, Tadaaki Tani 1995) to measure.Specifically be the gray scale exposure of the coating thing of silver emulsion being given 0.1 second, in the redox of various current potentials is bathed, flood the current potential that the research sub-image is bleached before the video picture.

Silver emulsion of the present invention is implemented chemical sensitization usually.For the chemical sensitization method, can be separately or and in order to add the sulphur sensitizing that unstable sulphur compound is representative, be the noble metal sensitizing of representative with golden sensitizing, or reduction sensitization etc.About the compound that uses in the chemical sensitization, preferably use the special compound of putting down in writing in 22 pages of upper right hurdles, the 18th page of hurdle to the, bottom right in clear 62-215272 number of opening.In these, preferably implement golden sensitizing.By implementing golden sensitizing, be because when utilizing laser etc. to carry out scan exposure, can further reduce the change of photographic property.

Silver emulsion of the present invention is being implemented in the golden sensitizing, can utilized various inorganic gold compounds and gold (I) complexing body with inorganic ligand, and gold (I) compound with organic coordination.As inorganic gold compound, for example can use chlorination auric acid or its salt, as the gold with inorganic ligand (I) complex compound, for example can use compounds such as two thiosulfuric acid gold compounds such as curing cyanic acid gold compounds such as curing cyanic acid gold (I) potassium and two gold aurothiosulfates (I), 3 sodium.

Silver emulsion of the present invention is preferably used colloidal state shape aurosulfo or golden network stability constant log β ₂Be that 21～35 golden sensitizer carries out golden sensitizing.The manufacture method of colloidal state shape aurosulfo is documented in research, in open (Reserch Disclosure, 37154), ionization solid-state (Solid State lonics) the 79th volume, 60～66 pages, nineteen ninety-five periodical, Compt.Rend.Hebt.Seances Acad.Sci.Sect.B the 263rd volume, 1328 pages, 1966 annuals etc.As colloidal state shape aurosulfo, can utilize various sizes, can utilize particle diameter 50nm following.Addition can according to circumstances change in wide range, and as gold atom, per 1 mole of silver halide is 5 * 10 ^-7～5 * 10 ^-3Mole, best 5 * 10 ^-6～5 * 10 ^-4Mole.Among the present invention, also can be with golden sensitizing and other sensitizing method, for example, sulphur sensitizing, selenium sensitizing, tellurium sensitizing, reduction sensitization, or use noble metal sensitizing beyond the gold compound etc. to make up.

Below about the network stability constant log β of gold ₂Be that 21～35 golden sensitizer describes.

Network stability constant log β for gold ₂Mensuration, can use the assay method of putting down in writing in the following document, as comprehensive Coordinative Chemistry (Comprehenslve Coordination Chemistry, the 55th chapter, 864 pages, 1987), electrochemistry of element encyclopedia (Encyclopedia of Electrochemistry of theElements, IV-3 chapter, 1975), dutch royal chemistry association magazine (Journal of the RoyalNetherlands Chemical Soci ety 101 volumes, 164 pages, nineteen eighty-two), and their list of references.Measuring temperature is 25 ℃, and PH is adjusted into 6.0 with potassium dihydrogen phosphate, sodium hydrogen phosphate damping fluid, and ionic strength calculates log β by the golden potential value that obtains under the condition of 0.1M (KBr) ₂Value obtain.In this assay method, the log β of thiocyanogen acid ion ₂Value be 20.5, obtained and document (comprehensive Coordinative Chemistry (Comprehensive Coordination Chemitry 1987, the 55th chapter, 864 pages, table 2)) in 20 very approaching values of record.

The network stability constant log β of gold among the present invention ₂Be 21～35 golden sensitizer, the most handy following general expression (I) expression.

General expression (I) { (L ¹) _x(Au) _y(L ²) _zQ _q} _p

In the formula (I), L ¹And L ²Expression log β ₂Value be compound between 21～35.Good is 22～31 compound is more preferably 24～28 compound.

For example, L ¹And L ²Expression contain at least 1 with silver halide reaction can generate the unstable sulfenyl of silver sulfide the interior uride compound of compound, Z, sulfide compound, meso-ionic compound ,-SR ', heterogeneous ring compound, phosphine compound, amino acid derivativges, sugar derivatives, thiocyanogen, these can be identical, also can be different.Wherein R ' represents aliphatic hydrocarbon, aryl, heterocyclic radical, acyl group, carbamyl, thiocarbamoyl or sulfonyl.

Needed to negative ion or to kation when Q is illustrated in electric charge with compound and forms neutrality, X and Z represent that 0～4 integer, y and p represent 1 or 2, and q represents to contain 0～1 value of decimal.But any one can not be 0 X and Z.

As the good compound of general expression (I) expression, L ¹And L ²Expression contain at least 1 with silver halide react the unstable sulfenyl can generate silver sulfide compound, hydantoin compound, sulfide compound, meso-ionic compound ,-SR ', heterogeneous ring compound or phosphine compound, x, y and z represent 1 respectively.

As the compound of general expression (I) expression, better L ¹And L ²Expression contain at least 1 with silver halide react the unstable sulfenyl can generate silver sulfide compound, meso-ionic compound or-SR ', x, y and z represent 1 respectively.

Below the gold compound of general expression (I) expression is described in more detail.

As L in the general expression (I) ¹And L ²Have and the silver halide reaction of expression can generate the compound of the unstable sulfenyl of silver sulfide, in thioketones class (for example, sulphur urine class, sulfonyl amine or thiocyanic acid class etc.), group thiophosphate, thiosulfuric acid class.

Can generate the best compound of the unstable sulfenyl of silver sulfide as containing one at least with silver halide reaction, thioketones class (preferably sulphur urine class, sulfonyl amine etc.), thiosulfuric acid class are arranged.

Below, in general expression (I), with L ¹And L ²The hydantoin compound of expression for example has or not the hydantoins, N-methyl hydantoins of displacement etc.; As sulfide compound, the 1-8 of containing sulfenyl arranged, by their the displacement or do not have displacement straight or branched alkylene base (for example, ethene, triethylene etc.) or the chain that connects with the penylene base or thioether (for example, two hydroxyethyl thioethers, 3,6-two sulfo-s-1 of ring-type, 8-ethohexadiol, 1,4,8,11-tetrathiacyclotetradecane etc.); As meso-ionic compound, have mesoionic-3-sulfydryl-1,2,4-triazole type (for example ,-1,4 of mesoionic, 5-trimethyl-3-are dredged base-1,2,4-triazole etc.) etc.

As L in the general expression (I) ¹And L ²During expression-SR ', aliphatic alkyl with R ' expression, the displacement of 1-30 carbon atom is arranged or do not have the displacement straight or branched alkyl (for example, methyl, ethyl, isopropyl, the n-propyl group, the n-butyl, the t-butyl, the 2-amyl group, the n-hexyl, the n-octyl group, the t-octyl group, the 2-ethylhexyl, 1,5-dimethyl hexyl, the n-decyl, the n-dodecyl, the n-myristyl, the n-cetyl, hydroxyethyl, hydroxypropyl, 2, the 3-hydroxypropyl, ethyloic, carboxyethyl, sulfoethyl sodium, diethyl ethyl ammonia, diethyl propyl group ammonia, fourth oxygen propyl group, the ethoxy ethoxyethyl, n-hexyl oxygen propyl group etc.), the displacement of 3-18 carbon atom or (for example do not have the displacement cyclic alkyl, cyclopropyl, cyclopentyl, cyclohexyl, the ring octyl group, the Buddha's warrior attendant ammonium, cyclo-dodecyl etc.), the alkenyl of 2-16 carbon atom (for example, allyl, the 2-butenyl group, 3-pentenyl etc.), the alkynyl of 2-10 carbon atom (for example, propine, 3-pentyne etc.), the aralkyl of 6-16 carbon atom (for example, benzyl etc.); As aryl, the displacement of 6-20 carbon atom is arranged or do not have displacement phenyl and naphthyl (for example, do not have the displacement phenyl, do not have displacement naphthyl, 3,5-3,5-dimethylphenyl, 4-butoxyphenyl, 4-dimethylamino phenyl, 2-carboxy phenyl etc.) etc.; As heterocyclic radical, for example there is the nitrogen heterocyclic ring of replacing or not having displacement (for example to encircle for 5 yuan, imidazole radicals, 1,2,4-triazolyl, tetrazole radical,  di azoly, thiadiazolyl group, benzene imidazole radicals, purine radicals etc.), replace or do not have a displacement (for example contain 6 yuan of rings of azepine, pyridine radicals, piperidyl, 1,3,5-triazinyl, 4,6-dimercapto-1,3,5-triazinyl etc.), furyl or thienyl; As acyl group, acetyl, benzoyl etc. are for example arranged; As carbamyl, formyl-dimethylamino etc. is for example arranged; As thiocarbamoyl, diethyl thiocarbamoyl etc. is for example arranged; As sulfonyl, the displacement of 1-10 carbon atom is arranged or do not have displacement alkyl sulphonyl (for example methane sulfonyl, ethane sulfonyl etc.), a 6-16 carbon atom displacement or do not have the phenyl sulfonyl (for example, phenyl sulfonyl etc.) of displacement.

As L ¹And L ²Expression-SR ', good R ' be aryl or heterocyclic radical, is more preferably heterocyclic radical, especially good is the nitrogen heterocycle of 5 yuan or 6 yuan, the nitrogen heterocycle that preferably water-soluble base (for example, sulfo group, carboxyl, hydroxyl, amino etc.) is replaced.

In general expression (I), L ¹And L ²The heterogeneous ring compound of expression, the nitrogenous 5 yuan of heterocyclic that displacement arranged or do not have a displacement (for example, pyroles, imidazoles, pyrazoles, 1,2, the 3-triazole type, 1,2, the 4-triazole type, the tetrazolium class, the  azole, different  azole, the isothiazole class, the  diazoles, thiadiazole, pyrrolidines, the pyrrolin class, the imidazoles alkanes, imidazolines, the pyrazoles alkanes, pyrazolines, hydantoins etc.), with the heterocyclic (indoles that contain these 5 yuan of rings, isoindoles, the indoles alkanes, indazole, the benzene imidazoles, the purine class, 124 Triazole, carbazoles, four a word used for translation indenes classes, the benzene thiazoles, indoline-like etc.), displacement or nitrogenous 6 yuan of heterocyclic of not having a displacement are (for example, pyridines, the pyrazine class, miazines, pyridazine class, triazines, diazthines, piperidines, piperazines, morpholine class etc.), with the heterocyclic that contains these 6 yuan of rings (for example, quinolines, iloquinoline derivative, the phthalazines class, the naphthyridines class, the quinolizine class, quinazoline ditosylate salt, the pyridine class of talking endlessly, the phenanthridines class, acridine, non-around the quinoline class, azophenlyene class etc.), replace or do not have the furans of displacement, replace or do not have the thiophene-based of displacement, benzene thiazole  salt etc.

As L ¹And L ²The heterogeneous ring compound of expression, preferably undersaturated nitrogenous 5 yuan or 6 yuan of heterocyclic, or contain their heterocyclic, for example, pyroles is arranged, imidazoles, pyrazoles, 1,2, the 4-triazole type, the  diazoles, thiadiazole, imidazolines, indoles, Yin pyridine class, the indazole class, the benzene imidazoles, the purine class, the 124 Triazole class, carbazoles, four a word used for translation indenes classes, the benzene thiazoles, pyridines, the pyrazine class, miazines, pyridazine class, triazines, quinolines, iloquinoline derivative, phthalazines class etc., and then, in this area as antifoggant, best known heterogeneous ring compound (for example, indazole class, the benzene imidazoles, the 124 Triazole class, four a word used for translation indenes classes etc.).

As L in the general expression (I) ¹And L ²The phosphine compound of expression, the aliphatic alkyl of 1-30 carbon atom of expression, the aryl of a 6-20 carbon atom, heterocyclic radical are (for example, pyridine radicals), replace or the amino that do not have a displacement (for example, dimethylamino etc.) and/or alkyl oxy (for example, methoxyl, ethoxy etc.) displacement phosphorus hydrogen type, preferably by the phosphorus hydrogen type (for example, triphenyl phosphatization hydrogen, triethyl phosphatization hydrogen etc.) of the aryl displacement of the alkyl of 1-10 carbon atom or 6-12 carbon atom.

And then, at above-mentioned L ¹And L ²The meso-ionic compound of expression ,-SR ' and, in the heterogeneous ring compound, preferably by generating unstable sulfenyl (for example, the sulfonyl urea groups etc.) displacement of silver sulfide with the silver halide reaction.

L in above-mentioned general expression (I) ¹, L ²Also can have the sub stituent that can limit in the compound of expression; as sub stituent; for example have; halogen atom (as; fluorine atom; the chlorine atom; bromine atoms etc.); aliphatic alkyl (for example; methyl; ethyl; isopropyl; the n-propyl group; the t-butyl; the n-octyl group; cyclopentyl; cyclohexyl etc.); alkenyl (for example; allyl; 2-butenyl group 3-pentenyl etc.); alkynyl (for example; propinyl; 3-pentynyl etc.); aralkyl (for example; benzyl; phenethyl etc.); aryl (for example; phenyl; naphthyl; 4-tolyl etc.); heterocyclic radical (for example; pyridine radicals; furyl; imidazole radicals; piperidyl; morpholinyl etc.); alkyl oxy (for example; methoxyl; ethoxy; butoxy; the 2-ethyl hexyl oxy; the ethoxy ethoxy; methoxyethoxy etc.); aryloxy group (for example; phenoxy group; 2-naphthoxy etc.); amino (for example; it is amino not have displacement; dimethylamino; lignocaine; dipropyl amino; dibutylamino; ethylamino; dibenzyl amino; anilino-etc.); acylamino-(for example; acetylamino; benzoyl amino etc.); urea groups (for example; there is not the displacement urea groups; N-methyl urea groups; N-phenyl urea groups etc.); ghiourea group (for example; there is not the displacement ghiourea group; N-methylthiourea base; N-phenylthiourea base etc.); the selenourea base (for example; there is not displacement selenourea base etc.); hydrogen phosphide selenide base (as diphenyl phosphatization hydrogen selenide etc.); the tellurium urea groups (for example; there is not displacement tellurium urea groups etc.); urethane groups (for example; the methoxy carbonyl amino; carbonyl phenoxy amino etc.); sulfoamido (for example; sulfonyloxy methyl amine; phenyl-sulfamide etc.); sulfamoyl (for example; there is not the displacement sulfamoyl; N; N-dimethylamino sulfonyl; N-phenyl sulfamoyl base etc.); carbamyl (for example; there is not the displacement carbamyl; N; N-diethylamino formoxyl; N-phenyl amino formoxyl etc.); sulfonyl (for example; methane sulfonyl; P-tosyl etc.); sulfinyl (for example; methylsulfinyl; phenyl sulfinyl etc.); alkoxy carbonyl group (for example; methoxycarbonyl group; carbethoxyl group etc.); aryloxy carbonyl (for example; carbobenzoxy etc.); acyl group (for example; acetyl group; benzoyl group; formoxyl; propiono etc.); acyloxy (for example; acetoxyl group; benzoyloxy group etc.); the phosphoamide base (for example; N; N-diethyl phosphoamide etc.); alkylthio group (for example; methyl mercapto; ethylmercapto group etc.); arylthio (for example; thiophenyl etc.); cyano group; sulfo group; the sulphur acidic group; the hydrogen phosphide acidic group; carboxyl; hydroxyl; sulfydryl; inferior carboxyl; nitro; sulfino; amino (for example, three methylaminos etc.); the phosphorus base; diazanyl; thiazolyl; siloxy (t-butyl dimethyl silane oxygen base; t-butyl diphenyl siloxy) etc.Sub stituent is two when above, can be identical also can be different.

Below Q and q in the general expression (I) are described.

As Q in the general expression (I) represent to negative ion, halide ion (for example, F is arranged ^-, Cl ^-, Br ^-, I ^-), tetrafluoro boric acid salt ion (BF ₄ ^-), hexafluorophosphoric acid salt ion (PF ₆ ^-), sulfate ion (SO ₄ ^2-), aryl sulfonic acid salt ion (for example, P-toluenesulfonic acid salt ion, naphthalene-2,5-disulfonate ion etc.), carboxylic ions (for example, acetic acid ion, trifluoracetic acid ion, bromic acid ion, benzoic acid ion etc.); As represent with Q to kation, there is alkali metal ion (for example, lithium ion, sodion, potassium ion, rubidium ion, cesium ion etc.), the alkaline-earth metal ion (for example, magnesium ion, calcium ion etc.), replace or (for example do not have the displacement ammonium ion, do not have displacement ammonium ion, triethyl ammonium ion, tetramethyl ammonium ion etc.), replace or do not have the pyridine  ion (for example, not having displacement pyridine  ion, 4-phenylpyridine  ion etc.) of displacement etc.And then proton arranged.Q is the number of Q when making the electric charge of compound form neutrality, the value of expression 0-1, and this value can be decimal.

As Q represent to negative ion, halide ion (Cl for example preferably ^-, Br ^-), tetrafluoro boric acid salt ion, hexafluorophosphoric acid salt ion, sulfate ion.As Q represent to kation, preferably alkali metal ion (for example, sodion, potassium ion, rubidium ion, cesium ion etc.), replace or do not have displacement ammonium ion (for example, not having displacement ammonium ion, triethyl ammonium ion, tetramethyl ammonium ion etc.) or a proton.

Below show L ¹Or L ²The instantiation of expression compound, the present invention is not limited to these, the numeric representation log β in the bracket ₂Value.

[changing 1]

[changing 2]

The compound of general expression (I) expression, can be synthetic with reference to the known method of following record, for example, イ Application オ one ガ ニ Star Network ア Application De ニ ユ one Network リ ア ケ ミ ス ト リ one レ one ズ (INORG NUCLCHEM LETTERSVOL 10 641 pages 1974), transition metal chemistry (Transition Met.Chem.1,248 pages 1976), ア Network Network リ ス ロ グ ラ Off イ カ (Acta.Cryst.B32,3321 pages, 1976), Te Kaiping 8-69075 number, special public clear 45-8831 number, European patent 915371 A1 numbers, Te Kaiping 6-11788 number, Te Kaiping 6-501789 number, Te Kaiping 4-267249 number, open flat 9-118685 number etc. with the spy.

The concrete example of general expression (I) expression compound below is shown, but the invention is not restricted to these.

[changing 3]

[changing 4]

[changing 5]

Golden sensitizing among the present invention is normally added golden sensitizer, high temperature (best more than 40 ℃), and it is just passable that emulsion is stirred certain hour.The addition of gold sensitizer, different with various conditions, as standard, preferably per 1 mole of silver halide adds 1 * 10 ^-7～1 * 10 ^-4Mole.

As the golden sensitizer among the present invention, except above compound, can and with the gold compound of common usefulness (for example, chlorauride hydrochlorate, chlorination potassium oleate (カ リ ウ system Network ロ ロ オ-レ-ト), oiliness (オ-リ Star Network) trichloride, oiliness potassium thiocyanate, iodinated oleic acid potassium, the acid of four cyano oiliness, oiliness ammonium sulfocyanate, pyridine radicals trichlorine gold etc.).

Silver emulsion of the present invention except golden sensitizing, also can and be used other chemical sensitizations.As also using chemical sensitization, can use sulphur sensitizing, selenium sensitizing, tellurium sensitizing, the noble metal sensitizing beyond the gold, or reduction sensitization etc.The compound of using about chemical sensitization preferably uses special opening to put down in writing in page upper right hurdle, the 18th page of hurdle, bottom right～22nd in clear 62-215272 number.

In silver emulsion of the present invention, for the manufacture process that prevents photosensitive material, preserve in or the photographic fog in handling of taking a picture, be purpose perhaps to stablize photographic property, can add all cpds or their precursor.The concrete example of these compounds, can use the spy to open in the clear 62-215272 communique instructions record in the 39th page～the 72nd page, also can use the 5-virtue amino-1,2 of record in EP0447647 number, 3,4-sulfo-triazole compounds (having an electron attractivity base in this virtue residue at least).

Among the present invention, for improving the keeping quality of silver emulsion, also can use the compound of following middle record, promptly, the hydroxamic acid derivatives of putting down in writing in the Te Kaiping 11-109576 communique, put down in writing in the Te Kaiping 11-327094 communique in abutting connection with carbonyl, two ends have ring-type ketone (particularly general expression (S1) expression of two Multiple Bonds of amino or hydroxyl displacement, paragraph number 0036～0071 can be taken in the present specification), the catechol of the sulfo group displacement of putting down in writing in the Te Kaiping 11-143011 communique and hydroquinone type are (for example, 4,5-dihydroxy-1, the 3-benzenedisulfonic acid, 2,5-dihydroxy-1, the 4-benzenedisulfonic acid, 3, the 4-dihydroxy benzenes sulfonic acid, 2, the 3-dihydroxy benzenes sulfonic acid, 2, the 5-dihydroxy benzenes sulfonic acid, 3,4,5-trihydroxy benzene sulfonic acid and salt thereof etc.), (the 22nd row record on the 56th row～the 11 hurdle on the 4th hurdle in No. the 5556741st, the United States Patent (USP) of the hydroxyl Ammonia of general expression (A) expression in No. 5556741 instructions of United States Patent (USP), also be applicable to the application, take in into) as the part in this instructions, the water-soluble reductive agent of general expression (I)～(III) expression also can be applicable to the present invention in the Te Kaiping 11-102045 communique.

Photonasty in the desired optical wavelength territory has been shown in silver emulsion of the present invention,, can have contained the beam split sensitizing coloring matter for giving so-called minute photo sensitivity.As the beam split sensitizing coloring matter that beam split sensitizing in blue, green, the red field is used, F.M.Harmer work Heterocyclic Compounds-Cyanine dyes and related Compounds (John Wiley ﹠amp is arranged; Sons[New York, London] society's periodical 1964) in record.Can use above-mentioned spy to open in the clear 62-215272 communique particular compound example and the beam split sensitizing method of record in the 22nd page of upper right hurdle～38th page.As the red photosensitive beam split sensitizing coloring matter of the high silver halide emulsion particles of silver chloride containing ratio, open the beam split sensitizing coloring matter of putting down in writing in the flat 3-123340 communique the spy, consider from aspects such as stability, adsorption strength, exposure dependence on temperature, ideal.

Beam split sensitizing coloring matter in the green field, good is three methine anthocyanidins of following general expression (T) expression, preferably  three methine anthocyanidins or  azoles three methine anthocyanidins.

General expression (T)

[changing 1A]

General expression (T)

In the formula, Z ₁₀₁And Z ₁₀₂Expression forms nitrogen heterocyclic ring and examines needed atomic group respectively.As nitrogen heterocyclic ring nuclear, preferably contain nitrogen-atoms and other, as 5～6 yuan of nucleolus of sulphur atom, oxygen atom, selenium atom or tellurium atom as heteroatoms.Also can be in these rings in conjunction with condensed ring, and then can be in conjunction with sub stituent.As the concrete example of above-mentioned nitrogen heterocyclic ring nuclear, can enumerate thiazole nucleus, benzene thiazole nucleus, naphthothiazoles nuclear, selenazole nucleus, benzene selenazole nucleus, naphthalene selenazole nucleus,  azoles nuclear, benzene  azoles nuclear, naphthalene  azoles nuclear, imidazole nucleus, benzene imidazole nucleus, naphthalene imidazole nucleus, 4-quinoline nuclei, pyrrolin nuclear, pyridine nucleus, tetrazolium nuclear, indolenine nuclear, phenyl indolenine nuclear, indole nucleus, tellurium azoles nuclear, benzene tellurium azoles nuclear, naphthalene tellurium azoles nuclear etc.R ₁₀₁And R ₁₀₂Represent alkyl, alkenyl, alkynyl or aralkyl respectively.These bases and below the base told about use with the meaning that contains its replacement respectively.For example, with the alkyl example when telling about, comprise not having displacement and displacement alkyl, these bases are straight chain, side chain or ring-types.The carbon number of alkyl is preferably 1-8.

As the sub stituent example of displacement alkyl, can enumerate halogen atom (fluorine, chlorine, bromine, iodine etc.), cyano group, alkoxy, replaced or not have displacement amino, carboxylic acid group, sulfonic group, hydroxyl etc., also can utilize in these 1 or several to be combined into line replacement.As the concrete example of alkenyl, can enumerate the ethene methyl.As the concrete example of aralkyl, benzyl and phenethyl can have been enumerated.

m ₁₀₁Expression 1.R ₁₀₃Expression hydrogen atom, low alkyl group, aralkyl or aryl.As the concrete example of above-mentioned aryl, displacement is arranged or do not have the displacement phenyl.R ₁₀₄The expression hydrogen atom.j ₁₀₁, K ₁₀₁Expression 0 or 1, X ₁₀₁ ^-The expression acidic anionic, n ₁₀₁Expression 0 or 1.

Below list the concrete example of general expression (T) expression compound, yet, be not limited to these.

[changing 3A]

[changing 4A]

The addition of these beam split sensitizing coloring matters according to circumstances can change in wide range, and per 1 mole of silver halide can add 0.5 * 10 ^-6～1.0 * 10 ^-2Mole.Better interpolation 1.0 * 10 ^-6～5.5 * 10 ^-3Mole.

Below silver halide photographic sensitive material of the present invention is described.

Silver halide photographic sensitive material of the present invention can be a black and white, also can be colored, but preferably uses silver emulsion of the present invention in silver halide colour photographic sensitive material.

Use the silver halide colour photographic sensitive material (following only be called sometimes " photosensitive material ") of silver emulsion of the present invention, be on supporter, to form the silver halide colour photographic sensitive material that has at least with one deck in the lower floor, promptly, contain the silver halide emulsion layer that forms the uranidin colour coupler, contain the silver halide emulsion layer that forms peony pigment colour coupler and contain the silver halide emulsion layer that forms cyanogen pigment colour coupler, it is characterized in that in the above-mentioned silver halide emulsion layer that one deck contains silver emulsion of the present invention at least.In the present invention, contain the silver halide emulsion layer that forms the uranidin colour coupler, bring into play function as yellow chromonic layer; Contain the silver halide emulsion layer that forms the deep erythronium colour coupler, bring into play function as the peony chromonic layer; With the silver halide emulsion layer that contains formation cyanogen pigment colour coupler, bring into play function as the cyanogen chromonic layer.The silver emulsion that contains separately in this yellow chromonic layer, peony chromonic layer and cyanogen chromonic layer, the light (for example, the light in blue look field, green field and red field) for mutual different wave length field preferably has photonasty.

Photosensitive material of the present invention, except above-mentioned yellow chromonic layer, peony chromonic layer and cyanogen chromonic layer, as requested can also contain following water wettability colloidal state layer, dizzy layer, middle layer and dyed layer disappear.

Known photograph material and adjuvant before can using in the photosensitive material of the present invention.

For example, use supporter, can use infiltration type supporter and reflection-type supporter as taking a picture.As the infiltration type supporter, preferably use at transparent films such as nitrous acid cellulose membrane and tygon terephalic acid esters.And then, 2, the polyester of the polyester of 6-naphthalene dicarboxylic acids (NDCA) and ethylene glycol (EG) and NDCA and terephalic acid, EG etc. is provided with information recording layers such as magnetosphere.As the reflection-type supporter, preferably form lamination by number layers of polyethylene layers and polyester layer, on one deck at least of this water-resistant resin layer (lamination), contain the reflection supporter of Chinese white such as titanium dioxide.

As better reflection supporter among the present invention, also have being provided with to have on the paper substrate body of silver halide emulsion layer side to contain small pore polyolefin layer.Polyolefin layer can be formed by multilayer, at this moment, the polyolefin layer adjacent with the gelatin layer of silver halide emulsion layer side do not have small pore (for example, polypropylene, tygon), be more preferably and formed by the polyolefin (for example polypropylene, tygon) that has small pore near the paper substrate side.The density of these multilayers between paper substrate body and photograph formation layer or the polyolefin layer of individual layer, that good is 0.40～1.0g/ml, more preferably 0.50～0.70g/ml.The thickness of these multilayers between paper substrate body and photograph formation layer or the polyolefin layer of one deck, that good is 10～100 μ m, more preferably 15～70 μ m.The thickness of polyolefin layer and paper substrate body than good be 0.05～0.2, more preferably 0.1～0.15.

Be provided with polyolefin layer constituting on the opposite side of layer (back side), consider that from the rigidity that improves the reflection supporter ideal, what at this moment the polyolefin layer at the back side was good is the tygon or the polypropylene of frosting, is more preferably polypropylene with the photograph of above-mentioned paper substrate body.That the polyolefin layer at the back side is good is 5～50 μ m, 10～30 μ m more preferably, 0.7～1.1g/ml that density is good.In reflection supporter of the present invention, about being located at the best form of the polyolefin layer on the paper substrate body, as the spy open flat 10-333277 number, with 10-333278 number, with 11-52513 number, with the example of record in 11-65024 number, EP0880065 number and EP0880066 number.

In above-mentioned water-resistant resin layer, can contain fluorescer.Also can form the water wettability colloidal state layer that disperses to contain fluorescer in addition.As above-mentioned fluorescer, the fluorescer of good use benzene  azoles system, coumarin series, pyrazoline system better uses benzene  azoles naphthalene system and benzene  azoles talan to be.Though consumption does not have particular determination, 1～100mg/m preferably ²Mixing ratio when in water-resistant resin, mixing, with respect to resin good be 0.0005～3 quality %, 0.001～0.5 quality % more preferably.

As the reflection-type supporter, also can be at the infiltration type supporter, or be coated with the water wettability colloidal state layer that contains Chinese white on the reflection-type supporter as described above.The reflection-type supporter also can be the supporter with specular reflective or the 2nd kind of scattered reflection metal surface.

As the supporter that uses in the photosensitive material of the present invention, can use demonstration is supporter with white polyester, or is provided with the supporter that contains the Chinese white layer on the supporter with silver halide emulsion layer side.In order to improve clarity, be preferably in the anti-dizzy layer of coating on the silver halide emulsion layer coated side of supporter or the back side.No matter be under the reflected light, or under the transmitted light, all can watch demonstration, the transmission density of supporter preferably is set in 0.35～0.8 scope.

Photosensitive material of the present invention, with the sharpness that improves portrait etc. is purpose, on water wettability colloidal state floor, add in the European patent EP 0337490 A2 number the dyestuff that passes through to handle to decolour (wherein oxygen alcohol based dye) of record in the 27th～76 page, photosensitive material is reached more than 0.70 the optical reflection concentration of 680nm, (more than the better 14 quality %) carry out the surface-treated titanium dioxide with 2～4 valency alcohols (for example, trimethylolethane) etc. more than the 12 quality % in good containing in the water-resistant resin layer of supporter.

In photosensitive material of the present invention, to prevent irradiation and halation, improving the safety lamp security is purpose, is preferably in to add the dyestuff of putting down in writing in the 27th～76 page in the European patent EP O 337490A2 instructions (wherein oxygen alcohol dyestuff, cyanine dye) that processing can be decoloured that passes through in the water wettability colloidal state floor.The dyestuff of putting down in writing in No. 819977 instructionss of European patent EP O also can add in the present invention.In these water-soluble dyes, when increasing consumption, look is separated and safety lamp security deterioration.As the dyestuff that look separate to be worsened, preferably special open flat 5-127324 number, with 5-127325 number, with the water-soluble dye of record in 5-216185 number.

Among the present invention, the dyed layer that the processing of use and water-soluble dye and usefulness can be decoloured replaces water-soluble dye.The dyed layer that used processing can be decoloured, can be directly and emulsion layer join the configuration of also can joining by the middle layer of containing the anti-blending agent of processing such as gelatin and quinhydrones.This dyed layer be preferably disposed on painted color be primary colors of the same race carry out the emulsion layer of color development lower floor (support side) on.All corresponding with each primary colors dyed layer is provided with respectively, and in these, only some can select arbitrarily to be provided with.Also can be provided with and the corresponding painted dyed layer of several former colour gamuts.The optical reflection concentration of dyed layer, in the wavelength domain that uses in the exposure (in the common print exposure, the wavelength of the scan exposure light source that uses in the visible light field of 400～700nm, during scan exposure), what the optical concentration value in the highest optical concentration wavelength was good is 0.2～3.0, more preferably 0.5～2.5, especially good is 0.8～2.0.

In order to form dyed layer, known method before can using.For example, following method is arranged, open the dyestuff of putting down in writing in page hurdle, lower-left, flat 3-7931 number 3 pages of upper right hurdle～11 as special dyestuff, the He Te that opens in flat 2-282244 number record in 3 pages of upper right hurdle～8 page, state with the solia particle molecular dispersion, be included in the method in the water wettability colloidal state layer, with the method for anionic property pigment mordant dyeing on cationic polymer; With the method for chromatopexis in having adsorbed atomic layers such as silver halide; The method of the use collargol of record in Te Kaiping 1-239544 number, or the like.As the method that the pigment fine powder is disperseed with the solid shape, for example, be documented in the spy and open the method in the 4th～13 page in flat 2-308244 number, be contain water insoluble below PH6 at least, but the method for water-soluble fine powder dyestuff more than PH8 at least.For example, as with the method for anionic property pigment mordant dyeing on cationic polymer, be documented in the spy and open in flat 2-84637 number in the 18th～26 page.About collargol modulator approach, shown in United States Patent (USP) No. 2688601, No. 3459563 as light absorber.In these methods, contain the method for fine powder dyestuff, preferably use the method for collargol etc.

Silver halide photographic sensitive material of the present invention, though can be used for colored negative film, colored positive film, colour reversal film, colour reversal photographic paper, clour-printing paper etc., wherein, preferably as clour-printing paper.Clour-printing paper, preferably make each all formation of each layer at least of yellow color emissivity silver halide emulsion layer, peony color emissivity silver halide emulsion layer and cyanogen color emissivity silver halide emulsion layer with having, these silver halide emulsion layers generally are from beginning to be followed successively by yellow color emissivity silver halide emulsion layer, peony color emissivity silver halide emulsion layer, cyanogen color emissivity silver halide emulsion layer near supporter.

Yet, also can take the layer different to constitute with it.

The silver halide emulsion layer that contains yellow colour former, on configurable any position on supporter, when in containing this yellow colour former layer, containing the dull and stereotyped particle of silver halide, preferably be coated on than the silver halide emulsion layer that contains the peony colour coupler or contain on the position of at least one leafing spending support body in the silver halide emulsion layer of cyanogen colour coupler.From promoting the color development video picture, promote the desilverization, reduce because of sensitizing coloring matter causes residual look aspect and consider, contain the silver halide emulsion layer of yellow colour former, preferably be coated on than on the farther position of other silver emulsion leafing supporters.And then, consider that from reducing the Blix aspect of fading the silver halide emulsion layer that contains the cyanogen colour coupler is the middle layer of other silver halide emulsion layers preferably, consider that from reducing the light aspect of fading the silver halide emulsion layer that contains the cyanogen colour coupler is preferably orlop.Each color emissivity layer of yellow, peony and cyanogen can form by 2 layers or 3 layers.For example, the spy open flat 4-75055 number, with 9-114035 number, with record in No. the 5576159th, 10-246940 number, United States Patent (USP) etc. like that, the color former layer that does not contain silver emulsion is arranged in abutting connection with silver halide emulsion layer, form chromonic layer.

As silver emulsion that uses among the present invention and other materials (adjuvant etc.), the formation of taking a picture layer (layer configuration etc.), and suitable facture and the processing adjuvant of handling this photosensitive material, preferably use and specially open clear 62-215272 number, spy and open record in flat 2-33144 number, European patent EP O 355660A2 number, better use record among European patent EP O 355660A2 number.And then can also use the spy open flat 5-34889 number, with 4-359249 number, with 4-313753 number, with 4-270344 number, with 5-66527 number, with 4-34548 number, with 4-145433 number, with 2-854 number, with 1-158431 number, with 2-90145 number, with 3-194539 number, disclose 0520457A2 number etc. with 2-93641 number, European patent in the silver halide colour photographic sensitive material and the disposal route thereof of record.

Among the present invention, about above-mentioned reflection-type supporter and silver emulsion and then, the different metal ionic species that mixes in the silver halide particle, the preserving stabilizer of silver emulsion or antifoggant, chemical sensitization method (sensitizer), beam split sensitizing method (branch light sensitizer), cyanogen, peony, yellow colour former and emulsification dispersion method thereof, the layer of colour keeping quality modifying agent (anti-coloring agent and anti-stripping agent), dyestuff (dyed layer), gelatin kind, photosensitive material constitutes and the tunicle PH of photosensitive material etc., uses preferably that patent is put down in writing shown in the following table 1 everywhere.

Key element	Te Kaiping 7-104448 number	Te Kaiping 7-77775 number	Te Kaiping 7-301895 number
				The reflection-type support	12 row～12 hurdles, the 7th hurdle, 19 row	43 row～44 hurdles, the 35th hurdle, 1 row	40 row～9 hurdles, the 5th hurdle, 26 row
Silver emulsion	29 row～74 hurdles, the 72nd hurdle, 18 row	36 row～46 hurdles, the 44th hurdle, 29 row	48 row～80 hurdles, the 77th hurdle, 28 row
				The different metal ionic species	The 74th hurdle 19 row～with hurdle 44 row	30 row～47 hurdles, the 46th hurdle, 5 row	29 row～81 hurdles, the 80th hurdle, 6 row
Preserving stabilizer or prevent the photographic fog agent	The 75th hurdle 9 row～with hurdle 18 row	The 47th hurdle 20 row～with hurdle 29 row	11 row～31 hurdles, the 18th hurdle, 37 row (particularly sulfhydryl heterocycle compound)
				Chemical sensitization method (chemical sensitizer)	45 row～75 hurdles, the 74th hurdle, 6 row	The 47th hurdle 7 row～with hurdle 17 row	The 81st hurdle 9 row～with hurdle 17 row
Beam split sensitizing method (branch light sensitizer)	19 row～76 hurdles, the 75th hurdle, 45 row	30 row～49 hurdles, the 47th hurdle, 6 row	21 row～82 hurdles, the 81st hurdle, 48 row
				The cyanogen colour coupler	20 row～39 hurdles, the 12nd hurdle, 49 row	50 row～the 63 hurdle, the 62nd hurdle, 16 row	49 row～89 hurdles, the 88th hurdle, 16 row
Yellow colour former	40 row～88 hurdles, the 87th hurdle, 3 row	The 63rd hurdle 17 row～with hurdle 30 row	The 89th hurdle 17 row～with hurdle 30 row
				The peony colour coupler	The 88th hurdle 4 row～with hurdle 18 row	3 row～64 hurdles, the 63rd hurdle, 11 row	44 row the 88th hurdle, 34 row～77 hurdles, the 31st hurdle, 32 row～with hurdle 46 row
Become the emulsification dispersion method of bag agent	3 row～72 hurdles, the 71st hurdle, 11 row	The 61st hurdle 36 row～with hurdle 49 row	The 87th hurdle 35 row～same 48 row
				Colour keeping quality modifying agent (preventing colorant)	50 row～70 hurdles, the 39th hurdle, 9 row	50 row～62 hurdles, the 61st hurdle, 49 row	49 row～88 hurdles, the 87th hurdle, 48 row
Anti-stripping agent	10 row～71 hurdles, the 70th hurdle, 2 row
				Dyestuff (colorant)	42 row～78 hurdles, the 77th hurdle, 41 row	3 row～51 hurdles, 42 row the 50th hurdle, 14 row～19 hurdle, the 7th hurdle, 14 row	27 row～18 hurdles, the 9th hurdle, 10 row
The gelatin kind	The 78th hurdle 42 row～with hurdle 48 row	The 51st hurdle 15 row～with hurdle 20 row	The 83rd hurdle 13 row～with hurdle 19 row
				The layer of photosensitive material constitutes	The 39th hurdle 11 row～with hurdle 26 row	The 44th hurdle 2 row～with hurdle 35 row	38 row～32 hurdles, the 31st hurdle, 33 row
The tunicle pH of photosensitive material	The 72nd hurdle 12 row～with hurdle 28 row
				Scan exposure	6 row～77 hurdles, the 76th hurdle, 41 row	7 row～50 hurdles, the 49th hurdle, 2 row	49 row～83 hurdles, the 82nd hurdle, 12 row
The permanent agent of guarantor in the imaging liquid	19 row～89 hurdles, the 88th hurdle, 22 row

The cyanogen look that uses among the present invention, peony and yellow colour coupler, other can also use the colour coupler of following middle record, that is, the spy opens in clear 62-215272 number that～121 pages of upper left hurdles of 4 row, the 91st page of upper right hurdle 6 row, spies open in flat 2-33144 number in the 3rd page of upper right hurdle-18 pages of upper left hurdle footlines of 14 row and the 30th page of upper right hurdle hurdle, 6～35 pages of bottom rights of row 11 row and EPO355660A2 number that the 4th page of 15 row～27 row ,～28 pages of footlines of 5 page of 30 row, 45 page of 29 row～31 are gone, puts down in writing in～63 page of 50 row of 47 page of 23 row.

The present invention preferably also add general expression in WO-98/33760 number (II) and (III), the spy opens the compound of the expression of general expression (D) in flat 10-221825 number.

The colour coupler of spendable formation cyanogen pigment among the present invention (only being called " cyanogen colour coupler " sometimes), can use the pyrrolo-triazole to be tied to form toner, preferably the spy opens general expression (I) in flat 5-313324 number or (II) colour coupler of general expression (I) expression in the colour coupler of expression and the flat 6-347960 of Te Kai number, and the example colour coupler of putting down in writing in these patents.Also can use the cyanogen look colour coupler of phenol system, naphthols system, for example, the spy opens the cyanogen look colour coupler of general expression (ADF) expression of record in flat 10-333297 number.As the cyanogen look colour coupler beyond above-mentioned; can also use pyrroles's azoles type cyanogen look colour coupler of putting down in writing in European patent EP O488248 instructions and the EPO491197A1 instructions; in No. the 5888716th, the United States Patent (USP) 2 of record, 5-diamido phenol colour coupler; No. the 4873183rd, United States Patent (USP); has the electron attractivity base on the 6th of record in same No. 4916051; the pyrazoline azoles type cyanogen look colour coupler of hydrogen bond base; Te Kaiping 8-171185 number; with 8-311360 number; with the pyrazoline azoles type cyanogen look colour coupler that has carbamyl on the 6th of record in 8-339060 number.

Except the spy opens the diphenyl-imidazole of putting down in writing in the flat 2-33144 communique is the cyanogen look colour coupler, can also use the 3-pyridone of putting down in writing in the European patent EP O333185A2 instructions be cyanogen look colour coupler (wherein, having chlorine in 4 equivalent colour couplers of the colour coupler of enumerating as concrete example (42) breaks away from base and forms 2 equivalents, colour coupler (6) and (9) are best) and special open the active methene of the ring-type of putting down in writing in the clear 64-32260 communique be cyanogen look colour coupler (wherein, the colour coupler example of enumerating as concrete example 3,8,34 is good especially), pyrroles's pyrazoles type cyanogen look colour coupler of putting down in writing in the European patent EP O456226A1 instructions, the Allercur type cyanogen look colour coupler of record in European patent EP O484909 number.

In these cyanogen look colour couplers, pyrroles's azoles of the spy opens general expression (I) expression of putting down in writing in the flat 11-282138 communique that good especially is is a cyanogen look colour coupler, comprise example cyanogen look colour coupler (1)～(47 of putting down in writing in the 0012-0059 paragraph in this patent), intactly be applicable to the application, so take in into as the part of present specification.

Be formed into toner (being called " peony colour coupler " sometimes) as the peony pigment that uses among the present invention, can use the 5-pyrrolinone of known document record in the above-mentioned table is that peony colour coupler and pyrrolin azoles are the peony colour coupler, wherein with regard to the stability of phase look and image, aspects such as color emissivity are considered, preferably use the colour coupler of putting down in writing in the following document, promptly, the spy opens the pyrrolin triazole colour coupler that is connected to 2 grades or 3 grades alkyl on 2,3 or 6 of pyrrolin triazole ring of record in clear 61-65245 number, the spy opens the pyrrolin azoles colour coupler that the molecule of putting down in writing in clear 61-65246 number contains sulfoamido, the spy opens the pyrrolin azoles colour coupler with alkoxyphenyl radical sulfonamide carrier band balance base of record in clear 61-147254 number, with the pyrrolin azoles colour coupler that has alkoxy and aryloxy group on 6 of record in European patent 226849A and 294785A number.As the peony colour coupler, be more preferably the pyrrolin azoles colour coupler that the spy opens general expression (M-1) expression of record in flat 8-122984 number, 0009～0026 paragraph also is applicable to the application in this patent, includes into as the part in the present specification.In addition, can also use European patent No. 854384, with the pyrrolin azoles colour coupler that on 3 and 6, all has the steric hindrance base of record in No. 884640.

Be formed into toner (only being called " yellow colour former " sometimes) as xanthein; the compound of in above-mentioned table, putting down in writing; can also use following document to put down in writing; that is the acyl group acetamide type yellow colour former of, putting down in writing in the European patent EP O447969A1 instructions that on acyl group, has 3～5 yuan of ring-shaped structures; the third two diphenyl aniline type yellow colour formers of putting down in writing in the European patent EP O482552A1 instructions with ring-shaped structure; Europe publication 953870A1 number; with 953871A1 number; with 953872A1 number; with 953873A1 number; with 953874A1 number; pyrroles-2 who puts down in writing in the 953875A1 grade or 3-acyl or indoles-2 or 3-acyl carbonyl acetoxyphenyl group aniline are tied to form toner together; the acyl group acetamide type yellow colour former of putting down in writing in No. 5118599 instructions of United States Patent (USP) with two  structure.Wherein, preferably using acyl group is the third two diphenyl aniline type yellow colour formers that a side of acyl group acetamide type yellow colour former, the phenylaniline of 1-alkyl trimethylene-1-carbonyl constitutes indole ring.These colour couplers can use separately or and use.

The colour coupler that uses among the present invention, being preferably in the high boiling organic solvent of putting down in writing in the above-mentioned table exists down (or under not existing) to be soaked by thiocyanic acid type latex polymer (for example No. the 4203716th, United States Patent (USP)), or dissolve with the polymkeric substance of water-insoluble and organic soluble, in water wettability colloidal state aqueous solution, carry out emulsification and disperse.The polymkeric substance of the most handy water-insoluble and organic solvent solubility has single polymers or the multipolymer put down in writing in the 12nd page～30 pages in the open WO88/00723 instructions in the 7th hurdle～15 hurdles and the world in No. 4857449 instructions of United States Patent (USP).Be more preferably methacrylate ester or acrylic acid amides based polymer,, better use the acrylic acid amides based polymer just as considerations such as color stabilities.

Though can use known anti-blending agent among the present invention, put down in writing in the wherein preferably following patent.

For example, the most handy spy open the phenidone of record in No. the 4923787th, oxidation-reduction type compound, the WO98/33760 United States Patent (USP) etc. of high molecular of flat 5-333501 number record and hydrazine based compound, spy open flat 5-249637 number, the spy opens flat 10-282615 number and Deutsche Bundespatent 19629142A1 number etc. in the white colour coupler of record.At the pH that improves imaging liquid, when making video picture rapid, the oxidation-reduction type compound of record in better use Deutsche Bundespatent 19618786A1 number, European patent 839623A1 number, European patent 842975A1 number, Deutsche Bundespatent 19806846A1 number and the French Patent (FRP) 2760460A1 number etc.

Among the present invention,, preferably use compound, for example can use the compound of putting down in writing in the following patent with the high triazine skeleton of molar absorptivity as ultraviolet light absorber.These preferably add photosensitive layer to or/and in the non-photosensitive layer.For example, can use the spy open clear 46-3335 number, with 55-152776 number, spy open flat 5-197014 number, with 5-232630 number, 5-307232 number, with 6-211813 number, with 8-53427 number, with 8-234364 number, with 8-239368 number, with 9-31067 number, with 10-115898 number, with 10-147577 number, with the compound of record in 10-182621 number, Deutsche Bundespatent 19739797A number, European patent 711804A number and the special table flat 8-501291 number etc.

As spendable bond or protecting colloid in the photosensitive material of the present invention, use gelatin very convenient, also can be separately or use other hydrophilic colloid with gelatin.As best gelatin,, good below 5ppm, better below 3ppm with the heavy metal that impurity such as iron, copper, zinc, manganese contain.The amount of institute's calcic in the photosensitive material is good at 20mg/m ²Below, better at 10mg/m ²Below, be preferably in 5mg/m ²Below.

Among the present invention, cause image degradation, preferably add special fungi-proofing, the antifoggant of putting down in writing in the clear 63-271247 communique of opening in order to prevent that various moulds and bacterium from breeding in hydrophilic colloid layer.What the tunicle pH of photosensitive material was good is 4.0～7.0, more preferably 4.0～6.5.

Among the present invention, consider, can in photosensitive material, add surfactant from the coating stability that improves photosensitive material, the anti-aspects such as static, accommodation zone electric weight that produce.As surfactant, it is that surfactant, kation are that surfactant, betaine are that surfactant, nonionic are surfactant that negative ion is arranged, and for example, the spy opens in flat 5-333492 number record.As the surfactant that uses among the present invention, can be the surfactant that contains fluorine atom.The better surfactant that uses contain fluorine atoms.The surfactant of these contain fluorine atoms can use separately, also can with other known surfactant and usefulness, preferably with other known surfactants and use.The addition of these surfactants in photosensitive material be not though have particular determination, normally 1 * 10 ^-5～1g/m ², good is 1 * 10 ^-4～1 * 10 ^-1G/m ², be more preferably 1 * 10 ^-3～1 * 10 ^-2G/m ²

Photosensitive material of the present invention according to image information, by light-struck exposure process with make above-mentioned light-struck photosensitive material carry out the videograph process of video picture, can form image.

Photosensitive material of the present invention except being used for using the print system of negative printing machine usually, also is applicable to the scan exposure mode of using cathode line (CRT).The leonard's tube exposure device compares with the device that uses laser, and is easy, and miniaturization, and expense is low, and optical axis and tone are easy to adjust.The leonard's tube that uses in image exposure can use the luminous various luminophors of demonstration in the spectrum field as required.For example, use any a kind in emitting red light body, green emitting body, the blue look luminophor, or mix more than 2 kinds and use.The spectrum field has more than and is defined in above-mentioned redly, green, blue, also can use luminous fluorophor in yellow, orange, purple or infrared field.Each all being to use mixed the white luminous leonard's tube of formation with these luminophors.

Photosensitive material has different several photosensitive layers that divide photo sensitivity to distribute, when the cathodic pipe presents several luminous fluorophor in having the spectrum field, can be to several color single exposures, promptly, in the picture signal input leonard's tube with several colors, luminous by the pipe face.Also can adopt at every turn versicolor picture signal is imported successively, shades of colour can carry out luminous successively, by filter disc the color beyond this color is cut away the method (face exposure successively) of exposing, generally, face exposure method successively, owing to can use the leonard's tube of high image resolution, obtain high-quality portrait, so ideal.

Photosensitive material of the present invention, preferably use the digital scanning Exposure mode, this digital scanning Exposure mode has been to use gas laser, light emitting diode, semiconductor laser or with semiconductor laser or the second high frequency illuminating source monochromatic high density light such as (SHG) that uses Solid State Laser that semiconductor laser makes exciting light source and nonlinear optics crystallization to make up.With regard to system's miniaturization, cheap, the second high frequency generation light source (SHG) that preferably uses semiconductor laser or nonlinear optics crystallization and semiconductor laser or Solid State Laser are made up.Small-sized in order to be designed to, cheap, device that the life-span is long, that stability is high preferably use semiconductor laser, and at least one preferably uses semiconductor laser in the exposure light source.

When using such scan exposure light source, the branch photo sensitivity maximum wavelength of photosensitive material of the present invention can be set arbitrarily with the wavelength of light source according to used scan exposure.When semiconductor laser is used in the SHG light source that the Solid State Laser of exciting light source or semiconductor laser and nonlinear optics crystallization combination obtain, owing to the oscillation wavelength of laser can be divided into half, obtain blue coloured light, green light, therefore, the maximum of photosensitive material divides photo sensitivity can remain in orchid, green, red three the wavelength fields.The time shutter of this scan exposure is defined as, the time of when picture element density is taken as 400dpi the picture element size being exposed, as the good time shutter 10 ^-4Below second, better 10 ^-6Below second.

Silver halide colour photographic sensitive material of the present invention, preferably with following known data in exposure, the imaging system put down in writing make up.As above-mentioned imaging system, there is the spy to open the automatic printing and the imaging system of record in flat 10-333253 number, the spy opens the photosensitive material input media of record in 2000-10206 number, the register system that contains image read-out of record in Te Kaiping 11-215312 number, Te Kaiping 11-88619 number and the special exposure system that constitutes by the coloured image recording mode of opening record in flat 10-202950 number, the digital light print system of the telediagnosis mode that contains of record in Te Kaiping 10-210206 number, the light print system that contains image recording structure of being willing in flat 10-159187 number record with the spy.

About being suitable for most scan exposure mode of the present invention, be documented in the patent that in above-mentioned table, discloses.

When photosensitive material of the present invention carries out print exposure, preferably use the wave band of record in No. the 4880726th, the United States Patent (USP) to end filtrator, can remove mixed light like this, significantly improve the repeatability of color.

Among the present invention, as European patent EP O789270A1 and with record in EPO789480A1 number like that, before giving image information, the little dot pattern to yellow carries out prior exposure in advance, also can implement to duplicate to restrict.

For the processing of photosensitive material of the present invention, preferably use and specially open in flat 2-207250 number the 26th page of hurdle, bottom right 1 row～34 pages of upper right hurdles 9 row and specially open in flat 4-97355 number the processing material and the disposal route of record in hurdle, 17～18 pages of bottom rights of row, the 5th page of upper left hurdle 20 row.As the permanent agent of the guarantor who uses in this imaging liquid, preferably use and disclose the compound of putting down in writing in the patent in the above-mentioned table.

The present invention preferably is applicable to the photosensitive material with suitable fast processing, when carrying out fast processing, the color development time of developing good below 60 seconds, better below 50 seconds more than 6 seconds, best below 30 seconds more than 6 seconds.Equally, the blix time good below 60 seconds, better below 50 seconds more than 6 seconds, be preferably in below 30 seconds more than 6 seconds.Washing or stabilization time good below 150 seconds, better below 130 seconds more than 6 seconds.

So-called color development time of developing is meant the back time in the following one treatment process bleach-fixing liquid of packing into from color development imaging liquid that photosensitive material is packed into.For example, with processing such as automatic developing devices the time, time (time in the so-called liquid) that photosensitive material is flooded in the color development imaging liquid and make photosensitive material leave the color development imaging liquid, the blix of downward one treatment process is bathed, the time of carrying in air (so-called in-flight time), both time adds up to and is called the color development time of developing.Equally, the so-called blix time is meant behind bleach-fixing liquid that photosensitive material is packed into, to wash together down or the stabilizer bath of packing in time.So-called washing or stabilizing take are meant from after the photosensitive material washing or the stabilizing solution of packing into, to dry run, and the time that in liquid, exists (time in the so-called liquid).

As the method for will carry out video picture after the photosensitive material exposure of the present invention, the method of using the imaging liquid contain alkaline agent and imaging main agent to carry out video picture in the past, imaging main agent is built in the photosensitive material, carry out the method for video picture etc. with the alkalies isoreactivity solution that does not contain imaging main agent, except these wet type modes, can also use hot video picture mode without treating fluid etc.Activation method, owing to do not contain imaging main agent in the treating fluid, so treating fluid is manageable and processing, load is optimal method with regard to environmental protection seldom during liquid waste processing.

In activation method, as imaging main agent in the interior plant photosensitive material or its precursor, preferably special open flat 8-234388 number, with 9-152686 number, with 9-152693 number, with 9-211814 number, with the hydrazine type compound of record in 9-160193 number.

Also can use and reduce photosensitive material silver coating amount, use the developing method of the image amplification processing (auxiliary process) of hydrogen peroxide.Preferably the method is used for activation method.Specifically, preferably use the special method that flat 8-297354 number, the activate solution that contains hydrogen peroxide with the use of record in 9-152695 number form image of opening.In above-mentioned activation method, after using the activate solution-treated, carry out desilverization processing usually, and use the image amplification disposal route of the photosensitive material of low silver amount, saved desilverization processing, carry out the simple and easy method of what is called washing or stabilization processes.When using scanner etc.,, also can adopt the processing form that does not need desilverization processing even use the high silver amount photosensitive material of picture shooting with photosensitive material etc. from the mode of photosensitive material reading images information.

The activate solution that uses among the present invention can use the processing material and the disposal route of known desilverization liquid (bleaching/stop bath), washing and stabilization liquid.Preferably use リ サ one the 536th page～the 541st page of チ デ イ ス Network ロ one ジ ヤ-Item36544 (in September, 1994), spy to open in flat 8-234388 number record.

Description of drawings

Fig. 1 is bromide and the concentration profile figure of iodide ion on emulsion G-4 particle depth direction among the embodiment 2.

Followingly specify the present invention according to embodiment, but the present invention is not limited by these examples.

Embodiment 1

(modulation of emulsion B-1)

1000ml lime treatment gelatin 3% aqueous solution is adjusted to pH3.3, pCl1.7, and strong agitation limit, limit is added simultaneously mixing at 66 ℃ and is contained the 2.12 equimolar silver nitrate aqueous solution and contain the 2.2 mole nacl aqueous solution. When silver nitrate adds 80%～90% to, add K₄[Ru(CN) ₆] aqueous solution, make the Ru amount of producing, to per 1 mole of silver halide, reach 3 * 10^-5The amount of mole. When silver nitrate adds 83%～88% to, add K₂[IrCL ₆] aqueous solution, make the Ir amount of producing, to per 1 mole of silver halide, reach 3 * 10^-8The amount of mole. When silver nitrate adds 92%～98% to, add K₂[Ir(H ₂O)Cl ₅] aqueous solution, make the Ir amount of producing, for per 1 mole of silver halide, reach 1 * 10^-6The amount of mole. After 40 ℃ of lower enforcement dechlorinations are processed, add 168g lime treatment gelatin, adjust to pH5.7, pCl1.8. The gained particle is the length of side 0.6 μ m, the three-dimensional silver chloride emulsion of coefficient of alteration 11%.

40 ℃ of dissolvings, relatively per 1 mole of silver halide adds 2 * 10 with this emulsion^-5The thiosulfonic acid sodium of mole as the sulphur sensitizer, uses sodium thiosulfate 5 hydrates and golden sensitizer (S-2) to reach optimum 60 ℃ of maturations. After cooling to 40 ℃, add 2 * 10 for per 1 mole of silver halide^-4The sensitizing coloring matter A of mole, add 1 * 10 for per 1 mole of silver halide^-4The sensitizing coloring matter B of mole, add 2 * 10 for per 1 mole of silver halide^-4The 1-phenyl of mole-5-mercapto-tetrazole adds 2 * 10 for per 1 mole of silver halide^-4Mole 1-(5-MU phenyl)-5-mercapto-tetrazole, add 2 * 10 for per 1 mole of silver halide^-3The KBr of mole. With these emulsions that obtain as emulsion B-1.

(sensitizing coloring matter A)

(sensitizing coloring matter B)

(modulation of emulsion B-2)

When silver nitrate adds 90% end to, the limit is strongly mixed the limit and is added potassium iodide aqueous solution, for per 1 mole of silver halide, make the amount that I amount reaches 0.2 % by mole of producing, being modulated into the emulsion different from emulsion B-1, is the cube silver iodochloride emulsion that obtains the particle length of side 0.6 μ m, coefficient of alteration 11%. The emulsion that obtains like this is taken as emulsion B-2.

The iodide ion CONCENTRATION DISTRIBUTION of gained emulsion B-2 is utilized the analysis of etch/TOF-SIMS method, and iodide ion concentration is maximum at particle surface as can be known, and concentration reduces gradually to the inside. Even the particle inboard (silver nitrate adds 90% position) that is added on of iodide salt solution terminates, iodide ion oozes out towards particle surface. The particle shape of producing and emulsion B-1 and B-2 do not have difference, think that emulsion B-2 contains in that particle is the most surperficial to contain the silver iodochloride particle that silver iodide form stratiform mutually.

(modulation of emulsion B-3)

Interpolation at silver nitrate reaches for 80%～90% the moment, the limit is strongly mixed the limit and is added KBr, for per 1 mole of silver halide, make the amount that Br amount reaches 2 % by mole of producing, being modulated into the emulsion different from emulsion B-1, is that the gained particle length of side is the cube bromine silver chloride emulsion of 0.6 μ m, coefficient of alteration 11%. The emulsion that obtains like this is taken as emulsion B-3.

When the bromide ion CONCENTRATION DISTRIBUTION of gained emulsion B-3 is analyzed with etch/TOF-SIMS method, maximum in inside particles bromide ion concentration as can be known. Present at the particle that adds bromide salt solution inboard (silver nitrate adds 80%～90% position) and to contain the silver bromide phase. The particle shape of producing and emulsion B-1 and B-3 almost do not have difference, think that emulsion B-3 contains to make at inside particles to contain the bromine silver chlorate particle that silver bromide forms stratiform mutually.

(modulation of emulsion B-4)

The interpolation of silver nitrate reaches for 90%～100% the moment, the limit is strongly mixed the limit and is added KBr, for per 1 mole of silver halide, make the amount that Br amount reaches 2 % by mole of producing, being modulated into the emulsion different with emulsion B-1, is that the gained particle length of side is that 0.6 μ m, coefficient of alteration are 11% cube bromine silver chloride emulsion. The emulsion that obtains like this is taken as emulsion B-4.

When the bromide ion CONCENTRATION DISTRIBUTION of gained emulsion B-4 was analyzed with etch/TOF-SIMS method, bromide ion mainly was distributed near surface as can be known. Contain the silver bromide phase what carry out that (silver nitrate adds 90%～100% position) near the particle surface that bromide salt solution adds present formation. The particle shape of producing and emulsion B-1 and B-4 roughly do not have difference, think that emulsion B-4 contains to make near surface to contain the bromine silver chlorate particle that silver bromide forms stratiform mutually.

(modulation of emulsion B-5)

The interpolation of silver nitrate reaches 80%～100% constantly, and the limit is strongly mixed the limit and added KBr, for per 1 mole of silver halide, makes and produces the Br amount and reach 4 % by mole amount, is modulated into the emulsion different from emulsion B-1. That the gained particle length of side is the cube bromine silver chloride emulsion of 0.6 μ m, coefficient of alteration 11%. The emulsion that obtains like this is taken as emulsion B-5.

When the bromide ion CONCENTRATION DISTRIBUTION of gained emulsion B-5 was analyzed with etch/TOF-SIMS method, bromide ion was from inside particles to surface distributed as can be known. What side direction surface in the particle that adds bromide salt solution (silver nitrate adds 80%～100% position) presented formation contains the silver bromide phase. The particle shape of producing and emulsion B-1 and B-5 do not have difference, think that emulsion B-5 contains to contain the bromine silver chlorate particle that silver bromide forms stratiform mutually from the inside particles to the surface.

(modulation of emulsion B-6)

The moment of the interpolation of silver nitrate from 80%～90%, the strong mixing and the interpolation KBr, for per 1 mole of silver halide, make the amount that Br amount reaches 2 % by mole of producing, and then reach moment of 90% termination in the interpolation of silver nitrate, strongly mix and add potassium iodide aqueous solution, for per 1 mole of silver halide, make and produce the amount that I amount reaches 0.2 % by mole, be modulated into the emulsion different from emulsion B-1. Be that the gained particle length of side is that 0.6 μ m, coefficient of alteration are 11% cube iodine bromine silver chloride emulsion, the emulsion that obtains like this is taken as emulsion B-6.

When the iodide ion of gained emulsion B-6 and bromide ion CONCENTRATION DISTRIBUTION were analyzed with etch/TOF-SIMS method, very big in particle surface iodide ion concentration as can be known, concentration decline was in contrast, very big in inside particles bromide ion concentration to the inside. Even the interpolation termination at particle inboard (silver nitrate adds 90% position) iodide salt solution, iodide ion oozes out to particle surface, contains the silver bromide phase what carry out that particle inboard (silver nitrate adds 80%～90% position) that bromide salt solution adds presents formation. The particle shape of producing and emulsion B-1 and B-6 do not have difference, think that emulsion B-6 contains to contain silver bromide at inside particles and form mutually stratiform, contain the iodine bromine silver chlorate particle that silver iodide form stratiform mutually in that particle is the most surperficial.

(modulation of emulsion B-7)

Reach the moment of 90% termination in the interpolation of silver nitrate, the limit is strongly mixed the limit and is added potassium iodide aqueous solution, make the amount that I amount reaches 0.2 % by mole of producing for per 1 mole of silver halide, and then, reaching 90%～100% moment limit in the interpolation of silver nitrate strongly mixes the limit and adds KBr, make for per 1 mole of silver halide and to produce the amount that Br amount reaches 2 % by mole, be modulated into the emulsion different from emulsion B-1. Be that the gained particle length of side is the cube iodine bromine silver chloride emulsion of 0.6 μ m, coefficient of alteration 11%, the emulsion that obtains like this is taken as emulsion B-7.

When the iodide ion of gained emulsion B-7 and bromide ion concentration are issued and are analyzed with etch/TOF-SIMS method, very big in particle surface iodide ion concentration as can be known, concentration decline to the inside, bromide ion mainly is distributed near surface. Even the interpolation termination at particle inboard (silver nitrate adds 90% position) iodide salt solution, the ion of iodate oozes out to particle surface, and what (silver nitrate add 90%～100% position) presented formation near the particle surface that adds bromide salt solution contains the silver bromide phase. The particle shape of producing and emulsion B-1 and B-7 do not have difference, think that emulsion B-7 contains to make from the teeth outwards to contain silver bromide phase and the iodine bromine silver chlorate particle that contains silver iodide and form mutually stratiform.

(modulation of emulsion B-8)

The interpolation of silver nitrate reaches for 80%～100% the moment, the limit is strongly mixed the limit and is added KBr, for per 1 mole of silver halide, make the amount that Br amount reaches 4 % by mole of producing, and then reaching moment of 90% termination in the interpolation of silver nitrate, the limit is strongly mixed the limit and is added potassium iodide aqueous solution, for per 1 mole of silver halide, make and produce the amount that I amount reaches 0.2 % by mole, be modulated into the emulsion different from emulsion B-1. Be that the gained particle length of side is that 0.6 μ m, coefficient of alteration are 11% cube iodine bromine silver chloride emulsion, the emulsion that obtains like this is taken as emulsion B-8.

When the iodide ion of gained emulsion B-8 and bromide ion CONCENTRATION DISTRIBUTION are analyzed with etch/TOF-SIMS method, very big in particle surface iodide ion concentration as can be known, and concentration decline to the inside, opposite with it, bromide ion is from inside particles to surface distributed. Even in particle inboard (silver nitrate adds 90% position) iodide salt solution termination, iodide ion oozes out to particle surface, in the particle that adds bromide salt solution side direction surface (silver nitrate adds 80%～100% position), present to form and contain the silver bromide phase. The particle shape of producing and emulsion B-1 and B-8 do not have difference, think that emulsion B-8 contains to make to the surface from inside particles to contain silver bromide and form mutually stratiform, contain the iodine bromine silver chlorate particle that silver iodide form stratiform mutually the most surperficial the making of particle.

Two sides with the polyvinyl resin coated paper, on the supporting body surface that so forms, after real discharge corona is processed, setting contains coating under the gelatin of neopelex, and then apply successively the photograph constituting layer of ground floor～layer 7, make the silver halide colour photographic sensitive material test portion that layer shown below consists of. The coating fluid that each constituting layer of taking a picture is used is pressed such as modulated.

The modulation of ground floor coating fluid

57g yellow colour former (Exy), 7g are dissolved in 21g solvent (Solv-1) and the 80ml ethyl acetate as colouring stabilizer (Cpd-8) as colouring stabilizer (Cpd-3), 2g as colouring stabilizer (Cpd-2), 7g as colouring stabilizer (Cpd-1), 4g, with this solution in the 220g of the neopelex that contains 4g 23.5 quality % aqueous gelatin solutions, carry out emulsion dispersion with high-speed stirred mulser (dissolvers), add entry and be modulated into 900g emulsion dispersion thing A.

On the other hand, with above-mentioned emulsion dispersion thing A and emulsion B-1 mixed dissolution, be modulated into the ground floor coating fluid of following composition. Emulsion coating weight be expressed as the converting coating weight of silver amount.

The coating fluid that the second layer～layer 7 is used is also with the method modulation identical with the ground floor coating fluid. As the gelatin hardener of each layer, use 1-oxygen-3,5-two chloro-S-triazine sodium salts (H-1), (H-2), (H-3). Add respectively Ab-1, Ab-2, Ab-3 and Ab-4 in each layer, total amount reaches respectively 15.0mg/m²、60.0mg/m ²、 5.0m/m ²And 10.0mg/m²。

(H-1) hard coat agent

(H-2) hard coat agent

(H-3) hard coat agent

[changing 8]

(Ab-1) anticorrisive agent (Ab-2) anticorrisive agent

(Ab-3) anticorrisive agent

(Ab-4) anticorrisive agent

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

A, b, c, 1: 1: 1 of d: 1 mixture (mol ratio)

In the bromine silver chloride emulsion of green and red perceptual emulsion layer, use respectively following light splitting sensitizing coloring matter.

Green perceptual emulsion layer

[changing 9]

(sensitizing coloring matter D)

(sensitizing coloring matter E)

(sensitizing coloring matter F)

(sensitizing coloring matter D: for per 1 mole of silver halide, large scale emulsion is added 3.0 * 10^-4Mole adds 3.6 * 10 to small size emulsion^-4Mole. Sensitizing coloring matter E: for per 1 mole of silver halide, large scale emulsion is added 4.0 * 10^-5Mole adds 7.0 * 10 to small size emulsion^-5Mole. Sensitizing coloring matter F: for per 1 mole of silver halide, large scale emulsion is added 2.0 * 10^-4Mole adds 2.8 * 10 to small size emulsion^-4Mole. )

Red perceptual emulsion layer

(sensitizing coloring matter G and H: respectively for per 1 mole of silver halide, large chi emulsion is added 8.0 * 10^-5Mole adds 10.7 * 10 to small size emulsion^-5Mole. And then in the perceptual emulsion layer of redness, for per 1 mole of silver halide, add 3.0 * 10^-3The following compound of mole. )

(Compound I)

In the perceptual emulsion layer of green and red perceptual emulsion layer, respectively for per 1 mole of silver halide, add 1.0 * 10^-3Mole and 5.9 * 10^-4The 1-(3-methylurea phenyl) of mole-5-mercapto-tetrazole.

And then, in the second layer, the 4th layer, layer 6 and layer 7, add respectively and reach 0.2mg/m²、 0.2mg/m ²、0.6mg/m ²、0.1mg/m ²。

In blue color sensation emulsion layer and green perceptual emulsion layer, respectively for per 1 mole of silver halide, add 1 * 10^-4Mole, 2 * 10^-4The 4-hydroxyl of mole-6-methyl isophthalic acid, 3,3a, 7-tetrazine decane.

In the perceptual emulsion layer of redness, add 0.05g/m²Methacrylic acid and the copolymer emulsion (mass ratio 1: 1, mean molecule quantity 200000～400000) of butyl acrylate.

In the second layer, the 4th layer and the layer 6, add respectively 6mg/m²、6mg/m ²、18mg/m ²Catechol-3,5-disulfonic acid disodium.

In order to prevent irradiation, add following dyestuff (expression coating weight in the bracket).

(layer consists of)

The formation of each layer below is shown. Numeral coating weight (q/m²), silver emulsion represents silver-colored conversion coating weight.

Supporter

Polyvinyl resin lamination paper

[in the polyvinyl resin of ground floor side, contain Chinese white (TiO₂: containing ratio 4 quality %), fluorescent whitening agent (4,4 '-two (5-toluene  azoles base) stilbene containing ratio 16 quality %, ZnO:. Containing ratio 0.03 quality %) and blue dye (ultramarine)]

Ground floor (blue color sensation emulsion layer)

Emulsion B-1 0.24

Gelatin 1.25

Yellow colour former (ExY) 0.57

Picture colouring stabilizer (Cpd-1) 0.07

Picture colouring stabilizer (Cpd-2) 0.04

Picture colouring stabilizer (Cpd-3) 0.07

Picture colouring stabilizer (Cpd-8) 0.02

Solvent (Solv-1) 0.21

The second layer (anti-colour mixture layer)

Gelatin 0.99

Anti-blending agent (Cpd-4) 0.09

Picture colouring stabilizer (Cpd-5) 0.018

Picture colouring stabilizer (Cpd-6) 0.13

Picture colouring stabilizer (Cpd-7) 0.01

Solvent (Solv-1) 0.06

Solvent (Solv-2) 0.22

The 3rd layer (green perceptual emulsion layer)

Bromine silver chloride emulsion BB (1: 3 mixture (silver-colored mol ratio) of the cube of golden sulphur sensitizing, average particle size 0.45 μ m large scale emulsion and 0.35 μ m small size emulsion. The coefficient of alteration of particle size distribution is respectively 0.10 and 0.08. Each size emulsion contains 0.15 % by mole of silver iodide near particle surface, contain 0.4 % by mole silver bromide in the particle surface part) 0.14

Gelatin 1.36

Peony colour coupler (ExM) 0.15

Ultra-violet absorber (UV-A) 0.14

Picture colouring stabilizer (Cpd-2) 0.02

Picture colouring stabilizer (Cpd-4) 0.002

Picture colouring stabilizer (Cpd-6) 0.09

Picture colouring stabilizer (Cpd-8) 0.02

Picture colouring stabilizer (Cpd-9) 0.03

Picture colouring stabilizer (Cpd-10) 0.01

Picture colouring stabilizer (Cpd-11) 0.0001

Solvent (Solv-3) 0.11

Solvent (Solv-4) 0.22

Solvent (Solv-5) 0.20

The 4th layer (anti-colour mixture layer)

Gelatin 0.71

Anti-colour mixture layer (Cpd-4) 0.06

Picture colouring stabilizer (Cpd-5) 0.013

Picture colouring stabilizer (Cpd-6) 0.10

Picture colouring stabilizer (Cpd-7) 0.007

Solvent (Solv-1) 0.04

Solvent (Solv-2) 0.16

Layer 5 (red perceptual emulsion layer)

Bromine silver chloride emulsion CC (5: 5 mixtures (silver-colored mol ratio) of the cube of golden sulphur sensitizing, average particle size 0.40 μ m large scale emulsion and 0.30 μ m small size emulsion. The coefficient of alteration of particle size distribution is respectively 0.09 and 0.11. Each size emulsion contains 0.1 % by mole silver iodide near particle surface, contain 0.8 % by mole silver bromide in the particle surface part) 0.12

Gelatin 1.11

Cyanogen colour coupler (ExC-2) 0.13

Cyanogen colour coupler (ExC-3) 0.03

Picture colouring stabilizer (Cpd-1) 0.05

Picture colouring stabilizer (Cpd-6) 0.06

Picture colouring stabilizer (Cpd-7) 0.02

Picture colouring stabilizer (Cpd-9) 0.04

Picture colouring stabilizer (Cpd-10) 0.01

Picture colouring stabilizer (Cpd-14) 0.01

Picture colouring stabilizer (Cpd-15) 0.12

Picture colouring stabilizer (Cpd-16) 0.03

Picture colouring stabilizer (Cpd-17) 0.09

Picture colouring stabilizer (Cpd-18) 0.07

Solvent (Solv-5) 0.15

Solvent (Solv-5) 0.05

Layer 6 (UV-absorbing layer)

Gelatin 0.46

Ultra-violet absorber (UV-B) 0.45

Compound (S1-4) 0.0015

Solvent (Solv-7) 0.25

Layer 7 (protective layer)

Gelatin 1.00

The acrylic acid sex change copolymer (sex change degree 17%) 0.04 of polyvinyl alcohol

Liquid Paraffin 0.02

Surfactant (Cpd-13) 0.01

[changing 13]

(ExY) yellow colour former

[changing 14]

(ExM) peony colour coupler

[changing 15]

(ExC-2) cyanogen colour coupler

(ExC-3) cyanogen colour coupler

[changing 16]

(Cpd-1) colour stabilizing agent

(Cpd-2) colour stabilizing agent

(Cpd-3) colour stabilizing agent

(Cpd-4) anti-blending agent

[changing 17]

(Cpd-5) colour stabilization agent

(Cpd-6) colour stabilization agent

(Cpd-7) colour stabilization agent (Cpd-8) colour stabilization agent

(Cpd-9) colour stabilization agent (Cpd-10) colour stabilization agent

[changing 18]

(Cpd-11)

(Cpd-13) interfacial agent

[changing 19]

(Cpd-14)                                           (Cpd-15)

(Cpd-16) (Cpd-17)

(Cpd-18)

(Cpd-19) colour mixture prevents agent

[changing 20]

(UV-1) ultraviolet light absorber (UV-2) ultraviolet light absorber

(UV-3) ultraviolet light absorber (UV-4) ultraviolet light absorber

(UV-5) ultraviolet light absorber (UV-6) ultraviolet light absorber

(UV-7) ultraviolet light absorber

The potpourri of UV-A:UV-1/UV-2/UV-3/UV-4=4/2/2/3 (mass ratio)

The potpourri of UV-B:UV-1/UV-2/UV-3/UV-4/UV-5/UV-6=9/3/3/4/5/3 (mass ratio)

The potpourri of UV-C:UV-2/UV-3/UV-6/UV-7=1/1/1/2 (mass ratio)

[changing 21]

(Solv-1) (Solv-2)

(Solv-3) (Solv-4)

O＝P(OC ₆H ₁₃(n)) ₃

(Solv-5) (Solv-7)

(Solv-8)

[changing 22]

(S1-4)

With the above test portion that obtains as test portion B-1.Replace emulsion B-1 in the blue color sensation emulsion layer with emulsion B-2 to B-8, make the same with test portion B-1 obtains test portion B-2 respectively to B-8.

For the photographic property of studying these test portions carries out following experiment.

To each coating test portion, with high illumination exposure sensitometer (Denso under the mountain (strain) system HIE type).Give the gray scale exposure that sensitometry is used.Fuji's photographic film (strain) system SP-1 color filter is installed is carried out 10 ^-8High illumination exposure second.

Carry out color development video picture shown below after the exposure and handle A.

Treatment process below is shown.

[handling A]

The test portion of above-mentioned photosensitive material is processed into the wide web-like of 127mm, after using the small-sized darkroom photo printer thereof PP1258AR of Fuji's photographic film (strain) system to carry out image exposure, handle (flow test) continuously in order to following treatment process, till additional 2 times colorful visualization tankage.To handle as handling A with this flow.

Treatment process temperature-time magnitude of recruitment *

38.5 ℃ of 45 seconds 45ml of colorful visualization

38.0 ℃ of 45 seconds 35ml of blix

Wash (1) 38.0 ℃ 20 seconds-

Wash (2) 38.0 ℃ 20 seconds-

38.0 ℃ of (3) * * of flushing 20 seconds-

38.0 ℃ of 30 seconds 121ml of flushing (4) * *

* every 1m ²The magnitude of recruitment of photosensitive material

* is installed in the flushing cleaning system RC50D of photographic film society of Fuji system in the flushing (3), by the washing fluid of flushing (3) taking-up, by being pumped into counter soaking in the film memory (RC50D).By the permeate water that same groove obtains send into flushing (4), condensed water is returned flushing (3).To the anti-water yield that sees through of soaking into memory, utilize the adjustment pump pressure to remain on 50～300ml/ minute, carry out temperature adjustment in 10 hours in 1 day circulation.

(flushing is adopted from (1) to (4) groove to the type of flow)

Each treating fluid composed as follows.

[colorful visualization liquid] [tank liquor] [replenishing liquid]

Water 800ml 800ml

Dimethyl polysiloxane is surfactant 0.1g 0.1g

(シ リ コ one chemical industry society of Application KF351A/ SHIN-ETSU HANTOTAI system)

Three (isopropyl alcohol) amine 8.8g 8.8g

Ethylene diamine tetra acetic acid 4.0g 4.0g

Polyethylene glycol (molecular weight 300) 10.0g 10.0g

4.5-dihydroxy benzenes-1,3-sodium disulfonate 0.5g 0.5g

Potassium chloride 10.0g-

Potassium bromide 0.040g 0.010g

The amino stilbene of triazine is fluorescence 2.5g 5.0g

Whitening agent (the clear and chemical society of Ha Star コ one Le FWA-SF/ system)

Sodium sulphite 0.1g 0.1g

Disodium-N, N-two (sulfonate ethyl) hydramine 8.5g 11.1g

N-ethyl-N-(β-amsacrine ethyl)-3-methyl-4-

Amino-4-amino aniline 3/2 sulfuric acid 1 water salt

5.0g 15.7g

Sal tartari 26.3g 26.3g

Add water 1000ml 1000ml

PH (25 ℃/with potassium hydroxide and sulfuric acid adjustment) 10.15 12.50

[bleach-fixing liquid] [tank liquor] [replenishing liquid]

Water 700ml 600ml

Ethylene diamine tetra acetic acid iron (III) ammonium 47.0g 94.0g

Ethylene diamine tetra acetic acid 1.4g 2.8g

M-carboxyl benzenesulfinic acid 8.3g 16.5g

Nitric acid (67%) 16.5g 33.0g

Imidazoles 14.6g 29.2g

ATS (Ammonium thiosulphate) (750g/L) 107.0ml 214.0ml

Ammonium sulfite 16.0g 32.0g

Ammonium bisulfite 56to 70 23.1g 46.2g

Add water 1000ml 1000ml

PH (25 ℃/acetic acid and adjust with ammonia) 6.0 6.0

[washing fluid] [tank liquor] [replenishing liquid]

Chlorination fulminuric acid sodium 0.02g 0.02g

Deionized water (electrical conductivity 5 μ s/cm are following) 1000ml 1000ml

pH 6.5 6.5

Measure the yellow color development concentration of each test portion after handling, obtain 10 ^-6The family curve of high illumination exposure second.Sensitivity regulation has the anti-number of giving than the exposure of the high 0.7 color development concentration of minimum color development concentration, and the sensitivity of test portion B-1 is taken as at 100 o'clock, represents with relative value.The point of concentration 0.5 and concentration 2.0 is connected straight line, obtains gray scale by its degree of tilt.The results are shown in table 2.

[table 2]

Test portion	The Br layer		The I layer		Sensitivity	Gray scale	Remarks
								The position	Amount	The position	Amount
	B-1	Do not have	-	Do not have								-	100	1.8	Comparative example
B-2					Do not have	-	90％	0.2 mole %	230	1.6	Comparative example
	B-3	80％～90％	2 moles of %	Do not have								-	130	2.0	Comparative example
B-4					90％～100％	2 moles of %	Do not have	-	140	1.9	Comparative example
	B-5	80％～100％	4 moles of %	Do not have								-	140	2.0	Comparative example
B-6					80％～90％	2 moles of %	90％	0.2 mole %	280	2.8	The present invention
	B-7	90％～100％	2 moles of %	90％								0.2 mole %	260	2.4	The present invention
B-8					80％～100％	4 moles of %	90％	0.2 mole %	260	2.6	The present invention

As shown in Table 2, in blue color sensation photosensitiveness emulsion layer, contain and of the present inventionly contain silver bromide mutually and contain test portion B-6, B-7 and the B-8 that silver iodide form the iodine bromine silver chloride emulsion of stratiform mutually respectively, confirm that blue color sensation photosensitiveness is significant high sensitivity, is vigour.

Embodiment 2

(modulation of emulsion G-1)

Lime treatment gelatin 3% aqueous solution of 1000ml is adjusted to pH3.3, pCl 1.7, and the aqueous solution that mixing contains 2.12 equimolar silver nitrate aqueous solution and contains 2.2 mole nacls is added on strong agitation limit, limit simultaneously under 56 ℃.Interpolation at silver nitrate reaches 80%～90% constantly, adds K ₄[Ru (CN) ₆] aqueous solution, for 1 mole of silver halide, make and produce Ru amount and reach 5 * 10 ^-5The amount of mole.Interpolation at silver nitrate reaches 83%～88% constantly, adds K ₂[IrCl ₆] aqueous solution, for 1 mole of silver halide, make and produce Ir amount and reach 5 * 10 ^-8The amount of mole.The silver nitrate interpolation reaches 92%～98% constantly, adds K ₂[Ir (5-methylthiazol) Cl ₅] aqueous solution, for 1 mole of silver halide, make and produce Ir amount and reach 1 * 10 ^-6The amount of mole.After 40 ℃ of enforcement desalting processing, add 168g lime treatment gelatin, adjust pH5.7, pCl1.8.The particle that obtains is that the length of side is that 0.4 μ m, coefficient of alteration are 11% cube silver chloride emulsion.

This emulsion 40 ℃ of dissolvings, is added 2 * 10 for per 1 mole of silver halide ^-5The sulfo-sulfinic acid sodium of mole uses sodium thiosulfate 5 hydrates as the sulphur sensitizer, uses (S-2) as golden sensitizer, arrives optimum 60 ℃ of maturations.After dropping to 40 ℃, add 5 * 10 for per 1 mole of silver halide ^-4The sensitizing coloring matter D of mole, add 2 * 10 for per 1 mole of silver halide ^-41-phenyl-5-the mercapto-tetrazole of mole, add 4 * 10 for per 1 mole of silver halide ^-41-(5-methylurea the phenyl)-5-mercapto-tetrazole of mole adds 7 * 10 for per 1 mole of silver halide ^-3The potassium bromide of mole.The emulsion that obtains like this is as emulsion G-1.

(modulation of emulsion G-2)

Interpolation at silver nitrate reaches 90% termination constantly, and the limit is mixed the limit strongly and added potassium iodide aqueous solution, makes for per 1 mole of silver halide and produces the amount that the I amount reaches 0.3 mole of %, is modulated into the emulsion different with emulsion G-1.The gained particle is that the length of side is that 0.4 μ m, coefficient of alteration are 11% cube silver iodochloride emulsion, with the emulsion that obtains like this as emulsion G-2.

(modulation of emulsion G-3)

The interpolation of silver nitrate reaches 80%～100% constantly, the limit is mixed the limit strongly and is added potassium bromide, make the amount that the Br amount reaches 4 moles of % of producing for per 1 mole of silver halide, be modulated into the emulsion different with emulsion G-1, the gained particle is that the length of side is that 0.4 μ m, coefficient of alteration are 11% cube bromine silver chloride emulsion, with the emulsion that obtains like this as emulsion G-3.

(modulation of emulsion G-4)

The interpolation of silver nitrate reaches 80%～100% constantly, the limit is mixed the limit strongly and is added potassium bromide, make the amount that the Br amount reaches 4 moles of % of producing for per 1 mole of silver halide, and then, add 90% termination to constantly at silver nitrate, the limit is mixed the limit strongly and is added potassium iodide aqueous solution, makes for per 1 mole of silver halide and produces the amount that the I amount reaches 0.3 mole of %, is modulated into the emulsion different with emulsion G-1.The gained particle is that the length of side is that 0.4 μ m, coefficient of alteration are 11% cube iodine bromine silver chloride emulsion, with the emulsion that obtains like this as emulsion G-4.

Utilize bromide and the iodide ion CONCENTRATION DISTRIBUTION of etch/TOF-SIMS method mensuration, the results are shown in Fig. 1 to emulsion G-4 particle depth direction.Even terminate at the inboard iodide salt solution that adds of particle, iodide ion oozes out to particle surface, and concentration is very big on the most surperficial, concentration decay to the inside.On the other hand, very big in the inner bromide ion concentration of particle.Think that thus containing silver bromide compares with containing silver iodide, forms stratiform respectively in the inboard of particle.

Constitute by following change layer, making is than the test portion of embodiment 1 test portion of thin layerization more.

The making of test portion

Ground floor (blue color sensation emulsion layer)

Emulsion B-1 0.24

Gelatin 1.25

Yellow colour former (ExY) 0.57

Picture colouring stabilizer (Cpd-1) 0.07

Picture colouring stabilizer (Cpd-2) 0.04

Picture colouring stabilizer (Cpd-3) 0.07

Picture colouring stabilizer (Cpd-8) 0.02

Solvent (Solv-1) 0.21

The second layer (anti-colour mixture layer)

Gelatin 0.60

Anti-blending agent (Cpd-19) 0.09

Picture colouring stabilizer (Cpd-5) 0.007

Picture colouring stabilizer (Cpd-7) 0.007

Ultraviolet light absorber (UV-C) 0.05

Solvent (Solv-5) 0.11

The 3rd layer (green perceptual emulsion layer)

Emulsion G-1 0.14

Gelatin 0.73

Peony colour coupler (ExM) 0.15

Ultraviolet light absorber (UV-A) 0.05

Picture colouring stabilizer (Cpd-2) 0.02

Picture colouring stabilizer (Cpd-7) 0.008

Picture colouring stabilizer (Cpd-8) 0.07

Picture colouring stabilizer (Cpd-9) 0.03

Picture colouring stabilizer (Cpd-10) 0.009

Picture colouring stabilizer (Cpd-11) 0.0001

Solvent (Solv-3) 0.06

Solvent (Solv-4) 0.11

Solvent (Solv-5) 0.06

The 4th layer (anti-colour mixture layer)

Gelatin 0.48

Anti-colour mixture layer (Cpd-4) 0.07

Picture colouring stabilizer (Cpd-5) 0.006

Picture colouring stabilizer (Cpd-7) 0.006

Ultraviolet light absorber (UV-C) 0.04

Solvent (Solv-5) 0.09

Layer 5 (red perceptual emulsion layer)

Bromine silver chloride emulsion CC (identical emulsion) 0.12 with test portion B-1

Gelatin 0.59

Cyanogen colour coupler (ExC-2) 0.13

Cyanogen colour coupler (ExC-3) 0.03

Picture colouring stabilizer (Cpd-7) 0.01

Picture colouring stabilizer (Cpd-9) 0.04

Picture colouring stabilizer (Cpd-15) 0.19

Picture colouring stabilizer (Cpd-18) 0.04

Ultraviolet light absorber (UV-7) 0.02

Solvent (Solv-5) 0.09

Layer 6 (UV-absorbing layer)

Gelatin 0.32

Ultraviolet light absorber (UV-C) 0.42

Solvent (Solv-7) 0.08

Layer 7 (protective seam)

Gelatin 0.70

The acrylic acid sex change multipolymer (sex change degree 17%) 0.04 of polyvinyl alcohol (PVA)

Liquid Paraffin 0.01

Surfactant (Cpd-13) 0.01

Dimethyl silicone polymer 0.01

Silicon dioxide 0.003

Emulsion as the perceptual emulsion layer of green will use the test portion of above-mentioned emulsion G-1 as test portion G-1.Test portion G-1 also equally makes test portion with the test portion that substitutes the emulsion G-1 of green perceptual emulsion layer with emulsion G-2～G-4, is respectively test portion G-2～G-4.

In order to study the photographic property of these test portions, carry out following experiment.

Use high illumination exposure to each coating test portion, to give the gray scale exposure that sensitometry is used, Fuji's photographic film (strain) system SP-2 color filter is installed, carry out 10 with sensitometer (Denso under the mountain (strain) system HIE type) ^-6High illumination exposure second.

Luminous video picture to each test portion of exposure is handled, according to video picture treatments B shown below, and super rapid processing.

[treatments B]

The test portion of above-mentioned photosensitive material is processed into the wide web-like of 127mm, the experiment treating apparatus that the small-sized darkroom photo printer thereof PP350 of Fuji's photographic film (strain) system is transformed in use, the change processing time, treatment temperature, the photosensitive material test portion is carried out image exposure by the negative film of mean concentration, handle (flow test) continuously by following treatment process, reach up to the capacity that used color development video picture replenishes liquid till 0.5 times of color development video picture tankage.

Treatment process temperature-time magnitude of recruitment *

45.0 ℃ of 15 seconds 45ml of color development video picture

40.0 ℃ of 15 seconds 35ml of blix

Wash 1 40.0 ℃ 8 seconds-

Wash 2 40.0 ℃ 8 seconds-

Washed 40.0 ℃ of 3 * * 8 seconds-

Wash 4 38.0 ℃ of 8 seconds 121ml

Dry 80.0 ℃ 15 seconds

The every 1m of (notes) * ²The magnitude of recruitment of photosensitive material

* installs Fuji's photographic film (strain) system flushing cleaning system RC50D in flushing (3), from the washing fluid that flushing (3) is taken out, by being pumped into counter soaking in the memory (RC50D), supply with flushing by the permeate water that this groove is sent, and concentrate returns in the flushing (3).Utilize and adjust pump pressure, the anti-water yield that sees through of soaking into memory was remained on 50～300ml/ minute, carry out temperature adjustment in 10 hours in 1 day circulation.Flushing adopts 4 concentrated flows of from (1) to (4) to mode.

Each treating fluid composed as follows.

[color development imaging liquid] [tank liquor] [replenishing liquid]

Water 800ml 600ml

Fluorescer (FL-1) 5.0g 8.5g

Triisopropanolamine 8.8g 8.8g

P-toluenesulfonic acid sodium salt 20.0g 20.0g

Ethylene diamine 4 acetic acid 4.0g 4.0g

Sodium sulphite 0.10g 0.50g

Potassium chloride 10.0g-

4,5-dihydroxyphenyl-1,3-sodium disulfonate 0.50g 0.50g

Disodium one N, N-two (sulfonate ethyl) hydramine 8.5g 14.5g

4-amino-3-methyl-N-ethyl-N-(β-amsacrine ethyl)

Aniline 3/2 sulfate 1 hydrate

10.0g 22.0g

Sal tartari 26.3g 26.3g

Add water inventory 1000ml 1000ml

PH (25 ℃ are adjusted with sulfuric acid and KOH) 10.35 12.6

[bleach-fixing liquid] [tank liquor] [replenishing liquid]

Water 800ml 800ml

ATS (Ammonium thiosulphate) (750g/ml) 107ml 214ml

Succinic acid 29.5g 59.0g

Ethylene diamine 4 ferric acetates (III) ammonium 47.0g 94.0g

Ethylene diamine 4 acetic acid 1.4g 2.8g

Nitric acid (67%) 17.5g 35.0g

Imidazoles 14.6g 29.2g

Ammonium sulfite 16.0g 32.0g

Ammonium meta-bisulfite 23.1g 46.2g

Add water inventory 1000ml 1000ml

PH (25 ℃) 6.00 6.00 with nitric acid and ammoniacal liquor adjustment

[washing fluid] [tank liquor] [replenishing liquid]

Chlorination fulminuric acid sodium 0.02g 0.02g

Deionized water (electrical conductivity 5 μ s/cm are following) 1000ml 1000ml

pH(25℃) 6.5 6.5

Measure the peony color development concentration of each test portion of outer reason back, obtain 10 ^-6Second high illumination Hurter and Driffield curve.Sensitivity regulation has the anti-number of giving than the exposure of the high 0.7 color development concentration of minimum color development concentration, and the sensitivity of test portion G-1 is taken as at 100 o'clock, represents with relative value.The point of concentration 0.5 and concentration 2.0 is connected straight line, obtains gray scale from its degree of tilt.

In order to study the sub-image keeping quality, when obtaining exposure and beginning to handle in back 10 seconds and the family curve when beginning to handle in back 10 minutes of exposing, the concentration change under the exposure of concentration 1.0 is given in research when beginning to handle after 10 seconds.And then for studying the dependence of exposure to humiture, obtain under 10 ℃, 55% environment, expose when beginning to handle after 10 seconds, with 30 ℃, the exposure down of 30% environment, family curve when beginning to handle after 10 seconds, research is when exposure began to handle after 10 seconds under 10 ℃, 55% environment, the concentration change under the exposure of giving concentration 1.0.These the results are shown in table 3.

Test portion	The Br layer		The I layer		Sensitivity	Gray scale	The sub-image keeping quality	Exposure is to the humiture dependence	Remarks
										The position	Amount	The position	Amount
	G-1	Do not have	-	Do not have										-	100	1.9	0.20	0.15	Comparative example
G-2					Do not have	-	90％	0.3 mole %	180	1.6	0.21	0.12	Comparative example
	G-3	80％～100％	4 moles of %	Do not have										-	140	2.0	0.09	0.13	Comparative example
G-4					80％～100％	4 moles of %	90％	0.3 mole %	210	2.6	0.03	0.05	The present invention

As from table 3 result clear and definite, in the green photonasty emulsion layer, contain respectively and contain the silver bromide phase and contain the test portion G-4 that silver iodide form stratiform iodine bromine silver chloride emulsion mutually by of the present invention, green photonasty is remarkable high sensitivity, be vigour, confirm that sub-image keeping quality and exposure are all very good to the humiture dependence.

And then in test portion G-4, only the emulsion B-1 with ground floor becomes emulsion B-8, makes different test portion G-4 ', carries out above-mentioned evaluation, obtains and the roughly the same result of test portion G-4.

Embodiment 3

Use the test portion of embodiment 2, utilize laser scanning exposure to carry out imaging.

As LASER Light Source, by having the LiNbO of counter-rotating farmland light structure ₃The SHG crystallization make the YAG Solid State Laser (oscillation wavelength 946 μ m) of making exciting light source with semiconductor laser GaAlAs (oscillation wavelength 808.5nm), carry out 473nm that wavelength Conversion takes out and by having the LiNbO of counter-rotating farmland light structure ₃The SHG crystallization make the YVO that makes exciting light source with semiconductor laser GaAlAs (oscillation wavelength 808.7nm) ₄Solid State Laser (oscillation wavelength 1064nm) carries out wavelength Conversion and takes out 532nm and use AlGaInP (wave of oscillation is about 680nm: Panasonic's electricity produces type No.LN9R20).Utilize polygon prism that the light of each laser of 3 kinds of colors is moved as vertical direction with respect to the direction of scanning, on test portion, carry out scan exposure successively.The light quantity that semiconductor laser is caused by temperature changes, and can utilize the Pei Erdi element to suppress, and temperature is kept constant.Actual effectively beam diameter is 80 μ m, and sweep span is 42.3 μ m (600dpi), and the mean exposure time of per 1 picture element is 1.7 * 10 ^-7Second.

After the exposure, the same when utilizing color development video picture treatments B to handle with the result of high illumination exposure among the embodiment 2, test portion G-4 of the present invention, green sense layer demonstrates very high sensitivity and gray scale.Blue sense layer of test portion G-4 ' expression of the present invention and very high sensitivity and the gray scale of green sense layer are applicable to any laser scanning exposure imaging as can be known.

Embodiment 4

(modulation of emulsion A)

In 3% aqueous solution of lime treatment gelatin, add 3.3g sodium chloride, add sulfuric acid and the 25ml 1 of 42.8ml 1N, 8-dihydroxy-3,6-two sulfo-octanes (1% aqueous solution).In this aqueous solution, aqueous solution of mixing to contain 2.12 equimolar silver nitrates and the aqueous solution that contains 2.18 mole nacls are added at 68 ℃ in strong agitation limit, limit.Subsequently, in 40 ℃ of sedimentations, washing, implement desalination.Add 168.0g lime treatment gelatin, the pH and the pAg of emulsion is adjusted into 7.3 and 5.6 respectively.Utilize electron micrograph, as can be known particle be shaped as cube, average particle size is 0.76 μ m, coefficient of alteration is 10%.

In this emulsion, add golden sensitizer (colloidal aurosulfo) 6 * 10 ^-5The blue color sensation beam split sensitizing coloring matter 3.1 * 10 of moles/mole Ag, embodiment 1 record ^-4Moles/mole Ag, 60 ℃ of chemical sensitizations that suit and beam split sensitizing are added 1-(5-methyl urea phenyl)-5-mercapto-tetrazole 4.4 * 10 again ^-4Moles/mole Ag is modulated into emulsion A.

(modulation of emulsion B)

During emulsion particles forms, in 80～81% stages of adding total silver amount, add the silver iodide particulate emulsion that contains 0.4 mole of % iodide ion with respect to total silver amount, in addition, according to the modulator approach of emulsion A.The modulation of the silver iodide particulate emulsion that uses, available spy opens the stirring mixer of putting down in writing in the flat 10-43570 instructions and carries out.

(modulation of emulsion C)

In emulsion particles forms, adding in 99～100% stages that always silver is measured, with respect to the potassium iodide aqueous solution of 0.4 mole of % of total silver amount interpolation, in addition, according to the modulator approach of emulsion A.

(modulation of emulsion D)

In emulsion particles forms, adding in 94～95% stages that always silver is measured, with respect to the potassium iodide aqueous solution of 0.4 mole of % of total silver amount interpolation, in addition, according to the modulator approach of emulsion A.

(modulation of emulsion E)

In emulsion particles forms, adding in 85～86% stages that always silver is measured, with respect to the potassium iodide aqueous solution of 0.4 mole of % of total silver amount interpolation, in addition, according to the modulator approach of emulsion A.

Make with embodiment 1 in test portion B-1 the test portion (101) of following different silver halide colour photographic sensitive material is arranged.The beam split sensitizing coloring matter of silver emulsion in the green and red perceptual emulsion layer, in each, all the test portion B-1 with embodiment 1 is identical to large scale emulsion, small size emulsion, also is with amount to the consumption of per 1 mole of silver halide.The test portion B-1 of interpolation and embodiment 1 is with the Compound I of amount in the perceptual emulsion layer of redness.

Difference with embodiment 1

Only change the emulsion kind of ground floor, the 3rd layer and layer 5.

Ground floor has changed emulsion A, the 3rd layer and has changed chlorine silver bromide emulsion Em-1 (1: 3 potpourri (silver-colored mol ratio) of the large scale emulsion of the cube of golden sulphur sensitizing, average particle size 0.45 μ m and the small size emulsion of 0.35 μ m.The coefficient of alteration of particle size distribution is 0.10 and 0.08, each size emulsion contains the silver iodide of 0.15 mole of % near particle surface, the silver bromide of 0.4 mole of % is contained in the particle surface part), layer 5 changed chlorine silver bromide emulsion Em-2 (5: 5 potpourris (silver-colored mol ratio) of the large scale emulsion of the cube of golden sulphur sensitizing, average particle size 0.40 μ m and the small size emulsion of 0.30 μ m.The coefficient of alteration of particle size distribution is respectively 0.09 and 0.11.Each size emulsion contains the silver iodide of 0.1 mole of % near particle surface, contain the silver bromide of 0.8 mole of % in the particle surface part).

Equally, the emulsion A of test portion (101) is changed to emulsion B～E and be made into test portion (102)～(105).

For studying the photographic property of these test portions, carry out following experiment.

Experiment A: sensitometry

To each coating test portion, usability photometry (Fuji's photographic film (strain) system FWH type) is given the gray scale exposure that sensitometry is used.The SP-1 color filter is installed is carried out the low-light (level) exposure in 10 seconds.

Use high illumination exposure with sensitometer (Denso under the mountain (strain) system HIE type), give the gray scale exposure that sensitometry is used, the SP-1 color filter is installed, carry out 10 ^-4The high illumination exposure of second.After the exposure, A[processing A is handled in the color development video picture of carrying out among the embodiment 1] (different is to make flow only to use above-mentioned photosensitive material 101).

Measure the yellow color development concentration of each test portion after handling, obtain the tunicle concentration of emulsion A～E, 10 seconds exposure low-light (level) sensitivity and 10 respectively ^-4The high illumination sensitivity of exposure second.Sensitivity regulation has the anti-number of giving than the exposure of the high 1.0 color development concentration of minimum color development concentration, with the video picture of test portion (101) is handled sensitivity be taken as 100 o'clock to value representation.The silver iodide ratio of the corner portions located of each emulsion and first type surface part (=utilize and analyze the first type surface part silver iodide containing ratio that electricity shows the corner portions located silver iodide containing ratio that method obtains/utilize the ESCA method to obtain) in contrast, these results are shown in table 4 in the lump.

[table 4]

Test portion	Emulsion	The silver iodide ratio	Tunicle concentration	The low-light (level) sensitivity	High illumination sensitivity
						101	A (comparison)	-	0.07	100	100
102	B (comparison)	0.95	0.07	120	135
						103	C (the present invention)	2.1	0.11	210	220
104	D (the present invention)	1.6	0.08	193	210
						105	E (the present invention)	1.2	0.07	150	170

As known from Table 4, chlorosulfonylation silver emulsion sensitivity of the present invention is higher, and the reciprocity law characteristic of high illumination is very good.Before forming particle 98%, termination is added the emulsion of the present invention of iodide ion, clear picture, and be the emulsion of high sensitivity.

Embodiment 5

(modulation of emulsion F)

In 5% aqueous solution of lime treatment gelatin, add 5.6g sodium chloride, add the sulfuric acid of 42.8ml 1N and the N of 1.1ml again, N '-methylimidazole quinoline-2-thion (1% aqueous solution).In this aqueous solution, add to mix at 61 ℃ while stirring and contain 0.21 equimolar silver nitrate aqueous solution and contain 0.21 mole nacl aqueous solution.Continue to keep 61 ℃, interpolation while stirring mixes and contain 1.27 equimolar silver nitrate aqueous solution, contains 1.27 mole nacl aqueous solution and every mole of total silver amount contains 1 * 10 ^-8Mole K ₂[Ru (NO) Cl ₅] the transition metal complex aqueous solution, add mixing more while stirring and contain 0.21 equimolar silver nitrate aqueous solution and contain 0.21 mole nacl aqueous solution, continuation interpolation while stirring mixes and contain 0.21 equimolar silver nitrate aqueous solution, contains 0.21 mole nacl aqueous solution and every mole of always silver-colored measuring contains 2 * 10 ^-5Mole K ₄[Ru (CN) ₅] the transition metal complex aqueous solution.Under 61 ℃, add mixing while stirring and contain 0.02 equimolar silver nitrate aqueous solution and contain 0.02 mole nacl aqueous solution again.Continuation interpolation while stirring mixes and contain 0.11 equimolar silver nitrate aqueous solution, contains 0.11 mole nacl aqueous solution and every mole of total silver-colored measuring contains 2 * 10 ^-8The K of mole ₂[Ir (H ₂O) Cl ₅] the transition metal complex aqueous solution, continuation interpolation while stirring mixes and contain 0.04 equimolar silver nitrate aqueous solution, contains 0.04 mole nacl aqueous solution and every mole of total silver-colored measuring contains 4 * 10 ^-8Mole K ₂[IrCl ₆] the transition metal complex aqueous solution, continue to add down to mix at 61 ℃ while stirring to contain 0.04 equimolar silver nitrate aqueous solution and contain 0.04 mole nacl aqueous solution.Under 40 ℃, carry out sedimentation, washing subsequently, implement desalination.Add 168.0g lime treatment gelatin again, the pH and the pAg of emulsion is adjusted into 7.3 and 5.6 respectively.Utilize electron microscope observation, shape of particle is a cube, and average particle size is 0.62 μ m, and coefficient of alteration is 10%.

In this emulsion, add 1.5 * 10 ^-5The golden sensitizer of moles/mole Ag (tetrafluoro boric acid gold (I)=(1,4,5-trimethyl-1,2,4-triazole -3-sulfate), 6 * 10 ^-7The sulphur sensitizer (sodium thiosulfate) and 2.3 * 10 of moles/mole Ag ^-4Moles/mole Ag and 1.5 * 10 ^-4The blue color sensation beam split sensitizing coloring matter (A and B) of record in 60 ℃ of chemical sensitizations that suit and beam split sensitizing, adds 4.4 * 10 again among the embodiment 1 of moles/mole Ag ^-4The 1-of moles/mole Ag (5-methylurea phenyl)-5-mercapto-tetrazole.

(modulation of emulsion G)

In the emulsion particles shape, adding in 90～91% stages that always silver is measured, with respect to the potassium iodide aqueous solution of 0.6 mole of % of total silver amount interpolation, in addition, according to the modulator approach of emulsion F.

(modulation of emulsion H)

Except not adding K ₂[IrCl ₆] outside the transition metal complex body, according to the modulator approach of emulsion G.

Layer constitutes fully identical with embodiment 4, with the emulsion of emulsion F～H displacement ground floor, makes test portion (201)～(203).These test portions are carried out experiment A and the following experiment B of embodiment 4.

Experiment B: the latent-image stability after the exposure

For each test portion, change by above-mentioned 10 ^-4Second, the time of handling A was arrived in high illumination exposure back, carried out sensitometry, and the sensitivity of obtaining aftertreatment in 60 minutes and aftertreatment in 7 seconds is poor.These the results are shown in table 5.

[table 5]

Test portion	Emulsion	Tunicle concentration	The low-light (level) sensitivity	High illumination sensitivity	The sensitivity of aftertreatment in 7 seconds and aftertreatment in 60 fens is poor
						201	F (comparison)	0.07	100	100	25
202	G (the present invention)	0.07	240	260	5
						203	H (the present invention)	0.07	235	235	10

As known from Table 5, chlorosulfonylation silver emulsion sensitivity of the present invention is very high, be low photographic fog emulsion, and the latent-image stability after the exposure is very good.

Embodiment 6

(modulation of emulsion I)

Based on the emulsion F modulation method of record among the embodiment 5,, outside N '-methylimidazole quinoline-2-thion (1% aqueous solution), carry out same particle and form except adding N.Observe with electron micrograph, shape of particle is cubical, and average particle size is 0.38 μ m, and coefficient of alteration is 8%.

In this emulsion, add 2.4 * 10 ^-5The golden sensitizer of moles/mole Ag (tetrafluoro boric acid gold (I)=(1,4,5-trimethyl-1,2,4-triazole -3-sulfate)), 1 * 10 ^-7The sulphur sensitizer (sodium thiosulfate) and 3.6 * 10 of moles/mole Ag ^-4Moles/mole Ag, 7.0 * 10 ^-5Moles/mole Ag and 2.8 * 10 ^-4The green perceptual beam split sensitizing coloring matter (D, E and F) of record in 60 ℃ of chemical sensitizations that suit and beam split sensitizing, adds 4.4 * 10 again among the embodiment 1 of moles/mole Ag ^-4The 1-of moles/mole Ag (5-methylurea phenyl)-5-mercapto-tetrazole.

(modulation of emulsion J)

During emulsion particles forms, in 90～91% stages of adding total silver amount, add 0.002 mole potassium iodide aqueous solution, in addition, according to the modulator approach of emulsion I.

(modulation of emulsion K)

Except not adding K ₂[IrCl ₆] outside the transition metal complex body, according to the modulator approach of emulsion J.

In the layer of embodiment 5 constitutes, the 3rd layer green perceptual emulsion Em-1 is replaced as above-mentioned emulsion I～K, make test portion (301)～(303).Implement the processing identical for these test portions, measure and handle the peony color development concentration of each test portion afterwards, carry out the experiment A of embodiment 4,5 and the evaluation of B with embodiment 5.The result is shown in table 6 in the lump.

[table 6]

Test portion	Emulsion	Tunicle concentration	The low-light (level) sensitivity	High illumination sensitivity	The sensitivity of aftertreatment in 7 seconds and aftertreatment in 60 fens is poor
						301	I (comparison)	0.07	100	100	22
302	J (the present invention)	0.07	180	202	4
						303	K (the present invention)	0.07	179	185	8

As known from Table 6, chlorosulfonylation silver emulsion sensitivity of the present invention is very high, be low photographic fog emulsion, and the latent-image stability after the exposure is good.

Embodiment 7

Constitute by following change layer, the test portion of modulation thin layerization carries out the experiment A of embodiment 4 and the experiment B of embodiment 5 to these test portions.

Layer formation illustrates with test portion (401).Test portion (402), (403) are the test portions that the emulsion F of test portion (401) is altered to emulsion G and H respectively.

Result and embodiment 4 come to the same thing, and can confirm that from this result the test portion of thin layerization promptly uses supper-fast processing also can realize effect of the present invention.

The making of test portion 401

The test portion 401 of photosensitive silve halide material is in the test portion G-1 of embodiment 2, only by the silver emulsion kind in following change ground floor, the 3rd layer and the layer 5.

Ground floor has changed that emulsion F, the 3rd layer have changed Em-1, layer 5 has changed Em-2.Em-1 and Em-2 be with embodiment 4 in the identical emulsion of silver emulsion of record.

Each test portion of making, carry out the same exposure of experiment B with experiment A and the embodiment 5 of embodiment 4, video picture treatments B [treatments B] according to embodiment 2 (making of flow different be the photosensitive material that only uses embodiment 7) is handled in the color development video picture, carries out supper-fast processing.

Embodiment 8

Use test portion (401)～(403), utilize laser scanning exposure to carry out imaging.

As LASER Light Source, by having the LiNbO of counter-rotating farmland light structure ₃The SHG crystallization make with semiconductor laser GaAlAs (oscillation wavelength 808.5nm) and carry out 473nm that wavelength Conversion takes out as the YAG Solid State Laser (oscillation wavelength 946nm) of exciting light source and by having the LiNbO of counter-rotating farmland light structure ₃The SHG crystallization to will be with the YVO of semiconductor laser GaAlAs (oscillation wavelength 808.7nm) as exciting light source ₄Solid State Laser (oscillation wavelength 1064nm) carries out 532nm and AlGaInP (wave of oscillation is about 680nm: Panasonic's electricity produces type No.LN9R20) that wavelength Conversion is taken out.The light of the various laser of 3 kinds of colors by polygon prism, moves as vertical direction with respect to the direction of scanning, scan exposure successively on test portion.The light quantity change that the semiconductor laser temperature influence causes utilizes the Pei Erdi element to suppress, and can keep stationary temperature.Actual effectively beam diameter is 80 μ m, and sweep span is 42.3 μ m (600dpi), and the mean exposure time of per 1 picture element is 1.7 * 10 ^-7Second.

After the exposure, utilize color development video picture treatments B to handle, obtain with embodiment 5 in the identical result of high illumination exposure, test portion of the present invention (402), (403) demonstrate very high sensitivity, are applicable to the imaging with laser scanning exposure as can be known.

Effect of the present invention

According to the present invention, namely use the digit explosure as laser scanning exposure one class, also can obtain high sensitivity, the silver emulsion of vigour gray scale and its silver halide photographic sensitive material of use. And then according to the present invention, can obtain the sub-image keeping quality, exposure relies on the good silver emulsion of humiture and uses its silver halide photographic sensitive material. And then utilize silver halide photographic emulsions of the present invention, can obtain high sensitivity, low photographic fog, with the reciprocity law characteristic good of high illumination, and until sensitivity and the very little effect of gray scale temporal evolution during post-exposure processes.

Claims (11)

1, a kind of silver emulsion, be to form at 90 moles of silver halide particles more than the % by the silver chloride containing ratio, it is characterized in that the maximum containing ratio of silver iodide of the corner portions located of this silver halide particle is higher than the silver iodide containing ratio of this particle first type surface part, and above-mentioned silver halide particle contains 1 at least with H ₂O, OH, O, OCN, thiazole or displacement thiazole are made dentate, all the other dentates are formed, are 6 ligand complex bodies of central metal with Ir by Cl, Br or I.

2, according to the silver emulsion of claim 1 record, it is characterized in that above-mentioned silver halide particle is cube or 14 body particles.

3, according to the silver emulsion of claim 1 record, the electronics release time that it is characterized in that above-mentioned silver halide particle is from 10 ^-5Second was by 10 seconds.

4, according to the silver emulsion of claim 1 record, the sub-image oxidizing potential that it is characterized in that above-mentioned silver emulsion is than 70mV height.

5, according to the silver emulsion of claim 1 record, it is characterized in that above-mentioned silver emulsion carries out golden sensitizing.

6,, it is characterized in that above-mentioned silver emulsion is the complexing stability constant log β with colloidal aurosulfo or gold according to the silver emulsion of claim 5 record ₂Be that 21～35 golden sensitizer carries out golden sensitizing.

7, according to the silver emulsion of claim 1 record, it is characterized in that the first type surface of above-mentioned silver halide particle is made of (100) face.

8, according to the silver emulsion of claim 1 record, it is characterized in that carrying out beam split sensitizing with three methine anthocyanidins.

9, according to the silver emulsion of claim 1 record, the containing ratio that it is characterized in that iodide ion is 0.06 mole more than the % with respect to total silver amount of total emulsion particles.

10,, it is characterized in that the iodide ion containing ratio is 0.1 mole more than the % with respect to total silver amount of total emulsion particles according to the silver emulsion of claim 1 record.

11, a kind of silver halide photographic sensitive material is characterized in that containing the silver emulsion that claim 1 is put down in writing.