CN1278180C - Silver halide photosensitive emulsion, and silver halide photosensitive material - Google Patents

Abstract

This invention provides a silver halide photographic emulsion having high sensitivity and small processing dependence. The silver halide photographic emulsion is characterized in that the variation coefficient of equivalent-circle diameters of all grains is 40% or less, and 50% or more of the total projected area are accounted for by tabular grains meeting conditions (i) to (v) below:(i) the tabular grains are silver iodobromide or silver bromochloroiodide tabular grains having (111) faces as major surfaces, (ii) an equivalent-circle diameter is 3.5 mum or more and a thickness is 0.25 mum or less, (iii) a silver iodide content is 2 to 6 mol %, (iv) a silver chloride content is 3 mol % or less, (v) a silver iodide distribution has a quintuple or a higher-order multiple structure.

Description

Silver halide magenta-sensitive emulsion and the photosensitive silve halide material that adopts this emulsion

This application is based on following Japanese patent application and requires their right of priority: 11-271280 number and 2000-145051 number of application on May 17th, 2000 of the application on September 24th, 11-218868 number 1 of the application on August 2nd, 11-208021 number 1 of application on July 22nd, 1999, the whole contents of these patented claims is incorporated herein by reference at this.

The present invention relates to a kind of silver halide magenta-sensitive emulsion that is used for photosensitive silve halide material, more specifically relate to the good quick silver halide magenta-sensitive emulsion of a kind of dependence of developing.

As everyone knows, need adopt " sheet silver halide particle " (hereinafter referred to as " platy shaped particle ") or adopt large-sized silver halide particle for obtaining quick photosensitive silve halide material.But extremely increase owing to compare the equal circle diameter of particle with conventional silver halide particle, make that it is difficult coming super-sens by increase platy shaped particle size.A possible reason is because the extreme increase of photoelectron diffusion length can not concentrate on the position it, causes latent image effectively not form.For addressing this problem, U.S.P.5,612,175,5,612,176,5,612,177 and 5,614,359 disclose a kind of process for increasing sensitivity, and wherein silver chloride being grown nonparasitically upon another plant is connected on the large-size flaky particle.The method that connects has increased KBr dependence in the developing process owing to the being partly dissolved property of growing nonparasitically upon another plant is unstable but unfortunately this employing silver chloride is grown nonparasitically upon another plant.So this method can not be widely used in the conventional intensifying material.

U.S.P.5 discloses a kind of process for increasing sensitivity in 709,988, and wherein the dislocation line of introducing in the platy shaped particle marginal portion is more finer and close than the dislocation line of introducing on the particle first type surface.Although but super-sens to a certain extent, this method can not solve owing to increasing the development that the platy shaped particle size causes and postpone.That is to say that the problem that the processing procedure dependence is increased that adopts the large-size flaky particle to be caused is not resolved.

U.S.P.5 discloses a kind of technology of improving light sensitivity/graininess ratio in 780,216, wherein adopts a kind of platy shaped particle emulsion with five layers or more multi-layered structure.But unfortunately in this patent the shell agi content up to 15 to 40mol%.Therefore this method can not solve the problem of developing and postponing in the processing procedure, even this method can not be dealt with problems when being applied to large-size flaky particle that the present invention adopts.

An object of the present invention is to provide a kind of silver halide magenta-sensitive emulsion, this emulsion can increase the light sensitivity of the large-size flaky particle of high aspect ratio, solve the processing procedure dependence simultaneously, delay problems such as big as development, the present invention also provides a kind of photosensitive material that adopts this emulsion.

Adopt following (1) to (15) to achieve the above object.

(1) a kind of silver halide magenta-sensitive emulsion, wherein the variation factor of the equal circle diameter of all particles is 40% or littler, simultaneously 50% of the total projection area or more by meet following condition (i) to (platy shaped particle v) occupies:

(i) platy shaped particle is to have iodine silver bromide or a bromine chlorosulfonation silver strip shape particle that (111) crystal face is a first type surface,

(ii) equal circle diameter is 3.5 μ m or bigger, and thickness is 0.25 μ m or littler,

(iii) agi content is 2 to 6mol%,

(iv) silver chloride content is 3mol% or littler,

(v) silver iodide distribute and have five layers or more multi-layered structure.

(2) silver halide magenta-sensitive emulsion described in the above-mentioned clauses and subclauses (1), wherein silver iodide distribute and have six layers or more multi-layered structure.

(3) silver halide magenta-sensitive emulsion described in above-mentioned clauses and subclauses (1) or (2), wherein when adopting the 325nm electromagnetic beam irradiation of 6K, emulsion produces the induced fluorescence of 575nm, and its intensity is 1/3 of the hyperfluorescence emission that induces in 490 to the 560nm wavelength coverages at least.

(4) silver halide magenta-sensitive emulsion described in the above-mentioned clauses and subclauses (1) to one of (3), wherein the average silver iodide content on all particle surfaces is 5mol% or still less.

(5) silver halide magenta-sensitive emulsion described in the above-mentioned clauses and subclauses (1) to one of (4) suppose that wherein It is the average silver iodide content of whole particle, and Is is the average silver iodide content on the particle surface, and then following relational expression is set up:

0.3·It≤Is

(6) silver halide magenta-sensitive emulsion described in the above-mentioned clauses and subclauses (1) to one of (5), wherein at least a portion has the hole capture district in the silver halide.

(7) silver halide magenta-sensitive emulsion described in the above-mentioned clauses and subclauses (1) to one of (6) wherein satisfies in the clauses and subclauses (1) listed condition (i) to (platy shaped particle v) has dislocation line near the particle corner.

(8) silver halide magenta-sensitive emulsion described in the above-mentioned clauses and subclauses (1) to one of (7), wherein the equal circle diameter variation factor of all particles is 25% or littler.

(9) silver halide magenta-sensitive emulsion described in the above-mentioned clauses and subclauses (1) to one of (8), wherein listed condition (ii) is that equal circle diameter is 3.5 μ m or bigger in the clauses and subclauses (1), thickness is 0.15 μ m or littler.

(10) silver halide magenta-sensitive emulsion described in the above-mentioned clauses and subclauses (1) to one of (8), wherein listed condition (ii) is that equal circle diameter is 4.0 μ m or bigger in the clauses and subclauses (1), thickness is 0.15 μ m or littler.

(11) silver halide magenta-sensitive emulsion described in the above-mentioned clauses and subclauses (1) to one of (8), wherein listed condition (ii) is that equal circle diameter is 4.0 μ m or bigger in the clauses and subclauses (1), thickness is 0.10 μ m or littler.

(12) silver halide magenta-sensitive emulsion described in the above-mentioned clauses and subclauses (1) to one of (11) wherein carries out spectral sensitization by spectral sensitizing dye to emulsion.

(13) silver halide magenta-sensitive emulsion described in the above-mentioned clauses and subclauses (1) to one of (12), wherein emulsion contains 400 to 2, the calcium ion of 500ppm and/or 50 to 2, the magnesium ion of 500ppm.

(14) silver halide magenta-sensitive emulsion described in the above-mentioned clauses and subclauses (1) to one of (13), wherein emulsion is selenium sensitizing, and contain at least a type by the water-soluble mercapto-tetrazole compound of formula (I-1) expression and the water-soluble mercapto-triazole compound by formula (I-2) expression of at least a type:

Formula (I-1)

R wherein ₅Be at least by a kind of being selected from-SO ₃M ,-COOM ,-OH and-NHR ₂Organic residue of replacing of group, M represents hydrogen atom, alkali metal atom, quaternary ammonium group or quaternary phosphonium father-in-law group, R ₂Represent hydrogen atom, C ₁-C ₆Alkyl ,-COR ₃,-COOR ₃, or-SO ₂R ₃, R ₃Represent hydrogen atom, alkyl or aryl;

Formula (I-2)

R wherein ₆Represent hydrogen atom, replacement or non-substituted alkyl or replacement or non-substituted aryl, R ₅Be at least by a kind of being selected from-SO ₃M ,-COOM ,-OH and-NHR ₂Organic residue of replacing of group, M represents hydrogen atom, alkali metal atom, quaternary ammonium group or quaternary phosphonium father-in-law group, R ₂Represent hydrogen atom, C ₁-C ₆Alkyl ,-COR ₃,-COOR ₃, or-SO ₂R ₃, R ₃Represent hydrogen atom, alkyl or aryl;

(15) a kind of photosensitive silve halide material, it comprises photographic layer, and this photographic layer contains the silver halide magenta-sensitive emulsion described in the above-mentioned clauses and subclauses (1) to one of (14).

To list other purpose of the present invention and advantage thereof in the following description, their parts are described by invention and are embodied, and maybe can understand by practice of the present invention.Can and understand objects and advantages of the present invention by following means of refering in particular to and combination understanding.

Accompanying drawing as an ingredient of patent specification has been described the preferred embodiment of the invention, and they and above-mentioned summary and following DESCRIPTION OF THE PREFERRED one are used from explains principle of the present invention.

Accompanying drawing is a cut-open view that shows the profile of the stirring apparatus structure that is adopted in one embodiment of the invention.

Below silver halide magenta-sensitive emulsion of the present invention will be described.

In the present invention, sheet-like particle refers to have the silver halide particle of two relative parallel (111) first type surfaces. Silver halide particle of the present invention has a twin plane or two or more parallel twin planes. Twin plane refers to that the ion on all lattice-sites of its both sides has (111) crystal face of minute surface enantiomorphic relationship.

From seeing that perpendicular to the direction of first type surface this flat crystal is triangle, hexagon or blunt triangle or hexagon. Each shape has the outer surface that is parallel to each other.

Adopt replica to utilize transmission electron microscopy to take a picture and obtain sheet-like particle equal circle diameter and thickness. Be that equal circle diameter refers to the diameter of a circle that equates with each particle projection area area. Shade length computation thickness by surface replica.

In sheet-like particle of the present invention, 50% or more total projection area (summation of each particle projection area) by equal circle diameter be preferably 3.5 μ m or more, more preferably 4.0 μ m or particle more, that most preferably be 4.5 to 20 μ m occupy.

If diameter can not obtain the high photosensitivity energy less than 3.5 μ m, not very serious by process dependency problem solved by the invention. If diameter surpasses 20 μ m, increase and reach and be maintained at the highest limit by increasing the obtained speed of size, so that speed can not further improve.

In sheet-like particle of the present invention, 50% or more total projection area by thickness be preferably 0.25 μ m or still less, more preferably 0.15 μ m or still less, the particle that most preferably is 0.1 to 0.03 μ m occupies.

If thickness surpasses 0.25 μ m, then be difficult to show the advantage of sheet-like particle super-sens. If thickness less than 0.03 μ m, then no longer can guarantee the stability of shape, thereby the problem that can not the solution process relies on.

In emulsion of the present invention, 50% or more total projection area by aspect ratio be preferably 14 or more, more preferably 23 or more, most preferably be 40 or more sheet-like particle occupy. Aspect ratio numerical value by equal circle diameter divided by the thickness gained.

In emulsion of the present invention, the equal circle diameter variation coefficient of all particles is 40% or littler. Emulsion of the present invention is preferably monodispersed. In emulsion of the present invention, the equal circle diameter variation coefficient of all silver halide particles is preferably 30% or littler, and more preferably 25% or littler, most preferably be 20% or littler. If variation coefficient surpasses 40%, the uniformity decreases of particle, thus increased the process dependence. The equal circle diameter variation coefficient refers to the value that the standard deviation of the equal circle diameter distribution of each silver halide particle obtains divided by average equal circle diameter.

In emulsion of the present invention, all particle total projection areas are preferably 50% or more to the length of long face in the emulsion for the hexagon sheet particle of 2 to 1 times of the shortest face length degree accounts for, and more preferably 70 % most preferably are 90%. If sneak into the sheet-like particle except above-mentioned hexagon particle, then uniform particles decline and process dependence increase.

Sheet-like particle of the present invention is the silver halide that contains silver iodide, i.e. iodine silver bromide or iodine chlorine silver bromide. As detailed below, the distribution of silver iodide has five layers or more multi-layered structure. The sandwich construction that silver iodide distribute refers in the structure that the difference of agi content is preferably 1mol% or more between one deck and another layer, more preferably 2mol% or more.

Can calculate the silver iodide distributed architecture by the addition in the particle preparation process simply. Between layers at the interface agi content changes suddenly or slowly in structure. For confirming this situation, must consider the accuracy of analytical test, it is effective in general adopting EPMA method (electron probe microanalysis (EPMA) method). Form the mutual sample that disperses non-contiguously of a kind of emulsion grain and use electron beam irradiation. By analyzing the X-ray of emission, can analyze the element by the microcell of electron beam irradiation. For preventing that sample is destroyed by electron beam, preferably is cooled to low temperature with sample and measures. Adopt same procedure to distribute along the agi content on the first type surface vertical direction in the analysing particulates. Solidified sample also becomes very thin part with the sample micro-dissections, might analyze thus the distribution of agi content in a certain zone of sheet-like particle.

The scope of agi content is preferably 2 to 6mol % in sheet-like particle of the present invention, and more preferably 3 to 5mol%. If agi content surpasses this scope, even adopt sandwich construction of the present invention, large-size flaky particle, the dependent effect of improving of process is still little.

The silver chloride content scope is preferably 3mol% or still less in the sheet-like particle of the present invention, and 2mol% or still less more preferably most preferably is 1mol% or still less. The content of silver iodide is preferably as much as possible few, because the dependence of KBr consumption descends in the Treatment Solution.

When containing silver chlorate, for reducing the dependence of KBr consumption in the Treatment Solution, the part that contains silver chlorate preferably is in granule interior as much as possible. More specifically, preferably the 4th or subsequently shell (referring to following description) in chloride containing silver not, more preferably chloride containing silver not in specific shell (referring to following description).

Sheet-like particle with sandwich construction of the present invention below will be described.

The characteristics of large-size flaky particle of the present invention be agi content between 2 to 6mol%, and particle has five layers or more multi-layered structure, wherein agi content differs 1 mol% or more between each layer. Sheet-like particle of the present invention is at least five-layer structure, comprising nuclear, and outside tactic first shell of nuclear, second shell, the 3rd shell and the 4th shell. Sheet-like particle also can adopt six layers or more multi-layered structure, as long as the ratio of agi content and total silver amount substantially satisfies following relation and then can in the content of silver iodide in nuclear and each shell, nuclear and each shell. If numerical value can not satisfy relational expression, even adopt sandwich construction can not obtain effect of the present invention. In the present invention, nuclear, first shell, second shell, the 3rd shell and the 4th shell are corresponding with the time sequencing of silver halide particle manufacturing. Each preparation process can be carried out in this order continuously, perhaps increases washing and dispersion steps between each step. Namely after nuclear is made, might wash and disperse and utilize prepared karyosome emulsion to consist of the first, second, third and the 4th shell as crystal seed emulsion. Similarly, nuclear be can be used as crystal seed emulsion by the emulsion that first shell covers.

In sheet-like particle of the present invention, the mol% silver amount that comprises in nuclear, first shell, second shell, the 3rd shell and the 4th shell preferably satisfies relational expression described below.

In the present invention, the ratio of the nuclear of sheet-like particle be total silver amount 1 to 40mol%, the average silver iodide content of nuclear is 0 to 5mol%. " ratio of nuclear " refers to for the manufacture of the silver-colored consumption of nuclear and the ratio of the silver-colored consumption of making whole particle. " average silver iodide content " refers to for the manufacture of the silver iodide consumption of nuclear and the ratio of the silver-colored consumption of making whole particle. It can be uniform or inhomogeneous that silver iodide distribute. More specifically, in total silver amount, the ratio of nuclear is preferably 3 to 30mol%, and the average silver iodide content of nuclear is preferably 0 to 3mol%. Can adopt several different methods manufacturing nuclear.

For example, can adopt Cleve, " Photography Theory and Practice (1930) ", the 131st page; Gutoff, " Photographic Science and Engineering ", Volume Four, 248-257 page or leaf (1970); U.S.P.4,434,226,4,414,310,4,433,048 and 4,439,520 and BP 2,112,157 in the method manufacturing nuclear described.

Make nuclear and substantially comprise three steps: nucleation, maturation and growth. In making the nuclear of particle that the present invention adopts, employing U.S.P4,797,354 and Japanese Patent Application Publication (it is very effective that following table is shown the method for describing among the 2-838 of JP-A-).

In the nucleation step of the particles used nuclear of the present invention, such as U.S.P.4,713,320 and 4,942, adopt the gelatin that contains a small amount of methionine described in 120, such as U.S.P.4, adopt high pBr to carry out nucleation described in 914,014, and to carry out at short notice nucleation described in JP-A-2-222940 all be very effective. In the maturing step of nuclear sheet-like particle emulsion of the present invention, such as U.S.P.5,254,453 is described in the presence of low concentration alkali or such as U.S.P.5, and carrying out maturation described in 013,641 under high pH is effective sometimes.

The method that U.S.P.5, the employing polyalkylene oxide compounds of describing in 147,771,5,147,772,5,147,773,5,171,659,5,210,013 and 5,252,453 consist of sheet-like particle is preferred for making during the used nuclear particle of the present invention makes.

For obtaining single sheet-like particle that disperses of high aspect ratio, sometimes in the particle forming process, add gelatin. Be used for this kind purpose gelatin and be preferably the chemical modification gelatin that JP-A-10-148897 and JP-A-11-143002 describe or the gelatin that contains a small amount of methionine of in US4713320 and US4942120, describing. The former chemical modification gelatin is characterised in that at least newly introduces two carboxyls when an amino is by chemical modification in the gelatin. Preferred amber acidifying gelatin or the trimellitic acid gelatin of using. Preferably before growth step or more preferably after nucleation, add immediately the chemical modification gelatin. Be formed with granules the weighing scale of total dispersion medium in the process, addition is 50% or more, is preferably 70% or more.

First shell is formed on the above-mentioned nucleation sheet-like particle. In total silver amount, the ratio of first shell is 10 to 50mol%, and the average silver iodide content of first shell is 1 to 15mol%. More preferably, the ratio of first shell is 20 to 40mol%, and the average silver iodide content of first shell is 2 to 10mol%. First shell can be along the direction that increases aspect ratio in the growth of nuclear on the sheet-like particle, also can be along the direction that reduces aspect ratio. The growth of first shell is to add silver nitrate aqueous solutions and contain iodine and the halogen aqueous solution of bromine carries out by two gunitees basically. Preferably, it is rarer than silver nitrate aqueous solution to contain the halogen aqueous solution of iodine and bromine. The temperature of system and pH, the type of protective colloid agent such as gelatin and concentration, and the existence of ag halide solvent whether, type and concentration, can in wide scope, change.

PBr is preferably 2.5 or littler in the first shell growth course, and more preferably 2 or littler. Suppose that iodide ion 100% and silver ion and the bromide ion of silver ion reaction and remainder react, pBr refers to the negative logarithm of bromide ion concentration in the unreacted system. Except utilize two gunitees to add silver nitrate aqueous solutions and contain iodine and the halogen solution of bromine, such as U.S.P.4,672,027 and 4, described in 693,964, add simultaneously silver nitrate aqueous solution, the brominated halogen aqueous solution and silver iodide fine particle emulsion also is effective. Also can form first shell by interpolation and ripe IBr particulate emulsion. If adopt this practice, it is particularly preferred using ag halide solvent.

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

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

When using any these solvents, basically can be by the washing step desolventizing after above-mentioned first shell forms step.

Second shell is formed in above-mentionedly to has on nuclear and the sheet-like particle of first shell. In total silver amount, the ratio of second shell is 5 to 30mol%, and the second shell average silver iodide content is 0 to 5mol%. More preferably, the ratio of second shell is 10 to 20mol%, and the average silver iodide content of second shell is 0 to 3mol%. Second shell can be along the direction that increases aspect ratio in the growth that has on nuclear and the sheet-like particle of first shell, also can be along the direction that reduces aspect ratio. The growth of second shell is to adopt two gunitees interpolation silver nitrate aqueous solutions and the brominated halogen aqueous solution to carry out basically. Perhaps after the brominated halogen aqueous solution adds, adopt single gunite to add silver nitrate aqueous solution. The temperature of system and pH, the type of protective colloid agent such as gelatin and concentration, and the existence of ag halide solvent whether, type and concentration, can in wide scope, change. In the present invention, particularly preferred situation is after second shell forms, in all side crystal faces that opposed with sheet-like particle (111) first type surface is connected 75% or still less be made of (111) crystal face.

" 75% or all side crystal faces still less be made of (111) crystal face " refers to that non-(111) crystal face accounts for the ratio of all side crystal faces greater than 25%.Non-(111) crystal face is generally understood as (100) crystal face, but some crystal face as (110) crystal face or more the crystal face of high index also may exist.When 70% or still less all side crystal faces when being made of (111) crystal face, effect of the present invention is tangible.

From the projection electron micrograph of the particle of carbon replica gained, can easily determine 70% or all side crystal faces still less whether constitute by (111) crystal face.When in the sexangle sheet particle 75% or more side crystal face when being made of (111) crystal face, six side crystal faces that are directly connected in (111) oikocryst face alternately are connected with the obtuse angle by acute angle.Say that from another point of view when in the sexangle sheet particle 70% or still less all side crystal faces when being made of (111) crystal face, all six side crystal faces are pressed the obtuse angle and are connected with (111) oikocryst face.When projection under 50 ° or littler angle, might distinguish the angle that constitutes with first type surface is acute angle or obtuse angle.Preferably 10 ° to 30 ° following projections so that distinguish obtuse angle and acute angle.

As a kind of method of determining (111) crystal face and (100) crystal face ratio, it also is effective utilizing the method for sensitizing dye absorption.Adopt Journal of Japan Chemical Society, 1984, Vol.6, the method among the pp.942-947 can quantitatively obtain the ratio of (111) crystal face and (100) crystal face.That is,, might calculate the ratio of (111) crystal face in all side crystal faces by adopting this ratio and platy shaped particle equal circle diameter and the thickness of describing in the document.Suppose that in this case platy shaped particle is a right cylinder of taking equal circle diameter and thickness.Based on this hypothesis, can obtain the ratio of side crystal face and total surface.Divided by the ratio of side crystal face and the gained merchant be multiply by 100 numerical value that draw is exactly the ratio that (100) crystal face accounts for all side crystal faces, wherein (100) crystal face ratio obtains by above-mentioned sensitizing dye absorption with (100) crystal face ratio.From 100, deduct this numerical value and obtain the ratio that (111) crystal face accounts for all side crystal faces.In the present invention, the ratio of (111) crystal face in all side crystal faces most preferably is 65% or still less.

Below with description make in the platy shaped particle emulsion of the present invention 75% or still less all side crystal faces be the method for (111) crystal face.The most generally speaking, in making the platy shaped particle emulsion second shell process, can determine the ratio of (111) crystal face in all side crystal faces in the iodine silver bromide platy shaped particle emulsion by pBr.Preferably, (111) crystal face ratio in the side crystal face is descended, promptly, make under (100) crystal face pBr condition that ratio raises in the side crystal face, having 30% or more constitute the required silver amount of second shell and be added.More preferably, under the pBr condition that (111) crystal face ratio in the side crystal face is descended, have 50% or more constitute the required silver amount of second shell and be added.

As another kind of method, after total silver amount is added, under the pBr condition that makes the ratio rising in the side crystal face of (100) crystal face, carry out maturation, also might increase the ratio of (100) crystal face in the side crystal face.

According to for example system temperature and pH, the type of protective colloid agent such as gelatin and concentration, the existence of ag halide solvent whether, type and concentration, (100) crystal face pBr that ratio raises in the side crystal face can be changed in wide region.Usually pBr is preferably 2.0 to 5, and more preferably excellent is 2.5 to 4.5.As mentioned above, owing to the existence as ag halide solvent, the value of pBr can easily change.

EP515894A1 can be used as a kind of method that changes the indices of crystal plane of platy shaped particle emulsion side crystal face.As U.S.P.5, the polyalkylene oxide compound of describing in 252,453 also can use.Use for example at U.S.P.4,680,254,4,680,255,4,680,256 and 4,684, the indices of crystal plane improver described in 607 is effective.The conventional radiography spectral sensitizing dye also can be used as indices of crystal plane improver.

The 3rd shell be formed in have nuclear, on the platy shaped particle of first shell and second shell.Preferably, in total silver amount, the ratio of the 3rd shell is 1 to 10mol%, and the average silver iodide content of the 3rd shell is 20 to 100mol%.More preferably, the ratio of the 3rd shell is 1 to 5mol%, and the average silver iodide content of the 3rd shell is 25 to 100mol%.The 3rd shell has nuclear, and growth is to adopt two gunitees by adding silver nitrate aqueous solution and containing iodine and the halogen aqueous solution of bromine is carried out basically on the platy shaped particle of first shell and second shell.In addition, also can adopt two gunitees to add silver nitrate aqueous solution and contain the halogen aqueous solution of iodine, or adopt single gunite to add the halogen aqueous solution that contains iodine.Under latter event, suppose that the second shell halogen conversion ratio is 100%, the ratio that deducts second shell from total silver amount obtains the ratio of the total relatively silver amount of the 3rd shell.The content of silver iodide is 100mol% in supposing to form.

Can separately or unite the use said method.From the average iodine content of the 3rd shell as can be seen, during the 3rd shell forms except that iodine silver bromide mixed crystal also precipitable silver iodide.Under these two kinds of situations, silver iodide disappear and all change into iodine silver bromide mixed crystal during the 4th shell forms.

The preferred method of adding iodine silver bromide or silver iodide particulate emulsion that adopts constitutes the 3rd shell.For these particles, can adopt previously prepared fine grained.More preferably, after preparation of granules, use immediately.

When using previously prepared particle, the method that can adopt interpolation, maturation and dissolve these particles.More preferable methods is to add the silver iodide fine particle emulsion, adds silver nitrate aqueous solution then or adds silver nitrate aqueous solution simultaneously and the halogen aqueous solution.In this method, because the adding of silver nitrate aqueous solution makes the fine grain insoluble increase of silver iodide.Suppose that its agi content is 100mol%, the silver-colored consumption of the silver iodide fine particle emulsion that is added will reach the requirement of the 3rd shell ratio.The silver nitrate aqueous solution that is added is used to calculate the 4th shell ratio.The silver iodide fine particle emulsion is preferably unexpected adding.

" add the silver iodide fine particle emulsion suddenly " and refer to be preferably at 10min, more preferably in 7min, add the silver iodide fine particle emulsion.Condition can change according to following factor: for example add temperature, pBr, the pH of emulsion system, the type of protective colloid glue such as gelatin and concentration, the existence of ag halide solvent whether, type and concentration.Certainly as mentioned above the time short more then be preferred more.During adding, preferably do not add silver salt substantially, as silver nitrate aqueous solution.The temperature of system is preferably 40 ℃ to 90 ℃ during the interpolation, most preferably is 50 ℃ to 80 ℃.

The silver iodide fine particle emulsion can be essentially silver iodide, and can contain silver bromide and/or silver chloride, as long as mixed crystal can form.Emulsion is preferably 100% silver iodide.The silver iodide crystal structure can be β type, γ type, or as U.S.P.4,672,026 described be α type or class α type.In the present invention, crystal structure be there is no particular restriction, but be preferably the potpourri of β and γ type, or β type more preferably.As the silver iodide fine particle emulsion, preferably emulsion is carried out the washing of rule.Can adopt as U.S.P.4, the method for describing in 672,026 easily produces the silver iodide fine particle emulsion.The preferred employing fixedly using two adding methods that spray of silver salt solution and iodine salt water solution to form particle under the pI value condition.PI is I in the system ^-The negative logarithm of ion concentration.For temperature, pI and the pH of system, the type of protective colloid agent such as gelatin and concentration, the existence of ag halide solvent is whether, type and concentration is without particular limitation.For ease of enforcement of the present invention, particle diameter is preferably 0.1 μ m or littler, more preferably 0.07 μ m or littler.Though because particle is a fine grained and particle shape can not accurately be described, the variation factor of size distribution is preferably 25% or littler.When variation factor is preferably 20% or more hour, effect of the present invention is tangible especially.For the particle diameter and the size distribution of silver iodide fine particle emulsion, can be by the silver iodide fine grained being placed on the grid with electron microscopic observation or directly obtain with transmission beam method, but can not use the carbon replica.This is that adopting the carbon replica to observe has increased measuring error because because particle is tiny.Particle diameter is defined as the diameter of a circle that equates with the projected area area of observed particle.It also is that diameter of a circle calculating by equating with the projected area area gets that footpath distributes.In the present invention, the most effectively the fine grain particle diameter of silver iodide is 0.06 to 0.02 μ m, and the variation factor of size distribution is 18% or littler.

After constituting particle as mentioned above, adopt as U.S.P.2, the method in 614,929 is carried out regularity to the silver iodide fine particle emulsion and is washed, and to the concentration of pH, pI, protective colloid agent such as gelatin, comprise silver iodide concentration adjust.PH is preferably 5 to 7.The numerical value of pI preferably makes the silver iodide dissolubility reduce to minimum or is higher than this numerical value.As the protective colloid agent, preferably adopt mean molecular weight to be about 100,000 normal gelatin.Mean molecular weight be 20,000 or littler low molecular weight gelatine also be preferred the use.Sometimes using the gelatin mixture with different molecular weight is easily.In every kg emulsion, the gelatin consumption is preferably 10 to 100g, and more preferably 20 to 80g.In every kg emulsion, silver-colored consumption, promptly the content of silver atoms is 10 to 100g, more preferably 20 to 80g.For gelatin consumption and/or silver-colored consumption, preferred numerical value is adapted to the unexpected adding of silver iodide fine particle emulsion.

Before interpolation, usually the silver iodide fine particle emulsion is dissolved.During adding, the stirring efficiency of system fully must be raise.The rotating speed that stirs is preferably higher than routine.Foam formed during the interpolation defoamer can prevent to stir.More specifically, use as U.S.P.5 the defoamer of describing in 275,929 embodiments.

The method of using immediately after below will describing a kind of more preferred fine grained and making.About forming the fine grain mixer of silver halide detailed description is arranged in JP-A-10-43570.

Mixer is to mix the stirring apparatus of bathing a kind of comprising, and contains the charging aperture of predetermined quantity during this mixing is bathed, and is used to send to water soluble silver salt and water-soluble haloid for stirring, and a discharging opening, is used to discharge the silver halide fine particle emulsion that generates after stirring; Mixer also contains rabbling mechanism, stirs the stirring of fluid in the bath by the rotation control of stirring stirring arm in the bath.Preferably, stir by two or more stirring arm rabbling mechanisms that in stir bathing, rotate and mix.At least two stirring arms are separated mutually, in correspondence with each other, and by opposite direction rotation.Preferably, these paddles with place near the outer magneton magnetic coupling of stir bathing the wall, constitute a kind of nothing and pass through the structure that stirs the axle of bathing wall.Stir the rotation that the motor of bathing the outside makes corresponding outside magneton by placing, drive each paddle thus and rotate.With an outside magneton of paddle magnetic coupling is that a kind of N-is parallel with rotary middle spindle with S-utmost point terminal surface and overlap on two-sided bipolar magneton on the rotary middle spindle between the two separately.Another outside magneton is that a kind of N-and S-utmost point terminal surface are symmetrically placed in perpendicular to the horizontal double pole magneton on this center of rotation axial plane with respect to rotary middle spindle.

Accompanying drawing has shown the embodiment of mixer of the present invention (stirring apparatus).

Stir bathing 18 is bathed main body 19 and is constituted as stirring to bathe wall and be used for the closed diaphragm seal 20 of bathing main body 19 upper and lower opening ends that stirs by the stirring with vertical center axis.Paddle 21 and 22 separation mutually places stirring to bathe 18 corresponding top and bottom, and presses reverse direction and rotate.Paddle 21 and 22 and place near the outside magneton 26 magnetic couplings of stir bathing the walls outside paddle 21 and 22.That is, paddle 21 and 22 is by magnetic force and outside magneton 26 couplings separately.When the motor 28 and 29 of these magnetons 26 by separately drove, paddle 21 and 22 had been with to rotate.

Stir bath 18 and have solution inlet port 11,12 and 13, be used to carry silver salt solution and haloid aqueous solution, also can carry colloidal solution and discharging opening 16 if necessary, be used to discharge silver halide fine particle emulsion through stirring for stirring.Silver salt solution and haloid aqueous solution are preferably pressed the interpolation of paddle direction, and two solution inlet port 11 and 12 angles that constituted are preferably wide as much as possible.That is, 90 ° of ratios are preferred for 60 °, and 180 ° then more preferred.

The fine grain method of preparation halogen silver below will be described.More specifically, below will describe (a) speed of agitator, (b) residence time, (c) adding method and protective colloid type (d) are added solution temperature, (e) add solution concentration, and (f) potential energy.

(a) speed of agitator

When relative paddle was driven in mixer, rotating speed was preferably 1,000 to 8,000rpm, and more preferably 3,000 to 8,000rpm most preferably is 4,000 to 8,000rpm.If rotating speed surpasses 8,000rpm, the centrifugal force of stirring arm became strong, and disadvantageous situation is to form one adverse current at the charging aperture place.The rotating speed of agitator that rotates on opposed position can be identical or different.

(b) residence time

The residence time that adds the interpolation solution in the mixer is expressed from the next:

t＝60V/(a+b+c)

Wherein: t: the residence time (sec)

V: the volume of blending space (mL) in the mixer

A: the interpolation speed (mL/min) of silver salt solution

B: the interpolation speed (mL/min) of haloid solution

C: the interpolation speed (mL/min) of protective colloid solution.

Residence time t is preferably 0.1 to 0.5 sec, and more preferably 0.1 to 1sec, most preferably is 0.1 to 0.5sec.If the residence time surpasses 5sec, the silver halide fine grained that generates in mixer will grow up to bulky grain, and size distribution is broadened.If the interpolation solution that residence time t less than 0.1sec, gives off from mixer is not reaction still.

(c) adding method and protective colloid type

By the following method the protective colloid aqueous solution is added in the mixer.

A, protective colloid aqueous solution are injected in the mixer separately.The concentration of protective colloid is 0.5% or more, is preferably 1% to 20%.In the overall flow rate of silver salt solution and halide solution, the flow velocity of protective colloid is at least 20% to 30%, is preferably 50% to 200%.

B, protective colloid are comprised in the halide solution.Protective colloid concentration is 0.4% or more, is preferably 1% to 20%.

C, protective colloid are comprised in the silver salt solution.Protective colloid concentration is 0.4% or more, is preferably 1% to 20%.When using gelatin, silver ion and gelatin constitute albargin, and this albargin generates silver colloid through light or thermal decomposition.Therefore, preferably at once silver salt solution and gelatin solution are added before use.

Said method a to c can use separately, or both or three can use simultaneously.

In mixer of the present invention, gelatin often is used to do protective colloid, and often uses alkaline-process gelatin.Particularly preferred alkaline-process gelatin is handled through deionization and/or is removed foreign ion and impurity through hyperfiltration treatment.Except that alkaline-process gelatin, can use derivatization gelatin such as acid process gelatin, O-phthalic acidifying gelatin, trimellitic acid gelatin, amber acidifying gelatin, maleinization gelatin and esterification gelatin; Low molecular weight gelatine (molecular weight=1,000 is to 80,000, comprise the enzymatic degradation gelatin, through acid and/or basic hydrolysis gelatin, thermal decomposition gelatin); High molecular gelatin (molecular weight=110,000 are to 300,000); Contain the 40 μ mol/g or the gelatin of methionine still less; Contain the 20 μ mol/g or the gelatin of tyrosine still less; Oxidized gelatin; Through the alkylation gelatin that methionine forms that deactivates.Also can use the gelatin mixture that contains two or more gelatin.

In order to utilize mixer to obtain thinner silver halide particle, add solution temperature must keep low as much as possible.But 35 ℃ or more under the low temperature gelatin easily solidify.Therefore, the harmonic component gelatin that preferably uses even also do not solidify at low temperatures.The molecular weight of low molecular weight gelatine is 50,000 or littler, is preferably 30,000 or littler, more preferably 1,000 or littler.Simultaneously, also can use synthetic polymer in the present invention, because synthetic polymer does not solidify at low temperatures yet with silver halide particle protective colloid function.Similarly, a kind of neutral polymer of non-gelatin also can be used for the present invention.These polymkeric substance are being expressed as JP-B-7-111550 and Research Disclosure Vol.176, among the clauses and subclauses IX of No.17643 (in Dec, 1978) description are arranged.

(d) add the temperature of solution

Add solution temperature be preferably 10 ℃ to 60 ℃.But in order to reduce particle diameter and to improve preparation method's adaptability, add more preferably 20 ℃ to 40 ℃ of solution temperatures, most preferably be 20 ℃ to 30 ℃.Simultaneously, by the generation that prevents reaction heat in the mixer with generated the fine grain maturation of silver halide, preferably the temperature of mixer and pipeline is controlled.

(e) add the concentration of solution

Be equipped with in the mixer of reaction vessel in said external, generally must do not dilute original solution.Therefore, if use strong solution, formed silver halide particle diameter increases and the size distribution variation.But since above-mentioned mixer stir and mixed performance on be better than conventional whisk, even therefore during the employing strong solution, also can generate the ultra-fine silver halide particle of the tiny and narrow diameter distribution of particle.More specifically, add solution concentration and be preferably 0.4 to 1.2mol/ liter (also can be expressed as following " L "), more preferably 0.4 to 0.8mol/L.Because total silver amount descends, when adding solution concentration less than 0.4mol/L concentration cross low and unrealistic.

(f) potential energy

For the potential energy in hexagonal system silver halide ultra-fine grain forms (the excessive degree of halogen), for reducing particle diameter, particle preferably generates in the little pAg scope of solubleness.More specifically, pAg is preferably 8.5 to 11.5, and more preferably 9.5 to 10.5

The inventors of this patent have studied above-mentioned clauses and subclauses (a) in great detail to (f), and can to produce bulb diameter such as average be the hexagonal system silver halide ultra-fine grain of 0.008 to 0.019 μ m.

The silver halide ultra-fine grain that makes thus preferably adds in the reaction vessel immediately.Note " immediately " refer to 30min, be preferably 10min, more preferably in the 1min.This time is preferably short as far as possible, increases because pass ultra-fine silver iodide grain diameter in time.

The silver iodide superfine powder that forms in the above-mentioned mixer outside reactor can add to continuously in the reactor or after mixer stores and join in the reactor.These two kinds of methods also can adopt simultaneously.When particle was stored in the mixer, temperature was preferably 40 ℃ or lower, and more preferably 20 ℃ or lower, the storage time should be short as much as possible simultaneously.

Method for optimizing as a kind of formation the 3rd shell, as U.S.P.5, can adopt the iodide ion releasing agent to produce the iodide ion formation suddenly described in 496,694 and contain the silver halide phase of silver iodide, rather than utilize conventional iodide ion that method (adding the method for free-iodine ion) is provided.

With iodide ion release control agent (alkali and/or nucleopilic reagent) reaction, the iodide ion releasing agent discharges iodide ion.The preferred example of the nucleopilic reagent that is adopted be hydroxide ion, sulfite ion, azanol, thiosulfate ion, partially sulfurous acid hydrogen radical ion, hydroxamic acid, oxime, benzenediol, mercaptan, sulfinate, carboxylate, ammonia, amine, alcohol, urea, thiocarbamide, phenol, hydrazine, hydrazides, semicarbazides, phosphine and sulfide.

By control alkali or the concentration of nucleopilic reagent and the temperature of adding method or reaction solution, can control the release rate and the time of iodide ion.Preferred alkali is NaOH.

For producing iodide ion suddenly, the concentration of iodide ion releasing agent and iodide ion release control agent is preferably 1 * 10 ^-7To 20M, more preferably 1 * 10 ^-5To 10M, be preferably 1 * 10 again ^-4To 5M, most preferably be 1 * 10 ^-3To 2M.

If concentration surpasses 20M, the volume that forms container with particle is compared, and the iodide ion releasing agent that molecular weight is big and the addition of iodide ion release control agent become excessive.

If concentration is less than 1 * 10 ^-7, the iodide ion release reaction became slow, was difficult to produce suddenly the iodide ion releasing agent.

Temperature is preferably 30 to 80 ℃, more preferably 35 to 75 ℃, most preferably is 35 to 60 ℃.

Surpassing under 80 ℃ the high temperature, general iodide ion release reaction speed is very fast.When temperature was lower than 30 ℃, general iodide ion release reaction speed was very slow.Because the restriction of service condition, both of these case all is not preferred.

When using alkali to discharge iodide ion, also can utilize the change of pH value of solution.In this case, and control iodide ion release rate and the pH scope of time are preferably 2 to 12, and more preferably 3 to 11, be preferably 5 to 10 especially.The most preferably, be 7.5 to 10.0 through adjusted pH.Be under 7 the neutrallty condition at pH, the hydroxide ion that concentration is determined by hydrolytic dissociation is as controlling agent.

Can unite and use nucleopilic reagent and alkali.When the case, pH can be controlled within the above-mentioned scope, makes that iodide ion release rate and time are controlled.

When the iodine atom with the iodide ion form during by the release of iodide ion releasing agent, iodide ion can wholely discharge or the residual Undec iodide ion releasing agent of part.

The 4th shell forms on the above-mentioned platy shaped particle that contains nuclear, first shell, second shell and the 3rd shell.In total silver amount, the ratio of the 4th shell is 10 to 40mol%, and the average silver iodide content of the 4th shell is 0 to 5mol%.More preferably, the ratio of the 4th shell is 10 to 35mol%, and the average silver iodide content of the 4th shell is 0 to 3mol%.The growth of the 4th shell on the platy shaped particle with nuclear and first, second and the 3rd shell can be undertaken by aspect ratio that increases platy shaped particle or the direction that reduces its aspect ratio.The growth of the 4th shell utilizes two gunitees to add silver nitrate aqueous solution basically and the halogen aqueous solution is carried out.Perhaps after adding brominated silver-colored halogen aqueous solution, can utilize single gunite to add silver nitrate aqueous solution.The temperature of system and pH, the concentration of protective colloid agent such as gelatin and type, whether the existence of ag halide solvent to be, and type and concentration can change in wide region.The pBr that forms latter stage at the 4th shell preferably will be higher than the pBr of this layer of formation during the initial stage.Preferably, forming initial stage pBr at this shell is 2.9 or littler, is 1.7 or bigger and form latter stage pBr at shell.More preferably, forming initial stage pBr at shell is 2.5 or littler, is 1.9 or bigger and form latter stage pBr at shell.Most preferably, forming initial stage pBr at shell is 1 to 2.3, is 2.1 to 4.5 and form latter stage pBr at shell.

The side crystal face that connects (111) first type surface of final particle can be the mixing of (111) crystal face, (100) crystal face or (111) and (100) crystal face, perhaps also can contain the more crystal face of high index.The platy shaped particle emulsion that (111) crystal face ratio is low in the side crystal face of describing in EP515894A1 is preferred the use.

Platy shaped particle in emulsion of the present invention is cooled to less than 10 ° of K (in the present invention, adopt 6 ° of K as a reference) and be that the electromagnetic beam (as He-Cd laser) of 325nm is when inducing emulsion with wavelength, except that wavelength coverage inducing the emission peak between 490 to 560nm, its intensity of 575nm light of emulsion emission be in 490 to the 560nm scopes high emission intensity 1/3.In essence, the 575nm emission depends on the structure of the high agi content shell of corresponding above-mentioned the 3rd shell.The 575nm emissive porwer changes according to the formation method of silver content, agi content, the 3rd shell.When adopting the formation method of preferred the 3rd shell of the present invention, the emissive porwer of 575nm be preferably maximum emission intensity in 490 to the 560nm wavelength coverages 1/2 or more, more preferably 2/3 or more.

In the present invention, flat crystal preferably has dislocation line.As adopt J.F.Hamilton, Phot.Sci.Eng., 11,57, (1967) or T.Shiozawa, J.Soc.Phot.Sci.Japan, 35,213, (1972) but in the method described utilize dislocation line in the transmission electron microscope Direct observation platy shaped particle at low temperatures.That is, silver halide particle is taken out from emulsion carefully and the dislocation line that generates in the particle is not exerted pressure, and place the grid of Electronic Speculum to observe particle.Cooling prevents to cause damage (as shining (print out)) and adopt transmission beam method to observe because of electron ray to sample.In this case, the big more then divergent bundle of the thickness of particle is difficult more passes through it.Therefore, use high-pressure type (adopting 200kV or bigger voltage) electron microscopic observation particle more clear for 0.25 μ m thickness.From the particle photo of said method gained, might obtain the position and the number of dislocation line from each particle of seeing perpendicular to particle first type surface direction.

In each particle, the average number of dislocation line is preferably 10 or more, and more preferably 20 or more.Have dense or mutual intersection if observe dislocation line, just exact figures go out the number of dislocation line in each particle sometimes.Even but in this case, also can 10 be unit, go out the dislocation line number as 10,20 or 30 rough numbers, so just may with these particles with obviously only exist the granulomere of several dislocation lines to separate.The average dislocation line number of each particle is meant that counting 100 or each a plurality of particle dislocation line average and obtains.

The distribution of dislocation line number is preferably homogeneous in platy shaped particle of the present invention.In emulsion of the present invention, the silver halide particle that contains 10 or more a plurality of dislocation lines in each particle preferably accounts for 100 to 50% (in quantitative terms), and more preferably 100 to 70%, most preferably be 100 to 90%.Consider intergranular homogeneity, it is not preferred being lower than 50% number percent.

Dislocation line can be introduced into the platy shaped particle outer edge area for example near.In this case, dislocation line is basically perpendicular to outer rim and forms at the x% place of distance outer rim distance for platy shaped particle center and outer rim spacing.Numerical value x is preferably 10 to less than 100, most preferably is 30 to less than 99, most preferably is 50 to less than 98.In this case, though it is similar substantially to particle shape to connect the shape of dislocation line reference position gained, sometimes can not be similar fully because of distortion.Can not see this dislocation line in the particle central area.Being oriented in of dislocation line is about (211) direction on the crystallography.But dislocation line often is zigzag and intersects mutually sometimes.

The dislocation line that platy shaped particle has can be a certain ad-hoc location that is uniformly distributed in whole outer edge area basically or is in outer edge area.But dislocation line be preferably placed at corner near.In platy shaped particle with triangle or sexangle outside surface, when from the straight line between platy shaped particle center and each corner apart from x% position, platy shaped particle center when vertical line is drawn in two sidelines that constitute corner, refer near the corner by these vertical lines and two zones that the sideline constitutes, i.e. a 3D region around the whole thickness of particle.The value of x is 50 to less than 100, is preferably 75 to less than 100.

When platy shaped particle was circle, each corner was not obvious.Even in this platy shaped particle, also may obtain the tangent line at 3 or 6 edges and obtain point as corner, pitch mutually with straight line and platy shaped particle outer rim that the platy shaped particle center is constituted the point of crossing that connects these tangent lines simultaneously.

" dislocation line be positioned at corner near " refers to 60% or near be present in the corner of all dislocation lines more.Preferably, 80% of all dislocation lines or near be present in the corner more.When platy shaped particle has the sexangle outside surface, dislocation line can be arranged in six at least one corners of corner neighbouring maybe can be evenly distributed in six corners near.

Can dislocation line be incorporated near the corner by constituting a high special shell of agi content near the inside the particle corner.The shell of this high agi content comprises the discontinuous high agi content of formation zone.

For optionally at blapharoplast, near the formation of corner that has promptly constituted the particle of second shell has the shell of high agi content, be above the 3rd shell that describes in detail of the present invention, need control with formation condition the formation condition of blapharoplast with shell of high agi content.For the blapharoplast formation condition, the temperature during platy shaped particle outermost layer shell forms and the existence of pAg (the negative logarithm of concentration of silver ions) and ag halide solvent are whether, type, quantity and temperature be important factor.More specifically, during the outermost layer shell of blapharoplast formed, pAg was preferably 7.8 or littler, and more preferably 7.2 or littler.Perhaps to constitute the outermost layer shell ripe in above-mentioned pAg scope then not meeting under the above-mentioned pAg condition, also the layer-selective with high agi content can be formed near the corner.When above-mentioned outermost shell layer formation process carried out under the ag halide solvent existence condition, the threshold value of pAg became bigger.Ammonia, aminated compounds, thio-ether type compounds or thiocyanate are effective as halogen silver solvent.

The another kind of method that constitutes the shell with high agi content is under high temperature or high pAg condition iodide ion to be added in the blapharoplast emulsion, thereby optionally transforms (halogen conversion) near the blapharoplast corner.Thereby near the blapharoplast corner, form shell with high agi content.

Formed dislocation line also can pass through the zone that comprises two parallel first type surface centers of platy shaped particle.But compare with near the above-mentioned situation dislocation line is positioned at corner, this situation is not preferred.When dislocation line passes through first type surface whole when zone, the orientation of dislocation line be sometimes perpendicular to first type surface near (211) direction on the crystallography.In some cases, be oriented to (110) direction or disorderly and unsystematic.The length of each dislocation line is also irregular: the dislocation line on first type surface is short-term sometimes, sometimes again for extending to the long line on border (outward flange).Though dislocation line is straight sometimes, they often are zigzag.As a rule, dislocation line intersects mutually.

In the platy shaped particle of silver emulsion of the present invention, the position of dislocation line can be confined to outer edge, first type surface or part.Though can occur simultaneously in these positions, dislocation line is preferably placed near the corner as mentioned above.

In the present invention, preferred 100 particles of Direct observation at least, more preferably 200 or more a plurality of particle, most preferably be the dislocation line of 300 or more a plurality of particles, thereby obtain containing the proportion of particles of dislocation line and the number of dislocation line.

In the present invention, the variation factor that agi content between each silver halide particle distributes is preferably 20% or still less, and more preferably 15% or still less, most preferably be 10% or still less.If variation factor greater than 20%, then can not be obtained stable classification, the light sensitivity that causes when exerting pressure descends to be increased.The composition of employing X-X-ray microanalysis X instrument analysing particulates can be measured the content of silver iodide in each particle.The variation factor that silver iodide distribute between each particle refers to by the numerical value that relational expression (standard deviation/average silver iodide content) * the 100=variation factor is defined, and wherein the standard deviation of the agi content that is adopted and average silver iodide content are measured to few 100, more preferably 200, most preferably are that 300 emulsion grains obtain.Adopt as EP147, the method described in 868 is measured the agi content of each particle.In each particle agi content Yi (mol%) and etc. can have correlativity between the bulb diameter Xi (μ m), or do not have correlativity.But preferably there is not correlativity.

The inventors of this patent have carried out detailed research and have had been found that in platy shaped particle emulsion of the present invention, consider the light sensitivity of emulsion and the storage stability that contains the photosensitive silve halide material of this emulsion, the average silver iodide content of particle surface is 5mol% or still less is very preferred.Adopt XPS (the sub-spectrophotometric spectra method of X-ray photoelectric) to measure the average silver iodide content of particle surface of the present invention.People such as Junnich Aihara, the principle of using agi content in the nearly surface of XPS measuring silver halide particle has been described in " Spectra of Electrons " (Kyoritsu Library16, Kyoritsu Shuppan, 1978).The standard method of measurement of XPS is to adopt mg-K α to excite the X-ray that the silver halide of taking suitable sample form is shone and measures iodine in the silver halide (I) and photoelectron intensity (being generally I-3d5/2 and Ag-3d5/2) that silver-colored (Ag) launches.Can adopt the typical curve of the photoelectron intensity (intensity (I)/intensity (Ag)) of iodine (I) that the standard model of the known content of iodine of several types makes and silver (Ag) to calculate content of iodine.Can carry out XPS measuring to silver emulsion after must adopting the gelatin that will be adsorbed in the silver halide particle surface to remove as proteinase.When adopting XPS method analysis package to be contained in emulsion grain in the single emulsion, the particle surface agi content is that 5mol% or platy shaped particle emulsion of the present invention still less are that a kind of agi content is 5mol% or emulsion still less.If obviously be the mixing of two or more emulsions, before one type of emulsion is analyzed, must carry out suitable processing, as centrifuging or filtration.

And, the inventor studies in great detail according to this patent, as mentioned above when the average silver iodide content Is on the particle surface of platy shaped particle emulsion of the present invention be 5mol% or still less the time, and this average silver iodide content Is is favourable to light sensitivity when being represented by following relational expression with respect to the mutual relationship of the average silver iodide content It of whole particle:

0.3·It≤Is

In silver emulsion of the present invention, preferably form the hole capture band in inner at least one part of silver halide particle.This has greatly eliminated the ineffectivity that is produced as mentioned above when particle diameter increases.The hole capture band refers to have the zone of catching so-called hole function in the present invention, and the photoelectron that generates when wherein the hole is with optical excitation for example occurs in pairs.Formed zone when in the present invention, the hole capture band refers to by reduction sensitization consciously.

" reduction sensitization consciously " refers to by adding reduction sensitization agent part or all introducing hole capture galactic nucleus in silver halide particle inside in the present invention.The hole capture galactic nucleus is meant to have the low active galactic nucleus that develops.This galactic nucleus can prevent in the sensitizing process again in conjunction with loss and increase photonasty.

The known example of reduction sensitization agent has tin salt, ascorbic acid and derivant thereof, amine and polyamines, hydrazine derivate, carbonamidine base sulfinic acid, silane compound and borane compound.In reduction sensitization of the present invention, can select these known reduction sensitization agent for use or use the compound of two or more types simultaneously.Preferred compound as the reduction sensitization agent has stannous chloride, thiourea dioxide, dimethyamine borane and ascorbic acid and derivant thereof.Though the addition of reduction sensitization agent must select condition and decides according to emulsion system, in every mol silver halide, its preferable amount is 10 ^-7To 10 ^-3Mol.

Water-soluble or solvent adds gained solution as in alcohol, dibasic alcohol, ketone, ester or the acid amides in the particle growth process with the reduction sensitization agent.

In the present invention, preferably add the reduction sensitization agent after nucleation and physical ripening and before the particle growth at once and constitute the hole capture galactic nucleus.But also can form the back at particle adds the reduction sensitization agent and introduces the hole capture galactic nucleus at particle surface.

When adding the reduction sensitization agent during particle growth, some formed galactic nucleus may be in granule interior, but other then ooze out and constitute galactic nucleus at particle surface.Preferably, these galactic nucleus that ooze out are also as the hole capture galactic nucleus.

In the present invention, in each step during particle forms, preferably carrying out in the presence of the compound of representative by formula (II-1) or (II-2) at the inner reduction sensitization consciously that constitutes the hole capture galactic nucleus of silver halide particle.By formula (II-1) or (II-2) compound of representative infer the oxidation can prevent the oxidated free love base of galactic nucleus, thereby only stablely constitute the hole capture galactic nucleus.A kind of clearly experimental fact is when the reduction sensitization consciously that carries out in each step during particle forms under the compound condition that does not have formula (II-1) or (II-2) represent, and then is difficult to obtain effect of the present invention.

Each step during particle forms does not comprise the step after final desalination is finished.For example, be that this step is in not being included in owing to add the result's of silver salt solution or fine grained silver halide chemical sensitization step for step as the growth of silver halide particle wherein.

Formula (II-1) formula (II-2)

In formula (II-1) with (II-2), W ₅₁And W ₅₂Represent sulfo group or hydrogen atom respectively.But W ₅₁And W ₅₂In have at least one to represent sulfo group.Sulfo group is generally alkali metal salt such as sodium or sylvite or water soluble salt such as ammonium salt.Favourable concrete instance is 3,5-disulfo catechol disodium salt, 4-sulfo group catechol ammonium salt, 2, the sodium salt and 2 of 3-dihydroxy-7-sulfo group naphthalene, 3-dihydroxy-6, the sylvite of 7-disulfo naphthalene.Its preferable amount changes according to following factor: add temperature, pBr and the pH of system, the type of protective colloid such as gelatin and concentration, the existence of ag halide solvent whether, type and concentration.In general, in every mol silver halide, addition is preferably 0.0005 to 0.5mol, and more preferably 0.003 to 0.02mol.

The preferred oxygenant that uses silver during making silver emulsion of the present invention.When by reduction sensitization consciously only when the silver halide particle near surface constitutes the hole capture galactic nucleus, use the oxygenant of silver just to become particularly important.By inference when reduction sensitization only carries out in silver halide particle near surface zone consciously, be difficult to optionally form the hole capture galactic nucleus in that the oxygenant condition of not using silver is next.The oxygenant of silver refers to have the compound that argent is changed into the silver ion function.Especially, silver halide particle is formed and the chemical sensitization process in the very tiny silver-colored particle of the growing nonparasitically upon another plant compound that changes into silver ion be effective.The silver ion that is generated can form the silver salt that is insoluble in water such as silver halide, silver sulfide, or silver selenide, or silver salt soluble in water such as silver nitrate.The oxygenant of silver can be inorganic or organism.The example of inorganic oxidizer is an ozone, and hydrogen peroxide and addition product thereof are (as NaBO ₂H ₂O ₂3H ₂O, 2NaCO ₃3H ₂O ₂, Na ₄P ₂O ₇2H ₂O ₂And 2Na ₂SO ₄H ₂O ₂2H ₂O), peracid salt is (as K ₂S ₂O ₈, K ₂C ₂O ₆And K ₂P ₂O ₈), cross oxygen complex (as K[Ti (O ₂) C ₂O ₄] 3H ₂O, 4K ₂SO ₄Ti (O ₂) OHSO ₄2H ₂O and Na ₃[VO (O ₂) (C ₂H ₄) ₂6H ₂O]), permanganate is (as KMnO ₄), oxysalt such as chromate are (as K ₂Cr ₂O ₇) and halogen such as iodine and bromine, perhalide (as potassium metaperiodate), high-valency metal salt (close iron (II) as six cyanogen and change potassium), and thiosulfonate.

The example of organic oxidizing agent is quinone such as 1,4-benzoquinone, organic peroxide such as Peracetic acid and benzoyl hydroperoxide, the compound (as N-bromosuccinamide, toluene-sodium-sulfonchloramide and chloramine B) of release reactive halogen.

In the present invention, preferred inorganic oxidizer is ozone, hydrogen peroxide and addition product thereof, halogen and thiosulfonate, and preferred inorganic oxidizer is a quinone.Particularly preferred oxygenant is the thiosulfonate of describing among the JP-A-2-191938.

The oxygenant of above-mentioned silver can be before reduction sensitization consciously, and during the reduction sensitization, or reduction sensitization adds before or after finishing at once.Oxygenant also can divide several times and add.Although addition is decided according to oxidant type, in every mol silver halide, preferable amount is 1 * 10 ^-7To 1 * 10 ^-3Mol.Adopting gelatin is favourable as the protective colloid in the emulsion manufacturing of the present invention or as the bonding agent of other hydrophilic colloid layer.But other hydrophilic colloid also can be used for substituting gelatin.

The example of hydrophilic colloid is graft polymer and other polymkeric substance of gelatine derivative and gelatin; Albumen such as albumin and casein; Cellulose derivative such as carboxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfuric acid ester; Sugar derivatives such as sodium alginate and starch derivative; And multiple synthetic water wettability superpolymer and homopolymer or multipolymer, as polyvinyl alcohol (PVA), the polyvinyl alcohol (PVA) of part acetalation, poly-N-vinyl pyrrole alkane ketone, polyacrylic acid, polymethylacrylic acid, polyacrylamide, polyvinyl imidazol and polyvinyl pyrazoles.

The example of gelatin has the gelatin of lime treatment, acid-treated gelatin and at Bull, Soc, Sci, Photo, Japan, the gelatin that the enzyme of describing among the No.16, page30 (1996) is handled.In addition, also can use the hydrolysate or the enzyme decomposition product of gelatin.

Preferably emulsion of the present invention is washed reaching the purpose of desalination, and adopt freshly prepd protective colloid dispersion liquid to constitute the protective colloid dispersion liquid.Although can select wash temperature according to required purposes, temperature is preferably 5 ℃ to 50 ℃.Although can select pH according to designed use, pH is preferably 2 to 10, more preferably 3 to 8.Although can select washing pAg according to designed use, preferred pAg is 5 to 10.Washing methods comprises bar (noodle) washing, utilizes the semi-permeable diaphragm dialysis, centrifuging, coagulative precipitation, and ion-exchange.Can select to use sulfide for coagulative precipitation, organic solvent, the method for water-soluble polymers and gelatine derivative.

Preferably during emulsion preparation of the present invention (during particle formation, desalination or chemical sensitization, or coating is preceding), there is metal cation salt according to designed use.When metal cation salt is used to mix particle, preferably during particle forms, add, perhaps be used to modify particle surface or can form afterwards and chemical sensitization is finished preceding adding at particle during as chemical sensitizer when metal cation salt.Except that the method that whole particle is mixed, can adopt the method for the nuclear or the shell of the particle that only mixes.The example of adulterant is Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb and Bi.The form of these metals that added is soluble forms during particle forms, as ammonium salt, acetate, nitrate, sulfate, phosphate, contain hydrohalogenic acid salt, 6 coordinate complex salt or 4 coordinate complex salt.Its example has CdBr ₂, CdCl ₂, Cd (NO ₃) ₂, Pb (NO ₃) ₂, Pb (CH ₂COO) ₂, K ₃[F (CN) ₆], (NH ₄) ₄[Fe (CN) ₆], K ₃IrCl ₆, (NH ₄) ₃RhCl ₆, and K ₄Ru (CN) ₆The aglucon of complex salts can be selected from halogen, water, cyano group, cyanate radical, thiocyanate radical, nitrosyl radical, sulfo-nitrito-, oxygen and carbonyl.These metallic compounds can use separately or two or more compounds are united use.

In the preferred water-soluble or suitable organic solvent of metallic compound such as methyl alcohol or the acetone, and add with the solution form.For stablizing these solution, can add the aqueous solution of halogen acid (as HCl and HBr) or alkali halide (as KCl, NaCl, KBr and NaBr).Also might add acid or alkali if desired.Can be before particle forms or during these metallic compounds are added in the reactor.Perhaps metallic compound can add to water soluble silver salt (as AgNO ₃) or alkali halide (as NaCl, KBr and KI) aqueous solution in and during particle forms, add continuously with the solution form.In addition, can adopt water soluble salt or halogenated alkali metal salt to make metal compound solution respectively, and add the opportune moment in particle forms.Also can unite and use several different adding methods.

As U.S.P3, it is useful adding chalcogen compound sometimes described in 772,031 in the emulsion manufacturing.Except that S, Se and Te, can add cyanate, thiocyanate, selenium cyanic acid, carbonate, phosphate and acetate.

In silver halide particle of the present invention forms, can carry out the operation of at least a sulphur sensitizing, selenium sensitizing, golden sensitizing, palladium sensitizing or noble metal sensitizing and reduction sensitization in any step in the silver halide magenta-sensitive emulsion manufacture process.It is preferred adopting two or more process for increasing sensitivity.

Chemical sensitization step according to performed can prepare several dissimilar emulsions.The emulsion type can be divided into: the chemical sensitization spot is in the type of granule interior, and the chemical sensitization spot is in the type at the shallow table of particle place and the type that the chemical sensitization spot is in particle surface.In emulsion of the present invention, the position of chemical sensitization spot can be chosen according to designed use.Near but the preferred chemical sensitization spot that particle surface, constitutes at least a type.

Being preferred for chemical sensitization method of the present invention is a kind of of chalcogen compound sensitizing and noble metal sensitizing or the method for uniting use.As T.H.James, The Theory of the Photographic Process, 4th ed., Macmillan, 1977, can adopt active gelatin to carry out sensitizing described in the pp.67-76.As Reserch Disclosure, Vol.120, April, 1974,12008, Research Disclosure, Vol, 34, June, 1975,13452, U.S.P 2,642, and 361,3,297,446,3,772,031,3,857,711,3,901,714,4,266,018 and 3,904,415 and BrP 1,315, be 5 to 10 at pAg described in 755, pH is 5 to 8, temperature is under 30 to 80 ℃ the condition, use in sulphur, selenium, tellurium, gold, palladium and the iridium any one or unite to use and carry out sensitizing.In noble metal sensitizing, can use noble metal, as the salt of gold, platinum, palladium and iridium.Especially, golden sensitizing, palladium sensitizing, or the The combined use is preferred.In golden sensitizing, can use known compound, as gold chloride, potassium chloroaurate, thiocyanic acid gold potassium, aurosulfo and Auric selenide.Palladium compound refers to divalence or palladic salt.Preferred palladium compound is by R ₂PdX ₆Or R ₂PdX ₄Representative, wherein R represents hydrogen atom, alkali metal atom or ammonium, and X represents halogen atom, i.e. chlorine, bromine or iodine atom.

More specifically, palladium compound is preferably K ₂PdCl ₄, (NH ₄) ₂PdCl ₆, Na ₂PdCl ₄, (NH ₄) ₂PdCl ₄, Li ₂PdCl ₄, Na ₂PdCl ₆Or K ₂PdBr ₄Preferably gold compound and palladium compound and thiocyanate or selenium cyanate are united use.

The example of sulphur sensitizer is a hypo, ghiourea group compound, rhodanine based compound, and U.S.P.3, the sulfocompound of describing in 857,711,4,266,018 and 4,054,457.Also can in the presence of so-called chemical sensitization auxiliary agent, carry out chemical sensitization.The example of chemical sensitization auxiliary agent is included in the compound that can suppress ashing and super-sens in the chemical sensitization process, as azepine indenes, azepine pyridazine and aza-pyrimidine.At U.S.P 2,131,038,3,411,914 and 3,554,757, JP-A-58-126526 and G.F.Duffin, Photographic Emulsion Chemistry has described the example of chemical sensitization auxiliary agent and improver among the pp138-143.

Preferably emulsion of the present invention is also carried out golden sensitizing.The consumption of gold sensitizer is preferably 1 * 10 ^-4To 1 * 10 ^-7Mol, more preferably 1 * 10 ^-5To 5 * 10 ^-7Mol.The preferable amount of palladium compound is 1 * 10 ^-3To 5 * 10 ^-7The preferable amount of thiocyanation compound or selenium cyanogen compound is 5 * 10 ^-2To 1 * 10 ^-6

In every mol silver halide, the consumption of sulphur sensitizer is preferably 1 * 10 in the present invention ^-4To 1 * 10 ^-7Mol, more preferably 1 * 10 ^-5To 5 * 10 ^-7Mol.

Selenium sensitizing is the preferred process for increasing sensitivity of emulsion of the present invention.Disclosed selenium compound can be used as sensitizer of the present invention in well-known patent.Usually unsettled selenium compound and/or non-unsettled selenium compound are added in the emulsion and and stir the emulsion certain hour down at high temperature (being preferably 40 ℃ or higher).At JP-B-44-15748, JP-B-43-13489 discloses the preferred example of unstable selenium compound among JP-A-4-25832 and the JP-A-4-109240.

The example of unstable selenium compound is that different selenocyanates is (as different selenocyanic acid fat-based ester; as different selenocyanic acid allyl ester), seleno urea, seleno ketone; selenium substituted acid amide; seleno carboxylic acid (as 2-seleno propionic acid and 2-seleno butyric acid), the seleno ester, the diacyl selenide is (as two (3-chloro-2; 6-dimethoxy benzoyl) selenide); selenophosphates, the selenide of phosphine and colloidal metal selenium.

Though more than described the preferred example of unstable selenium compound, the present invention also not only is confined to these examples.It is very unimportant as the structure of the unstable selenium compound of photosensitive emulsion sensitizer that those skilled in the art think, as long as selenium is unsettled, and the organic moiety of selenium sensitizer molecule does not have vital role and only be play transhipment selenium and in emulsion maintenance its be the effect of non-steady state.In the present invention, it is favourable using the unstable selenium compound of this broad sense.

The example of non-unstable selenium compound of the present invention has description in JP-B-46-4553, JP-B-52-34492 and Jp-B-52-34491.The object lesson of non-unstable selenium compound is selenous acid, selenocyanic acid potassium, seleno pyrroles, seleno pyrroles's level Four salt, diaryl selenium, diaryl two selenium, selenium dialkyl, dialkyl group two selenium, 2-selenazoles alkane diketone, a 2-seleno oxazolidine thione, and the derivant of these compounds.

In these selenium sensitizers water-soluble or organic solvent such as methyl alcohol and ethanol or the ORGANIC SOLVENT MIXTURES, and during chemical sensitization, preferably begin preceding adding in chemical sensitization.Can only use a kind ofly, also can use two or more above-mentioned selenium sensitizer.Preferably unite and use unstable selenium compound and non-unstable selenium compound.

The addition of the used selenium sensitizer of the present invention was decided according to activity, silver halide type and the size of used selenium sensitizer and maturing temperature and time.In every mol silver halide, addition is preferably 1 * 10 ^-8Mol or more, more preferably 1 * 10 ^-7To 5 * 10 ^-5Mol.When using the selenium sensitizer, the temperature of chemical ripening is preferably 40 ℃ to 80 ℃, and pAg or pH can take arbitrary value.For example, in being 4 to 9 wide region, pH all can obtain effect of the present invention.

Selenium sensitizing is preferably united use with sulphur sensitizing and noble metal sensitizing one or the two.And, in the present invention, in chemical sensitization, preferably thiocyanate is added in the silver emulsion.The example of thiocyanate has potassium rhodanide, sodium thiocyanate and ammonium thiocyanate.In the general before use water-soluble or water-soluble solvent of thiocyanate.In every mole of silver halide, addition is preferably 1 * 10 ^-5To 1 * 10 ^-2Mol more preferably is taken as 5 * 10 ^-5To 5 * 10 ^-3Mol.

Silver emulsion of the present invention preferably contains an amount of calcium ion and/or magnesium ion.This has improved graininess, thereby has improved image quality and storage stability.Be preferably 400 to 2 in right amount, the calcium of 500ppm and/or 50 to 2, the magnesium of 000ppm.More preferably be 500 to 2,000ppm calcium and 200 to 2, the magnesium of 000ppm.When calcium content is 400 to 2500ppm and/or content of magnesium when being 50 to 2500ppm, have a kind of being in the afore mentioned rules scope in calcium and the magnesium at least.If calcium or content of magnesium are higher than these values since before the precipitations such as calcium salt, magnesium salts and inorganic salts that keep by gelatin, for the manufacturing of photosensitive material causes trouble.The content of calcium or magnesium is represented that by the weight of all calcics or magnesium compound as calcium atom in calcium ion, magnesium ion, calcium salt and the magnesium salts or magnesium atom, its unit representation is the concentration in the unit weight emulsion.

The calcium content of silver halide flaky grain emulsion of the present invention preferably adds calcium salt and adjusts during chemical sensitization.In being usually used in making the gelatin of emulsion,, generally contain 100 to 4, the calcium of 000ppm in solid-state gelatin.Therefore, under the situation that contains calcium, regulate calcium content by adding calcium salt.If necessary, also can adopt known method as washing or ion-exchange to gelatin desalination (decalcification) after, carry out the adjustment of calcium content by adding calcium salt again.For calcium salt, be preferably calcium nitrate and lime chloride, wherein calcium nitrate is the most preferred.Similarly, can during the emulsion manufacturing, add magnesium salts and carry out the adjustment of content of magnesium.Concerning magnesium salts, magnesium nitrate, magnesium sulphate and magnesium chloride are preferred, and wherein magnesium nitrate is the most preferred.Can adopt the IPC emission spectrometry method to measure calcium or content of magnesium.Calcium and magnesium can use separately or use with form of mixtures.It is more preferred adding calcium.Though can on the point of any time during silver emulsion is made, add calcium or magnesium, preferably form and add at once after finish back and spectral sensitization and chemical sensitization at particle, more preferably before adding back and chemical sensitization, adds sensitizing dye.

The increase that the mercapto-tetrazole compound of describing among the JP-A-16838 with water soluble group is specially adapted to reduce the ashing of silver emulsion and suppresses ashing between the storage life.This JP-A-16838 discloses to unite and has used mercapto-tetrazole compound and dimercaptothiodiazole compound to improve storage stability.The inventors of this patent attempt disclosed technology among the JP-A-16838 and multiple water-soluble sulfhydryl compound are applied in the emulsion, and wherein emulsion is to carry out selenium sensitizing by the sheet silver emulsion that the present invention is had the hole capture band to make.But light sensitivity reduces in most applications.The inventors of this patent have carried out studying in great detail and find to adopt a kind of special combination, promptly unite the water-soluble mercapto-tetrazole compound of use formula (I-1) representative and the water-soluble mercapto-triazole compound of formula (I-2) representative, can under the condition that does not reduce light sensitivity, improve storage stability.

The water-soluble mercapto-tetrazole compound of formula (I-1) representative at first, below will be described.

In formula (I-1), R ₅Representative is by at least a being selected from-SO ₃M ,-COOM ,-OH and-NHR ₂The organic group that replaces of group.More specifically, R ₅Represent 1 to 10 carbon alkyl (as methyl, ethyl, propyl group, hexyl and cyclohexyl) or 6 to 14 carbon aryl (as phenyl and naphthyl).

R in the formula (I-1) ₅Each group of representative can further be substituted; substituent example is a halogen atom (fluorine; chlorine; bromine and iodine); cyano group; nitro; ammonio (as trimethyl ammonio); phosphorus father-in-law base; sulfonic group (comprising salt); sulfinic acid base (comprising salt); carboxyl (comprising salt); phosphoryl (comprising salt); hydroxyl; sulfydryl; diazanyl; alkyl is (as methyl; ethyl; n-pro-pyl; isopropyl; tertiary butyl; n-octyl; cyclopentyl and cyclohexyl); alkenyl (allyl; 2-butenyl group and 3-butenyl group); alkynyl (as propargyl and 3-pentynyl); aralkyl (as benzyl and phenethyl); aryl is (as phenyl; naphthyl and 4-aminomethyl phenyl), heterocycle is (as pyridine radicals; furyl; imidazole radicals, piperidyl, and morpholinyl); alkoxy is (as methoxyl; ethoxy and butoxy), aryloxy group (as phenoxy group and 2-naphthoxy), alkylthio group (as methyl mercapto and ethylmercapto group); arylthio (as thiophenyl); amino (as non-substituted-amino, methylamino, dimethylamino; ethylamino and anilino-); acyl group (as acetyl group, benzoyl, formoxyl and valeryl); alkoxy carbonyl (methoxycarbonyl and ethoxy carbonyl); aryloxycarbonyl (as phenyloxycarbonyl), carbamyl is (as non-replacement carbamyl, N; N-dimethylamino formoxyl; N-ethyl carbamyl and N-phenylamino formoxyl), acyloxy (as acetoxyl group and benzoyloxy), acylamino-(as acetylamino and benzamido); alkoxycarbonyl amino (as methoxycarbonyl amino); aryloxycarbonyl amino (as phenyloxycarbonyl amino), and urea groups (as non-replacement urea groups, N-methyl urea groups; N-phenyl urea groups); alkyl sulfonyl amino (as sulfonyloxy methyl amino), Arenesulfonyl amino (as the phenyl sulfonamido), alkylsulfonyloxy (as sulfonyloxy methyl oxygen base); aryl-sulfonyl oxygen (as the phenyl sulfonyloxy); alkyl sulphonyl (as mesyl), aryl sulfonyl (as tosyl), alkoxy sulfonyl (as the methoxyl sulfonyl); aryloxy sulfonyl (as the phenoxy group sulfonyl); sulfamoyl (as the sulfamoyl of non-replacement, N, N-dimethylamino sulfonyl and N-phenyl sulfamoyl base); alkyl sulphinyl (as methylsulfinyl); aryl sulfonyl kia (as the phenyl sulfinyl), and amidophosphoric acid ester (as N, N-diethylamide phosphate).These genes can further be replaced.If have two or more a plurality of substituting group, they can be identical or different.

If R ₅There are two or more substituting group-SO ₃M ,-COOM ,-OH and-NHR ₂, they can be identical or different.

In formula (I-1), R ₂Represent hydrogen atom, 1 to 6 carbon alkyl ,-COR ₃,-CO ₂R ₃, or-SO ₂R ₃, R ₃Represent hydrogen atom, 1 to 20 carbon alkyl (as methyl, ethyl, propyl group, hexyl, cyclohexyl, dodecyl or octadecyl) or aryl (as phenyl or naphthyl).These groups can be by at substituent R ₅Cited group replaces.

At molecule or (I-1), M represents hydrogen atom, alkali metal atom (as lithium, sodium, or potassium), quaternary ammonium ion (as ammonio, tetramethyl amino, benzyl three methylaminos, or four fourth amino), or quaternary phosphonium father-in-law base (as the tetramethyl phosphonium base).

In formula (I-1), R ₅Be preferably by-SO ₃The phenyl that M replaces ,-phenyl that COOM replaces ,-NHR ₂The phenyl that replaces ,-SO ₃1 to the 4 carbon alkyl that M replaces or-1 to 4 carbon alkyl that COOM replaces, R ₂Be preferably hydrogen atom, 1-4 carbon alkyl or-COR ₃, R ₃1 to the 4 carbon alkyl that is preferably hydrogen atom or replaces by hydrophilic radical (as carboxyl, sulfonic group or hydroxyl), and M is preferably hydrogen atom or sodium atom.More preferably, R ₅Be-SO ₃The phenyl that M replaces or-phenyl that COOM replaces.Below will list the example of formula (I-1) representative compound, but the present invention also not only is confined to these examples.

Next the mercapto-triazole compound of formula (I-2) representative will be described.

M and R in the formula (I-2) ₅Respectively with middle M of formula (I-1) and R ₅Implication is identical.

In formula (I-2), R ₆Represent hydrogen atom, 1 to 10 carbon alkyl (as methyl, ethyl, propyl group, hexyl, or cyclohexyl), 6-15 carbon aryl.Can be by at R in the formula (I-1) ₅Cited substituting group replaces.

In formula (I-2), R ₆Be preferably hydrogen atom, 1 to 4 carbon alkyl or phenyl, R ₅In preferred be-SO ₃The phenyl that M replaces ,-phenyl that COOM replaces ,-NHR ₂The phenyl that replaces, ,-SO ₃1 to the 4 carbon alkyl that M replaces or-CO ₃1 to the 4 carbon alkyl that M replaces, R ₂Be preferably hydrogen atom, 1 to 4 carbon alkyl or-COR ₃, R ₃1 to the 4 carbon alkyl that is preferably hydrogen atom or replaces by hydrophilic radical (as carboxyl, sulfo group, or hydroxyl), and M is preferably hydrogen atom or sodium atom.More preferably, R ₆Be hydrogen atom, R ₅For-SO ₃The phenyl that M replaces or-phenyl that COOM replaces.

Below with the example of enumerative (I-2) representative compound, but the present invention and not only be confined to these examples.

Formula (I-1) or (I-2) compound of representative be well known to those skilled in the art and can be by below with reference to the preparation of the method described in the document: " The Chemistry of HeterocyclicChemistry ", 1,2,4-triazole), JOHN WILEY ﹠amp; SONS (1981), pp.404-442; S.R.Sandler, W, Karo, " Organic Functional Group Preparation ", AcademicPress (1968), pp, 312-315; Kevin T.Pott ed., " COMPREHENSIVEHETEROCYCLIC COMPOUNDS ", PERGAMON PRESS, VOl.5, pp.761-784 and 825-834; Robert C.Elderfield ed., " HETEROCYCLICCOMPOUNDS ", JOHN WILEY ﹠amp; SONS (1961), pp.425-445; And Frederic R.Benson ed., " THE HIGH NITROGEN COMPOUNDS ", JOHNWILEY ﹠amp; SONS (1984) pp.640-653.

Formula (I-1) or the compound of (I-2) representing are included in silver halide emulsion layer or water wettability protecting colloid layer (as middle layer, sealer, filter gold-tinted layer or anti-halation layer).Compound preferably is in halogenation emulsion or its adjacent layer.

The method that compound is added in the emulsion is the adding method of photosensitive emulsion adjuvant routine.For example, compound is soluble in the mixed solvent of methyl alcohol, ethanol, methyl cellosolve, acetone, water or these solvents, and adds in the solution mode.

Formula (I-1) or the compound of (I-2) representing can add in any step of photosensitive emulsion manufacturing.Compound can add before emulsion is made back and coating at once.Preferably add step as the present invention, after silver halide particle forms at once and after chemical ripening is finished, add compound at once.

In the silver halide of every mole of selenium sensitizing, formula (I-1) or (I-2) total addition level of compound of representative be generally 1 * 10 ^-6To 1 * 10 ^-1Mol is preferably 5 * 10 ^-6To 5 * 10 ^-3Mol.Although the formula of associating use (I-1) and its mol ratio of compound of (I-1) representing can be taked arbitrary value, mol ratio is preferably 99.5: 0.5 to 50: 50.The preferred compound that uses a small amount of formula (I-2) representative makes that mol ratio is 99: 1 to 70: 30.

When formula (I-1) and (I-2) compound of representative unite and be used for when of the present invention, these compounds can add in identical time or different time.For example, the compound of formula (I-2) representative adds after finishing with chemical ripening at once after silver halide particle formation is finished at once, and the compound of formula (I-1) representative adds after chemical ripening is finished at once.Though the interpolation order can be put upside down, above order is preferred.

For preventing ashing and the stable photography property in manufacturing, storage or photographic process, the used photosensitive emulsion of the present invention can comprise multiple compound.Adoptable compound is the compound that is called anti-fogging agent or stabilizing agent, as thiazole (as benzothiazolium salt); Nitroimidazole; Nitrobenzimidazole; Chloro-benzimidazole; The bromo benzimidazole; Thyroidan; Mercaptobenzothiazoler; Mercaptobenzimidazole; Dimercaptothiodiazole; Aminotriazole(ATA); Benzotriazole; Nitrobenzene and triazolam; Mercapto-tetrazole (particularly 1-phenyl-5-mercapto-tetrazole); Mercaptopyrimidine; Mercapto-triazine; Sulfo-ketonic compound such as oxazoline thioketones; Azepine indenes such as benzotriazole, the purine (particularly (1,3,3a, 7) purine of 4-hydroxyl replacement) and pentaaza indenes.For example, can use U.S.P.3,954,474 and 3,982,947 and JP-B-52-28660 in the compound described, a kind of preferred compound has been described in JP-A-63-212932.Use and can add anti-fogging agent and stabilizing agent according to design in any several periods, before forming as particle, during and afterwards, during the washing, between the dispersed phase of washing back, before the chemical sensitization, during and afterwards, before the coating.For obtaining its initially anti-ashing and stablizing effect, can in the emulsion manufacture process, add anti-fogging agent and stabilizing agent.In addition, anti-fogging agent and stabilizing agent can be used for multiple purpose, as crystal habit, reduction particle diameter, reduction particle dissolubility, control chemical sensitization and the control dye distribution of control particle.

For obtaining effect of the present invention, preferably adopt methine dyes etc. that the used photosensitive emulsion of the present invention is carried out spectral sensitization.Spendable dyestuff comprises cyanine dye, portion's cyanine dye, compound flower cyanine dyes, composite part cyanine dye, holopolar cyanine dye, hemicyanine dye, styryl dye and hemioxonole dyestuff.The most useful dyestuff is cyanine dye, portion's cyanine dye and composite part cyanine dye.Any parent nucleus that generally is used as alkaline heterocyclic stem nucleus in cyanine dye all can be applicable to these dyestuffs.Spendable parent nucleus example comprises pyrrolin nuclear, oxazoline nuclear, thiazoline nuclear, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazoline nuclear, imidazole nucleus, tetrazolium nuclear and pyridine nucleus; Aliphatic acyclic hydrocarbon condenses the nuclear that constitutes in above-mentioned parent nucleus; Aromatic hydrocarbon ring condenses the nuclear that above-mentioned parent nucleus constitutes, as indolenine nuclear, and benzo indolenine nuclear, indole nucleus, benzoxazole nucleus, aphthoxazoles nuclear, benzothiazole nucleus, aphthothiazoles nuclear, benzo selenazole nucleus, benzimidazole nucleus and quinoline nuclei.These parent nucleus can replace on a carbon atom.

Might in portion's cyanine dye or composite part cyanine dye, introduce 5 to 6 element heterocycle parent nucleus with ketone methylene structure parent nucleus.Example has pyrazolin-5-one nuclear, sulfo-hydantoin nuclear, 2-sulfo-oxazolidine-2,4-diketone nuclear, thiazolidine-2,4-diketone nuclear, rhodanine nuclear and thiobarbituricacid nuclear.

Though these sensitizing dyes can use separately, they also can unite use.Sensitizing dye is united the purpose that use is usually used in supersensitization.This example of uniting use is at U.S.P2, and 688,545,2,977,229,3,397,060,3,522,052,3,527,641,3,617,293,3,628,964,3,666,480,3,672,898,3,679,428,3,703,377,3,769,301,3,814,609,3,837,862 and 4,026,707, BrP 1,344,281 and 1,507,803, among JP-B-43-4936, JP-B-53-12375, JP-A-52-110618 and the JP-A-52-109925 description is arranged.

Except that sensitizing dye, can contain the dyestuff of no spectrum sensibilization in the emulsion or do not absorb visible light basically and present the material of supersensitization.

Sensitizing dye can add in the emulsion in the arbitrfary point of emulsion manufacturing, and the known this practice generally all is effective.More generally, after chemical sensitization is finished and before the coating, add.But as U.S.P3,628,969 and 4,225, described in 666, also can in the time identical, add with chemical sensitization, make quick and chemical quickly carry out simultaneously of spectrum.Also can as described in JP-A-58-113928, before chemical sensitization, add, or before the formation of silver halide particle precipitation is finished, begin spectral sensitization.Perhaps as U.S.P4,225,666 disclosed these compounds that like that in batches add; Part compound adds before chemical sensitization, and remainder is gone in after chemical sensitization, promptly comprises U.S.P4, and disclosed method is interior in 183,756, and compound can add in any time that silver halide particle forms.

In every mol silver halide, addition is 4 * 10 ^-6To 8 * 10 ^-3Mol.

In the photosensitive material that adopts gained silver emulsion of the present invention to make, must on carrier, form one deck silver halide emulsion layer at least, i.e. blue, the green or red beds of sense.There is no particular restriction for the quantity of these silver halide emulsion layers, non-photographic layer quantity and interlayer order.Typical example is a kind of photosensitive silve halide material, and it has at least one sense chromatograph that is made of the multilayer silver halide emulsion layer on carrier, and wherein each silver halide emulsion layer is substantially to the same color sensitivity but the light sensitivity difference.This photographic layer is a kind of unit photographic layer, and it is to a kind of sensitivity in blue light, green glow and the ruddiness.In the multilayer silver-halide color photoelement, to start at from carrier, these unit photographic layers are generally arranged by sense red, green and blue layer.But can put upside down, but perhaps to the sense chromatograph double team of same color sensitivity sense chromatograph to another color sensitivity according to this order of presentation of designed use.

Non-photographic layer such as middle layer can constitute at the light-sensitive silver halide interlayer, and non-photographic layer is also as the superiors and orlop simultaneously.

These middle layers can comprise colour coupler and the DIR compound described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037 and JP-A-61-20038, perhaps can comprise blend of colors inhibitor commonly used.

As Deutsches Reichs-Patent 1,121,470 or BrP 923,045 described in, the multilayer silver halide emulsion layer that constitutes each unit photographic layer is preferably two-layer, both at a high speed and the low speed emulsion layer.Preferably these layers being arranged makes light sensitivity reduce in proper order towards the carrier direction.And can constitute non-photographic layer at two-layer silver emulsion interlayer.In addition, described in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541 and JP-A-62-206543, can arrange, make the low speed emulsion layer constitute, and the high-speed emulsion layer constitute near carrier positions away from carrier positions to each layer.

More specifically, can be by the blue layer of low speed sense (BL)/the blue layer of sense (BH)/high speed green layer (GH)/low speed green layer (GL)/high speed felt red beds (RH)/low speed sense red beds (RL) at a high speed, the BH/BL/GL/GH/RH/RL order, or the BH/BL/GH/GL/RL/RH order is arranged each layer from the carrier distal-most end.

Perhaps as described in the JP-B-55-34932, to the carrier distal-most end by each layer of the blue layer/GH/RH/GL/RL series arrangement of sense.Also can arrange each layer from the carrier distal-most end by the blue layer/GL/RL/GH/RH of sense as described in JP-A-56-25738 and the JP-A-62-63936.

And as described in the JP-B-49-15495, can arrange three layers makes the silver halide emulsion layer with top high photographic sensitivity as the superiors, light sensitivity is lower than the silver halide emulsion layer on upper strata as the middle layer, and light sensitivity is lower than the silver halide emulsion layer in middle layer as lower floor; That is, have three layers of different light sensitivity in the series arrangement of on the carrier direction, successively decreasing by the light sensitivity order.When layer structure is made up of different three layers of light sensitivity, as described in JP-A-59-202464, can be from the carrier distal-most end by the series arrangement of middling speed emulsion layer/high-speed emulsion layer/low speed emulsion layer.

In addition, can be by high-speed emulsion layer/low speed emulsion layer/middling speed emulsion layer or low speed emulsion layer/middling speed emulsion layer/each layer of high-speed emulsion layer series arrangement.

Use the layer of emulsion of the present invention to be preferably at a high speed and the middling speed emulsion layer, more preferably, be the high-speed emulsion layer.The silver-colored consumption of each emulsion layer (in silver atoms weight) is preferably 0.3 to 3g/m ², more preferably 0.5 to 2g/m ²

And even put in order when constituting four layers or when more multi-layered, also can changing as mentioned above.

As mentioned above, can select different layers to form and arrangement according to the purpose of each intensifying material.

Though several as mentioned above different additive can be used in the silver emulsion of the present invention, also can adopt multiple other adjuvant according to designed use.

In Research Disclosures Item 17643 (December, 1978), the details of these adjuvants has been described among Item 18716 (November, 1979) and the Item 308119 (December, 1989), in following table, summarized these parts.

Adjuvant	RD17643	RD187116
			1. chemical sensitizer 2. light sensitivity reinforcing agents 3. spectral sensitizers, telegraphy photo etching 4. whitening agent, 5. anti-fogging agents and stabilizing agent 6. optical absorbing agents, filter dye, ultraviolet absorber 7. anti-stain agent 8. dye image stabilizing agents 9. rigidizers 10. bonding agents 11. plastifier, lubricant 12. coating auxiliary agents, surfactant 13. antistatic agent 14. matting agents	25 pages of 24 pages of 24-25 pages or leaves of 23 pages of 23-24 pages or leaves 25-26 pages or leaves, 27 pages of 25 pages of 26 pages of 26 pages of 27 pages of 26-27 pages or leaves in right hurdle	648 pages, 647 pages on page right hurdle, the same 648 pages of right hurdles to 649, right hurdle, 649 pages on right hurdle, 650 pages on page left hurdle, 649 pages of right hurdles to 650, right hurdle, 651 pages on hurdle, a left side to right hurdle, the same 650 pages of hurdle, a left side, right hurdle is the same

Adjuvant	RD308119
		1. chemical sensitizer 2. light sensitivity reinforcing agents 3. spectral sensitizers, telegraphy photo etching 4. whitening agent, 5. anti-fogging agents and stabilizing agent 6. optical absorbing agents, filter dye, ultraviolet absorber	998 pages on page right hurdle, 996 pages of 996 pages of right hurdles to 998,998 pages of right hurdles to 1, right hurdle, 000 page of right hurdle 1,000 page of left hurdle to 1,003 page of right hurdle

7. prevent stain agent 8. dye image stabilizing agents 9. curing agents 10. adhesives 11. plasticizer; Lubricant 12. coating auxiliary agents, surfactant 13. antistatic additive 14. delustering agents

1,002 page, right hurdle 1,002 page, right hurdle 1,004 page of right hurdle to 1,005 page of left hurdle 1,003 page of right hurdle to 1,1,006 page on 004 page of right hurdle, left hurdle to right hurdle 1,005 page of left hurdle to 1,1,006 page of right hurdle to 1,006 page of left hurdle, 007 page of left hurdle 1,008 page of left hurdle to 1,009 page of left hurdle

For preventing that formaldehyde gas from damaging photography property, preferably in photosensitive material, add as U.S.P.4, in 411,987 or 4,435,503 description can with formaldehyde reaction and the compound that makes it to fix.

Multiple colour former agent can be used among the present invention, and at above-mentioned Research Disclosure No.17643, VII-C to VII-G and No.307105 have described these colour couplers in the patent that VII-C to VII-G describes.

As U.S.P.3,933,501,4,022,620,4,326,024,4,401,752 and 4,248,961, JP-B-58-10739, BrP 1,425,020 and 1,476,760, U.S.P.3,973,968,4,314,023 and 4,511,649 and EP249, the preferred example of yellow colour former has been described among the 473A.

The example of magenta colour coupler is preferably 5-pyrazolone and pyrazolo oxazoline compound, more preferably as U.S.P.4,310,619 and 4,351,897, EP 73,636, U.S.P.3,061,432 and 3,725,067, Research Disclosure No.24220 (June 1984), JP-A-60-33552, Research Disclosure No.24230 (June 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034 and JP-A-60-185951, U.S.P.4,500,630,4,540,654 and 4,556,630, and the compound of describing among the WO88/04795.

The example of cyan coupler is phenol and naphthol compound, is preferably as U.S.P4 052,212,4,146,396,4,228,233,4,296,200,2,369,929,2,801,171,2,772,162,2,895,826,3,772,002,3,758,308,4,334,011 and 4,327,173, Deutsches Reichs-Patent discloses 3,329, and 729, EP121,365A, EP249,453A, U.S.P.3,446,622,4,333,999,4,775,616,4,451,559,4,427,767,4,690,889,4,254,212 and 4,296,199 and JP-A-61-42658 in the compound described.

At U.S.P3,451,820,4,080,211,4,367,282,4,409,320 and 4,576,910, BrP 2,102,137 and EP341, the exemplary that forms the colour coupler of polymeric dye is disclosed among the 188A.

The preferred example that can constitute the colour coupler with suitable diffusivity illuminating colour is at U.S.P.4,366,237, BrP 2,125,570, EP96,570 and Deutsches Reichs-Patent disclose 3,234, description is arranged in 533.

At Research Disclosure No.17643, VII-G and No.307105, VII-G, U.S.P.4,163,670, JP-B-57-39413, U.S.P.4,004,929 and 4,138,258 and BrP 1, the preferred example that is used to revise coloured dye colour former agent too much, unfavorable absorption has been described in 146,368.At U.S.P.4,774, described in 181 and a kind ofly discharge the colour coupler of the unnecessary absorption of fluorescent dye correction illuminating colour during by color development or can preferably use U.S.P.4, the colour coupler of describing in 774,120 with dyestuff former group that can form dyestuff with the developer reaction.

The present invention preferably uses the colour coupler that discharges the useful residue of photography when quality.At above-mentioned RDNo.17642, VII-F and RD No.307105, the patent of quoting among the VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350 and U.S.P.4,248,962 and 4, the DIR colour coupler has been described, i.e. the colour coupler of released development inhibitor in 782,012.

In BrP 2,097,140 and 2,131,188, described the preferred example that imaging for the benefit of discharges the colour coupler of nucleator or development accelerant among JP-A-59-157638 and the JP-A-59-170840.Also preferably use the compound of describing among JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and the JP-A-1-45687, they discharge as fogging agent, development accelerant, or discharge ag halide solvent with the oxidation product generation redox reaction of developer.

Other can be used for colour coupler example in the photosensitive material of the present invention for as U.S.P.4, the competitive colour coupler of description in 130,427; As U.S.P.4, the colour coupler of describing in 283,472,4,338,393 and 4,310,618 how of equal value; The colour coupler of the release DIR redox compound of in as JP-A-60-185950 and JP-A-62-24252, describing, discharge the colour coupler of DIR colour coupler, discharge the redox compound of DIR colour coupler, or discharge the redox compound of DIR redox potpourri; At EP173,302A and EP313, a kind of colour coupler that after release, is transformed into illuminating colour of the release of describing among the 308A; As RD.Nos.11449 and 24241 and JP-A-61-201247 in the colour coupler of the release bleach boosters described; As U.S.P.4, the colour coupler of the release part of describing in 555,477; The colour coupler of the release leuco dye of describing among the JP-A-63-75747; U.S.P.4, the colour coupler of the release fluorescent dye of describing in 774,181.

Can adopt multiple process for dispersing to add photosensitive material to being used for colour coupler of the present invention.

As U.S.P3, the example that is used in the high boiling organic solvent in the oil-in-water dispersion method has been described in 322,027.

Be used in the oil-in-water dispersion method, boiling point is that the example of 175 ℃ or higher high boiling organic solvent has phthalic acid ester (as dibutyl phthalate under the normal pressure, phthalic acid two hexamethylene fat, di-2-ethylhexyl phthalate, phthalic acid ester in the last of the ten Heavenly stems, phthalic acid two (2,4-two tertiary amyl phenyl) ester, different phthalic acid two (2,4-two tertiary amyl phenyl) ester, and phthalic acid two (1,1-diethyl propyl group) ester); Phosphate or replacement phosphate (as triphenyl phosphate, tricresyl phosphate catechu phenolic ester, phosphoric acid-2-ethylhexyl diphenyl, tricyclohexyl phosphate, tricresyl phosphate-2-Octyl Nitrite, lauryl alcohol phosphotriester, tributoxyethyl phosphate, TCPP, and phosphenylic acid two-2-Octyl Nitrite); Benzoic ether (as, benzoic acid-2-Octyl Nitrite, benzoic acid ten diester and p-hydroxybenzoic acid-2-Octyl Nitrite); Acid amides (as N, N-diethyl lauramide, N, N-diethyl lauramide and N-myristyl pyrrolidone); Alcohol or phenol (pure and mild 2 as iso stearyl, 4-two tert-amyl phenols); Aliphatic carboxylic acid esters,'s (as decanedioic acid two (2-ethylhexyl) ester, dioctyl azelate, glycerin tributyrate, lactic acid iso stearyl ester and trioctyl lemon acid); Anil (as N, the special octyl group aniline of N-dibutyl-2-butoxy-5-); And hydro carbons (as paraffin wax, dodecyl benzene, and diisopropyl naphthalene).Boiling point be about 30 ℃ or higher, be preferably 50 ℃ and can be used as cosolvent to about 160 ℃ organic solvent.The exemplary of cosolvent has ethyl acetate, ethyl ester butyl ester, ethyl propionate, methyl ethyl ketone, cyclohexanone, acetic acid-2-ethoxy-ethyl ester and dimethyl formamide.

As U.S.P.4,199,363 and Deutsches Reichs-Patent application (OLS) the 2nd, 541,274 and 2,541, the step of emulsion process for dispersing and the example of usefulness and dipping emulsion have been described in No. 230.

Phenylethyl alcohol and polytype antiseptic or mildewproof agent preferably are added in the color sensitive material of the present invention.The example of antiseptic and mildewproof agent have in JP-A-63-257747, JP-A-63-277248, JP-A-1-80941, describe 1,2-benzisothiazole-3-ketone, p-butoben, phenol, 4-chloro-3,5-xylenol, 2-phenoxetol and 2-(4-thiazolyl) benzimidazole.

The present invention can be applicable to multiple photosensitive material, in the particularly multiple color sensitive material.Its example is useful on the colour negative that general service or film are used, and is used for the colour reversal film of lantern slide or TV, color printing paper, colour positive, and colour reversal photographic paper.The present invention also is particularly preferred for the color dub film.

As the 28th page of RD.No.17643, RD.No.18716 is from page left hurdle, 647 pages of right hurdles to 648, and described among the 897th page of the RD.No.307105 and be applicable to carrier of the present invention.

In photosensitive material of the present invention, be preferably 28 μ m or littler at the total film thickness of all hydrophilic colloid layers of a side that emulsion layer is arranged, more preferably 23 μ m or littler are preferably 18 μ m or littler again, most preferably are 16 μ m or littler.Film swelling speed T _1/2Be preferably 30sec or littler, more preferably 20sec or littler.Thickness refers to measured film thickness under 25 ℃, the damp condition of relative humidity 55% (two days).Can measure film swelling speed T according to methods known in the art _1/2For example, can adopt Photogr.Sci Eng., A.Green et al., Vol.19, No.2, the swelling instrumentation amount film swelling speed T that describes among the pp.124-129 _1/290% of 30 ℃ of maximum swelling thickness that use down color developers to handle to be reached after 3 minutes 15 seconds are defined as saturated thickness, T _1/2Required time when being defined as reaching capacity thickness 1/2.

In as the gelatin of bonding agent, add the film rigidizer or after coating, change aging condition and can adjust film swelling speed T _1/2

In photosensitive material of the present invention, total build is that the hydrophilic colloid layer (being called backing layer) of 2 to 20 μ m preferably constitutes having on the corresponding opposite side of emulsion layer one side.Backing layer preferably contains for example above-mentioned optical absorbing agent, filter dye, ultraviolet absorber, antistatic agent, film rigidizer, bonding agent, plastifier, lubricant, coating auxiliary agent and surfactant.The swelling rate of backing layer is preferably 150% to 500%.

Can adopt the method for the routine of describing in RD.No.17643 28-29 page or leaf, the 615th page of left hurdle of RD No.18716 to right hurdle, the RD.No.307105 880-881 page or leaf that color sensitive material of the present invention is developed.

The color developer that is used for developing photosensitive material of the present invention is preferably the alkaline aqueous solution of mainly being made up of aromatic primary amine base color developer.As color developer,, preferably use the p-phenylenediamine (PPD) based compound though the amino-phenol based compound is effectively.The exemplary of p-phenylenediamine (PPD) based compound has 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-beta-hydroxyethyl aniline, 3-methyl-4-amino-N-ethyl-N-β-methylsulfonyl amido ethylaniline, 3-methyl-4-amino-N-ethyl-N-'beta '-methoxy ethylaniline and sulfate, hydrochloride and tosilate.In these compounds, the sulfate of 3-methyl-4-amino-N-ethyl-N-beta-hydroxyethyl aniline the most preferably.Can unite use according to using two or more these compounds.

Generally speaking, color developer contains the alkali metal salt of pH buffering agent such as carbonic acid, boric acid or phosphoric acid, and restriction agent or anti-fogging agent such as bromide, iodide, benzimidazole, benzothiazole or sulfhydryl compound develop.If necessary, color developer also can comprise antiseptic such as azanol, diethyl hydroxylamine, sulphite, hydrazine such as N, N-dihydroxymethyl hydrazine, Carbaphen, triethanolamine or catechu phenolic group sulfonic acid; Organic solvent such as ethylene glycol or diglycol; Development accelerant such as benzylalcohol, polyglycol, quaternary ammonium salt, or amine; Form the colour coupler of dyestuff, competitive colour coupler, and development promoter such as 1-phenyl-3-pyrazolidone; Tackifier; And multiple sequestrant, its representative has amino polyprotonic acid, amino polyphosphoric acid, alkyl phosphoric acid, and phosphono-carboxylic acids.The representation example of sequestrant has ethylenediamine tetraacetic acid, nitrogen base triacetic acid, diethylene-triamine pentaacetic acid, 1,2-diaminocyclohexane tetraacetic acid, hydroxyl ethyleneimine base oxalic acid, 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid, nitrogen base-N, N, N-trimethylene phosphonic, ethylenediamine-N, N, N, N-tetramethylene phosphonic acid, ethylenediamine-two (o-hydroxy phenylacetic acid) and these sour salt.

Develop for carrying out reversal film, carry out black-and-white development earlier, and then carry out colour development.As the black-and-white development agent, well-known black reagent such as benzenediol such as quinhydrones, 3-pyrazolidone such as 1-phenyl-3-pyrazolidone, and amino-phenol such as the N-methyl-p-aminophenol can use separately or two or more unite use.PH colored and the black-and-white development agent is generally 9 to 12.Though the supplementary rate of this developer is decided according to the processing color sensitive material, be generally 3 liters (rise also are expressed as following " L ") or still less in every square meter photosensitive material.Supplementary rate can be reduced to 500 milliliters (milliliter also is expressed as following " mL ") or still less by the concentration that reduces bromide ion in the developer.For reducing supplementary rate, the contact area that preferably should reduce Treatment Solution and air is to avoid evaporating and the solution oxidation by air.

The contact area of photograph processing solution and air can be by representing with undefined aperture rate in process tank:

The aperture rate=[contact area (m of Treatment Solution and air ²)] ÷ [volume (m of Treatment Solution ³)]

Above-mentioned aperture rate is preferably 0.1 or littler, and more preferably 0.001 to 0.05.For reducing the aperture rate, can in process tank, place shield member as the lid that floats in the surface of photograph processing solution.In addition, can adopt the slit developing method of describing among the method for the removable lid of describing among the JP-A-1-82033 of use and the JP-A-63-216050.Not only in colored and black-and-white development step and also all steps subsequently as bleaching, bleaching-photographic fixing, photographic fixing, washing and stabilizing step in preferred reduction aperture rate.In addition, the method for using the inhibition bromide ion to stop in developer solution also can reduce supplementary rate.

The colour development time was generally 2 to 5 minutes.High temperature, high pH are set and use the high-concentration colorful developer, can shorten the processing time.

Generally sensitive emulsion layer is bleached after the colour development.Bleaching can be carried out simultaneously or carry out separately with photographic fixing (bleaching-photographic fixing).In addition, be speed up processing, after bleaching, can bleach-photographic fixing.This process can be carried out in the bleaching-fixing bath with two continuous jars simultaneously, can carry out photographic fixing according to purposes before bleaching-photographic fixing, or carry out photographic fixing after bleaching-photographic fixing.The example of bleaching agent has compound, superoxide (particularly being adapted to the sodium peroxydisulfate of color film negative film), quinone and the nitro compound of polyvalent metal such as iron (III).The exemplary of bleaching agent is the organic coordination compound salt of iron (III), as amino polyprotonic acid such as ethylenediamine tetraacetic acid, diethylene-triamine pentaacetic acid, 1,2-diaminocyclohexane tetraacetic acid, methylene imine base oxalic acid and 1, the complex salts of 3-diaminopropanetetraacetic acid and glycoletherdiaminotetraacetic acid; The complex salts of citric acid, tartrate and maleic acid.In these compounds, the amino polyprotonic acid complex salts of iron (III) such as the ethylenediamine tetraacetic acid and 1 of iron (III), 3-diaminopropanetetraacetic acid complex salts are preferred, but because their speed up processing and preventing the pollution of the environment.The complex salts of the amino polyprotonic acid of iron (III) is useful especially in bleaching and bleaching-photographic fixing solution.Use the bleaching or the bleaching-photographic fixing solution of the amino polyprotonic acid complex salts of iron (III), its pH is generally 4.0 to 8.Be speed up processing, also can under lower pH condition, handle.

Can in liquid lime chloride, bleaching-photographic fixing solution and their prebaths, use bleach boosters if necessary.The example of the bleach boosters that can adopt has: as U.S.P.3,893,858, Deutsches Reichs-Patent 1,290,812 and 2,059,988, the compound of describing among JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424 and JP-A-53-141623, JP-A-53-18426 and the Research Disclosure No.17129 (July, 1978) that contains sulfydryl or disulfide group; The tetrahydrothiazole derivates of in JP-A-53-140129, describing; At JP-B-45-8506, JP-A-52-20832, JP-A-53-32735 and U.S.P.3, the thiourea compound of describing in 706,561; In Deutsches Reichs-Patent 1,127,715 and JP-A-58-16235 in the salt compounded of iodine described; In Deutsches Reichs-Patent 966,410 and 2,748, the polyoxyethylene compound of describing in 430; The polyamine compound of in JP-B-45-8836, describing; The compound of in JP-A-49-40943, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, JP-A-55-26506 and JP-A-58-163940, describing; And bromide ion.In these compounds, be preferably compound, because this compound accelerating effect is obvious with a sulfydryl or disulfide group.Especially, be preferably U.S.P.3,893,858, the compound described among Deutsches Reichs-Patent 1,290,812 and the JP-A-53-95630.At U.S.P.4, the compound of describing in 552,884 also is preferred.These bleach boosters can be added in the intensifying material.These bleach boosters are specially adapted to photograph in the bleaching-photographic fixing of color sensitizing material.

Except that above-claimed cpd, for preventing to bleach stain, bleaching or bleaching-photographic fixing solution preferably contain organic acid.Most preferred organic acid is that acid dissociation constant (pKa) is 2 to 5 compound, as acetate, propionic acid or glycolic acid.

The example of fixer and bleaching-fixer has thiosulfate, thiocyanate, thioether group compound, thiocarbamide and heavy dose of salt compounded of iodine.In these compounds, generally use thiosulfate, particularly the ATS (Ammonium thiosulphate) range of application is the widest.In addition, to unite use also be preferred for thiosulfate and for example thiocyanate, thioether group compound or thiocarbamide.As the antiseptic of stop bath and bleaching-stop bath, sulfide, disulfide, disulfide carbonyl addition product or EP249, the sulfinic acid compound of describing among the 769A are preferred.In addition, for stablizing stop bath or bleaching-stop bath, preferably polytype amino polybasic carboxylic acid or organic phospho acid are added in the solution.

In the present invention, be regulating pH, preferably is that 6.0 to 9.0 compound is added in stop bath or the bleaching-stop bath with 0.1 to 10mol/L pKa.Preferred 0.1 to 10mol/L imidazoles such as imidazoles, 1-methylimidazole, 1-ethyl imidazol(e) and the glyoxal ethyline of adding.

The T.T. of desilverization step is preferably short as much as possible, only otherwise desilverization defective takes place to get final product.Time is preferably 1 to 3 minute, more preferably 1 to 2 minute.Treatment temperature is 25 ℃ to 50 ℃, is preferably 35 ℃ to 45 ℃.In preferred temperature range, desilverization speed increases, and also can effectively prevent the generation of stain after treatment simultaneously.

In desilverization step, stirring is preferably strong as much as possible.The example of strengthening stirring method has the method for describing with Treatment Solution impinging jet intensifying material emulsion surface in JP-A-62-183460, and the utilization of describing in JP-A-62-183461 rotation strengthens the method for mixing effect.Other example comprises the method for mobile intensifying material, and wherein emulsion is starched with the wiping in being in solution and contacted the disturbance that causes the emulsion surface, thereby has improved mixing effect, and the method that increases flow in the entire process solution.These stir innovative approach to any liquid lime chloride, and bleaching-stop bath and stop bath are all effective.Infer that the improvement of stirring has increased bleaching agent and fixer enters the supply of emulsion film, thereby accelerated desilverization speed.When using bleach boosters, above-mentioned stirring innovative approach is then more effective, and promptly this method has obviously increased accelerating velocity or the photographic fixing eliminated due to the bleach boosters is disturbed.

The automatic film developer of processing intensifying material of the present invention preferably has the intensifying material transshipment acitivity as describing among JP-A-60-191257, JP-A-191258 or the JP-A-60-191259.As disclosed among the JP-A-60-191257, this transshipment acitivity can reduce the amount of carrying secretly that Treatment Solution is bathed to the back from prebath greatly, thereby has effectively prevented the Treatment Solution mis-behave.The supplementary rate that the special feature of this effect is obviously to have shortened the processing time of various processes and has reduced each Treatment Solution.

After the desilverization, generally to wash and/or stabilizing step photosensitive silve halide material of the present invention.According to the character of intensifying material (such as by the character that determined of employing material such as colour coupler), the number (number of step) of the purposes of material, water temperature, water pot, compensation process such as adverse current or forward flow process and other different condition, water consumption can be set arbitrarily in a wide scope in the washing step.Utilize " Journal of the Society of Motion Picture and Television Engineering ", Vol.64, the method of describing among the pp.248-253 (May, 1955) can draw the relational expression between water consumption and water pot number in the rapid counter-current of multistep.

According to the rapid counter-current of above-mentioned multistep, the slurry amount can reduce greatly.Because slurry is in the jar for a long time, bacterium can breed and floating substance can adhere on the intensifying material.Be to solve this problem that in color sensitizing material processed of the present invention, is run into, can extremely effectively utilize the reduction calcium described among the JP-A-62-288838 and the method for magnesium ion.Also can use isothiazolone compounds, cyabendazoles, and the chlorinated isocyanurates sodium of describing among chloro germifuge such as the JP-A-57-8542, and at Hiroshi Horiguchi et al., " Chemistry of Antibacterialand Antifungal Agents ", (1986), Sankyo Shuppan, Eiseigijutsu-Kai ed., " Sterilization; Antibacterial, and Autifungal Techniques forMicroorganisms ", (1982), Kogyogijutsu-Kai, and Nippin Bokin BokabiGakkai ed., " Dictionary of Autibacterial and Antifungal Agents ", germifuge such as the benzotriazole described in (1986).

The slurry pH of intensifying material of the present invention is 4 to 9, is preferably 5 to 8.According to the character and the purposes of intensifying material, water temperature and wash time can change.20sec to 10min when in general wash time is 15 ℃ to 45 ℃, 30sec to 5min when being preferably 25 ℃ to 40 ℃.Can adopt stabilizing agent to substitute washing directly handles intensifying material of the present invention.All known methods of describing in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 all can be used in this stabilized treatment.

Sometimes handle at the laggard line stabilization of washing.An example is as the final stabilizer bath of bathing of photography color sensitizing material, wherein contains dye stabilizers and surfactant.The example of dye stabilizers is aldehyde such as formalin and glutaraldehyde, N-methylol compound, hexamethylenetetramine, and the addition product of aldehyde and sulphurous acid.Multiple sequestrant or antifungal agent can be added in the stabilizer bath.

The solution that washing and/or stabilizing solution are overflowed when replenishing can be reused in other step such as desilverization step.

In the processing of using automatic film developer etc.,, preferably add water to proofread and correct this concentrated effect if when above-mentioned each Treatment Solution thickens because of evaporation.

To simplify the process and increase processing speed, silver-halide color photoelement of the present invention can contain color developer.The polytype color developer precursor of preferred for this reason use.The example of precursor is U.S.P.3, the indoaniline based compound of describing in 342,597, as U.S.P.3,342,599 and ResearchDisclosure (RD) Nos.14,850 and 15, the azomethine compound of describing in 159, RD No.13, the aldol compound of describing in 924, U.S.P.3, the complex slaine of describing in 719,492, and the carbamate based compound of describing among the JP-A-53-135628.

If necessary, for quickening colour development, silver-halide color photoelement of the present invention can comprise multiple 1-phenyl-3-pyrazolidone compounds.The exemplary of these compounds has been described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

Each Treatment Solution of the present invention is used down at 10 ℃ to 50 ℃.Though the conventional processing temperature is 33 ℃ to 38 ℃, can under higher temperature, quicken treatment step for shortening the processing time, perhaps, can handle at a lower temperature for improving the stability of image quality or Treatment Solution.

Photosensitive silve halide material of the present invention can be applicable to as U.S.P.4, and 500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056 and EP210, the hot method developing photographic materials of describing among the 6660A2.

In the time of in the present invention is applied to as the film unit with camera lens of KP-B-2-32615 or Jpn.UM Appln.KOKOKUPublication No.3-39784 description, can more easily obtain effect of the present invention.

Describe the present invention by the following examples in detail.But the present invention also not only is confined to these embodiment.

Embodiment 1

The agi content and the silver iodide distributed architecture of the large-size flaky particle that it is characterized by high aspect ratio of the present invention's employing below will be described.

The preparation of crystal seed emulsion a

With 1, it is that the aqueous solution of 20,000 oxidized gelatins is in 35 ℃ of constant temperature and stir that 164mL contains 0.017g KBr and 0.4g mean molecular weight.In 48sec, adopt three gunitees to add AgNO ₃Aqueous solution (1.6g), KBr aqueous solution and mean molecular weight are 20,000 oxidized gelatin.In the interpolation process be with reference to silver-colored electromotive force is remained 13mV with the saturated calomel electrode.Add the KBr aqueous solution silver-colored electromotive force is become-66mV, and temperature is risen to 60 ℃.When the 21g mean molecular weight is after 100,000 amber acidifying gelatin adds, to add NaCl aqueous solution (5.1g).In 61min, adopt two gunitees to add AgNO ₃Aqueous solution (206.3g) and KBr aqueous solution, flow velocity is accelerated around here.In the interpolation process, serve as with reference to silver-colored electromotive force is remained-44mV with saturated calomel electrode.With adding mean molecular weight after the desalination of gained material is 100,000 amber acidifying gelatin, and under 40 ℃ pH and pAg is adjusted to 5.8 and 8.8 respectively, thereby prepares crystal seed emulsion.In every kg emulsion, this crystal seed emulsion contains 1mol Ag and 80g gelatin.It is that 0.81 μ m, equal circle diameter variation factor are 28%, average thickness is that 0.046 μ m, average aspect ratio are 39 platy shaped particle that this emulsion contains average equal circle diameter.

[formation of nuclear]

With 1, it is that the aqueous solution of 100,000 amber acidifying gelatin is in 75 ℃ of following constant temperature and stir that 200mL contains 134g crystal seed emulsion a, 1.9g KBr and 22g mean molecular weight.Before adding at once with AgNO ₃Aqueous solution (43.9g), KBr aqueous solution and mean molecular weight are that 20,000 gelatin mixes in another chamber of the magnetic coupling induction type stirrer that JP-A-10-43570 describes, then in 25min.Be reference with the saturated calomel electrode in the interpolation process, silver-colored electromotive force remains-40mV.

[formation of first shell]

After above-mentioned karyosome forms, before adding at once with AgNO ₃Aqueous solution (43.9g), KBr aqueous solution and mean molecular weight are that the aqueous solution of 20,000 gelatin is mixed in above-mentioned another chamber, add in 20min then.Be reference with the saturated calomel electrode in the interpolation process, silver-colored electromotive force remains-40mV.

[formation of second shell]

After above-mentioned first shell forms, before adding at once with AgNO ₃Aqueous solution (42.6g), KBr aqueous solution and mean molecular weight are that the aqueous solution of 20,000 gelatin is mixed in above-mentioned another chamber, add in 17min then.Be reference with the saturated calomel electrode in the interpolation process, silver-colored electromotive force remains-20mV.After this temperature is risen to 55 ℃.

[formation of the 3rd shell]

After above-mentioned second shell forms, with silver-colored potential regulating to-55mV, before adding at once with AgNO ₃Aqueous solution (7.1g), KI aqueous solution (6.9g) and mean molecular weight are that 20,000 aqueous gelatin solution mixes in above-mentioned another chamber, add in 5min then.

[formation of the 4th shell]

After above-mentioned the 3rd shell forms, in 30min, adopt two gunitees with fixed flow rate with AgNO ₃Aqueous solution (66.4g) and KBr aqueous solution add.Adding mid-term, adding chlordene and close iridium potassium and potassium ferrocyanide.During the interpolation be with reference to silver-colored electromotive force is remained 30mV with the saturated calomel electrode.Carry out regular washing, add gelatin, and under 40 ℃, pH and pAg are adjusted to 5.8 and 8.8 respectively, thereby obtain emulsion b.It is that 4.1 μ m, equal circle diameter variation factor are 21%, average thickness is that 0.090 μ m, average aspect ratio are 46 platy shaped particle that this emulsion contains average equal circle diameter.Simultaneously 70% of the total projection area or more be that 4.1 μ m or more, thickness are that 0.090 μ m or platy shaped particle still less occupy by equal circle diameter.

The KBr aqueous solution that employing contains KI substitutes the KBr aqueous solution that is used for first and second shells, prepares the first and second shell agi contents different emulsion c, d, e, f, g, h and i, and the feature of each emulsion is summarized in the following table 1.

Table 1

Emulsion	Agi content (Imol%) and silver content (Ag%): Imol%/Ag%					Agi content (Imol%)	Structure	Explanation
									Nuclear	First shell	Second shell	The 3rd shell	The 4th shell
	b	0 29.4	0 19.4	0 18.8	100 3.1									0 29.3	3.1	Three layers	Comparative Examples
c						0 29.4	0 19.4	10 18.8	100 3.1	0 29.3	5.0	Four layers	Comparative Examples
	d	0 29.4	20 19.4	0 18.8	100 3.1									0 29.3	7.0	Five layers	Comparative Examples
e						0 29.4	2.0 19.4	10 18.8	100 3.1	0 29.3	8.9	Five layers	Comparative Examples
	f	0 29.4	5.0 19.4	15 18.8	100 3.1									0 29.3	6.9	Five layers	Comparative Examples
g						0 29.4	3.0 19.4	3.0 18.8	100 3.1	0 29.3	4.3	Four layers	Comparative Examples
	h	0 29.4	3.0 19.4	1.5 18.8	100 3.1									0 29.3	4.3	Five layers	The present invention
i						0 29.4	0 19.4	0 18.8	100 3.1	0 29.3	3.7	Five layers	The present invention

Though the thickness of each emulsion c to i is slightly different with emulsion b, in each emulsion simultaneously 70% of the total projection area or more be 4.1 μ m or more by equal circle diameter, thickness is that 0.090 μ m or platy shaped particle still less occupy, each emulsion meets U.S.P.5 simultaneously, 709, the condition of describing in 998 is wherein introduced dislocation line in the platy shaped particle edge.

Emulsion b to i is heated to 56 ℃, and adds following sensitizing dye I, II, III and following Compound I, potassium rhodanide, gold chloride, sodium thiosulfate and N, N-dimethyl selenourea carries out optimum chemical sensitizing.Notice that sensitizing dye uses with the form of the thin solid dispersion described among the JP-A-11-52507.That is to say, 0.8 weight portion sodium nitrate and 3.2 weight portion sodium sulphate are dissolved in the 43 weight portion deionization exchanged waters.Add 13 weight portion sensitizing dyes, and adopt 2, the dissolver oar of 000rpm under 60 ℃ with gained dispersion of materials 20min, thereby obtain the solid dispersion of sensitizing dye.

Sensitizing dye I

Sensitizing dye II

Sensitizing dye III

Compound I

To be coated on through the emulsion b to i of above-mentioned chemical sensitization on the cellulose triacetate film carrier with undercoat under the listed coating condition of table 2, and constitute protective seam.Constitute sample in this way 1 to No. 8.

Table 2 emulsion coating condition

(1) emulsion layer

Emulsion ... multiple emulsion (silver 2.1 * 10 ^-2Mol/m ²)

Colour coupler (1.5 * 10 ^-3Mol/m ²)

Phosphoric acid trimethylbenzene phenolic ester (1.10g/m ²)

Gelatin (2.30g/m ²)

(2) protective coating

2,4-two chloro-6-hydroxyls-s-triazine sodium salt (0.08g/m ²)

Gelatin (1.80g/m ²)

These samples are placed 14hr under 40 ℃, the condition of relative humidity 70%.The gained sample passes through Fuji Photo Film Co., SC-50 gelatin filter that Ltd. makes and continuous wedge exposure 1/100sec.

Use Fuji Photo Film Co., the FP-350 negative film developing machine that Ltd. makes is handled by the following method through the sample of exposure (be up to the accumulative total magnitude of recruitment of each solution mother liquor tank volume three times till).

Purging method

Step	Time	Temperature	Magnitude of recruitment *
				Colour development	3 minutes 15 seconds	38℃	45ml
Bleaching	1 minute 00 second	38℃	20ml
				The bleaching liquid overflow is sent in bleaching-fixing tank fully
Blix	3 minutes 15 seconds	38℃	30ml
				Washing	40 seconds	35℃	By (2) to (1) convection current
Washing (2)	1 minute 00 second	35℃	30ml
				Stable	40 seconds	38℃	20ml
Dry	1 minute 15 seconds	55℃

^*Magnitude of recruitment is with the wide sample of the 35mm of the 1.1m value representation of (being equivalent to the effect of 24Ex. film).

Shown in washing fluid composed as follows.

Color developer

Form	Jar solution (g)	Replenish liquid (g)
			Diethylene triamine pentacetic acid (DTPA)	1.0	1.1
1-hydroxy ethylene-1, the 1-di 2 ethylhexyl phosphonic acid	2.0	2.0
			Sodium sulphite	4.0	4.4
Sal tartari	30.0	37.0
			Potassium bromide	1.4	0.7
Potassium iodide	1.5mg	-
			Hydroxylamine sulfate	2.4	2.8
4-[N-ethyl-N-(beta-hydroxy ethyl) amino]-2-aminotoluene sulfate	4.5	5.5
			Add and add water to	1.0L	1.0
PH (regulating) with potassium hydroxide and sulfuric acid	10.05	10.10

Bleaching liquid

Form	Jar solution and additional liquid phase are with (g)
		The ferric ammonium ethylene diamine tetraacetate dihydrate	120.0
Disodium ethylene diamine tetraacetate	10.0
		Ammonium bromide	100.0
Ammonium nitrate	10.0
		Bleach boosters	0.005mol

(CH 3) 2N-CH 2CH 2-S-S-CH 2-CH 2-N(CH 3) 2·2HCl
		Ammoniacal liquor (27%)	15.0ml
Add and add water to	1.0L
		PH (regulating) with ammoniacal liquor and sulfuric acid	6.3

Bleaching-fixing bath

Form	Jar solution (g)	Replenish liquid (g)
			The ferric ammonium ethylene diamine tetraacetate dihydrate	50.0	-
Disodium ethylene diamine tetraacetate	5.0	2.0
			Ammonium sulfite	12.0	20.0
Thiosulfuric acid aqueous ammonium (700g/L)	240.0ml	400.0ml
			Ammoniacal liquor (27%)	6.0ml	-
Add and add water to	1.0L	1.0L
			PH (regulating) with ammoniacal liquor and acetate	7.2	7.3

Washings (jar solution and additional liquid phase are together)

Tap water is delivered in the mixed bed column, and this column filling has H type strong-acid cation-exchange resin (Amberlite IR-120B: can be from Rohm ﹠amp; Haas Co. obtains) and OH type alkalescence anion-exchange resin (Amberlite IR-400), the concentration of calcium and magnesium is set at 3mg/l or lower.Subsequently, add the sodium sulphate of the isocyanuric acid dichloride sodium 0.15g/l of 20mg/l.The pH scope of solution is 6.5-7.5.

Stabilizing agent

Form	Jar solution and additional liquid phase are with (g)
		SPTS	0.03
The single nonylplenyl ether (average degree of polymerization 10) of polyoxyethylene-p-	0.2
		Disodium ethylene diamine tetraacetate	0.05
1,2, the 4-triazole	1.3
		1,4-two (1,2,4-triazol-1-yl methyl) piperazine	0.75
Add and add water to	1.0L
		pH	8.5

By changing the processing time evaluation development dependence of color developer.Measure the density of each treated sample by green optical filter.

The sensitivity value of having listed in the following table 3 in ashing density+0.2 o'clock, ashing value, γ value (slope of the characteristic curve in ashing density+0.2 and ashing density+0.7 o'clock).

Table 3

Sample number	Emulsion	Explanation	Ashing			Light sensitivity			The γ value
												2’45”	3’15”	3’45”	2’45”	3’15”	3’45”	2’45”	3’15”	3’45”
			1	b	Comparative Examples	0.18	0.22	0.30	61	100	106										0.53	0.88	0.92
2	c	Comparative Examples										0.18	0.22	0.30	48	88	94	0.44	0.70	0.78
			3	d	Comparative Examples	0.16	0.20	0.26	78	121	130										0.48	0.84	0.90
4	e	Comparative Examples										0.18	0.21	0.33	40	83	94	0.40	0.66	0.73
			5	f	Comparative Examples	0.17	0.23	0.33	38	80	88										0.36	0.60	0.69
6	g	Comparative Examples										0.17	0.22	0.29	66	105	113	0.50	0.79	0.84
			7	h	The present invention	0.18	0.22	0.29	92	134	141										0.60	0.86	0.90
8	i	The present invention										0.17	0.21	0.28	101	141	150	0.66	0.90	0.92

As shown in table 3, it is higher that the emulsion b of the emulsion h that has five-layer structure particle of the present invention under close ashing value and i and three-decker particle and four-layer structure particle have emulsion c and j to compare light sensitivity.And the processing time dependence of light sensitivity and γ value shows that the development process is very fast.Though corresponding to U.S.P.5, the emulsion d of 780,216 five-layer structure particle also has ISO, the processing time dependence of light sensitivity and γ value is big, so can not obtain the effect that emulsion h and i of the present invention are shown.Similarly, agi content can not satisfy the effect that the emulsion e of five-layer structure particle of necessary condition of the present invention and f do not obtain the present invention yet and shown.Have only before this when agi content and silver iodide distributed architecture satisfy requirement of the present invention and can obtain effect of the present invention.

Embodiment 2

Equal circle diameter, the thickness of platy shaped particle emulsion of the present invention, the effect of equal circle diameter variation factor below will be described.

Change gelatin, temperature, flow velocity, silver-colored electromotive force and agi content in the crystal seed emulsion a preparation, with at temperature, flow velocity, silver-colored electromotive force in forming of nuclear and the first, second, third and the 4th shell, whether before interpolation, use mixing chamber at once, and agi content, prepare emulsion j, k, l, m, n, o, p and q thus.Listed the feature of these emulsions in the following table 4.Each emulsion meets U.S.P.5, and 709,988 described conditions are wherein introduced dislocation line at the platy shaped particle edge.

Table 4

Emulsion	Imol％/Ag％					Agi content (mol%)
							Nuclear	The 1st shell	The 2nd shell	The 3rd shell	The 4th shell
	j	0/29.4	3.0/19.4	3.0/18.8	100/3.1							0/29.3	4.2
k						0/29.4	19/19.4	0/18.8	100/3.1	0/29.3	6.8
	l	0/29.4	4.5/19.4	0/18.8	100/3.1							0/29.3	4.0
m						0/29.4	3.0/19.4	3.0/18.8	100/3.1	0/29.3	4.2
	n	0/29.4	4.5/19.4	0/18.8	100/3.1							0/29.3	4.0
o						0/29.4	1.5/19.4	1.5/18.8	100/3.1	0/29.3	3.7
	p	1/29.4	2.5/19.4	0/18.8	100/3.1							0/29.3	33.9
q						0/29.4	2.5/19.4	0/18.8	100/3.1	0/29.3	3.6

Table 4 (continuing)

Emulsion	Structure	Equal circle diameter (μ m)	Equal circle diameter variation factor (%)	Thickness (μ m)	Explanation
						j	Four layers	3.1	24	0.26	Comparative Examples
k	Five layers	3.1	24	0.26	Comparative Examples
						l	Five layers	3.1	24	0.26	Comparative Examples
m	Five layers	3.72	18	0.19	Comparative Examples
						n	Five layers	3.72	18	0.19	The present invention
o	Four layers	4.80	27	0.090	Comparative Examples
						p	Five layers	4.80	27	0.090	The present invention
q	Five layers	4.79	23	0.091	The present invention

Carry out chemical sensitization and coating according to method identical among the embodiment 1, make sample 101 to 108.Similarly, colored development time among the embodiment is changed into 3 minutes and 15 seconds and estimate light sensitivity and ashing.Changed into 3 minutes and 15 seconds the colour development processing time simultaneously, and potassium bromide content increases to 3 times with pH reduction by 0.3 in the color developer.Estimate the difference of γ value between this facture and aforementioned processing method.The results are shown in Table 5.

Table 5

Sample	Emulsion	Explanation	Ashing	Light sensitivity	γ is poor
						101	j	Comparative Examples	0.23	100	0.08
102	k	Comparative Examples	0.20	126	0.07
						103	l	Comparative Examples	0.21	110	0.07
104	m	Comparative Examples	0.25	122	0.16
						105	n	The present invention	0.23	160	0.10
106	o	Comparative Examples	0.24	139	0.23
						107	p	The present invention	0.22	181	0.11
108	q	The present invention	0.21	181	0.09

Though table 5 shows platy shaped particle emulsion j, the k and the l that do not meet equal circle diameter given to this invention and thickness requirement and satisfies necessary two conditions of the present invention, be the agi content of five-layer structure and 2 to 6mol%, change the effect that causes that the γ value changes because of development conditions but can not obtain improvement.In contrast, platy shaped particle emulsion m and n that contrast meets defined equal circle diameter of the present invention and thickness requirement show, obviously improved as the five-layer structure of a necessary condition of the present invention and changed the γ value change that causes because of developing.With emulsion o, p compares this effect with q more obvious.The effect of equal circle diameter variation factor also is conspicuous simultaneously.

Embodiment 3

Below the effect of present invention will be further described six layers of structure particles.

In embodiment 2, add silver iodide fine grained before the emulsion q chemical sensitization, the emulsion of six layers of structure particles of preparation in silver 0.13mol%.When estimating by embodiment 2 identical methods, ashing, light sensitivity and γ difference are respectively 0.22,188 and 0.07, have promptly obtained good effect.

Embodiment 4

The effect of emulsion of the present invention in the multi layer colour photosensitive material below will be described.

Prepare silver emulsion Em-A to Em-O by the following method.

The preparation of emulsion Em-A

It is that 97% molecular weight is that the aqueous solution of 15,000 low molecular weight gelatine and 31.7g KBr is 35 ℃ of following vigorous stirring that 42.2L is contained 31.7g O-phthalic acidifying ratio.Adopt two gunitees to add 1,583mL contains 316.7g AgNO ₃Aqueous solution and 1,583mL contains the aqueous solution that 221.5g KBr and 52.7g molecular weight are 15,000 low molecular weight gelatine.Add 52.8gKBr after adding immediately, and adopt two gunitees to add 2 in 2min, 485mL contains 398.2g AgNO ₃Aqueous solution and 2,581mL contains the aqueous solution of 291.1g KBr.Add and add 44.8g KBr immediately after finishing.After this temperature is risen to 40 ℃ and ripe this material.It is 100,000 that ripe back adds the 923g molecular weight, and O-phthalic acidifying ratio is 97% gelatin, and 79.2g KBr.Adopt two gunitees to add 15 then in 10min, 947mL contains 5.103g AgNO ₃Aqueous solution and KBr aqueous solution, accelerate flow velocity around here and make that final flow rate is 1.4 times of initial flow rate.In the interpolation process, be with reference to silver-colored electromotive force is remained-60mV with the saturated calomel electrode.The washing back adds gelatin, and pH and pAg are adjusted to 5.7 to 8.8 respectively, in every kg emulsion, silver content is adjusted to 131.8g and 64.1g respectively, thereby prepares crystal seed emulsion.With 1, it is that the aqueous solution of 97% O-phthalic acidifying gelatin and 1.7g KBr is 75 ℃ of following vigorous stirring that 121mL contains 46g O-phthalic acidifying ratio.After adding 9.9g crystal seed emulsion, add 0.3g modified silicon oil (by the L7602 of Nippon Uniker K.K. manufacturing).Add H ₂SO ₄Transfer pH to 5.5, in 6min, adopt two gunitees to add 67.6mL then and contain 7.0gAgNO ₃Aqueous solution and KBr aqueous solution, increase flow velocity around here and make that final flow rate is 5.1 times of initial flow rate.In the interpolation process, be reference with the saturated calomel electrode, silver electrode remains-20mV.Add 2mg sodium benzenethiosulfonate and 2mg thiourea dioxide, in 56min, adopt two gunitees to add 328mL then and contain 105.6g AgNO ₃Aqueous solution and KBr aqueous solution, increase flow velocity around here and make that final flow rate is 3.7 times of initial flow rate.Adding particle diameter simultaneously under the flow velocity that increases during the interpolation is the AgI fine particle emulsion of 0.037 μ m, makes agi content reach 27mol%.Be with reference to silver-colored electromotive force is remained-50mV simultaneously with the saturated calomel electrode.In 22min, adopt two gunitees to add 121.3mL then and contain 45.6g AgNO ₃Aqueous solution and KBr aqueous solution.During the interpolation be to maintain+20mV with reference to silver-colored electromotive force with the saturated calomel electrode.Temperature is risen to 82 ℃, with the saturated calomel electrode be with reference to add KBr with silver-colored potential regulating to-80mV, in KI weight, add the above-mentioned AgI fine particle emulsion of 6.33g.Promptly be engraved in the interior 206.2mL of interpolation of 16min after the interpolation and contain 66.4AgNO ₃Aqueous solution.At the initial 5min that adds, use the KBr aqueous solution to keep silver-colored electromotive force to be-80mV.The washing back adds gelatin, under 40 ℃ pH and pAg is adjusted to 5.8 to 8.7 respectively.Add compound 11 and 12 and temperature risen to 60 ℃.After sensitizing dye 11 and 12 adds, add potassium rhodanide, gold chloride, sodium thiosulfate and N, N-dimethyl selenourea carries out optimum chemical sensitizing to emulsion.When finishing, chemical sensitization adds compound 13 and 14." optimum chemical sensitizing " refers to that the consumption of each sensitizing dye and compound is selected from 10 in every mol silver halide ^-1To 10 ^-8Mol.

Compound 11

Compound 12

Sensitizing dye 11

Sensitizing dye 12

Compound 13

Compound 14

The preparation of emulsion Em-B

With 1,192mL contains the aqueous solution of 0.96g low molecular weight gelatine and 0.9g KBr 40 ℃ of following vigorous stirring.In 30sec, adopt two gunitees to add 37.5mL and contain 1.49g AgNO ₃Aqueous solution and the 37.5mL aqueous solution that contains 1.05g KBr.After adding 1.2g KBr, temperature is risen to 75 ℃ of maturing materials.It is 100,000 trimellitic acid gelatin by the molecular weight of trimellitic acid chemical modification that ripe back adds 35g amino, is 7 with pH regulator.Add the 6mg thiourea dioxide.Adopt two gunitees to add 116mL and contain 29g AgNO ₃Aqueous solution and KBr aqueous solution, accelerate flow velocity around here and make that final flow rate is 3 times of initial flow rate.In the interpolation process, be with reference to silver-colored electromotive force is remained-20mV with the saturated calomel electrode.In 30min, adopt two gunitees to add 440.6mL and contain 110.2g AgNO ₃Aqueous solution and KBr aqueous solution, increase flow velocity around here and make that final flow rate is 5.1 times of initial flow rate.In the interpolation process, under the flow velocity that increases, add the AgI fine particle emulsion that is used to prepare Em-A, make agi content reach 15.8mol%.Be with reference to silver-colored electromotive force is remained 0mV simultaneously with the saturated calomel electrode.In 3min, adopt two gunitees to add 96.5mL then and contain 24.1g AgNO ₃Aqueous solution and KBr aqueous solution, silver-colored electromotive force remains 0mV during the interpolation.After adding 26mg ethylenebis dithiocarbamate sodium sulfonate, cool the temperature to 55 ℃, add KBr with silver-colored potential regulating to-90mV, add the above-mentioned AgI fine particle emulsion of 8.5g in KI weight.At once utilize 5min to add 228mL after the interpolation and contain 57g AgNO ₃Aqueous solution.During adding, add the KBr aqueous solution, make silver-colored electromotive force when adding end be+20mV.Gained emulsion after washing by the essentially identical method chemical sensitization of Em-A.

The preparation of emulsion Em-C

With 1,192mL contains the aqueous solution of 1.02g O-phthalic acidifying gelatin and 0.9g KBr 35 ℃ of following vigorous stirring, and wherein every g gelatin comprises 35 μ mol methionines, and O-phthalic acidifying ratio is 97%, and molecular weight is 100,000.In 9sec, adopt two gunitees to add 42mL and contain 4.47gAgNO ₃Aqueous solution and the 42mL aqueous solution that contains 3.16g KBr.After adding 2.6g KBr, temperature is risen to 63 ℃ of maturing materials.The molecular weight that ripe back adds 41.2g use in the Em-B preparation is 100,000 trimellitic acid gelatin and adds 18.5g NaCl.After pH is adjusted to 7.2.Add the 8mg dimethyamine borane.Adopt two gunitees to add 203mL and contain 26g AgNO ₃Aqueous solution and KBr aqueous solution, accelerate flow velocity around here and make that final flow rate is 3.8 times of initial flow rate.In the interpolation process, be with reference to silver-colored electromotive force is remained-30mV with the saturated calomel electrode.In 24min, adopt two gunitees to add 440.6mL and contain 110.2g AgNO ₃Aqueous solution and KBr aqueous solution, increase flow velocity around here and make that final flow rate is 5.1 times of initial flow rate.In the interpolation process, under the flow velocity that increases, add the AgI fine particle emulsion that is used to prepare Em-A, make agi content reach 2.3mol%.Be with reference to silver-colored electromotive force is remained-20mV simultaneously with the saturated calomel electrode.After 10.7mL 1N potassium rhodanate adds, in 2 minutes and 30 seconds, adopt two gunitees to add 153.5mL and contain 24.1g AgNO ₃Aqueous solution and KBr aqueous solution, silver-colored electromotive force remains 10mV during the interpolation.Adding KBr is adjusted to silver-colored electromotive force-70mV.In KI weight, add the above-mentioned AgI fine particle emulsion of 6.4g.Promptly be engraved in the interior 404mL of interpolation of 45min after the interpolation and contain 57g AgNO ₃Aqueous solution.Add KBr, make silver-colored electromotive force when adding end be-30mV.Gained emulsion after washing by the essentially identical method chemical sensitization of Em-A.

The preparation of emulsion Em-D

In the preparation of emulsion Em-C, with AgNO between the nucleation period ₃Consumption increase by 2.3 times.Add 404mL at last and contain 57g AgNO ₃Aqueous solution.Add KBr, make silver-colored electromotive force when adding end be+90mV.Except above-mentioned points, the preparation of emulsion Em-D is identical with Em-C.

The preparation of emulsion Em-E

With 1, it is that aqueous solution that 15,000 low molecular weight gelatine, 0.9g KBr and 0.2g are used for the modified silicon oil of Em-A preparation remains on 39 ℃ of vigorous stirring down and under the pH1.8 condition that 200mL contains the 0.75g molecular weight.In 16sec, adopt two gunitees to add and contain 0.45g AgNO ₃Aqueous solution and contain the KBr aqueous solution of 1.5mol%KI.The excessive concentrations of KBr keeps constant during the interpolation.Temperature is risen to 54 ℃ of maturing materials.Ripe back adds 20g O-phthalic acidifying gelatin, and wherein every g gelatin comprises 35 μ mol methionines, and O-phthalic acidifying ratio is 97%.PH is adjusted to 5.9 backs adds 2.9g KBr.In 53min, adopt two gunitees to add 228mL and contain 28.8g AgNO ₃Aqueous solution and KBr aqueous solution.In the interpolation process, add the AgI fine particle emulsion that is used to prepare Em-A, make agi content reach 4.1mol%.Be with reference to silver-colored electromotive force is remained-60mV simultaneously with the saturated calomel electrode.After adding 2.5g KBr, in 63min, adopt two gunitees to add and contain 87.7g AgNO ₃Aqueous solution and KBr aqueous solution, increase flow velocity around here and make that final flow rate is 1.2 times of initial flow rate.In the interpolation process, under the flow velocity that increases, add above-mentioned AgI fine particle emulsion, make agi content reach 10.5mol%.Silver-colored electromotive force remains-70mV simultaneously.After adding the 1mg thiourea dioxide, in 25min, adopt two gunitees to add 132mL and contain 41.8gAgNO ₃Aqueous solution and KBr aqueous solution, the interpolation of KBr aqueous solution makes silver-colored electromotive force be+20mV when add finishing.After adding 2mg ethylenebis dithiocarbamate sodium sulfonate, pH is adjusted to 7.3 and add KBr and regulate silver-colored electromotive force and be-70mV.After this, in KI weight, add the above-mentioned AgI fine particle emulsion of 5.73g.Promptly be engraved in the interior 609mL of interpolation of 10min after the interpolation and contain 66.4g AgNO ₃Aqueous solution.At the initial 6min that adds, use the KBr aqueous solution to keep silver-colored electromotive force to be-70mV.The washing back adds gelatin, under 40 ℃ pH and pAg is adjusted to 6.5 to 8.2 respectively.Add compound 1 and 2 and temperature risen to 56 ℃.After adding the above-mentioned AgI fine particle emulsion of 0.0004mol, add sensitizing dye 13 and 14 in every mol silver.Add potassium rhodanide, gold chloride, sodium thiosulfate and N, N-dimethyl selenourea carries out optimum chemical sensitizing to emulsion.When finishing, chemical sensitization adds compound 13 and 14.

Sensitizing dye 13

Sensitizing dye 14

The preparation of emulsion Em-F

Remove between the nucleation period AgNO ₃Consumption increase by 4.12 times outside, preparation and the Em-E of emulsion Em-F are basic identical.Attention changes the sensitizing dye among the Em-E into sensitizing dye 12,15,16 and 17.

Sensitizing dye 15

Sensitizing dye 16

Sensitizing dye 17

The preparation of emulsion Em-G

With 1, it is that aqueous solution that 15,000 low molecular weight gelatine, 0.9g KBr, 0.175gKI and 0.2g are used for the modified silicon oil of Em-A preparation remains on 33 ℃ of vigorous stirring down and under the pH1.8 condition that 200mL contains the 0.70g molecular weight.In 9sec, adopt two gunitees to add and contain 1.8g AgNO ₃Aqueous solution and contain the KBr aqueous solution of 3.2mol%KI.The excessive concentrations of KBr keeps constant during the interpolation.Temperature is risen to 62 ℃ of maturing materials.Ripe back adds the trimellitic acid gelatin that 20g amino is modified by trimellitic acid, and wherein every g gelatin comprises 35 μ mol methionines, and molecular weight is 100,000.PH is adjusted to 6.3 backs adds 2.9g KBr.In 37min, adopt two gunitees to add 270mL and contain 27.58g AgNO ₃Aqueous solution and KBr aqueous solution.In the interpolation process, adding particle diameter is the AgI fine particle emulsion of 0.008 μ m, makes agi content reach 4.1mol%.In another chamber of the described magnetic coupling of JP-A-10-43570 induction type stirrer before adding at once combined molecular weight be 15,000 low molecular weight gelatine aqueous solution, AgNO ₃Aqueous solution and KI aqueous solution, preparation AgI fine particle emulsion.Be with reference to silver-colored electromotive force is remained-60mV simultaneously with the saturated calomel electrode.After adding 2.6g KBr, in 49min, adopt two gunitees to add and contain 87.7gAgNO ₃Aqueous solution and KBr aqueous solution increase flow velocity around here and make that final flow rate is 3.1 times of initial flow rate.In the interpolation process,, make agi content reach 7.9mol% adding the AgI fine particle emulsion that is just preparing before above-mentioned the interpolation under the flow velocity that increases.Silver-colored electromotive force remains-70mV simultaneously.After adding the 1mg thiourea dioxide, in 20min, adopt two gunitees to add 132mL and contain 41.8gAgNO ₃Aqueous solution and KBr aqueous solution, the interpolation of KBr aqueous solution makes silver-colored electromotive force be+20mV when add finishing.When temperature rise to 78 ℃ and pH is adjusted to 9.1 after, add KBr and regulate silver-colored electromotive force and be-60mV.In KI weight, add 5.73g used AgI fine particle emulsion when preparing Em-A.Promptly be engraved in the interior 321mL of interpolation of 4min after the interpolation and contain 66.4g AgNO ₃Aqueous solution.At the initial 2min that adds, use the KBr aqueous solution to keep silver-colored electromotive force to be-60mV.Gained emulsion carries out chemical sensitization by the essentially identical method of emulsion Em-F after washing.

The preparation of emulsion Em-H

The aqueous solution that will contain the 17.8g molecular weight and be 100,000 the gelatin through ion-exchange, 6.2g KBr, 0.46gKI is 45 ℃ of following vigorous stirring.In 45sec, adopt two gunitees to add and contain 11.85gAgNO ₃Aqueous solution and contain the aqueous solution of 3.8g KBr.Temperature rises to after 63 ℃ that to add the 24.1g molecular weight be 100,000 the gelatin maturing material through ion-exchange.Ripe back adopts two gunitees addings to contain 133.4g AgNO in 20min ₃Aqueous solution and KBr aqueous solution, its final flow rate is 2.6 times of initial flow rate.In the interpolation process, be with reference to silver-colored electromotive force is remained+40mV with the saturated calomel electrode.The K that after adding beginning 10min, adds 0.1mg ₂IrCl ₆After adding 7g NaCl, in 12min, adopt two gunitees to add and contain 45.6g AgNO ₃Aqueous solution and KBr aqueous solution.In the interpolation process, be with reference to silver-colored electromotive force is remained+90mV with the saturated calomel electrode.During adding beginning 6min, add the aqueous solution that 100mL contains the 29mg potassium ferrocyanide simultaneously.After adding 14.4g KBr,, add 6.3g used AgI fine particle emulsion when preparing Em-A in KI weight.At once utilize 11min to add after the interpolation and contain 42.7g AgNO ₃Aqueous solution and KBr aqueous solution.Keep silver-colored electromotive force to be+90mV during the interpolation.Gained emulsion carries out chemical sensitization by the essentially identical method of emulsion Em-F after washing.

The preparation of emulsion Em-I

Except that between the nucleation period temperature is changed into 35 ℃, preparation and the Em-H of emulsion Em-I are basic identical.

The preparation of emulsion Em-J

With 1,200mL contain 0.38g O-phthalic acidifying ratio be 97% and molecular weight be that the aqueous solution of 100,000 O-phthalic acidifying gelatin and 0.9g KBr remains on 60 ℃ of vigorous stirring down and under the pH2 condition.In 30sec, adopt two gunitees to add and contain 1.96g AgNO ₃Aqueous solution and contain 1.67g KBr and the aqueous solution of 0.172g KI.Ripe back adds the trimellitic acid gelatin that 12.8g amino is modified by trimellitic acid, and wherein every g gelatin comprises 35 μ mol methionines, and molecular weight is 100,000.PH is adjusted to 6.3 backs adds 2.99g KBr and 6.2g NaCl.In 31min, adopt two gunitees to add 60.7mL and contain 27.3g AgNO ₃Aqueous solution and KBr aqueous solution.During adding be with reference to silver-colored electromotive force is remained-50mV with the saturated calomel electrode.In 37min, adopt two gunitees to add and contain 65.6g AgNO ₃Aqueous solution and KBr aqueous solution, increase flow velocity around here and make that final flow rate is 2.1 times of initial flow rate.In the interpolation process, under the flow velocity that increases, add AgI fine particle emulsion used when preparing Em-A, make agi content reach 6.5mol%.Silver-colored electromotive force remains-50mV simultaneously.After adding the 1.5mg thiourea dioxide, in 13min, adopt two gunitees to add 132mL and contain 41.8g AgNO ₃Aqueous solution and KBr aqueous solution, the interpolation of KBr aqueous solution makes silver-colored electromotive force be+40mV when add finishing.Add and to add KBr behind the 2mg ethylenebis dithiocarbamate sodium sulfonate and regulate silver-colored electromotive force and be-100mV.In KI weight, add the above-mentioned AgI fine particle emulsion of 6.2g.Promptly be engraved in the interior 300mL of interpolation of 8min after the interpolation and contain 88.5g AgNO ₃Aqueous solution.Interpolation KBr aqueous solution is regulated silver-colored electromotive force when adding end.The washing back adds gelatin, under 40 ℃ pH and pAg is adjusted to 6.5 to 8.2 respectively.Add compound 11 and 12 and temperature risen to 61 ℃.Add sensitizing dye 18,19,20 and 21.After this add K ₂IrCl ₆, potassium rhodanide, gold chloride, sodium thiosulfate and N, N-dimethyl selenourea carries out optimum chemical sensitizing to emulsion.When finishing, chemical sensitization adds compound 13 and 14.

Sensitizing dye 18

Sensitizing dye 19

Sensitizing dye 20

Sensitizing dye 21

The preparation of emulsion Em-K

With 1, it is that the aqueous solution of 15,000 low molecular weight gelatine and 5.3g KBr is 60 ℃ of following vigorous stirring that 200mL contains the 4.9g molecular weight.In 1min, adopt two gunitees to add 27mL and contain 8.75gAgNO ₃Aqueous solution and the 36mL aqueous solution that contains 6.45g KBr.Temperature risen to 75 ℃ of maturing materials and in 2min, add 21mL and contain 6.9g AgNO ₃Aqueous solution.Order adds 26g NH ₄NO ₃With behind the 56mL 1N NaOH material is carried out maturation.After the maturation pH is adjusted to 4.8.Adopt two gunitees to add 438mL and contain 141g AgNO ₃Aqueous solution and the 458mL aqueous solution that contains 106.2g KBr, make that final flow rate is 4 times of initial flow rate.Cool the temperature to 55 ℃, in 5min, adopt two gunitees to add 240mL and contain 7.1g AgNO ₃Aqueous solution and contain the aqueous solution of 6.46gKI.After adding 7.1g KBr, add the K of 4mg ethylenebis dithiocarbamate sodium sulfonate and 0.05mg ₂IrCl ₆In 8min, adopt two gunitees to add 177mL and contain 57.2g AgNO ₃Aqueous solution and the 223mL aqueous solution that contains 40.2gKBr, gained emulsion carries out chemical sensitization by the essentially identical method of emulsion Em-J after washing.

The preparation of emulsion Em-L

Except that between the nucleation period temperature is changed into 40 ℃, preparation and the Em-K of emulsion Em-L are basic identical.

The preparation of emulsion Em-M, Em-N and Em-O

Except that being undertaken the chemical sensitization by the essentially identical method of Em-J, the preparation of emulsion Em-M, Em-N and Em-O and Em-H or Em-I are basic identical.

The eigenwert of silver emulsion Em-A to Em-O is summarised in the table 6.

Table 6

Emulsion number	Equal circle diameter (μ m) variation factor (%)	Thickness (μ m) variation factor (%)	Aspect ratio variation factor (%)	Flatness
					Em-A	1.98 23	0.198 28	12 35	51
Em-B	1.30 25	0.108 27	12 38	111
					Em-C	1.00 31	0.083 26	12 27	145
Em-D	0.75 31	0.075 18	10 29	133
					Em-E	2.02 31	0.101 19	20 42	198
Em-F	1.54 26	0.077 18	20 33	260
					Em-G	1.08 18	0.072 15	15 19	208
Em-H	0.44 16	0.22 13	2 9	9

(continuation)

Table 6

Emulsion number	Twin plane distance (μ m) variation factor (%)	The ratio (%) of platy shaped particle in the total projection area	(100) ratio (%) of crystal face in the side crystal face	Content of iodine (mol%) variation factor (%)	Chlorinity (mol%)	Surface content of iodine (mol%)
							Em-A	0.014 32	92	23	15 17	0	4.3
Em-B	0.013 30	93	22	11 16	0	4.6
							Em-C	0.012 30	93	18	4 8	1	1.8
Em-D	0.010 27	91	33	7 7	2	1.9
							Em-E	0.013 33	99	20	7 7	0	2.4
Em-F	0.013 26	99	23	6 5	0	2.5
							Em-G	0.008 22	97	23	3 6	0	2.0
Em-H	0.013 18	90	38	3 6	2	1

(continuation)

Table 6

Emulsion number	Equal circle diameter (μ m) variation factor (%)	Thickness (μ m) variation factor (%)	Aspect ratio variation factor (%)	Flatness
					Em-I	0.33 17	0.165 13	2 12	12
Em-J	1.83 18	0.122 20	15 22	123
					Em-K	1.09 16	0.156 18	7 19	45
Em-L	0.84 17	0.12 18	7 19	58
					Em-M	0.55 16	0.275 13	2 9	7
Em-N	0.44 17	0.22 13	2 12	9
					Em-O	0.33 17	0.165 13	2 12	12

(continuation)

Table 6

Emulsion number	Twin plane distance (μ m) variation factor (%)	The ratio (%) of platy shaped particle in the total projection area	(100) ratio (%) of crystal face in the side crystal face	Content of iodine (mol%) variation factor (%)	Chlorinity (mol%)	Surface content of iodine (mol%)
							Em-I	0.013 18	88	42	3 6	2	1
Em-J	0.012 19	98	23	5 6	1	1.8
							Em-K	0.013 16	99	22	3 7	0	2.7
Em-L	0.013 16	99	25	3 7	0	2.7
							Em-M	0.013 18	90	38	2 6	2	1
Em-N	0.013 18	88	42	2 6	2	1
							Em-O	0.013 18	88	46	1 6	2	0.5

(continuation)

1, carrier

The carrier that following formation is used in the present embodiment.

Dry 100 weight portions poly-2, P.326 6-(ethylene naphthalate) polymkeric substance and 2 weight portions (are made by Ciba-Geigy Co.) as the Tinuvin of ultraviolet absorber, 300 ℃ of following fusions, then by extruding in the T-die head.The gained material is 3.3 times of 140 ℃ of following longitudinal stretchings, 3.3 times of 130 ℃ of following cross directional stretchs, 250 ℃ of following heat fixations 6 seconds, makes thick PEN (PEN) film of 90 μ m thus then.Note, in this PEN film, add indigo plant, magenta and the weld (I-1, the I-4, I-6, I-24, I-26, I-27 and the II-5 that in Journal of Technical Disclosure No.94-6023, describe) of appropriate amount.This PEN film is wrapped on the stainless steel core that diameter is 20cm, heat-treated under 110 ℃ 48 hours then, the carrier that manufactures has the anti-crimpiness of height.

2, the coating of undercoat

Two surfaces of above-mentioned carrier are carried out halation discharge, UV discharge and glow discharge and are handled.Afterwards, each surface of carrier applies (10ml/m with base coat solution ², use the coating rod), this base coat solution is by 0.1g/m ²Gelatin, 0.01g/m ²Alpha-sulfo two-2-ethylhexyl sodium succinate, 0.04g/m ²Salicylic acid, 0.2g/m ²Parachlorophenol, 0.012g/m ²(CH ₂=CHSO ₂CH ₂CH ₂NHCO) ₂CH ₂, and 0.02g/m ²Polyamide-based-chloropropylene oxide polycondensation product form, when stretching, at high temperature on a side, form undercoat thus.Under 115 ℃, carry out dry 6 minutes (all rollers in the arid region and travelling belt all are 115 ℃).

3, the coating of backing layer

On a surface of the carrier of undercoat coating, applying antistatic layer, magnetic recording layer and sliding layer, they composed as follows as backing layer.

The coating of 3-1, antistatic layer

Surface 0.2g/m ²Mean grain size is the dispersion (secondary agglomeration particle diameter=0.08 μ m) and the 0.05g/m of the particulate powders (is 5 Ω cm than resistance) of tin oxide-antimony oxide compound substance of 0.005 μ m ²Gelatin, 0.02g/m ²(CH ₂=CHSO ₂CH ₂CH ₂NHCO) ₂CH ₂, 0.05g/m ²Polyoxyethylene nonylphenol (degree of polymerization is 10) and resorcinol are applied.

The coating of 3-2, magnetic recording layer

Use the excellent coated surfaces of coating, wherein use 0.06g/m ²(specific surface is 43m with the cobalt-gamma-iron oxide of poly-(degree of polymerization is 15) oxygen ethene-propoxyl group trimethoxy silane (the 15 weight %) coating of 3- ²/ g, main shaft 0.14 μ m, countershaft 0.03 μ m, saturation magnetization 89Am ²/ kg, Fe ²⁺/ Fe ³⁺=6/94, handle with aluminium oxide that contains 2 weight % iron oxide and monox on the surface) and 1.2g/m ²Diacetyl cellulose (iron oxide disperses with opening kneader and sand mill), and use 0.3g/m ²C ₂H ₅C (CH ₂OCONH-C ₆H ₃(CH ₃) NCO) 3 as rigidizer, acetone, methyl ethyl ketone and cyclohexanone form the thick magnetic recording layer of 1.2 μ m thus as solvent.Add 10mg/m ²Silica dioxide granule (0.3 μ m) as matting agent, add 10mg/m then ²Gather the aluminium oxide (0.15 μ m) of (degree of polymerization is 15) polyoxyethylene-propoxyl group trimethoxy silane (15 weight %) coating as brilliant polish with 3-.Under 115 ℃, carry out dry 6 minutes (all rollers in the arid region and travelling belt all are 115 ℃).The colour density increase DB that measures magnetic recording layer with X-ray (blue filter) is about 0.1.The saturation magnetic moment of magnetic recording layer, coercive force and verticality are respectively 4.2Am ²/ kg, 7.3 * 10 ⁴A/m and 65%.

The preparation of 3-3, sliding layer

Diacetyl cellulose (25mg/m is used on the surface then ²) and C ₆H ₁₃CH (OH) C ₁₀H ₂₀COOC ₄₀H ₈₁(compound a, 6mg/m ²)/C ₅₀H ₁₀₁O (CH ₂CH ₂O) ₁₆H (compound b, 9mg/m ²) potpourri coating.What note is, this potpourri is in fusion in dimethylbenzene/propylene monomethyl ether (1/1) under 105 ℃, at room temperature topples over then and is dispersed in the propylene monomethyl ether (10 times amounts).Afterwards, the gained potpourri is configured as dispersion (mean grain size is 0.01 μ m) in acetone before interpolation.Add 15mg/ ²Silica dioxide granule (0.3 μ m) as matting agent, add 15mg/ then ²Gather the aluminium oxide (0.15 μ m) of (degree of polymerization is 15) oxygen ethene-propoxyl group trimethoxy silane (15 weight %) coating as brilliant polish with 3-.Under 115 ℃, carry out dry 6 minutes (all rollers in the arid region and travelling belt all are 115 ℃).The gained sliding layer has excellent characteristic, and kinetic friction coefficient is 0.06 (the stainless steel hard sphere of 5mm diameter, load 100g, speed 6cm/min), and coefficient of static friction is 0.07 (clip method).Kinetic friction coefficient between emulsion surface (as described below) and the sliding layer is also very excellent, is 0.12.

4, the coating of photographic layer

On away from the carrier surface on aforesaid backing layer one side, apply a plurality of layers, form sample, make sample 501 thus as the colour negative photosensitive material with following composition.

The composition of photographic layer

The used following classification of principal ingredient in each layer, but its use is not limited to following particular compound.

ExC: cyan colour coupler

UV: ultraviolet absorber

ExM: magenta colour coupler

HBS: high boiling organic solvent

ExY: yellow colour coupler

H: gelatin hardener

(in the following description, particular compound all has the numeral of following behind its symbol.The structural formula of these compounds as shown below).The numeral unit of each component is g/m ²Coating amount.The coating amount of silver halide shows with the scale of silver.

Ground floor (the first anti-halation layer)

The black collargol	Silver 0.155
		Iodine silver bromide emulsion T	Silver 0.01
Gelatin	0.87
		ExC-1	0.002
ExC-3	0.002
		Cpd-2	0.001
HBS-1	0.004
		HBS-2	0.002

The second layer (the second anti-halation layer)

The black collargol	Silver 0.066
		Gelatin	0.407
ExM-1	0.050
		ExF-1	2.0×10 -3
HBS-1	0.074
		Solid disperse dye ExF-2	0.015
Solid disperse dye ExF-3	0.020

The 3rd layer (middle layer)

0.07 μ m bromo-iodide (2)	0.020
		ExC-2	0.022
Polyethyl acrylate latex	0.085
		Gelatin	0.294

The 4th layer (low speed magenta-sensitive emulsion layer)

Iodine silver bromide emulsion M	Silver 0.065
		Iodine silver bromide emulsion N	Silver 0.100
Iodine silver bromide emulsion O	Silver 0.158
		ExC-1	0.109
ExC-3	0.044
		ExC-4	0.072
ExC-5	0.011
		ExC-6	0.003
Cpd-2	0.025

Cpd-4	0.025
		HBS-1	0.17
Gelatin	0.80

Layer 5 (middling speed magenta-sensitive emulsion layer)

Iodine silver bromide emulsion K	Silver 0.21
		Iodine silver bromide emulsion L	Silver 0.62
ExC-1	0.14
		ExC-2	0.026
ExC-3	0.020
		ExC-4	0.12
ExC-5	0.016
		ExC-6	0.007
Cpd-2	0.036
		Cpd-4	0.028
HBS-1	0.16
		Gelatin	1.18

Layer 6 (high speed magenta-sensitive emulsion layer)

Iodine chlorine silver bromide emulsion J	Silver 1.47
		ExC-1	0.18
ExC-3	0.007
		ExC-6	0.029
ExC-7	0.010
		ExY-5	0.008
Cpd-2	0.046

Cpd-4	0.077
		HBS-1	0.25
HBS-2	0.12
		Gelatin	2.12

Layer 7 (middle layer)

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

The 8th layer (layer of intermediate imagery effect is provided to the sense red beds)

Iodine silver bromide emulsion E	Silver 0.560
		Cpd-4	0.030
ExM-2	0.096
		ExM-3	0.028
ExY-1	0.031
		ExG-1	0.006
HBS-1	0.085
		HBS-3	0.003
Gelatin	0.58

The 9th layer (low speed green-sensitive emulsion layer)

Iodine silver bromide emulsion g

Silver 0.39

Iodine silver bromide emulsion H	Silver 0.28
		Iodine silver bromide emulsion I	Silver 0.35
ExM-2	0.36
		ExM-3	0.045
ExG-1	0.005
		Cpd-3	0.010
HBS-1	0.28
		HBS-3	0.01
HBS-4	0.27
		Gelatin	1.39

The tenth layer (middling speed green-sensitive emulsion layer)

Iodine silver bromide emulsion F	Silver 0.20
		Iodine silver bromide emulsion g	Silver 0.25
ExC-6	0.009
		ExM-2	0.031
ExM-3	0.029
		ExY-1	0.006
ExM-4	0.028
		ExG-1	0.005
HBS-1	0.064
		HBS-3	2.1×10 -3
Gelatin	0.44

Eleventh floor (high speed green-sensitive emulsion layer)

Iodine silver bromide emulsion o among the embodiment 2

Silver 0.99

ExC-6	0.004
		ExM-1	0.016
ExM-3	0.036
		ExM-4	0.020
ExM-5	0.004
		ExY-5	0.003
ExM-2	0.013
		ExG-1	0.005
Cpd-4	0.007
		HBS-1	0.18
Polyethyl acrylate latex	0.099
		Gelatin	1.11

Floor 12 (Yellow filter layer)

Yellow colloidal silver	Silver 0.01
		Cpd-1	0.16
Solid disperse dye ExF-5	0.010
		Solid disperse dye ExF-6	0.010
HBS-1	0.082
		Gelatin	1.057

The 13 layer (low speed blue-sensitive emulsion layer)

Iodine silver bromide emulsion B	Silver 0.18
		Iodine silver bromide emulsion C	Silver 0.20
Iodine chlorine silver bromide emulsion D	Silver 0.07

ExC-1	0.041
		ExC-8	0.012
ExY-1	0.035
		ExY-2	0.71
ExY-3	0.10
		ExY-4	0.005
Cpd-2	0.10
		Cpd-3	4.0×10 -3
HBS-1	0.24
		Gelatin	1.41

The 14 layer (high speed blue-sensitive emulsion layer)

Iodine silver bromide emulsion A	Silver 0.75
		ExC-1	0.013
ExY-2	0.31
		ExY-3	0.05
ExY-6	0.062
		Cpd-2	0.075
Cpd-3	1.0×10 -3
		HBS-1	0.10
Gelatin	0.91

The 15 layer (first protective seam)

0.07Mm AgBrI(2)	Silver 0.30
		UV-1	0.21
UV-2	0.13

UV-3	0.20
		UV-4	0.025
F-18	0.009
		F-19	0.005
F-20	0.005
		HBS-1	0.12
HBS-4	5.0×10 -2
		Gelatin	2.3

The 16 layer (second protective seam)

H-1	0.40
		B-1 (diameter 1.7 μ m)	5.0×10 -2
B-2 (diameter 1.7 μ m)	0.15
		B-3	0.05
S-1	0.20
		Gelatin	0.75

Removing said components is, for improving storage stability, flushable property, resistance to pressure, antibiotic and mildew resistance, antistatic behaviour and screening characteristics, each layer can comprise W-1 to W-5, B-4 to B-6, F-1 to F-18, molysite, lead salt, golden salt, palladium salt, platinum salt, iridium salt, ruthenium salt and rhodium salt.In addition, with respect to every mol silver halide, can the 8th and the coating solution of eleventh floor in add 8.5 * 10 respectively ^-3G and 7.9 * 10 ^-3The calcium of g, it is the form of calcium nitrate aqueous solution.

In the 11th layer coating, constitute sample 202 with the emulsion o in the emulsion r alternate embodiment 2 of embodiment 3 preparations.

The preparation of organic solid disperse dyes

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

According to above identical method, make solid dispersions ExF-4.The mean grain size of this thin dye granule is respectively 0.45 μ m.Use EP549, the described microdeposit dispersion method of the embodiment of 489A is disperseed ExF-2.Its mean grain size is 0.06 μ m.

In order to following method dispersing solid dispersion ExF-6.

The water of 4.0kg and the 3%W-2 aqueous solution of 376g are added in the moist cake of ExF-6 of 2800g, and this cake comprises 18% water, stirs the gained material then, and formation concentration is 30% ExF-6 slurries.Next, with the 1700ml mean grain size be the ULTRA VISO MILL (UVM-2) of the zirconia ball filling Imex K.K. manufacturing of 0.5mm.Make above-mentioned slurries by passing through in this mill, ground these slurries thus 8 hours, the circumferential speed of this mill is about 10m/sec, and loading is 0.5L/min.Mean grain size is 0.52 μ m.

Below for being used to constitute the compound of each layer.

The HBS-1 lindol

HBS-2 phthalic acid di-n-butyl ester

X/y=10/90 (weight ratio) mean molecular weight: about 35000

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

Mean molecular weight: about 750,000

Mean molecular weight: about 10,000

These samples carry out film sclerosis 14 hours under 40 ℃, the condition of 70% relative humidity.The gained sample exposed 1/100 second by SC-39 gelatin light filter (it is Fuji Photo Film Co., the long wavelength light transmitting filter that Ltd. makes, its cutoff wavelength is 390nm) and continuous wedge.The as described below development of FP-360B automatic film developer of using Fuji Photo Film to make.Notice that this developing machine re-constructs, make the overflow solution of bleaching bath can not be carried in next the bath, but all these all are disposed in the waste liquid tank.The FP-360B developing machine is equipped with the evaporation compensated device of describing in Journal ofTechnical Disclosure No.94-4992.

Below will describe development step and washing fluid forms.

Purging method

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

^*Magnitude of recruitment is with the wide sample of the 35mm of the 1.1m value representation of (being equivalent to the effect of 24Ex. film).

Stabilizing agent and stop bath are according to the order convection current of (2) to (1), and all washings overflow part are introduced in the fixing bath (2).What note is, the amount that is carried into developer in the blanching step, is carried into the bleaching liquid in the photographic fixing step and is carried into the fixer in the washing step is respectively 2.5ml, 2.0ml and 2.0ml for the wide photosensitive material of the 35mm of 1.1m.Each intersection time is 6 seconds, and this time was included in the processing time of various processes.

The open area that is used for the above-mentioned developing machine of color developer and bleaching liquid is respectively 100cm ²And 120cm ², and the open area that is used for other solution is about 100cm ²

Shown in washing fluid composed as follows.

Color developer

Form	Jar solution (g)	Replenish liquid (g)
			Diethylene triamine pentacetic acid (DTPA)	3.0	3.0
Catechol-3,5-disulfonic acid disodium	0.3	0.3
			Sodium sulphite	3.9	5.3
Sal tartari	39.0	39.0
			Disodium-N, N-two (2-sulfonic group ethyl) azanol	1.5	2.0
Potassium bromide	1.3	0.3
			Potassium iodide	1.3mg	-
4-hydroxyl-6-methyl isophthalic acid, 3,3a, the 7-purine	0.05	-
			Hydroxylamine sulfate	2.4	3.3
2-methyl-4-[N-ethyl-N-	4.5	6.5

(beta-hydroxy ethyl) amino]-aniline sulfate
			Add and add water to	1.0L	1.0L
PH (regulating) with potassium hydroxide and sulfuric acid	10.05	10.18

Bleaching liquid

Form	Jar solution (g)	Replenish liquid (g)
			1,3-diaminopropanetetraacetic acid iron ammonium dihydrate	113	170
Ammonium bromide	70	105
			Ammonium nitrate	14	21
Succinic acid	34	51
			Maleic acid	28	42
Add and add water to	1.0L	1.0L
			PH (regulating) with ammoniacal liquor	4.6	4.0

Fixer (1) jar solution

5: 95 (V/V) potpourris of above-mentioned bleaching tank solution and following fixing tank solution, pH is 6.8.

Fixer (2)

Form	Jar solution (g)	Replenish liquid (g)
			Thiosulfuric acid aqueous ammonium (750g/L)	240ml	720ml
Imidazoles	7	21
			First thiosulfonic acid ammonium	5	15

First sulfo-sulfinic acid ammonium	10	30
			Ethylenediamine tetraacetic acid	13	39
Add and add water to	1L	1L
			PH (regulating) with ammoniacal liquor and acetate	7.4	7.45

Washings

Tap water is delivered in the mixed bed column, and this column filling has H type strong-acid cation-exchange resin (Amberlite IR-120B: can be from Rohm ﹠amp; Haas Co. obtains) and OH type alkali anion exchange resins (Amberlite IR-400), the concentration of calcium and magnesium is set at 3mg/l or lower.Subsequently, add the isocyanuric acid dichloride sodium of 20mg/l and the sodium sulphate of 0.15g/l.The pH scope of solution is 6.5-7.5.

Stabilizing agent

Form	Jar solution and additional liquid phase are with (g)
		SPTS	0.03
The single nonylplenyl ether (average degree of polymerization 10) of polyoxyethylene-p-	0.2
		1,2-benzisothiazole-3-ketone sodium	0.10
Disodium ethylene diamine tetraacetate	0.05
		1,2, the 4-triazole	1.3
1,4-two (1,2,4-triazole-1-ylmethyl) piperazine	0.75
		Add and add water to	1.0L

pH

8.5

As shown in table 7, adopt solvent of the present invention can obtain light sensitivity height and the improved intensifying material of development dependence.

Table 7

Sample	Explanation	Emulsion	Standard is developed		Half supplementary rate
							Ashing	Light sensitivity	Ashing	Light sensitivity
			201	Comparative Examples	o	0.14					100	0.11	79
201	The present invention	r					0.13	131	0.11	118

Embodiment 5

Below description is helped induced fluorescence of the present invention.

Gelatin-1 to the gelatin-5 that is used as dispersion medium in emulsion described below has following character.

Gelatin-1: the bone collagen gelatin of making by ox bone of conventional alkali treatment.In this gelatin, do not have-NH ₂Group is by chemical modification.

Gelatin-2: it is the following gelatin that makes: add phthalic anhydride and cause chemical reaction under the condition of 50 ℃ and pH9.0 in the aqueous solution of gelatin-1, remove residual phthalic acid, then the material of dry gained.In the gelatin chemical modification-NH ₂The quantity ratio of group is 95%.

Gelatin-3: it is the following gelatin that makes: add trimellitic anhydride and cause chemical reaction under the condition of 50 ℃ and pH9.0 in the aqueous solution of gelatin-1, remove residual trimellitic acid, then the material of dry gained.In the gelatin chemical modification-NH ₂The quantity ratio of group is 95%.

Gelatin-4: it is the following gelatin that makes: make enzyme act on gelatin-1, reduce the molecular weight of this gelatin, make that mean molecular weight is 15000, make enzyme deactivation, then the material of dry gained.In this gelatin, do not have-NH ₂Group is by chemical modification.

Gelatin-5: it is by making hydrogen peroxide act on the gelatin that forms with oxidation methionine group on the gelatin-4.Methionine content is 3.4mol/g.Molecular weight is 15000, and is identical with gelatin-4.In this gelatin, do not have-NH ₂Group is by chemical modification.

All above-mentioned gelatin-1 to gelatin-5 all is deionization, and is 6.0 at 35 ℃ of pH that regulate its 5% aqueous solution.

The preparation of emulsion A-1

Stir the aqueous solution 1300ml (first formulations prepared from solutions) that comprises 1.0g potassium bromide and 1.1g aforesaid gelatin-4 down at 35 ℃.In 30 seconds time, add aqueous solution X-1 (in 100ml, comprising the 5.2g potassium bromide) and the 4ml aqueous solution G-1 (in 100ml, comprising 8.0g aforesaid gelatin-4) of (adding 1) 18ml water solution A g-1 (silver nitrate that in 100ml, comprises 4.9g), 13.8ml with fixed rate with three gunitees.Afterwards, add the potassium bromide of 6.5g, elevate the temperature then to 75 ℃.Carry out maturing step after 12 minutes, adding 300ml aqueous solution G-2 (in 100ml, comprising 12.7g aforesaid gelatin-3).Order is added 4 of 2.1g, 5-dihydroxy-1, the thiourea dioxide of 3-disulfonic acid disodium salt monohydrate and 0.002g in 1 minute interval.

Next, in 14 minutes time, add water solution A g-2 (silver nitrate that in 100ml, comprises 22.1g) and the aqueous solution X-2 (potassium bromide that in 100ml, comprises 15.5g) of 157ml by two gunitees.The flow velocity of water solution A g-2 during accelerating to add makes that final flow rate is 3.4 times of initial flow rate.Also add aqueous solution X-2, make that the pAg of raw emulsion is 8.30 (adding 2) in the reaction vessel.Subsequently, in 27 minutes time, add water solution A g-3 (silver nitrate that in 100ml, comprises 32.0g) and the aqueous solution X-3 (in 100ml, comprising the potassium bromide of 21.5g and the potassium iodide of 1.2g) of 329ml by two gunitees.The flow velocity of water solution A g-3 during accelerating to add makes that final flow rate is 1.6 times of initial flow rate.Equally, add aqueous solution X-3, make that the pAg of raw emulsion is 8.30 (adding 3) in the reaction vessel.In addition, in 17 minutes time, add water solution A g-4 (silver nitrate that in 100ml, comprises 32.0g) and the aqueous solution X-4 (potassium bromide that in 100ml, comprises 22.4g) of 156ml by two gunitees.Add water solution A g-4 with constant flow rate.With adding aqueous solution X-4, make that the pAg of raw emulsion is 8.15 (adding 4) in the reaction vessel.

Afterwards, add 0.0025g sodium benzenethiosulfonate and 125ml aqueous solution G-3 (in 100ml, comprising 12.0g aforesaid gelatin-1) with 1 minute intervening sequences.Add the potassium bromide of 43.7g then, the pAg of raw emulsion is 9.00 in the conditioned reaction container.Add the silver iodide fine particle emulsion (comprising the 13.0g mean grain size in 100g is the silver iodide fine grained of 0.047 μ m) of 73.9g.After 2 minutes, add 249ml water solution A g-4 and aqueous solution X-4 by two gunitees.In 9 minutes time, add water solution A g-4 with fixed rate.The interpolation of aqueous solution X-4 was only carried out at 3.3 minutes, made that the pAg of raw emulsion remains on 9.00 in the reaction vessel.In remaining 5.7 minutes, do not add aqueous solution X-4, make that the pAg of raw emulsion finally is 8.4 (adding 5) in the reaction vessel.Afterwards, carry out desalination by normal flocculation.Stirring and 56 ℃ of following interpolation water, NaOH and aforesaid gelatin-1, and respectively pH and pAg are being adjusted to 6.4 and 8.6.

The sheet silver halide particle that constitutes gained emulsion has following feature: waiting bulb diameter is 1.47 μ m, and equal circle diameter is 2.57 μ m, and thickness is 0.32 μ m, and average aspect ratio is 8.0, and average A gI content is 3.94mol%.The first type surface that platy shaped particle is parallel to each other is (111) crystal face, and AgI content is 2.1mol% through XPS measuring on the silver halide particle surface.

Subsequently, sequentially add sensitizing dye Exs-1, potassium rhodanide, gold chloride, sodium thiosulfate and N as described below, N-dimethyl selenourea carries out chemical sensitization to emulsion thus best.Add water-soluble sulfhydryl compound MER-1 and MER-2 as follows with 4: 1 ratios, make that total amount is that every mol silver halide is 3.6 * 10 ^-4Mol, thus this chemical sensitization finished.

Sensitizing dye of the present invention uses with the form of thin solid dispersions, and it is to form with the method described in the JP-A-11-52507.That is to say, the sodium nitrate of 0.8 weight portion and the sodium sulphate of 3.2 weight portions are dissolved in the ion exchange water of 43 weight portions, use the dissolver blade of 2000rpm rotating speed to disperse this material 20 minutes down then, obtain the thin solid dispersions of sensitizing dye Exs-1 thus at 60 ℃.

Emulsion A-2 preparation

Change the preparation condition of above-mentioned emulsion A-1 in the following manner, prepare emulsion A-2 thus:

1. after (add 4) finishes, in 10min, cool the temperature to 55 ℃, add 18.5gKBr then, the pAg value of raw emulsion in the reactor is adjusted to 9.51.

2. prepare the AgI fine particle emulsion that 2min adds before (adding 5) operation in accordance with the following methods.(every 100mL contains AgNO to add water solution A g-5 simultaneously in outside of the present invention is equipped with the mixer of reactor ₃7.31g) and aqueous solution X-5 (every 100mL contains KI22.4g and gelatin-47.4g), preparation fine particle emulsion (contain the thin silver iodide particle of 13.0g, it on average waits bulb diameter is 0.025 μ m, and size distribution is 28%).

Gained emulsion is similar through bulb diameters such as XPS mensuration, aspect ratio, silver halide particle surfaces A gI content and emulsion A-1.

When the consumption of sensitizing dye Exs-1 is identical with emulsion A-1, can reach optimum chemical sensitizing.

The preparation of emulsion A-3

Change the preparation condition of above-mentioned emulsion A-1 in the following manner, prepare emulsion A-3 thus:

1. after (add 4) finishes, in 10min, cool the temperature to 55 ℃, add 10.8gKBr then, the pAg value of raw emulsion in the reactor is adjusted to 9.36.

2. prepare the AgI fine particle emulsion that 2min adds before (adding 5) operation in accordance with the following methods.(every 100mL contains AgNO to add water solution A g-5 simultaneously in outside of the present invention is equipped with the mixer of reactor ₃10.96g) and aqueous solution X-5 (every 100mL contains KI 10.95g and gelatin-4 11.1g), preparation fine particle emulsion (contain the thin silver iodide particle of 13.0g, it on average waits bulb diameter is 0.010 μ m, and size distribution is 22%).

Gained emulsion is similar through bulb diameters such as XPS mensuration, aspect ratio, silver halide particle surfaces A gI content and emulsion A-1.

When the consumption of sensitizing dye Exs-1 is identical with emulsion A-1, can reach optimum chemical sensitizing.

Emulsion B-1 preparation

Change the preparation condition of above-mentioned emulsion A-1 in the following manner, prepare emulsion B-1 thus:

1. rise to 75 ℃ and the gelatin in the G-2 aqueous solution-2 that carries out being added after the slaking of 12min in temperature and become gelatin-3.

2. change the interpolation flow velocity of Ag-2 aqueous solution in (adding 2), make the interpolation time become 14 minutes and 30 seconds, addition remains 157mL simultaneously.Accelerate flow velocity and make that final flow rate is 3.4 times of initial flow rate.The interpolation of X-2 aqueous solution simultaneously makes that the pAg value of raw emulsion remains 8.30 in the reactor.

3. change the interpolation flow velocity of Ag-3 aqueous solution in (adding 3), make the interpolation time become 34min, addition remains 329mL simultaneously.Accelerate flow velocity and make that final flow rate is 1.6 times of initial flow rate.The interpolation of X-3 aqueous solution simultaneously makes that the pAg value of raw emulsion remains 8.30 in the reactor.

The sheet silver halide particle that reaction product emulsion contains, its bulb diameter such as grade is 1.47 μ m, and equal circle diameter is 3.52 μ m, and average thickness is 0.17 μ m, and average aspect ratio is 15.0, average A gI content is 3.94mol.The parallel first type surface of platy shaped particle is (111) crystal face.The AgI content on silver halide particle surface is determined as 2.1mol% by XPS.The total projection area 60% or more be that 3.5 μ m or bigger, thickness are that the littler platy shaped particle of 0.19 μ m occupies by equal circle diameter.

Then add above-mentioned sensitizing dye Exs-1, potassium rhodanide, gold chloride, sodium thiosulfate and N, N-dimethyl selenourea carries out optimum chemical sensitizing to emulsion.The chemical sensitization effect is following to be finished: additional proportion is 4: 1 following sulfhydryl compound MER-1 and MER-2, and in every mole of silver halide, its total consumption is 1.75 * 10 ^-3Mole.In every mole of silver halide, add 2.07 * 10 ^-3Emulsion B-1 can reach optimum chemical sensitizing during molExs-1.

Emulsion B-2 preparation

Change the preparation condition of above-mentioned emulsion B-1 in the following manner, prepare emulsion B-2 thus:

1. the interpolation of aqueous solution X-2 makes that the pAg value of raw emulsion remains 8.19 in the reactor in (add 2).

2. after (add 4) finishes, in 10min, cool the temperature to 55 ℃, add 15.8g KBr then the pAg value of raw emulsion in the reactor is adjusted to 9.51.

3. prepare the AgI fine particle emulsion that 2min adds before (adding 5) operation in accordance with the following methods.(every 100mL contains AgNO to add water solution A g-5 simultaneously in outside of the present invention is equipped with the mixer of reactor ₃7.31g) and aqueous solution X-5 (every 100mL contains the preparation fine particle emulsion (comprise 13.0g AgI fine grained, it on average waits bulb diameter is 0.025 μ m) of KI 7.3g and gelatin-47.4g).

Gained emulsion is similar through bulb diameters such as XPS mensuration, aspect ratio, silver halide particle surfaces A gI content and emulsion B-1.

When the consumption of sensitizing dye Exs-1 is identical with emulsion B-1, can reach optimum chemical sensitizing.

Emulsion B-3 preparation

Change the preparation condition of above-mentioned emulsion B-1 in the following manner, prepare emulsion B-3 thus:

1. in (add 2 and add 3), add X-2 and X-3 aqueous solution respectively and make that the pAg value of raw emulsion remains 8.19 in the reactor.

2. after (add 4) finishes, in 10min, cool the temperature to 55 ℃, add 10.8g KBr then the pAg value of raw emulsion in the reactor is adjusted to 9.36.

In (adding 4), the ratio of the thickness of growing on thickness of growing on the first type surface direction and side surface direction is 0.055.

3. prepare the AgI fine particle emulsion that 2min adds before (adding 5) operation in accordance with the following methods.(every 100mL contains AgNO to add the Ag-5 aqueous solution simultaneously in outside of the present invention is equipped with the mixer of reactor ₃10.96g) and X-5 aqueous solution (every 100mL contains KI 10.95g and gelatin-4 11.1g) preparation fine particle emulsion (comprise 13.0g AgI fine grained, it on average waits bulb diameter is 0.010 μ m).

Gained emulsion is through bulb diameters such as XPS mensuration, aspect ratio, and silver halide particle surfaces A gI content and emulsion B-1 are similar.When wherein adopting the irradiation of 325nm electromagnetic beam during 6 ° of K, emulsion produces the 575nm induced fluorescence, and its intensity is 50% of the hyperfluorescence emission that induces in 490 to the 560nm wavelength coverages at least.

When the consumption of sensitizing dye Exs-1 is identical with emulsion B-1, can reach optimum chemical sensitizing.

Emulsion B-4 preparation

Change the preparation condition of above-mentioned emulsion B-1 in the following manner, prepare emulsion B-4 thus:

1. in (add 3), add the X-3 aqueous solution and make that the pAg value of raw emulsion remains 8.19 in the reactor.

2. change the interpolation flow velocity of Ag-2 aqueous solution in (adding 2), make the interpolation time become 16 minutes and 30 seconds, addition remains 157mL simultaneously.Accelerate flow velocity and make that final flow rate is 3.4 times of initial flow rate.The interpolation of X-2 aqueous solution simultaneously makes that the pAg value of raw emulsion remains 8.15 in the reactor.

3. change the interpolation flow velocity of Ag-3 aqueous solution in (adding 3), make the interpolation time become 38min, addition remains 329mL simultaneously.Accelerate flow velocity and make that final flow rate is 1.6 times of initial flow rate.The interpolation of X-3 aqueous solution simultaneously makes that the pAg value of raw emulsion remains 8.15 in the reactor.

4. the interpolation flow velocity that changes Ag-4 aqueous solution in (adding 4) makes the interpolation time become 13min, and addition remains 156mL simultaneously.Accelerate flow velocity and make that final flow rate is 1.6 times of initial flow rate.The interpolation of X-4 aqueous solution simultaneously makes that the pAg value of raw emulsion remains 8.15 in the reactor.In (add 4), on thickness of growing on the first type surface direction and side surface direction, grow the ratio of thickness be 0.03.

5. prepare the AgI fine particle emulsion that 2min adds before (adding 5) operation in accordance with the following methods.(every 100mL contains AgNO to add the Ag-5 aqueous solution simultaneously in outside of the present invention is equipped with the mixer of reactor ₃10.96g) and X-5 aqueous solution (every 100mL contains KI 10.95g and gelatin-4 11.1g) preparation fine particle emulsion (comprise 13.0g AgI fine grained, it on average waits bulb diameter is 0.010 μ m).

Gained emulsion is similar through bulb diameters such as XPS mensuration, aspect ratio, silver halide particle surfaces A gI content and emulsion B-1.

When the consumption of sensitizing dye Exs-1 is identical with emulsion B-1, can reach optimum chemical sensitizing.

Emulsion C-1 preparation

Change the preparation condition of above-mentioned emulsion B-1 in the following manner, prepare emulsion C-1 thus:

1. (adding 2) changes by following:

(every 100mL contains AgNO to add 157mL Ag-2 aqueous solution simultaneously in outside of the present invention is equipped with the mixer of reactor in 28min ₃22.1g) and 157mL X-6 aqueous solution (every 100mL contains KBr 15.5g and gelatin-4 23.1g).Prepared AgBr fine particle emulsion (the fine grain average bulb diameter such as grade of AgBr is 0.025 μ m) is added in the reactor continuously.During the interpolation in the reactor pAg value of raw emulsion remain 8.30.

2. (adding 3) changes by following:

(every 100mL contains AgNO to add 329mL Ag-3 aqueous solution simultaneously in outside of the present invention is equipped with the mixer of reactor in 53min ₃32.0g) and 329mL X-7 aqueous solution (every 100mL contains KBr 21.5g, 1.5g KI and gelatin-4 33.1g).Prepared AgBr fine particle emulsion (the fine grain average bulb diameter such as grade of AgBrI is 0.028 μ m) is added in the reactor continuously.During the interpolation in the reactor pAg value of raw emulsion remain 8.30.

Gained emulsion contains the sheet silver halide particle, and its bulb diameter such as grade is 1.47 μ m, and equal circle diameter is 4.35 μ m, and thickness is 0.112 μ m, and average aspect ratio is 33.8, and average A gI content is 3.94mol.The parallel first type surface of platy shaped particle is (111) crystal face.The AgI content on silver halide particle surface is determined as 2.1mol% by XPS.The total projection area 60% or more be that 4.0 μ m or bigger, thickness are that the littler platy shaped particle of 0.14 μ m occupies by equal circle diameter.

Then add above-mentioned sensitizing dye Exs-1, potassium rhodanide, gold chloride, sodium thiosulfate and N, N-dimethyl selenourea carries out optimum chemical sensitizing to emulsion.The chemical sensitization effect is following to be finished: additional proportion is 4: 1 following sulfhydryl compound MER-1 and MER-2, and in every mole of silver halide, its total consumption is 2.9 * 10 ^-3Mole.In every mole of silver halide, add 3.41 * 10 ^-3Emulsion C-1 can reach optimum chemical sensitizing during molExs-1.

Emulsion C-2 preparation

Change the preparation condition of above-mentioned emulsion C-1 in the following manner, prepare emulsion C-2 thus:

1. in (add 2 and add 3), add X-2 and X-3 aqueous solution respectively and make that the pAg value of raw emulsion remains 8.19 in the reactor.

2. after (add 4) finishes, in 10min, cool the temperature to 55 ℃, add 15.8g KBr then the pAg value of raw emulsion in the reactor is adjusted to 9.51.

3. prepare the AgI fine particle emulsion that 2min adds before (adding 5) operation in accordance with the following methods.(every 100mL contains AgNO to add the Ag-5 aqueous solution simultaneously in outside of the present invention is equipped with the mixer of reactor ₃7.31g) and X-5 aqueous solution (every 100mL contains KI 7.3g and gelatin-4 7.4g) preparation fine particle emulsion (comprise 13.0g AgI fine grained, it on average waits bulb diameter is 0.025 μ m).

Gained emulsion is similar through bulb diameters such as XPS mensuration, aspect ratio, silver halide particle surfaces A gI content and emulsion C-1.

When the consumption of sensitizing dye Exs-1 is identical with emulsion C-1, can reach optimum chemical sensitizing.

Emulsion C-3 preparation

Change the preparation condition of above-mentioned emulsion C-1 in the following manner, prepare emulsion C-3 thus:

1. in (add 2 and add 3), add X-2 and X-3 aqueous solution respectively and make that the pAg value of raw emulsion remains 8.01 in the reactor.

2. after (add 4) finishes, in 10min, cool the temperature to 55 ℃, add 15.8g KBr then the pAg value of raw emulsion in the reactor is adjusted to 9.51.

In (adding 4), the ratio of the thickness of growing on thickness of growing on the first type surface direction and side surface direction is 0.055.

3. prepare the AgI fine particle emulsion that 2min adds before (adding 5) operation in accordance with the following methods.(every 100mL contains AgNO to add the Ag-5 aqueous solution simultaneously in outside of the present invention is equipped with the mixer of reactor ₃7.31g) and the X-5 aqueous solution (every 100mL contains the preparation fine particle emulsion (comprise 13.0g AgI fine grained, it on average waits bulb diameter is 0.010 μ m) of KI 7.3g and gelatin-47.4g).

Gained emulsion is similar through bulb diameters such as XPS mensuration, aspect ratio, silver halide particle surfaces A gI content and emulsion C-1.When wherein adopting the irradiation of 325nm electromagnetic beam during 6 ° of K, emulsion produces the 575nm induced fluorescence, and its intensity is 45% of the hyperfluorescence emission that induces in 490 to the 560nm wavelength coverages at least.

When the consumption of sensitizing dye Exs-1 is identical with emulsion C-1, can reach optimum chemical sensitizing.

Adopt the above-mentioned emulsion of transmission electron microscope observing A-1 to A-3, B-1 to B-4 and the C-1 to C-3 of 400-KV.Found that in emulsion A-1 to A-3, B-3, B-4 and C-3 and have 30 dislocation lines at least at platy shaped particle side crystal face.But on the first type surface of emulsion B-4, also observed dislocation line.

Attention adds 4 before at once (the adding 2) of emulsion preparation process in emulsion A-1 to A-3, B-1 to B-4 and C-1 to C-3,5-dihydroxy benzenes-1, and 3-disulfonic acid disodium and thiourea dioxide carry out reduction sensitization thus.

And, in making, emulsion adds sensitizing dye Exs-1 in the chemical sensitization step, and emulsion A-1 to A-3, B-1 to B-4 and C-1 to C-3 carry out spectral sensitization.Make that these emulsions are green silver halide emulsion, its spectral sensitivity is maximum at wavelength 55nm place.

According to the coating condition shown in embodiment 1 table 2 emulsion A-1 to A-3, B-1 to B-4 and C-1 to C-3 are applied on the cellulose triacetate carrier with undercoat.

The gained sample is carried out film sclerosis 14hr under 40 ℃, the condition of relative humidity 70%.The gained sample is by Fuji Photo Film Co., Ltd. the SC-50 gelatin filter of Zhi Zaoing (transmission long wave optical filter, cutoff wavelength 500nm) and continuous wedge exposure 1/100sec, and by program development (except that the time of colour development is changed to 2 minutes 45 seconds) same among the embodiment 1 develop.Each its photographic property of the sample of handling is assessed with a green filter density measurement.Light sensitivity is the relative value of the reciprocal value of required exposure amount when producing the density of ashing density+0.2.

Sample 101 to 110 corresponding and emulsion emulsion A-1 to A-3, B-1 to B-4 and the C-1 to C-3 that coat.From table 8 listed result as can be seen, the condition of claim 3 defined shows in high aspect ratio, large-size particle emulsion obviously the effect of light sensitivity.

Table 8

Sample number	The green silver halide sheet emulsion grain that is adopted
						Emulsion number	Equal circle diameter (μ m)	Thickness (μ m)	Aspect ratio	Silver iodide size (μ m) (variation factor (%))
	101 (Comparative Examples)	A-1	2.57	0.32	8						0.047(10.0)
102 (Comparative Examples)						A-2	2.57	0.32	8	0.025(28.0)
	103 (Comparative Examples)	A-3	2.57	0.32	8						0.010(22.0)
104 (the present invention)						B-1	3.52	0.17	20.7	0.047(10.0)
	105 (the present invention)	B-2	3.52	0.17	20.7						0.025(28.0)
106 (the present invention)						B-3	3.52	0.17	20.7	0.010(22.0)
	107 (the present invention)	B-4	3.52	0.17	20.7						0.010(22.0)
108 (the present invention)						C-1	4.53	0.112	38.8	0.047(10.0)
	109 (the present invention)	C-2	4.53	0.112	38.8						0.025(28.0)
110 (the present invention)						C-3	4.53	0.112	38.8	0.010(22.0)

(continuation)

Table 8

Sample number
					Quantity at the edge dislocation line	The emission at 575nm place (%)	Light sensitivity	Graininess
	101 (Comparative Examples)	Greatly	50	97					98
102 (Comparative Examples)					Greatly	50	100	100
	103 (Comparative Examples)	Greatly	50	104					100
104 (the present invention)					Little	25	87	94
	105 (the present invention)	Normally	35	100					100
106 (the present invention)					Greatly	50	120	108
	107 (the present invention)	A bit big, be present in the crystal face	45	109					104
108 (the present invention)					Very little	15	70	85
	109 (the present invention)	Little	25	100					100
110 (the present invention)					Greatly	45	138	110

^*Light sensitivity and graininess are relative values, wherein hypothesis:

For sample 101 to 103, sample 102 is 100,

For sample 104 to 107, sample 105 be 100 and

For sample 108 to 110, sample 109 is 100,

^*The big more light sensitivity of numerical value is big more, and numerical value bulky grain more is high more.

Embodiment 6

Present embodiment shows, as the equal circle diameter that comprises sheet silver emulsion in the photographic emulsion of platy shaped particle is when increasing, and has invalid phenomenon in equal circle diameter 3.5 μ m or the bigger zone, and improves corresponding to the light sensitivity that granule surface area increases and to be difficult to realize.Show equally in the present embodiment that the present invention has the silver emulsion of hole capture band than those silver emulsions that does not have the hole capture band, and higher light sensitivity absolute value and lower ineffectivity are arranged.

Be used to gelatin for preparing silver emulsion and preparation method thereof

Gelatin-1 to the gelatin-3 that is used to prepare the protective colloid dispersion medium has following characteristic:

Gelatin-1: the bone collagen gelatin that the conventional base of being made by ox bone is handled, in the gelatin-NH ₂Group is not by chemical modification.

Gelatin-2: under 50 ℃, pH9.0 condition, succinic anhydride added in gelatin-1 aqueous solution chemical reaction takes place, remove remaining succinic acid, dry reaction product and forming.In this gelatin-NH ₂Group chemical modification rate is 95%.

Gelatin-3: by the enzyme effect molecular weight of gelatin-1 being reduced to mean molecular weight is 15,000, makes enzyme deactivation, dry reaction product and forming.In this gelatin-NH ₂Group is not by chemical modification.

Above-mentioned all gelatin-1 to gelatin-3 through deionization, transfer to 6.0 25 ℃ of pH value of water solution with 5%.

Be used for the preparation of the thin solid dispersion of sensitizing dye of silver emulsion spectral sensitization

In following emulsion preparation, the sensitizing dye preparation method with the effect of thin solid dispersion form who is used for spectral sensitization has explanation at JP-A-11-52507.For example, the thin solid dispersion of sensitizing dye Exs-11, Exs-14 and Exs-15 is prepared as follows: the NaNO of 0.8 weight portion ₃With 3.2 weight portion Na ₂SO ₄Add in the ion exchange water of 43 weight portions, and will be altogether sensitizing dye Exs-11, Exs-14 and the Exs-15 of 3 weight portions add at 76: 18: 6 with mol ratio, with 2,000rpm was 60 ℃ of raw material dispersion 20 minutes with the dissolver lodicule.

The preparation of emulsion EM-1A

Stir the aqueous solution 1300ml (first formulations prepared from solutions) that comprises 1.0g potassium bromide and 1.1g aforesaid gelatin-3 down at 35 ℃.In 30 seconds time, add aqueous solution X-1 (in 100ml, comprising the 3.2g potassium bromide) and the 12ml aqueous solution G-1 (in 100ml, comprising 4.8g gelatin-3) of (adding 1) 54ml water solution A g-1 (silver nitrate that in 100ml, comprises 3.0g), 41ml with fixed rate with three gunitees.Afterwards, add the potassium bromide of 6.3g, elevate the temperature then to 75 ℃, with ripe material.Before finishing, maturation adds 300ml aqueous solution G-2 (in 100ml, comprising 12.7g aforesaid gelatin-2) immediately.

Next, in 33 minutes time, add water solution A g-2 (silver nitrate that in 100ml, comprises 22.1g) and the aqueous solution X-2 (potassium bromide that in 100ml, comprises 15.5g) of 157ml by two gunitees.The flow velocity of water solution A g-2 during accelerating to add makes that final flow rate is 3.4 times of initial flow rate.Also add aqueous solution X-2, make that the pAg of raw emulsion is 8.30 (adding 2) in the reaction vessel.

Subsequently, in 57 minutes time, add water solution A g-3 (silver nitrate that in 100ml, comprises 32.0g) and the aqueous solution X-3 (in 100ml, comprising the potassium bromide of 21.5g and the potassium iodide of 1.2g) of 329ml by two gunitees.The flow velocity of water solution A g-3 during accelerating to add makes that final flow rate is 1.6 times of initial flow rate.Also add aqueous solution X-3, make that the pAg of raw emulsion is 8.30 (adding 3) in the reaction vessel.

In addition, in 18 minutes time, add water solution A g-4 (silver nitrate that in 100ml, comprises 32.0g) and the aqueous solution X-4 (potassium bromide that in 100ml, comprises 22.4g) of 156ml by two gunitees.Add water solution A g-4 with constant flow rate.Add aqueous solution X-4, make in 9 minutes that the pAg of raw emulsion is 8.30 in the reaction vessel, and in remaining 9 minutes in the reaction vessel pAg of raw emulsion be 6.70 (adding 4).

Afterwards, add 0.0025g sodium benzenethiosulfonate and 125ml aqueous solution G-3 (in 100ml, comprising 12.0g aforesaid gelatin-1), and temperature is reduced to 55 ℃ with 1 minute intervening sequences.Add the potassium bromide of 11.8g then, the pAg of raw emulsion is 9.35 in the conditioned reaction container.Afterwards, in 1 minute 40 seconds time, add the silver iodide fine particle emulsion that particle diameter is 0.009 μ m (following preparation immediately before interpolation: mixed nitrate brine solution, potassium iodide aqueous solution and gelatin-3 aqueous solution in described another chamber with magnetic coupling induction type stirrer) (interpolation 5) with the amount that is equivalent to 6.95g nitrate as JP-A-10-43570 with fixing speed.After 10 seconds after interpolation 5 beginnings, add 249ml water solution A g-4 and aqueous solution X-4 by two gunitees.In 21 minutes time, add water solution A g-4 with fixed rate.The interpolation of aqueous solution X-4 was only carried out at 18 minutes, made that the pAg of raw emulsion remains on 9.35 in the reaction vessel.In remaining 3 minutes, do not add aqueous solution X-4, make that the pAg of raw emulsion finally is 9.0 (adding 6) in the reaction vessel.Afterwards, carry out desalination by normal flocculation.Stirring and 56 ℃ of following interpolation water, NaOH and aforesaid gelatin-1, and respectively pH and pAg are being adjusted to 5.8 and 8.8.

Gained emulsion comprises the sheet silver halide particle, and the average bulb diameter such as grade of this particle is 1.04 μ m, and the average equal circle diameter of first type surface is 2.03 μ m, the particle average thickness is 0.18 μ m, average aspect ratio is 11.3, and the variation factor of equal circle diameter is 18.7%, and average A gI content is 3.94mol%.The parallel first type surface of platy shaped particle is (111) crystal face.The content of silver halide particle surfaces A gI is 2.8mol% through XPS measuring.

Then, be 76: 18: 6 following sensitizing dye Exs-11 by adding mol ratio, Exs-14 and Exs-15 then add potassium rhodanide, gold chloride, sodium thiosulfate and N then, and N-dimethyl selenourea is so that emulsion optimum chemical sensitizing.The chemical sensitization effect is following finishing: additional proportion is 4: 1 following sulfhydryl compound MER-1 and MER-2, and total amount is every mole of silver halide 3.6 * 10 ^-4The mole sulfhydryl compound.When sensitizing dye adds 6.90 * 10 by every mole of silver halide ^-4During mol, emulsion EM-1A can be optimized sensitizing.

Emulsion EM-2A preparation

Change the preparation condition of above-mentioned emulsion EM-1A in the following manner, prepare emulsion EM-2A thus:

1. the addition of Ag-1, X-1 and G-1 aqueous solution is become 29.4,22.6 and 6.7mL respectively in (add 1).

2. the KBr that adds at once after (adding 1) is become 6.8g.

3. the joining day of (add 1), (adding 3), (adding 4) and (adding 6) increases by 1.22 times, and 0.82 times of corresponding flow velocity increase.

Gained emulsion contains the sheet silver halide particle, and the bulb diameter such as grade of this particle is 1.27 μ m, and the average equal circle diameter of first type surface is 2.55 μ m, average particle thickness is 0.21 μ m, average aspect ratio is 12.1, and the equal circle diameter variation factor is 19.5%, and average A gI content is 3.94mol%.The parallel first type surface of platy shaped particle is (111) crystal face.The AgI content on silver halide particle surface is determined as 2.5mol% by XPS.

When sensitizing dye is pressed every mole of silver halide 5.86 * 10 ^-4Mol adds fashionable, and emulsion EM-2A can be optimized sensitizing.

The preparation of emulsion EM-3A

Change the preparation condition of above-mentioned emulsion EM-1A in the following manner, prepare emulsion EM-3A thus:

1. the addition of Ag-1, X-1 and G-1 aqueous solution is become 19.2,6.4 and 4.4mL respectively in (add 1).

2. the KBr that adds at once after (adding 1) is become 7.5g.

3. the joining day of (add 1), (adding 3), (adding 4) and (adding 6) increases by 1.42 times, and 0.7 times of corresponding flow velocity increase.

Gained emulsion contains the sheet silver halide particle, and the bulb diameter such as grade of this particle is 1.47 μ m, and the average equal circle diameter of first type surface is 3.02 μ m, average particle thickness is 0.23 μ m, average aspect ratio is 13.1, and the equal circle diameter variation factor is 20.0%, and average A gI content is 3.94mol%.The parallel first type surface of platy shaped particle is (111) crystal face.The AgI content on silver halide particle surface is determined as 2.3mol% by XPS.In this emulsion, all projected areas 50% or mostly be to be that 3.5 μ m or more and grain thickness 0.25 μ m or less silver halide particle occupy by equal circle diameter.

When sensitizing dye is pressed every mole of silver halide 5.30 * 10 ^-4Mol adds fashionable, and emulsion EM-3A can be optimized sensitizing.

Emulsion EM-4A preparation

Change the preparation condition of above-mentioned emulsion EM-1A in the following manner, prepare emulsion EM-4A thus:

1. the addition of Ag-1, X-1 and G-1 aqueous solution is become 14.0,12.3 and 3.7mL respectively in (add 1).

2. the KBr that adds at once after (adding 1) is become 8.6g.

3. the joining day of (add 2), (adding 3), (adding 4) and (adding 6) increases by 1.59 times, and 0.63 times of flow rate corresponding increase.

Products therefrom emulsion contains the sheet silver halide particle, and the bulb diameter such as grade of this particle is 1.62 μ m, and the average equal circle diameter of first type surface is 3.45 μ m, average particle thickness is 0.24 μ m, average aspect ratio is 14.4, and the equal circle diameter variation factor is 20.5%, and average A gI content is 3.94mol%.The parallel first type surface of platy shaped particle is (111) crystal face.The AgI content on silver halide particle surface is determined as 2.0mol% by XPS.In this emulsion, all projected areas 50% or mostly be to be that 3.5 μ m or more and grain thickness 0.25 μ m or less silver halide particle occupy by equal circle diameter.

When sensitizing dye is pressed every mole of silver halide 5.05 * 10 ^-4Mol adds fashionable, and emulsion EM-4A can be optimized sensitizing.

Emulsion EM-5A preparation

Change the preparation condition of above-mentioned emulsion EM-3A in the following manner, prepare emulsion EM-5A thus:

1. the gelatin-2 in (adding 2) preceding aqueous solution G-2 that adds at once becomes gelatin-1.

2. the pAg value of the initial raw material emulsion in (adding 2), (adding 3) and (adding 4) becomes 7.75.

Gained emulsion contains the sheet silver halide particle, and the bulb diameter such as grade of this particle is 1.47 μ m, and the average equal circle diameter of first type surface is 2.14 μ m, average particle thickness is 0.46 μ m, average aspect ratio is 4.7, and the equal circle diameter variation factor is 16.0%, and average A gI content is 3.94mol%.The parallel first type surface of platy shaped particle is (111) crystal face.The AgI content on silver halide particle surface is determined as 1.7mol% by XPS.

When sensitizing dye is pressed every mole of silver halide 3.30 * 10 ^-4Mol adds fashionable, and emulsion EM-5A can be optimized sensitizing.

Emulsion EM-6A preparation

Change the preparation condition of above-mentioned emulsion EM-3A in the following manner, prepare emulsion EM-6A thus:

1. the gelatin-2 in (adding 2) preceding aqueous solution G-2 that adds at once becomes gelatin-1.

2. the pAg value of the initial raw material emulsion in (adding 2), (adding 3) and (adding 4) becomes 7.95.

Reaction product emulsion contains the sheet silver halide particle, and the bulb diameter such as grade of this particle is 1.47 μ m, and the average equal circle diameter of first type surface is 2.60 μ m, average particle thickness is 0.31 μ m, average aspect ratio is 8.4, and the equal circle diameter variation factor is 17.8%, and average A gI content is 3.94mol%.The parallel first type surface of platy shaped particle is (111) crystal face.The AgI content on silver halide particle surface is determined as 1.9mol% by XPS.

When sensitizing dye is pressed every mole of silver halide 4.24 * 10 ^-4Mol added 1 o'clock, and emulsion EM-6A can be optimized sensitizing.

Emulsion EM-7A preparation

Change the preparation condition of above-mentioned emulsion EM-3A in the following manner, prepare emulsion EM-7A thus:

1. the quantitative change at (adding 2) preceding aqueous solution G-2 that adds at once is 180mL.

2. the pAg value of the initial raw material emulsion in (adding 2), (adding 3) and (adding 4) becomes 8.35.

Gained emulsion contains the sheet silver halide particle, and the bulb diameter such as grade of this particle is 1.47 μ m, and the average equal circle diameter of first type surface is 3.74 μ m, average particle thickness is 0.15 μ m, average aspect ratio is 24.9, and the equal circle diameter variation factor is 23.2%, and average A gI content is 3.94mol%.The parallel first type surface of platy shaped particle is (111) crystal face.The AgI content on silver halide particle surface is determined as 2.7mol% by XPS.In this emulsion, all projected areas 50% or mostly be by etc. the circle size diameter be that 3.5 μ m or more and grain thickness 0.15 μ m or silver halide particle still less occupy.

When sensitizing dye is pressed every mole of silver halide 7.62 * 10 ^-4Mol adds fashionable, and emulsion EM-7A can be optimized sensitizing.

Emulsion EM-8A preparation

Change the preparation condition of above-mentioned emulsion EM-3A in the following manner, prepare emulsion EM-8A thus:

1. the amount at (adding 2) preceding aqueous solution G-2 that adds is at once become 100mL.

2. the pAg value of the initial raw material emulsion in (adding 2), (adding 3) and (adding 4) becomes 8.45.

3. raw emulsion pAg value 6.7 the time of being controlled in reduces by half in the second half section of (add 4), is the interpolation time that compensation reduces, and increases (adding 4) middle starting stage raw emulsion pAg value and is controlled in time of 8.45.

Gained emulsion contains the sheet silver halide particle, and the bulb diameter such as grade of this particle is 1.47 μ m, and the average equal circle diameter of first type surface is 4.65 μ m, average particle thickness is 0.097 μ m, average aspect ratio is 47.9, and the equal circle diameter variation factor is 29.8%, and average A gI content is 3.94mol%.The parallel first type surface of platy shaped particle is (111) crystal face.The AgI content on silver halide particle surface is determined as 3.3mol% by XPS.In this emulsion, all projected areas 50% or mostly be to be that 3.5 μ m or more and grain thickness are that 0.10 μ m or silver halide particle still less occupy by equal circle diameter.

When sensitizing dye is pressed every mole of silver halide 1.12 * 10 ^-4Mol adds fashionable, and emulsion EM-8A can be optimized sensitizing.

Emulsion EM-1B is to the preparation of EM-8B

Change the preparation condition of above-mentioned emulsion EM-1A to EM-8A in the following manner, prepare emulsion EM-1B to EM-8B thus:

1. add the 0.002g thiourea dioxide at once before and after adding the G-2 aqueous solution (adding 2).

Emulsion EM-1C is to the preparation of EM-8C

Change the preparation condition of above-mentioned emulsion EM-1A to EM-8A in the following manner, prepare emulsion EM-1C to EM-8C thus:

1. after (adding 2) adds with the G-2 aqueous solution before, be that intervening sequences adds 2.1g 4,5-dihydroxy-1,3-benzenesulfonic acid disodium salt monohydrate (equaling patent specification Chinese style II-1 compound) and 0.002g thiourea dioxide with 1 minute at once.

Emulsion EM-1A to EM-8A, EM-1B to EM-8B and EM-1C under liquid nitrogen temperature, utilize the 400-KV transmission electron microscope observation to EM-8C.Found that each particle all have 20 or more dislocation line exist, these dislocation lines are mainly near the platy shaped particle corner.

Equally, emulsion EM-1C has introduced the hole capture band to EM-8C through the following operation of reduction sensitization consciously in silver halide particle: promptly (the adding 2) in the emulsion preparation process adds 4,5-dihydroxy-1,3-benzenesulfonic acid disodium salt monohydrate before at once.Although (adding 2) adds the dioxy thiocarbamide before EM-1B has also been carried out reduction sensitization consciously to EM-2B, do not satisfy the optimal conditions of introducing hole capture band described in the invention.

And above-mentioned emulsion EM-1A is to EM-8A, and EM-1B reaches spectral sensitization by adding sensitizing dye to EM-8C to EM-8B and EM-1C in emulsion manufacturing process.Making gained emulsion is green silver halide emulsion, maximum when its spectral sensitivity is 550nm at wavelength.

Under the condition identical with embodiment 1 with emulsion EM-1A to EM-8A, EM-1B to EM-8B and EM-1C be applied to EM-8C on the primary cellulose acetate carrier with undercoat.

The gained sample does not harden under 40 ℃, the condition of relative humidity 70%.Afterwards, sample exposed 1/100 second by SC-50 gelatin filter (transmission long wave optical filter, cutoff wavelength 500nm) and continuous wedge, then by program development (except that the time of colour development is changed to 2 minutes 45 seconds) same among the embodiment 1.Each is handled the photographic property of sample and assesses with green filter density measurement.

The emulsion characteristic that coats and its photographic property assessment result see the following form 9 and 10.Light sensitivity is meant the relative value of the reciprocal value of the density required exposure amount that obtains ashing density+0.2.(light sensitivity of emulsion EM-1A is 100).

Table 9

Sample number	Deng bulb diameter (μ m)	The equal circle diameter of first type surface (μ m)	Grain thickness (μ m)	The average surface area of each silver halide particle	Reduction sensitization (use thiourea dioxide) consciously
						EM-1A (Comparative Examples)	1.04	2.03	0.18	100	Do not carry out
-2A (Comparative Examples)	1.27	2.55	0.21	155	Do not carry out
						-3A (the present invention)	1.47	3.02	0.23	216	Do not carry out
-4A (the present invention)	1.62	3.45	0.24	276	Do not carry out
						-5A (Comparative Examples)	1.47	2.14	0.46	135	Do not carry out
-6A (Comparative Examples)	1.47	2.60	0.31	173	Do not carry out
						-7A (the present invention)	1.47	3.74	0.15	311	Do not carry out

(continuation)

Table 9

Sample number	4,5-dihydroxy benzenes-1, the interpolation of 3-disulfonic acid disodium salt monohydrate	The addition of sensitizing dye (mol/ silver halide mol amount)	The content (mol%) of emulsification silver surface silver iodide	Light sensitivity
					EM-1A (Comparative Examples)	Do not add	6.90×10 -4	2.8	100
-2A (Comparative Examples)	Do not add	5.86×10 -4	2.5	148
					-3A (the present invention)	Do not add	5.30×10 -4	2.3	171
-4A (the present invention)	Do not add	5.05×10 -4	2.0	201
					-5A (Comparative Examples)	Do not add	3.30×10 -4	1.7	133
-6A (Comparative Examples)	Do not add	4.24×10 -4	1.9	163
					-7A (the present invention)	Do not add	7.62×10 -4	2.7	218

(continuation)

Table 9

Sample number	Deng bulb diameter (μ m)	The equal circle diameter of first type surface (μ m)	Grain thickness (μ m)	The average surface area of each silver halide particle	Reduction sensitization (use thiourea dioxide) consciously
						EM-8A (the present invention)	1.47	4.65	0.097	463	Do not carry out
-1B (Comparative Examples)	1.04	2.03	0.18	100	Carry out
						-2B (Comparative Examples)	1.27	2.55	0.21	155	Carry out
-3B (the present invention)	1.47	3.02	0.23	216	Carry out
						-4B (the present invention)	1.62	3.45	0.24	276	Carry out

(continuation)

Table 9

Sample number	4,5-dihydroxy benzenes-1, the interpolation of 3-disulfonic acid disodium salt monohydrate	The addition of sensitizing dye (mol/ silver halide mol amount)	The content (mol%) of emulsification silver surface silver iodide	Light sensitivity
					EM-8A (the present invention)	Do not add	1.12×10 -3	3.3	250
-1B (Comparative Examples)	Do not add	6.90×10 -4	2.8	117
					-2B (Comparative Examples)	Do not add	5.86×10 -4	2.5	173
-3B (the present invention)	Do not add	5.30×10 -4	2.3	199
					-4B (the present invention)	Do not add	5.05×10 -4	2.0	235

^*Be a relative value, suppose that the silver halide particle average surface area is 100 among the emulsion EM-1A.

Table 9 (continuing)

Sample number	Deng bulb diameter (μ m)	The equal circle diameter of first type surface (μ m)	Grain thickness (μ m)	The average surface area of each silver halide particle	Reduction sensitization (use thiourea dioxide) consciously
						EM-5B (Comparative Examples)	1.47	2.14	0.46	135	Carry out
-6B (Comparative Examples)	1.47	2.60	0.31	173	Carry out
						-7B (the present invention)	1.47	3.74	0.15	311	Carry out
-8B (the present invention)	1.47	4.65	0.097	463	Carry out
						EM-1C (Comparative Examples)	1.04	2.03	0.18	100	Do not carry out
-2C (Comparative Examples)	1.27	2.55	0.21	155	Do not carry out
						-3C (the present invention)	1.47	3.02	0.23	216	Do not carry out

(continuation)

Table 9 (continuing)

Sample number	4,5-dihydroxy benzenes-1, the interpolation of 3-disulfonic acid disodium salt monohydrate	The addition of sensitizing dye (mol/ silver halide mol amount)	The content (mol%) of emulsification silver surface silver iodide	Light sensitivity
					EM-5B (Comparative Examples)	Do not add	3.30×10 -4	1.7	155
-6B (Comparative Examples)	Do not add	4.24×10 -4	1.9	192
					-7B (the present invention)	Do not add	7.62×10 -4	2.7	253
-8B (the present invention)	Do not add	1.12×10 -4	3.3	295
					EM-1C (Comparative Examples)	Add	6.90×10 -4	2.8	125
-2C (Comparative Examples)	Add	5.86×10 -4	2.5	190
					-3C (the present invention)	Add	5.30×10 -4	2.3	255

(continuation)

Table 9 (continuing)

Sample number	Deng bulb diameter (μ m)	The equal circle diameter of first type surface (μ m)	Grain thickness (μ m)	The average surface area of each silver halide particle	Reduction sensitization (use thiourea dioxide) consciously
						EM-4C (the present invention)	1.62	3.45	0.24	276	Do not carry out
-5C (Comparative Examples)	1.47	2.14	0.46	135	Do not carry out
						-6C (Comparative Examples)	1.47	2.60	0.31	173	Do not carry out
-7B (the present invention)	1.47	3.74	0.15	311	Do not carry out
						-8C (the present invention)	1.47	4.65	0.097	463	Do not carry out

(continuation)

Table 9 (continuing)

Sample number	4,5-dihydroxy benzenes-1, the interpolation of 3-disulfonic acid disodium salt monohydrate	The addition of sensitizing dye (mol/ silver halide mol amount)	The content (mol%) of emulsification silver surface silver iodide	Light sensitivity
					EM-4C (the present invention)	Add	5.05×10 -4	2.0	307
-5C (Comparative Examples)	Add	3.30×10 -4	1.7	167
					-6C (Comparative Examples)	Add	4.24×10 -4	1.9	212
-7B (the present invention)	Add	7.62×10 -4	2.7	337
					-8C (the present invention)	Add	1.12×10 -3	3.3	485

^*Be a relative value, suppose that the silver halide particle average surface area is 100 among the emulsion EM-1A.

Can obviously draw by last table result to draw a conclusion.When the first increased when sheet silver halide equal circle diameter, equal circle diameter reached 3.5 μ m or occurs invalid phenomenon more for a long time, so to cause light absorption to increase and light sensitivity is improved be difficult corresponding to increasing granule surface area and sensitizing dye quantity.The present invention has the silver emulsion of hole capture band than those silver emulsions that does not have the hole capture band, and higher light sensitivity degree value and lower ineffectivity are extremely arranged.

Embodiment 7

The present embodiment explanation is by having a mind to reduction sensitization only at the hole capture band of introducing near the zone on silver halide particle surface among the present invention.

The preparation of emulsion EM-3D

Change the preparation condition of above-mentioned emulsion EM-3A in the following manner, prepare emulsion EM-3D thus:

Every mole of silver halide meter, increase adds 3.5 * 10 at once before the adding sensitizing dye in the chemical sensitization step ^-5The step of g dimethyamine borane and slaking 30min.

The preparation of emulsion EM-3E

Change the preparation condition of above-mentioned emulsion EM-3A in the following manner, prepare emulsion EM-3E thus:

In every mole of silver halide, increase adds 0.002g sodium benzenethiosulfonate and 3.5 * 10 at once before the adding sensitizing dye in the chemical sensitization step ^-5The step of g dimethyamine borane and slaking 30min.

Carrier is pressed program same among the embodiment 1 by the coating of the emulsion EM-3A among above emulsion EM-3D and EM-3E and the embodiment 6, and assesses its photographic property.In three kinds of emulsions, EM-3A is without having a mind to the emulsion of reduction sensitization.EM-3D is adding dimethyamine borane after slaking and reduction sensitization, but does not meet the emulsion of the preferred hole capture of the described acquisition of preamble of the present invention tape spare.Except that adding dimethyamine borane and maturation process, EM-3E adds the emulsion that provides preferred hole capture band as the sodium benzenethiosulfonate of silver-colored oxygenant.

Photographic property the results are shown in Table 10.Though emulsion EM-3D is reduction sensitization intentionally, do not meet the condition of the preferred hole capture band of the described acquisition of preamble of the present invention, its light sensitivity is identical with emulsion EM-3A, does not demonstrate the effect of reduction sensitization intentionally basically.In contrast, emulsion EM-3E meets the condition that obtains preferred hole capture band, and to compare its light sensitivity much higher with emulsion EM-3A; Emulsion EM-3C among its light sensitivity and the embodiment 6 is close.That is, obtained hole capture band of the present invention substantially, so effect of the present invention is achieved.

Table 10

Sample number	Deng bulb diameter (μ m)	The equal circle diameter of first type surface (μ m)	Grain thickness (μ m)	The average surface area of each silver halide particle	Reduction sensitization (use dimethyamine borane) consciously
						EM-3A (the present invention)	1.47	3.02	0.23	216	Do not carry out
-3D (the present invention)	1.47	3.02	0.23	216	Carry out
						-3E (the present invention)	1.47	3.02	0.23	216	Carry out

(continuation)

Table 10

Sample number	The interpolation of the oxygenant (sodium benzenethiosulfonate) of silver	The addition of sensitizing dye (mol/ silver halide mol amount)	The content (mol%) of emulsification silver surface silver iodide	Light sensitivity
					EM-3A (the present invention)	Do not add	5.30×10 -4	2.3	171
-3D (the present invention)	Do not add	5.30×10 -4	2.3	188
					-3E (the present invention)	Add	5.30×10 -4	2.3	246

^*Be a relative value, suppose that the silver halide particle average surface area is 100 among the emulsion EM-1A.

Embodiment 8

Present embodiment explanation silver halide particle surface agi content is to the influence of the light sensitivity and the storage-stable aspect of emulsion of the present invention.

Emulsion EM-3C-1 is different on the particle surface agi content to EM-3C-5, and it is prepared as follows: add in the emulsion EM-3C of embodiment 6 preparation method's chemical sensitization step and add silver bromide fine particle emulsion that mean grain size is 0.055 μ m or silver iodide fine particle emulsion and the slaking 30min of mean grain size 0.047 μ m before the sensitizing dye at once respectively.In every mole of silver emulsion, the addition of emulsion EM-3C-1 silver bromide fine particle emulsion and silver iodide fine particle emulsion in the EM-3C-5 and the particle surface agi content of measuring through XPS are as follows:

The thin silver bromide grain of emulsion EM-3C-1:0.0030 mole,

Surface agi content=0.8mol%

The thin silver bromide grain of emulsion EM-3C-2:0.0015 mole,

Surface agi content=1.3mol%

Emulsion EM-3C-3: do not add (emulsion E-3C itself),

Surface agi content=2.3mol%

The thin silver bromide grain of emulsion EM-3C-4:0.0015 mole,

Surface agi content=4.5mol%

The thin silver bromide grain of emulsion EM-3C-5:0.0030 mole,

Surface agi content=5.8mol%

Carrier is coated with above emulsion EM-3C-1 to EM-3C-5 with running program same among the embodiment 1, and assesses the photographic property and the storage-stable of each sample.The following assessment of storage-stable: under 50 ℃, 60%RH (relative humidity),, detect the program that ashing increases then to aging eight days of each emulsion coated sample.In above emulsion, EM-3C-1 does not also meet the requirement of claim 5 of the present invention, and the agi content that is to say particle surface is less than 0.3 times of the average content 3.94mol% of whole particle silver iodide.On the contrary, EM-3C-5 does not meet the requirement of claim 4 of the present invention, because the particle surface agi content has surpassed 5mol%.Other emulsion EM-3C-2 satisfies the requirement of the embodiment of the invention 4 and 5 to EM-3C-4.

Table 11 is the photographic property result.In above emulsion, the light sensitivity of EM-3C-1 is low, because the agi content of particle surface is low excessively.On the contrary, light sensitivity and the storage-stable of EM-3C-5 are low, because the agi content of particle surface is too high.The EM-3C-2 and the EM-3C-4 that satisfy claim 4 of the present invention and 5 requirements have kept ISO and high storage-stable.

The particle surface agi content that changes emulsion EM-8C among the embodiment 6 with above-mentioned same method prepares corresponding emulsion, or the middle mean grain size that adds of (the adding 5) of preparation EM-3C method is the content of the silver iodide fine particle emulsion of 0.009 μ m with change particle surface silver iodide in as embodiment 6, and assess as mentioned above.The result obtains and the similar result of top description.

Table 11

Sample number	Corresponding to claim 4 of the present invention	Corresponding to claim 5 of the present invention	Deng bulb diameter (μ m)	The equal circle diameter of first type surface (μ m)	Grain thickness (μ m)	Reduction sensitization (use thiourea dioxide) consciously
							EM-3C-1	Corresponding	Not corresponding	1.47	3.02	0.23	Carry out
-3C-2	Corresponding	Corresponding	1.47	3.02	0.23	Carry out
							-3C-3	Corresponding	Corresponding	1.47	3.02	0.23	Carry out
-3C-4	Corresponding	Corresponding	1.47	3.02	0.23	Carry out
							-3C-5	Not corresponding	Not corresponding	1.47	3.02	0.23	Carry out

(continuation)

Table 11

Sample number	4,5-dihydroxy benzenes-1, the interpolation of 3-disulfonic acid disodium salt monohydrate	Silver halide particle average silver iodide content (mol%)	The content (mol%) of emulsification silver surface silver iodide	Light sensitivity	The increase of aging 8 days ashing density under 50 ℃ and 60%RH condition
						EM-3C-1	Add	3.94	0.8	225	0.08
-3C-2	Add	3.94	1.3	250	0.10
						-3C-3	Add	3.94	2.3	255	0.13
-3C-4	Add	3.94	4.5	253	0.15
						-3C-5	Add	3.94	5.8	230	0.35

All emulsion samples are corresponding to emulsion of the present invention in this table

Embodiment 9

Present embodiment shows the effect of silver emulsion calcium ions of the present invention and magnesium ion.

As shown in table 12, emulsion EM-3A, EM-5A, EM-6A, EM-7A, EM-8A, EM-3C, EM-5C, EM-6C, EM-7C and EM-8C among the embodiment 6 makes the emulsion sample through changing calcium and magnesium ion content, and assesses the light sensitivity and the graininess of each sample.Notice that calcium ion adds with the magnesium nitrate form with calcium nitrate form, magnesium ion.These ions sensitizing dye in chemical sensitization add finish back and chemical sensitizer and add before adding at once.Because the chemical sensitization process postpones because of adding calcium or magnesium ion, so the time of prolongation chemical sensitization step is with this delay of indemnify.

The bulb diameter such as grade of noting the silver halide particle of all emulsions is 1.47 μ m, and therefore when only considering this factor of particle volume, these emulsions are had essentially identical graininess by hypothesis.

Light sensitivity is assessed by embodiment 1 same program.The light sensitivity that table 12 has been listed with emulsion EM-1 among the embodiment 6 is 100 o'clock, the sensitivity value of every kind of emulsion.The RMS value of supposing emulsion EM-3A is 100, and graininess is 0.1 o'clock relative value by density.

Above-mentioned evaluation the results are shown in Table 12.As seen from Table 12, when calcium ion or magnesium ion added in the silver emulsion of the present invention by recommended amounts of the present invention, RMS value descended and the graininess improvement.Along with the increase of first type surface equal circle diameter and surface area, the emulsion of this discovery has been realized ISO.But the graininess of emulsion slightly descends.Adding calcium ion or magnesium ion can be eliminated this defective in emulsion.Non-emulsion of the present invention is after adding calcium ion or magnesium ion, and its graininess is improved equally, but DeGrain.

Table 12

Sample number	Emulsion manufacture method as the basis *1	The content of Ca ion or Mg ion (ppm/ emulsion)	Deng bulb diameter (μ m)	The equal circle diameter of first type surface (μ m)	Grain thickness (μ m)
						401	EM-3A (the present invention)	Ca and Mg are all＜5	1.47	3.02	0.23
402	-5A (Comparative Examples)	Ca and Mg are all＜5	1.47	2.14	0.46
						403	-6A (Comparative Examples)	Ca and Mg are all＜5	1.47	2.60	0.31
404	-7A (the present invention)	Ca and Mg are all＜5	1.47	3.74	0.15
						405	-8A (the present invention)	Ca and Mg are all＜5	1.47	4.65	0.097
406	-3C (the present invention)	Ca and Mg are all＜5	1.47	3.02	0.23

(continuation)

Table 12

Sample number	The average surface area of each silver halide particle *2	Reduction sensitization (use thiourea dioxide) consciously	4,5-dihydroxy benzenes-1, the interpolation of 3-disulfonic acid disodium salt monohydrate	Light sensitivity	The RMS graininess
						401	216	Do not carry out	Do not add	171	100
402	135	Do not carry out	Do not add	133	96
						403	173	Do not carry out	Do not add	163	98
404	311	Do not carry out	Do not add	218	105
						405	463	Do not carry out	Do not add	250	110
406	216	Carry out	Add	255	110

(continuation)

Table 12

Sample number	Emulsion manufacture method as the basis *1	The content of Ca ion or Mg ion (ppm/ emulsion)	Deng bulb diameter (μ m)	The equal circle diameter of first type surface (μ m)	Grain thickness (μ m)
						407	-5C (Comparative Examples)	Ca and Mg are all＜5	1.47	2.14	0.46
408	-6C (Comparative Examples)	Ca and Mg are all＜5	1.47	2.60	0.31
						409	-7C (the present invention)	Ca and Mg are all＜5	1.47	3.74	0.15
410	-8C (the present invention)	Ca and Mg are all＜5	1.47	4.65	0.097

(continuation)

Table 12

Sample number	The average surface area of each silver halide particle *2	Reduction sensitization (use thiourea dioxide) consciously	4,5-dihydroxy benzenes-1, the interpolation of 3-disulfonic acid disodium salt monohydrate	Light sensitivity	The RMS graininess
						407	135	Carry out	Add	167	102
408	173	Carry out	Add	212	104
						409	311	Carry out	Add	337	116
410	463	Carry out	Add	485	121

^*1 with reference to embodiment 6

^*2 is relative values, and the silver halide particle average surface area of supposing emulsion EM-1A among the embodiment 6 is 100.

Table 12 (continuing)

Sample number	Emulsion manufacture method as the basis *1	The content of Ca ion or Mg ion (ppm/ emulsion)	Deng bulb diameter (μ m)	The equal circle diameter of first type surface (μ m)	Grain thickness (μ m)
						411	EM-3A (the present invention)	Ca1500	1.47	3.02	0.23
412	-5A (Comparative Examples)	Ca1500	1.47	2.14	0.46
						413	-6A (Comparative Examples)	Ca1500	1.47	2.60	0.31
414	-7A (the present invention)	Ca1500	1.47	3.74	0.15
						415	-8A (the present invention)	Ca1500	1.47	4.65	0.097
416	-3C (the present invention)	Ca250	1.47	3.02	0.23
						417	-3C (the present invention)	Ca600	1.47	3.02	0.23
418	-3C (the present invention)	Ca1500	1.47	3.02	0.23

(continuation)

Table 12 (continuing)

Sample number	The average surface area of each silver halide particle *2	Reduction sensitization (use thiourea dioxide) consciously	4,5-dihydroxy benzenes-1, the interpolation of 3-disulfonic acid disodium salt monohydrate	Light sensitivity	The RMS graininess
						411	216	Do not carry out	Do not add	170	99
412	135	Do not carry out	Do not add	133	96
						413	173	Do not carry out	Do not add	162	97
414	311	Do not carry out	Do not add	217	103
						415	463	Do not carry out	Do not add	257	107
416	216	Carry out	Add	254	110
						417	216	Carry out	Add	255	103
418	216	Carry out	Add	254	99

(continuation)

Table 12 (continuing)

Sample number	Emulsion manufacture method as the basis *1	The content of Ca ion or Mg ion (ppm/ emulsion)	Deng bulb diameter (μ m)	The equal circle diameter of first type surface (μ m)	Grain thickness (μ m)
						419	-3C (the present invention)	Mg100	1.47	3.02	0.32
420	-3C (the present invention)	Mg1500	1.47	3.02	0.32
						421	-5C (Comparative Examples)	Ca1500	1.47	2.14	0.46
422	-6C (Comparative Examples)	Ca1500	1.47	2.60	0.31
						423	-5C (the present invention)	Ca1500	1.47	3.74	0.15
424	-5C (the present invention)	Ca1500	1.47	4.65	0.097

(continuation)

Table 12

Sample number	The average surface area of each silver halide particle *2	Reduction sensitization (use thiourea dioxide) consciously	4,5-dihydroxy benzenes-1, the interpolation of 3-disulfonic acid disodium salt hydrate	Light sensitivity	The RMS graininess
						419	216	Carry out	Add	254	104
420	216	Carry out	Add	253	101
						421	135	Carry out	Add	165	100
422	173	Carry out	Add	211	102
						423	311	Carry out	Add	336	105
424	463	Carry out	Add	482	109

^*1 with reference to embodiment 6

^*2 is relative values, supposes among the embodiment 6 that the silver halide particle average surface area is 100 among the emulsion EM-1A.

Embodiment 10

Present embodiment shows the described effect of using water-soluble mercapto-tetrazole and mercapto-triazole in emulsion of the present invention of claim 14.

Prepare emulsion according to embodiment 6 emulsion EM-7C same programs, just will change the listed sulfhydryl compound of table 13 at the sulfhydryl compound MER-1 and the MER-2 of chemical sensitization adding in latter stage.

Estimate the light sensitivity and the storage stability of each emulsion sample.

Press embodiment 8 same programs and estimate light sensitivity and storage stability.

Table 13

Sample number	The emulsion manufacture method *1	Corresponding to claim 14 of the present invention	The sulfhydryl compound that is added	The addition of sensitizing dye (mol/ silver halide mol amount)	Light sensitivity	The increase of ashing density after aging 8 days under 50 ℃ and 60%RH condition
							501	EM-7C (the present invention)	Corresponding	MER-1 *2 MER-2	2.88×10 -40.72×10 -4	337	0.17
502	EM-7C (the present invention)	Not corresponding	MER-1	3.60×10 -4	335	0.24
							503	EM-7C (the present invention)	Not corresponding	MER-1	5.00×10 -4	316	0.18
504	EM-7C (the present invention)	Not corresponding	MER-2	3.60×10 -4	230	0.13
							505	EM-7C (the present invention)	Not corresponding	MER-2	1.44×10 -4	325	0.21
506	EM-7C (the present invention)	Not corresponding	MER-1 STO-A	2.88×10 -40.72×10 -4	304	0.19

^*1: reference example 6

^*2: MER-1 and MER-2 are respectively corresponding to the formula (I-1) of claim 14 of the present invention and water-soluble sulfhydryl compound (I-2) in this table

Control compound STO-A (compound that JP-A-4-16838 describes)

Control compound STO-A

As seen from Table 13, when formula I-1 mercapto-tetrazole compound of uniting use claim 14 recommendation of the present invention and formula I-2 mercapto-triazole compound, compare with known method (use mercapto-tetrazole compound or mercapto-tetrazole compound separately or unite use with the compound of dimercaptothiodiazole described in the JP-A-4-16838), the increase of ashing is littler and light sensitivity is identical or higher between the storage life.

Embodiment 11

Embodiment 6 to 10 prepared silver emulsions are introduced in the 11th layer of embodiment 4 colored multilayer negative film photosensitive materials, estimated light sensitivity and storage stability.Identical among the mutual relationship that the result shows each emulsion sample room and the embodiment 6 to 10.This shows even also obtained effect of the present invention in colored multilayer negative film photosensitive system.

Advantage or the improvement project of conceiving other to those skilled in the art will be easy.Therefore having more, the present invention of broad sense also not only is confined to detail and representative embodiment shown and that describe herein.Therefore under the spirit or scope condition that does not deviate from by claims and the key concept of the present invention that equivalent defined thereof, can carry out multiple improvement.

Claims (15)

1, a kind of silver halide magenta-sensitive emulsion, wherein, the variation factor of the equal circle diameter of all particles is 40% or littler, simultaneously 50% of the total projection area or more by meet following condition (i) to (platy shaped particle v) occupies:

(i) platy shaped particle is to have iodine silver bromide or a bromine chlorosulfonation silver strip shape particle that (111) crystal face is a first type surface,

(ii) equal circle diameter is 3.5 μ m or bigger, and thickness is 0.25 μ m or littler,

(iii) agi content is 2 to 6mol%,

(iv) silver chloride content is 3mol% or littler,

(v) silver iodide distribute and have five layers or more multi-layered structure.

2, silver halide magenta-sensitive emulsion as claimed in claim 1, wherein, silver iodide distribute and have six layers or more multi-layered structure.

3, silver halide magenta-sensitive emulsion as claimed in claim 1, wherein, when adopting the irradiation of 325nm electromagnetic beam during 6K, emulsion produces the 575nm induced fluorescence, and its intensity is 1/3 of the hyperfluorescence emission that induces in 490 to the 560nm wavelength coverages at least.

4, silver halide magenta-sensitive emulsion as claimed in claim 1, wherein, the average silver iodide content on all particle surfaces is no more than 5mol%.

5, silver halide magenta-sensitive emulsion as claimed in claim 1 wherein, supposes that It is the average silver iodide content of whole particle, and Is is the average silver iodide content on the particle surface, and then following relational expression is set up: 0.3It≤Is.

6, silver halide magenta-sensitive emulsion as claimed in claim 1, wherein, at least a portion has the hole capture band in the silver halide particle.

7, silver halide magenta-sensitive emulsion as claimed in claim 1 wherein, satisfies in the claim 1 listed condition (i) to (platy shaped particle v) has dislocation line near the particle corner.

8, silver halide magenta-sensitive emulsion as claimed in claim 1, wherein, the equal circle diameter variation factor of all particles is 25% or littler.

9, silver halide magenta-sensitive emulsion as claimed in claim 1, wherein, listed condition (ii) is that the round diameter such as grade is 3.5 μ m or bigger in the claim 1, thickness is 0.15 μ m or littler.

10, silver halide magenta-sensitive emulsion as claimed in claim 1, wherein, listed condition (ii) is that the round diameter such as grade is 4.0 μ m or bigger in the claim 1, thickness is 0.15 μ m or littler.

11, silver halide magenta-sensitive emulsion as claimed in claim 1, wherein, listed condition (ii) is that the round diameter such as grade is 4.0 μ m or bigger in the claim 1, thickness is 0.10 μ m or littler.

12, silver halide magenta-sensitive emulsion as claimed in claim 1, wherein, described emulsion carries out spectral sensitization with spectral sensitizing dye.

13, silver halide magenta-sensitive emulsion as claimed in claim 1, wherein, emulsion contains 400 to 2, the calcium ion of 500ppm and/or 50 to 2, the magnesium ion of 500ppm.

14, silver halide magenta-sensitive emulsion as claimed in claim 1, wherein, described emulsion is that selenium increases, and contain at least a type by the water-soluble mercapto-tetrazole compound of formula (I-1) expression and the water-soluble mercapto-triazole compound by formula (I-2) expression of at least a type:

Formula (I-1)

R wherein ₅Be at least by a kind of being selected from-SO ₃M ,-COOM ,-OH and-NHR ₂Organic residue of replacing of group, M represents hydrogen atom, alkali metal atom, quaternary ammonium group or quaternary phosphonium group, R ₂Represent hydrogen atom, C ₁-C ₆Alkyl ,-COR ₃,-COOR ₃, or-SO ₂R ₃, R ₃Represent hydrogen atom, alkyl or aryl;

Formula (I-2)

R wherein ₆Represent hydrogen atom, replacement or non-substituted alkyl or replacement or non-substituted aryl, R ₅Be at least by a kind of being selected from-SO ₃M ,-COOM ,-OH and-NHR ₂Organic residue of replacing of group, M represents hydrogen atom, alkali metal atom, quaternary ammonium group or quaternary phosphonium group, R ₂Represent hydrogen atom, C ₁-C ₆Alkyl ,-COR ₃,-COOR ₃, or-SO ₂R ₃, R ₃Represent hydrogen atom, alkyl or aryl.

15, a kind of photosensitive silve halide material, it comprises photographic layer on carrier, and this photographic layer contains silver halide magenta-sensitive emulsion as claimed in claim 1.