CN1249518C - Optical sensitive silver halide emulsion and photosensitive material therewith - Google Patents

Abstract

The present invention relates to a silver halide photographic photosensitive emulsion containing flat silver halide granules. Flat granules account for 50% or higher of the total projection area of all silver halide granules, every granule of the flat granules has a (111) surface as a parallel principal surface, the shaft diameter ratio is 2 or more, and every granule comprises 10 or more displacement lines; the photosensitive emulsion contains as least one compounds having formula (1) or formula (2). In formula (1) and formula (2), A, B, E, R1, R2, R3, R4 and X are defined in the specification.

Description

Photoactive silver-halide photographic emulsion and the silver halide photographic sensitive material that contains this emulsion

Technical field

The present invention relates to a kind of Photoactive silver-halide photographic emulsion, specifically, the present invention relates to a kind ofly have 2 or the flat silver halide particle photographic emulsion of higher diameter of axle ratio.The present invention also relates to a kind of silver halide photographic sensitive material that uses this emulsion.

Background technology

The manufacture method of flat particle and operation technique are disclosed in United States Patent (USP) 4,434, and 226,4,439,520,4,414,310,4,433,048,4,414,306 and 4,459,353.The advantage of known flat particle is photosensitive improvement, comprises the improvement of the color sensitive efficient of photosensitive pigment, and the improvement of photonasty/granularity relation.

The displacement of silver halide particle is described in the following list of references, for example: C.R.Berry, and J.Appl.Phys., 27,636 (1956), C.R.Berry, D.C.Skillman, J.Appl.Phys., 35,2165 (1964), J.F.Hamilton, Phot.Sci.Eng., 11,57 (1967), T.Shiozawa, J.Soc.Phot.Sci.Japan, 34,16, (1971), and T.Shiozawa, J.Soc.Phot.Sci.Japan, 35,213, (1972).These document descriptions can be observed displacement in the crystal by X-ray diffraction method or low temperature transmission electron microscope, and by having a mind to cause the distortion of crystal in crystal, to produce various displacements.

By flat silver halide particle being imported the method that the displacement that control is arranged improves various photographic properties is known.Japanese patent application publication No. (Jpn.Pat.Appln.KOKAI Publication No.) (hereinafter being called JP-A-) 63-220238 discloses a kind of method of introducing the displacement lining in the neighboring area of flat particle.JP-A-1-102547 discloses a kind of method of introducing the displacement lining on main of flat particle.JP-A-3-237450 discloses a kind of flat particle with displacement lining, and it has carried out chemical sensitization with selenium sensitizer, golden sensitizer and sulphur sensitizer, and has 3 or higher diameter of axle ratio.JP-A-6-27564 discloses a kind of flat particle that only has the displacement lining on the edge.

On the other hand, JP-A-61-43740 disclose a kind of by with double amidopyridine salt (bispyridinium salt) thereby and a kind of cyanine dye combination carry out spectral sensitization and have high red photosensitive emulsion.The preferred addition that JP-A-61-43740 has described this double amidopyridine salt is 0.25 to 100 times of cyanine dye addition by weight.In practice, mole such as double amidopyridine salt and cyanine dye adds or adds with higher amount.When a large amount of photosensitizing dye useful effect, the color sensitive efficient of these photosensitizing dyes will improve.But the inventor finds, in the system that a large amount of photosensitizing dyes are added into, even emulsion is had adsorbability double amidopyridine salt mole such as addition and cyanine dye or when higher the effect of photonasty raising very little.Thereby, need a kind of little addition of exploitation can obtain the technology that significant photonasty improves effect.

JP-A-6-242534 discloses a kind of material that contains the light-sensitive silver halide of two heteroaryl salt compounds.JP-A-6-242534 described contain 60% or the emulsion of higher silver chloride improve at the negative photosensitive material photographic property of the hard contrast that is used for taking a picture, it also contains a kind of hydrazine derivate.JP-A-10-83040 described use a kind of salt compound and atomizing in advance emulsion to the directly photonasty of positive sensitive photographic material and the improvement of bin stability.

As indicated above, with salt, for example to make up be known for double amidopyridine salt and photographic emulsion.But the effect of using this combination and having imported the flat particle of displacement lining is unknown.

Summary of the invention

The inventor has carried out deep research, has found a kind of by using specific salt can significantly improve the mode of photosensitive in a kind of specific flat particle that is imported into the displacement lining.

An object of the present invention is to provide a kind of high photosensitivity silver emulsion with high photonasty/photographic fog ratio.

Another object of the present invention provides a kind of silver halide photographic sensitive material that contains this emulsion.

Purpose of the present invention can reach by following silver emulsion and silver halide photographic sensitive material.

(I) a kind of silver halide photographic light-sensitivity emulsion, it with 50% or higher silver halide particle total projection area contain flat silver halide particle, each flat silver halide particle has (111) face as parallel interarea, the diameter of axle is than being 2 or more, and each particle comprises 10 or more a plurality of displacement line, and contains at least a compound by formula (1) or (2) expression:

Formula (1)

Formula (2)

Wherein, A represents the needed atomic group of a kind of formation nitrogen heterocyclic ring, and each B and E represent alkylidene, arlydene ,-O-,-S-,-SO ₂-,-CO ₂-and-N (R5)-in one or their combination.R5 represents hydrogen atom, alkyl, perhaps aryl.-O-,-S-,-SO ₂-,-CO ₂-with-N (R5)-in each is adjacent with alkylidene or arlydene and link to each other.B is not with combining with nitrogen-atoms that A forms heterocycle, and it combines with carbon atom by two keys.Each expression alkyl or aryl among R1 and the R2, and among R3 and the R4 each is represented a kind of substituting group.Though X represents a kind of anionic group, X does not exist under the situation of molecule inner salt.

(II) emulsion described in above-mentioned (I), wherein, this silver halide particle makes its red-light-sensing by a kind of sensitizing dye, and the addition of formula (1) or (2) compound is the 25mol% of this sensitizing dye addition or lower.

(III) (I) or the emulsion (II), wherein, the surperficial agi content of this silver halide particle is 5mol% or lower.

(IV) above-mentioned (I) wherein, falls sensitizing to silver halide particle and handles to the emulsion described in (III).

(V) one of any described emulsion in above-mentioned (I) to (IV), wherein, represent by following formula (3) by the compound of formula (2) expression:

Formula (3)

Wherein, D represent alkylidene and-or its alternate combinations among the O-.Each expression 0,1, perhaps 2 among m and the n.The alkyl of 4-to the 20-carbon of each expression among R6 and the R7, the aryl of 6-to a 20-carbon, the perhaps aralkyl of 7-to a 20-carbon.If m=2 and n=2, R6 or R7 can be used as phenyl ring and form condensed ring.Though X represents an anionic group, under the situation of molecule inner salt, do not need X.

(VI) a kind of silver halide photographic sensitive material, it has at least a silver halide emulsion layer on a carrier, and wherein, this silver halide emulsion layer contains above-mentioned (I) to the photosensitive emulsion described in (V).

Hereinafter will describe the present invention in detail.

Hereinafter will describe formula (1) in detail, (2) and (3).In these general formulas, A represents to form the needed atomic group of nitrogen heterocyclic ring, and can contain a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen-atoms, perhaps a sulphur atom.In addition, the cyclic condensation that can be further forms with A of phenyl ring.Preferred example is a pyridine ring, quinoline ring and isoquinoline ring.A also can be replacement.Preferred this substituent example is a hydrogen atom, the alkyl (for example, methyl and hydroxyethyl) of replacement or non-replacement; aryl replacement or non-replacement (for example; phenyl and rubigan), the aralkyl (for example, benzyl) of replacement or non-replacement; acyl group; hydroxyl, nitro, amide group; alkoxy, and carbamyl.

Each expression alkylidene among B and the E, arlydene ,-O-,-S-,-SO ₂-,-CO ₂-and-N (R5)-in one or their combination.To the number of these groups in the above-mentioned combination without limits, and two identical groups can be combined in and form each B and E together, as long as two ends of this combination are alkylidene or arlydene.Alkylidene can be replaced by the substituting group of for example hydroxyl.R5 represents hydrogen atom, alkyl, perhaps aryl.-O-,-S-,-SO ₂,-CO ₂-, with-N (R5)-in each is adjacent and link to each other at their two ends and alkylidene or arlydene.Group-O-,-S-,-SO ₂-,-CO ₂-and-N (R5)-can not represent B and E separately.B is not with linking to each other with nitrogen-atoms that A forms heterocycle, and it links to each other with carbon atom by two keys.Each expression alkylidene among preferred B and the E, arlydene ,-O-and-or their combination among the S-, for example, alkylidene-O-alkylidene-O-alkylidene.

Each expression alkyl or aralkyl among R1 and the R2.The alkyl (for example, butyl, hexyl, perhaps dodecyl) of 4-to the 20-carbon of each expression among preferred R1 and the R2 or the aralkyl (for example, benzyl, phenethyl, perhaps p-chlorobenzyl) of 7-to 20-carbon.

Each R3 and R4 represent a kind of substituting group.This substituent example is a hydrogen atom, halogen atom, and the alkyl of replacement or non-replacement is (for example, methyl and hydroxyethyl), the aryl (for example, phenyl and right-chlorphenyl) of replacement or non-replacement, with aralkyl (for example, benzyl) that replace or non-replacement.Each R3 and R4 can be replaced by one or more substituting groups.

Though X represents an anionic group, under the situation of molecule inner salt, do not need X.The example of X is a chlorion, bromide ion, iodide ion, nitrate ion, sulfate ion, p-methyl benzenesulfonic acid ion, and oxalate.

D represent alkylidene and-or their alternate combinations among the O-.The example of D comprises 1,3-propylidene, 1,5-pentylidene, heptamethylene, 1, the inferior nonyl of 9-,-CH ₂CH ₂OCH ₂CH ₂-,-(CH ₂CH ₂O) ₂-CH ₂CH ₂-and-(CH ₂CH ₂O) ₃-CH ₂CH ₂-.

Each expression 0,1, perhaps 2 among m and the n.The alkyl (for example, butyl, hexyl, perhaps dodecyl) of 4-to the 20-carbon of each expression among R6 and the R7, the aryl of 6-to a 20-carbon, the perhaps aralkyl of 7-to a 20-carbon (for example, benzyl, phenethyl, perhaps right-the benzyl chloride base).If m=2 and n=2, R6 or R7 can be used as phenyl ring and form condensed ring, can represent a quinoline ring or an isoquinoline ring.

By formula (1), in the compound of the present invention of (2) and (3) expression, preferably by the compound of formula (2) and (3) expression, the more preferably compound represented of formula (3).

Preferred example is in the reality: m=1 wherein, and n=1, R6 and R7 are phenyl, D is-(CH ₂CH ₂O) ₂-CH ₂CH ₂-and X be the compound of Cl; M=1 wherein, n=1, R6 and R7 are benzyl, D is-(CH ₂CH ₂O) ₂-CH ₂CH ₂-and X be the compound of Cl; M=2 wherein, n=2, R6 and R7 are the benzene condensed ring, D is-(CH ₂CH ₂O) ₂-CH ₂CH ₂-and X be the compound of Cl; Wherein R6 and R7 are phenyl, and D is 1, and 3-propylidene and X are the compound of Br; Wherein A is a pyridine ring, and R1 and R2 are right-benzyl chloride base, and B is 1, and 3-propylidene and X are the compound of p-toluenesulfonic acid.

Of the present invention by formula (1), the compound of (2) and (3) expression is preferably by being dissolved in a kind of water miscible solvent, water for example, and methyl alcohol, or ethanol, or add in the potpourri of these solvents.

Of the present invention by formula (1), the joining day of the compound of (2) and (3) expression can be before or after the joining day of sensitizing dye.These compounds are comprised in a kind of silver emulsion, and addition be preferably sensitizing dye 1 to 25mol%, more preferably 2 to 15mol%.If the addition of using among the present invention by the compound of formula (1) to (3) expression is excessive, the amount of the sensitizing dye that can be adsorbed by emulsion grain reduces.Thereby above-mentioned addition is preferred.

Compound by formula (1) to (3) expression of the present invention can by with Quart.Rev.16, the similar methods of describing in 163 (1962) of method are synthesized, its disclosed content all is incorporated herein by reference.

Use among the present invention by formula (1), the representational example of the compound of (2) and (3) expression is as shown in hereinafter, but the present invention is not limited to these examples.

The present invention relates to the flat grain emulsion of a kind of iodine silver bromide or bromine chlorosulfonylation silver.

The flat grain emulsion that the present invention uses is made up of opposed facing (111) interarea and the side that is connected these interareas.This flat grain emulsion is from iodine silver bromide or the preparation of bromine silver iodochloride.Though this emulsion also can contain silver chloride, the content of silver chloride is preferably 8mol% or lower, more preferably 3mol% or lower, most preferably 0mol%.The content of silver iodide is preferably 20mol% or lower, because the variation factor of particle size distribution is preferably 25% or lower in flat particle emulsion.Reduce the variation factor that agi content helps to reduce the particle size distribution of flat particle emulsion.Particularly, the variation factor of the particle size distribution of flat particle emulsion more preferably 20% or lower, and agi content is preferably 10mol% or lower.

No matter agi content how, the variation factor that agi content distributes between particle is preferably 20% or lower, preferred especially 10% or lower.

The flat grain emulsion that uses among the present invention preferably has a kind of granule interior structure aspect the silver iodide distribution.This silver iodide distributed architecture can be a dual structure, triplen, quadruple structure, or a kind of higher structure.

In flat grain emulsion of the present invention, 50% or more total projection area be by have the diameter of axle than be 2 or higher particle cause.The projected surface area of flat particle and diameter of axle ratio can be measured from electron micrograph, and this obtains flat particle by using carbon duplicate method (carbon replicamethod) with the projection of milk-globule object of reference.When the direction vertical with first type surface observed, flat particle has sexangle usually, triangle or circular shape.The diameter of axle is than being value by obtaining divided by the thickness of this particle with the projected surface area of flat particle diameter of a circle of the same area.For the shape of flat particle, hexagonal ratio is preferably high as much as possible.And the ratio of the length of hexagonal adjacent side is preferably 1: 2 or is lower.The diameter of axle is higher than more, and effect of the present invention is remarkable more.Thereby, in flat grain emulsion, the total projection surface area 50% or mostly be preferably 5 or higher by having diameter of axle ratio, more preferably 8 or higher particle cause.If the diameter of axle is than too high, the variation factor of above-mentioned particle size distribution is tending towards reducing.Thereby usually preferred diameter of axle ratio is 50 or lower.

In the present invention, flat grain emulsion is made up of (111) interarea and the side that is connected these interareas.Between two interareas, there is at least one twin plane.In flat particle emulsion of the present invention, observe two twin planes usually.As US 5,219,720 is described, and the interval of these two twin planes can be reduced to 0.012 μ m.And as described in JP-A-5-249585, the distance between (111) interarea can be increased to 15 or higher divided by the resulting value in twin plane interval.

In the present invention, especially preferably connect relative (111) interarea of flat particle emulsion all sides 75% or lower for (111) face." all sides 75% or lowlyer be made up of (111) face " are meant that the exist ratio of crystal plane in all sides that is not (111) face is 25% or higher.Though can think that usually this is (100) face, it also can be (110) face or a kind of face than high grade.

Flat particle of the present invention has displacement line (dislocation line).Displacement line in the flat particle can be observed by the direct method of using perspective electron microscope to carry out at low temperatures, for example, and J.F.Hamilton, Phot.Sci.Eng., 11,57, (1967) or T.Shiozawa, J.Soc.Phot.Sci.Japan, 35,213, described in (1972).That is to say, silver halide particle is extracted from emulsion carefully, in particle, do not produce displacement line thereon, place it in one and carry out electron microscope observation on the net thereby do not exert pressure.Observation is undertaken by transmission method, simultaneously with the sample cooling, to prevent that electron beam is with its damage (promptly shining).In this case, the thickness of particle is big more, and transmission electron beam passes difficult more.Thereby, use the electron microscope of high-pressure type can more clearly observe particle (being 200kV or higher) for particle with 0.25 μ m thickness.The photo of the particle that obtains from said method, observe the position and the quantity that can obtain displacement line each particle from the direction vertical with the interarea of particle.

The average of displacement line is preferably 10 or more in each particle, and more preferably 20 or more.If the intensive existence of displacement line or they intersect mutually when observing, be difficult to correctly count the displacement line in each particle sometimes.Even but in this case, can be that unit counts with 10 roughly to displacement line also, as 10,20, or 30 displacement lines, thereby these particles can be come from the particle difference of wherein only obviously observing several displacement lines.In each particle the average number of displacement line be by count 100 or more particles in the average that obtains of the number of displacement line.

Displacement line can be introduced in, and for example, near the part of the periphery of flat particle, hereinafter, this part is known as zone of nearly week.In this case, displacement is substantially perpendicular to outer rim, and result from length between the center and peripheral (outer rim) of flat particle apart from outer rim x% place.The value of X is preferably 10 to below 100, and more preferably 30 to below 99, and most preferably 50 to below 98.In this case, though the shape that obtains by the displacement reference position is linked to each other is almost similar to coating of particles, incomplete similarity produces distortion sometimes.Such displacement is not present in the central area of particle.The direction of displacement line is crystallographic, is approximately (211) direction.But displacement line normally tortuous and intersect mutually sometimes.

Flat particle can have the displacement line that almost passes zone of whole nearly week equably, perhaps is positioned at the displacement line of the ad-hoc location in zone of nearly week.That is to say that under the situation of hexagonal tabular silver halide particle, displacement line can be limited at the part near six angles, perhaps only near one part in six angles.Conversely, also displacement line only can be limited to except on the part near the part at six angles near the edge.

The formation of displacement line also can be passed the zone at the center of two parallel interareas that comprise flat particle.When displacement line passed the whole zone of interarea, the direction of displacement line was crystallographic sometimes, is approximately (211) direction with respect to the direction perpendicular to interarea.But in some cases, this direction is (a 110) direction or at random.The length of single displacement line also is at random; Observed displacement line is the short-term on the interarea sometimes, is the long line that arrives at edge (outer rim) sometimes.Though displacement line is straight sometimes, they are normally tortuous.In many cases, displacement line intersects mutually.

As indicated above, displacement can be positioned in the neighboring area or be positioned on the interarea, and perhaps these displacements can be limited on the regional area of neighboring area or interarea, and perhaps these displacements can be positioned in the combination of above-mentioned zone.That is to say, displacement line can be present in simultaneously on the neighboring area and interarea on.

In the present invention, displacement line most preferably passes through to above-mentioned silver bromide, chlorine silver bromide, bromine chlorosulfonylation silver, what perhaps the silver emulsion of adding microsolubility was introduced in the iodine silver bromide emulsion.Consider that from halogen compounds the silver emulsion of microsolubility is than the flat particle emulsion of the silver emulsion that wherein will add this microsolubility slightly soluble more, and silver iodide fine particle emulsion preferably.

In the present invention, displacement line is preferably introduced by rapid adding silver iodide fine particle emulsion in above-mentioned flat particle emulsion.This method consists essentially of two steps: a step is sharply to add silver iodide fine particle emulsion in flat particle emulsion, and another step is to introduce displacement line by growth silver bromide or iodine silver bromide.These two steps can be carried out sometimes fully dividually, also can carry out simultaneously.Preferred these two steps are separately carried out.Hereinafter will describe first step that in flat emulsion, sharply adds silver iodide fine particle emulsion in detail.

" sharply adding silver iodide fine particle emulsion " is to be preferably in 10 minutes, and more preferably adds silver iodide fine particle emulsion in 7 minutes.Temperature in the system that this condition can will add according to this fine particle emulsion, pBr, and pH, the type of protective colloid agent and concentration is gelatin for example, and the existence of ag halide solvent is whether, and type and concentration change.But as mentioned above, the short joining day is more preferred.In adition process, the preferred silver salt for example aqueous solution of silver nitrate is not to add.The temperature of system is preferably 40 ℃ to 90 ℃ in the adition process, preferred especially 50 ℃ to 80 ℃.In adition process, the pBr of silver iodide fine particle emulsion is not particularly limited.

It is essential to silver iodide fine particle emulsion that silver iodide are only arranged, and it can contain silver bromide and/or silver chloride, as long as can form mixed crystal.Preferred this emulsion is 100% silver iodide.The crystal structure of silver iodide can be the β body, the γ body, and perhaps as US4, the α body of 672,026 described (its content is incorporated herein by reference) or the similar structures of α body.In the present invention, crystal structure is had no particular limits, but the potpourri of preferred β and γ body, more preferably β body.Silver iodide fine particle emulsion can be at US5, the emulsion of preparing immediately before the described adding of 004,679 (its content is introduced one's own department or unit as a reference), or a kind of emulsion that passes through conventional washing step.In the present invention, used the emulsion of handling through conventional washing step.This silver iodide fine particle emulsion can easily pass through, for example, above-mentioned US4,672,026 methods of describing form.A kind of two jet (double-jet) adding methods of preferred use, this method is used a kind of silver salt solution and a kind of iodine salt water solution, and wherein particle formation is what to carry out with the pI value of photographic fixing.PI is the logarithm of the inverse of I-ion concentration in the system.To the temperature of system, pI, and pH, to the type and the concentration of protective colloid formulation example such as gelatin, and to the existence of ag halide solvent whether, type and concentration have no particular limits.But grain size is preferably 0.1 μ m or lower in the present invention, more preferably 0.08 μ m or lower.Though can't clearly characterize particle shape, because these particles are trickle particle, the variation factor of particle size distribution is preferably 25% or lower.When this variation factor is 20% or when lower, particular significant effect of the present invention.The size distribution of silver iodide fine particle emulsion and size are to be used for the online of electron microscope observation by the silver iodide fine particle is placed on, and obtain by transmission method rather than carbon duplicate method Direct observation particle.This is that the observation of being undertaken by carbon duplicate method can improve measuring error because the size of these particles is little.Grain size is to be limited by the diameter that has with the circle of the projected area equal areas of the particle of observing.Particle size distribution also by use this projected surface area etc.-circular diameter obtains.In the present invention, the particle that the most effective silver iodide fine particle has to little be 0.07 to, 0.02 μ m, the particle size distribution variation factor is 18% or lower.

After above-mentioned particle forms, preferably silver iodide fine particle emulsion is carried out conventional washing, as US2,614; 929 is described, and its content is incorporated herein by reference, and adjust pH; pI, the concentration of the concentration of protective colloid formulation example such as gelatin and the silver iodide that contain.PH is preferably 5 to 7.PI is preferably the dissolubility of the silver iodide value when minimum, perhaps a value more higher than this value.As the protective colloid preparation, preferably use common gelatin with mean molecular weight about 100000.The also preferred low molecular weight gelatine that uses with mean molecular weight 20000.Sometimes can use the potpourri of gelatin with different molecular weight.The amount of every kilogram emulsion gelatin is preferably 10 to 100g, and more preferably 20 to 80g.In every kilogram the emulsion, in silver atoms, the amount of silver is preferably 10 to 100g, and more preferably 20 to 80g.For the consumption of gelatin and/or the consumption of silver, the preferential numerical value of selecting to be suitable for sharply adding silver iodide fine particle emulsion.

The addition of silver iodide fine particle emulsion is preferably 1 to 10mol% in silver with respect to final flat particle emulsion, most preferably is, and 2 to 7mol%.By selecting this addition for use, preferably introduce displacement line, effect of the present invention is more obvious.Silver iodide fine particle emulsion is dissolved before adding usually.In adition process, need fully stir system.The rotational speed that stirs is set in than under the generally higher speed.Add anti-blowing agent, to prevent the formation of foam in the whipping process.Specifically, use for example US5, the anti-blowing agent described in 275,929.

After silver iodide fine particle emulsion was sharply added flat grain emulsion, growth silver bromide or iodine silver bromide were to introduce displacement line.Though the growth of silver bromide or iodine silver bromide can or begin before adding silver iodide fine particle emulsion simultaneously, the silver iodide fine particle emulsion that is grown in of preferred silver bromide or iodine silver bromide adds afterwards initial.The time that is added to silver bromide or iodine silver bromide growth beginning from silver iodide fine particle emulsion is preferably 10 minutes to 1 second, and more preferably 5 minutes to 3 seconds, most preferably within 1 minute.This time interval is preferably short as much as possible.

Preferably add back growth silver bromide at silver iodide fine particle emulsion.When using the iodine silver bromide, the content of the silver iodide in the iodine silver bromide to be grown is 3mol% or lower.Suppose that the total silver amount in the flat particle emulsion of finishing is 100, the silver amount in the layer of growing after adding the silver iodide grain emulsion is preferably 5 to 50, most preferably is 10 to 30.To the temperature in this layer formation process, pH and pBr have no particular limits.But temperature is generally 40 ℃ to 90 ℃, and more preferably 50 ℃ to 80 ℃, pH is generally 2 to 9, more preferably 3 to 7.In the present invention, form last pBr at this layer and preferably be higher than the pBr that layer forms the starting stage.Preferably forming the pBr of starting stage at layer is 2.9 or lower, and is 1.7 or higher at the pBr that layer forms final stage.The pBr that forms the starting stage particularly preferably in layer is 2.5 or lower, and is 1.9 or higher at the pBr that layer forms final stage.Most preferably forming the pBr of starting stage at layer is 1 to 2.3 or lower, and is 2.1 to 4.5 or higher at the pBr that layer forms final stage.In the method for the invention, preferably introduce displacement line by said method.

The sensitizing of falling of carrying out among the present invention is handled and can be selected from following method, a method is to add to fall sensitizer in silver emulsion, a method that is known as silver-colored slaking, wherein particle is grown or slaking in the low pAg environment of a pAg1 to 7, with a method that is known as high pH slaking, wherein particle is grown or slaking in the high pH environment of pH8 to 11.Also can be with two or more combination the in these methods.

It is preferred adding the method for falling sensitizer, because can regulate subtly the level of falling the sensitizing processing.

The known example that falls sensitizer is a tin chloride, ascorbic acid and derivant thereof, quinhydrones and derivant thereof, catechol and derivant thereof, azanol and derivant thereof, amine and polyamines, hydrazine and derivant thereof, p-phenylenediamine (PPD) and derivant thereof, formamidine sulfinic acid (thiourea dioxide), a kind of silane compound and a kind of borane compound.Fall in the sensitizing processing of the present invention, can select for use these this compounds that fall sensitizer or two or more types to use together.As falling the method that sensitizing is handled, can use to be disclosed in United States Patent (USP) 2,518,698,3,201,254,3,411,917,3,779,777 and 3,930,867 method, its content is incorporated herein by reference.Fall the method for sensitizer for use, can use to be disclosed in Japanese Unexamined Patent Publication No (hereinafter being called JP-B-) 57-33572, the method among JP-B-58-1410 and the JP-A-57-179835, its content is incorporated herein by reference.Preferably being used as the compound that falls sensitizer is tin chloride, thiourea dioxide, dimethyamine borane (borine-dimethyl amine compound), ascorbic acid and derivant thereof.Though should satisfy the working condition of emulsion to the selection of falling the sensitizer addition, suitable amount is that every mole of silver halide is 10 ^-7To 10 ^-2Mole.

Fall sensitizer and be dissolved in water or a kind of solvent, for example pure, glycol, ketone, ester, or acid amides, and preferably the solution that obtains is added in the particle growth process.

Preferably will fall sensitizer adds in the presence of the compound shown in following formula (4) or (5):

In formula (4) and (5), each expression sulfo group or hydrogen atom among W51 and the W52.At least one expression sulfo group among W51 and the W52.Sulfo group is generally alkali metal salt, for example sodium or potassium, perhaps water soluble salt ammonium salt for example.The real example of preferred compound is 3,5-disulfo catechol disodium salt, and 4-sulfo group catechol ammonium salt, 2,3-dihydroxy-7-sulfo group naphthalene sodium salt, and 2,3-dihydroxy-6,7-disulfo naphthalene sylvite.The temperature of the system that preferred addition can will add according to this compound, pBr, and pH, the type of protective colloid formulation example such as gelatin and concentration, and the existence of ag halide solvent is whether, type and concentration and change.But, every mole of silver halide, addition is preferably 0.005 to 0.5 mole, more preferably 0.003 to 0.02 mole.

The example that can be used for ag halide solvent of the present invention is described in for (a), for example, and United States Patent (USP) 3,271,157,3,531,289, with 3,574,628, organic thioether with JP-A-54-1019 and JP-A-54-158917, (b) be described in, for example, JP-A-53-82408, JP-A-55-77737, with the thiourea derivative of JP-A-55-2982, (c) be described in the ag halide solvent that having of JP-A-53-144319 is added in middle thiocarbonyl group between oxygen or sulphur atom and nitrogen-atoms, (d) be described in the imidazoles of JP-A-54-100717, (e) ammonia and (f) thiocyanate.

Particularly preferred solvent is a thiocyanate, ammonia, and tetramethyl thiourea.Though employed quantity of solvent changes according to the type of solvent, the amount of every mole silver halide thiocyanate is preferably 1 * 10 ^-4To 1 * 10 ^-2Mole.

Can be with reference to the method for the face amount number of the side of the variation flat particle emulsion described in EP515894A1 etc.And, can use to be described in, for example, US5,252,453 described polyoxyalkylene compounds.Use is described in, for example, US680,254, US4,680,255, US4,680,256, and US4,684,607 facial index modifier is very effective.Common photograph spectrum sensitizing dye also can be used as facial index modifier.

In the present invention, as long as satisfy above-mentioned required condition, can prepare iodine silver bromide or bromine chlorosulfonylation silver flat particle emulsion by various method.The method for preparing flat particle emulsion consists essentially of 3 steps, nucleation, slaking, and growth.In the nucleation step of flat particle emulsion of the present invention, use is described in US4,713,320 and US4,942,120 the gelatin that contains a small amount of methionine is effective especially, be described in US4, carrying out nucleogenesis under 914,014 the high pBr, and carrying out nucleogenesis in the short time of JP-A-2-222940 being described in, its full content is incorporated herein by reference.In the maturation stage of flat particle emulsion of the present invention, sometimes at US5, under the existence of 254,453 described low concentration alkali and at US5, it is very effective to carry out slaking under 013,641 the high pH.Its content is incorporated herein by reference.In the growth step of flat grain emulsion of the present invention, at US5,248,587 described low temperature are down with at US4, and it is effective especially to grow under the condition of the trickle silver iodide particle of 693,964 described uses, and its content is incorporated herein by reference.In addition, preferably, grow under the condition of iodine silver bromide and bromine chlorosulfonylation silver fine particle emulsion by adding and the slaking silver bromide.Also may provide these fine particle emulsion by the stirring apparatus that use is described in JP-A-10-43570, its content is incorporated herein by reference.

Agi content on the particle surface of flat particle emulsion of the present invention is preferably 10mol% or lower, preferred especially 5mol% or lower.Mensuration to the agi content on the particle surface of the present invention is undertaken by using XPS (the sub-spectroscope of X-ray photoelectric).The principles illustrated of XPS of agi content that is used to analyze the silver halide particle near surface is in Jurmich Aihara etc., " Spectra of Electrons " (Kyoritsu Library 16:issued Showa 53 byKyoritsu Shuppan).The measuring method of a kind of XPS of standard is to use Mg-K α as exciting the X-ray, and measures the intensity of the photoelectron (being generally I-3d5/2 and Ag-3d5/2) of the iodine (I) that discharges from the silver halide particle of suitable sample form and silver-colored (Ag).The content of iodine can calculate from a kind of typical curve, and this typical curve is by using iodine (I) that several standard models with known content of iodine the form photoelectron volume efficiency (intensity (I)/intensity (Ag)) to silver (Ag).Measuring for the XPS of silver emulsion must be at the gelatin quilt of the surface adsorption of silver halide particle, for example, proteinase decompose and remove after carry out.Wherein the agi content on the particle surface be 10mol% or lower flat particle emulsion be a kind of when this emulsion grain during by XPS analysis its agi content be 10mol% or lower emulsion.When if the emulsion of two or more types is mixed together significantly, must carry out suitable processing again, for example centrifuging or filtration analyzed one type emulsion then.

When the particle surface of flat particle emulsion of the present invention contained 10mol% or lower silver iodide, effect of the present invention was very obvious.The agi content of this particle surface is more preferably 1 to 5mol%.The structure optimization of flat particle emulsion of the present invention is triplen or a kind of more senior structure of silver bromide/iodine silver bromide/silver bromide.The boundary of the agi content between structure can be a kind of clear interface or a kind of interface that gradually changes continuously.Usually, when using the powder x-ray diffraction method to measure, agi content does not show any two tangible peaks; It shows a kind of X-ray diffraction curve, and its afterbody extends on the direction of high agi content.

In the present invention, agi content preferably is higher than surperficial content in a layer of interior surface (or phase); Agi content in the surface in layer is preferably 5mol% or higher, more preferably 7mol% or higher.

Photographic emulsion of the present invention has preferably carried out beam split sensitizing, makes its red-light-sensing." red-light-sensing " be meant emulsion carried out beam split sensitizing, has maximum photonasty at 600nm to 700nm after making beam split sensitizing.

Spendable sensitizing dye is described in, for example, JP-A-2-68539, the 4th page, the lower right hurdle, the 4th row, to the 8th page, lower right hurdle, and JP-A-2-58041, the 12nd page, bottom Zuo Lan, the 8th page, to the lower right hurdle, the 19th row, its content is incorporated herein by reference.The example of other of operable sensitizing dye is described in Deutsche Bundespatent 929,080, United States Patent (USP) 2,493,748,2,503,776,2,519,001,2,912,329,3,656,959,3,672,897, with 4,025,349, BrP 1,242,588, and JP-B-44-14030, its full content is incorporated herein by reference.

Though these sensitizing dyes can use separately, these sensitizing dyes also can be used in combination.The combination of these sensitizing dyes is normally used for the occasion of rich shade sensitizing.The representational example of this combination is described in United States Patent (USP) 2,688,545,2,977,229,3,397,060,3,522,052,3,527,641,3,617,293,3,628,964,3,666,480,3,672,898,3,679,428,3,703,377,3,769,301,3,814,609,3,837,862 and 4,026,707, BrP 1,344,281 and 1,507,803, JP-B-43-4936, JP-B-53-12375, JP-A-52-110618, and JP-A-52-109925, its full content is incorporated herein by reference.

In the present invention, especially preferably carry out red-light-sensing beam split sensitizing by the cyanine dye that adds two or more types.The cyanine dye of two or more types of not all this must be a red-light-sensing; Just after the cyanine dye of two or more types added, the beam split sensitizing that must carry out made the beam split zone of the photosensitive maximal value of beam split sensitizing at ruddiness.

Except sensitizing dye, emulsion also can contain the dyestuff with beam split sensitizing effect or must not absorb visible light and present the material of rich shade sensitizing.Sensitizing dye can add in the emulsion by any one point in the preparation emulsion process, and this point is known generally to be useful.Usually, adding is carried out after chemical sensitization is finished and before coating.But, also can when adding the chemical sensitization dyestuff, add, beam split sensitizing and chemical sensitization are carried out simultaneously, as United States Patent (USP) 3,628,969 and 4,225,666 is described, and its content is incorporated herein by reference.Also can add before chemical sensitization, as described in JP-A-58-113928, its content is incorporated herein by reference, perhaps beginning beam split sensitizing before finishing the formation of silver halide particle precipitation.Perhaps, as United States Patent (USP) 4,225,666 is described, and its content is incorporated herein by reference, and these compounds can separately add; Part compound can add before chemical sensitization, and rest parts adds after this.That is to say that these compounds can add in any time in the silver halide particle forming process, comprise being described in United States Patent (USP) 4,183,756 methods of describing, its content is incorporated herein by reference.

Every mole of silver halide of addition of sensitizing dye is preferably 2 * 10 in the flat particle emulsion of the present invention ^-4Mole or higher.

In the formation of silver halide particle of the present invention, any one point in the process of preparation silver emulsion can carry out sulphur sensitizing, selenium sensitizing and precious metal sensitizing and comprise golden sensitizing and palladium sensitizing and fall at least a in the sensitizing.Preferred two or more different process for increasing sensitivity that use.Can prepare several emulsions not type by changing time that chemical sensitization carries out.Emulsion is classified as: wherein in intragranular type, wherein it is by the type of heeling-in in the superficial part position of a close particle surface by heeling-in for the chemical sensitization spot, and wherein it is formed at the type on the surface of particle.In emulsion of the present invention, the position of chemical sensitization spot can be selected according to predetermined purposes.But, preferably form the chemical sensitization spot of at least a type near surface.

A kind of chemical sensitization of preferably carrying out is a chalcogen sensitizing in the present invention, precious metal sensitizing, perhaps their combination.Sensitizing can be undertaken by using active gelatin, as T.H.James, and TheTheory of the Photographic Process, 4th ed., Macmillan, 1977, the 67 to 76 pages are described.Sensitizing also can be by using sulphur, selenium, tellurium, gold, platinum, any in palladium and the iridium, or by using the multiple pAg 5 to 10 that is combined in these sensitizers, pH 5 to 8 and under 30 ℃ to 80 ℃ condition, carrying out, as described in following document: Research Disclosure (research is open), Vol.120, April, 1974,12008, Research Disclosure, Vol.34, June, 1975,13452, United States Patent (USP) 2,642,361,3,297,446,3,772,031,3,857,711,3,901,714,4,266,018 and 3,904,415 and BrP 1,315,755.In precious metal sensitizing, can use precious metal, for example the salt of gold, platinum, palladium and iridium.Preferred especially golden sensitizing, palladium sensitizing, perhaps their combination.In golden sensitizing, can use compound known, gold chloride for example, potassium chloroaurate, golden thiocyanate potassium, aurosulfo, and Auric selenide.Palladium compound is meant the palladium salt of a kind of divalence or tetravalence.Preferred palladium compound is expressed from the next: R ₂PdX ₆Perhaps R ₂PdX ₄Wherein, R represents hydrogen atom, alkali metal atom, and perhaps ammonium group, X represents halogen atom, i.e. chlorine, bromine, or iodine atom.

Specifically, palladium compound is preferably K ₂PdCl ₄, (NH ₄) ₂PdCl ₆, Na ₂PdCl ₄, (NH ₄) ₂PdCl ₄, Li ₂PdCl ₄, Na ₂PdCl ₆, perhaps K ₂PdBr ₄Preferred gold compound and palladium compound and thiocyanate or selenium cyanate are used in combination.

The example of sulphur sensitizer is for being described in United States Patent (USP) 3,857, and 711,4,266,018 and 4,054,457 hypo (hypo), a kind of is the compound of base with the thiocarbamide, a kind of is the compound of base with the rhodanine, and sulfocompound.Chemical sensitization also can a kind of be called as the chemical sensitization auxiliary agent in the presence of carry out.The example of spendable chemical sensitization auxiliary agent is, for example, the azepine indenes, azepine pyridazine, and aza-pyrimidine, they are known as and can suppress photographic fog and improve photosensitive compound in the chemical sensitization process.The example of chemical sensitization auxiliary agent and modifier is described in United States Patent (USP) 2,131, and 038,3,411,914 and 3,554,757, JP-A-58-126526, and G.F.Duffin, photographic emulsion chemistry, the 138th to 143 page.

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

With respect to silver halide particle of the present invention, the amount of every mole silver halide sulphur sensitizer is preferably 1 * 10 ^-4To 1 * 10 ^-7Mole, more preferably 1 * 10 ^-5To 5 * 10 ^-7Mole.

Selenium sensitizing is preferred process for increasing sensitivity for emulsion of the present invention.Known unsettled selenium compound is used to selenium sensitizing.The example of this selenium compound is a colloidal metal selenium, selenourea (for example, N, N-dimethyl selenourea and N, N-diethyl selenourea), selenium ketone and selenium acid amides.In some cases, preferably the combining of one or both in selenium sensitizing and sulphur sensitizing and the precious metal sensitizing carried out.

In the present invention, preferably before adding above-mentioned beam split sensitizing dye and chemical sensitizer, add thiocyanate.Preferably after particle forms, more preferably after the desalination step, add thiocyanate.Because preferably add thiocyanate in chemical sensitization, the adding of thiocyanate is carried out twice or repeatedly.The example of thiocyanate is a potassium rhodanide, sodium thiocyanate, and ammonium thiocyanate.

Thiocyanate adds by being dissolved in the aqueous solution or in the water-soluble solvent usually.Addition is preferably 1 * 10 in every mole silver halide ^-5To 1 * 10 ^-2Mole is preferably 5 * 10 ^-5To 5 * 10 ^-3Mole.

Using gelatin in preparation emulsion of the present invention is favourable as protective colloid, perhaps as other the bonding agent of hydrophilic colloid layer.But, also can use other hydrophilic colloid to replace gelatin.

The example of hydrophilic colloid is a protein, gelatine derivative for example, the graft polymer of gelatin and another kind of high molecular polymer, albumin, and casein; Sugar derivatives, cellulose derivative for example, for example, sulfate cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose, soda ash alginates, and starch derivative; With multiple synthetic high molecular weight hydrophilic polymer, for example homopolymer or multipolymer, polyglycol for example, polyalkylene glycol moiety acetal, the poly-N-vinyl pyrrolidone, polyacrylic acid, polymethylacrylic acid, polyacrylamide, polyvinyl imidazol and polyvinyl pyrazoles.

The example of gelatin is the gelatin of lime treatment, the gelatin that acid-treated gelatin and enzyme are handled, and as Bull.Soc.Sci.Photo.Japan.No.16, the 30th page (1966) are described.In addition, also can use the hydrolysate or the enzymatic degradation product of gelatin.

Preferred washing emulsion of the present invention, to form a kind of freshly prepd protective colloid dispersion, purpose is for desalination.Though the temperature for washing can be selected preferred 5 ℃ to 50 ℃ according to predetermined purposes.Though the pH of washing also can select according to predetermined purposes, is preferably 2 to 10, more preferably 3 to 8.The pAg of washing is preferably 5 to 10, though also can select according to predetermined purposes.Washing methods can be selected from the noodles washing, uses the dialysis of semi-permeable diaphragm, centrifuging, coagulating sedimentation, and ion-exchange.Coagulating sedimentation can be selected from the method for using sulfate, and method is with an organic solvent used the method for water-soluble polymers and the method for use gelatine derivative.

In the preparation of emulsion of the present invention, preferably make the salt of metallic ion be present in the formation of particle, desalination, or in the process of chemical sensitization, perhaps before the coating according to predetermined purposes.Metal cation salt preferably adds in the particle forming process when being mixed into particle, adds after particle forms and before chemical sensitization is finished when being used to repair particle surface or being used as chemical sensitizer.This salt can be incorporated into any one part of complete particle, only in the core of particle, and in the shell, the perhaps part of extension, and only be a kind of matrix granule.The example of metal 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., they all can add ammonium salt for example, acetate, nitrate, sulfate, phosphate, hydrochloride, 6-coordination complex salt, perhaps 4-coordination complex salt as long as dissolving these metals for the form of salt and in the forming process of particle.Concrete example is CdBr ₂, CdCl ₂, Cd (NO ₃) ₂, Pb (NO ₃) ₂, Pb (CH ₃COO) ₂, K ₃[Fe (CN) ₆], (NH ₄) ₄[Fe (CN) ₆], K ₃IrCl ₆, (NHN ₄) ₃RhCl ₆, and K ₄Ru (CN) ₆The part of ligand compound can be selected from halogen, hydration, cyano group, cyanate, thiocyanate, nitrosyl radical, sulphur nitrosyl radical, oxo, and carbonyl.These metallic compounds can use separately or two or more type combination are used.

These metallic compounds preferably are dissolved in the appropriate solvent, for example in methyl alcohol or the acetone, and add with the form of solution.For stabilizing solution, can add a kind of hydrogen halides (for example HCl and HBr) aqueous solution or a kind of alkali halide (for example, KCl, NaCl, KBr, and NaBr).Also can add acid or alkali if desired.Metallic compound can add reaction vessel before particle forms or in the process that forms.Perhaps, metallic compound can be added into water miscible silver salt (for example, AgNO ₃) or a kind of alkali halide solution (for example, NaCl, KBr, and KI) and in the process that silver halide particle forms the form with solution add continuously.And, this solution of metal compound can be independently with the form preparation of water soluble salt or alkali halide, and in granuloplastic process, add continuously at reasonable time.Also several different adding methods can be merged and use.

The method that adds a kind of chalcogen compound in the preparation process of emulsion is useful sometimes, and as United States Patent (USP) 3,772,031 is described.Except S, can there be cyanate in Se, and Te, thiocyanate, selenium cyanic acid, carbonate, phosphate, and acetate.

The preferred oxygenant that uses a kind of silver in the preparation process of emulsion of the present invention.But galactic nucleus is caught in the cavity that should keep on the particle surface to a certain extent.The oxygenant of silver is meant a kind of compound that argent can be changed into silver ion.Special compounds effective be a kind of silver halide particle is formed and the process of chemical sensitization in the trickle silver-colored particle as accessory substance formation change into silver ion.The silver ion that is produced can form a kind of water-soluble silver salt that is difficult to, silver halide for example, silver sulfide, perhaps silver selenide, perhaps a kind of water-soluble silver salt, for example silver nitrate of being easy to.The oxygenant of silver can be a kind of inorganic or organic material.The example of inorganic oxidizer is an ozone, hydrogen peroxide and addition product thereof (for example, NaBO ₂H ₂O ₂3H ₂O, 2NaCO ₃3H ₂O ₂, Na ₄P ₂O ₇2H ₂O ₂, and 2Na ₂SO ₄H ₂O ₂2H ₂O), peracid salt (for example, K ₂S ₂O ₈, K ₂C ₂O ₆, and K ₂P ₂O ₈), peroxide compound compound (for example, K ₂[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 (for example, KMnO ₄), hydroxy-acid salt, for example chromate (for example, K ₂Cr ₂O ₇), halogens is iodine and bromine for example, perhalide (for example, potassium metaperiodate), the salt of high-valency metal (for example, six cyano group potassium ferrates (II)), and thiosulfonate.

The example of organic oxidizing agent is a quinone, paraquinones for example, organic peroxide, for example peracetic acid and benzylhydroperoxide and discharge the compound (for example, N-bromine succinimide, toluene-sodium-sulfonchloramide, and chloramine B) of reactive halogen.

Preferred oxygenant is an ozone among the present invention, hydrogen peroxide and addition product thereof, halogen, inorganic oxidizer of thiosulfonate and the organic oxidizing agent of quinones.

The photographic emulsion that the present invention uses can contain multiple compound, to prevent preparation, stores, or the photographic fog of intensifying material in the photograph process, perhaps stablize photographic property.Spendable compound is known anti-photographic fog agent or stabilizing agent, for example, and thiazoles, benzothiazolium salt for example, nitroimidazole, nitrobenzimidazole, chloro benzimidazole, bromobenzene and imidazoles, mercaptothiazole, mercaptobenzothiazoler, mercaptobenzimidazole, dimercaptothiodiazole, aminotriazole(ATA), benzotriazole, nitrobenzene and triazolam, and mercapto-tetrazole (particularly 1-phenyl-5-mercapto-tetrazole); Mercaptopyrimidine; Mercapto-triazine; Thione compounds, for example oxadolinethione; The azepine indenes, benzotriazole for example, the purine (particularly (1,3,3a, 7) purine of hydroxyl-replacement) and pentaaza indenes.For example can use to be described in United States Patent (USP) 3,954 474 and 3,982,947 and the compound of JP-B-52-28660.A kind of preferred compound is described in Japanese patent application No.62-47225.Anti-photographic fog agent and stabilizing agent can add at any one time point in several different time points according to predetermined purposes, for example before particle forms, in the process that forms, add with forming afterwards, in the process that washes with water, in the dispersion process after washing, before chemical sensitization, in the process of sensitizing, add after the sensitizing, before coating, add.Anti-photographic fog agent and stabilizing agent can add in the preparation process of emulsion, prevent effect and stablizing effect with the original photographic fog that reaches them.In addition, anti-photographic fog agent can be used to different purposes with stabilizing agent, and for example, the crystal habit of control particle with the agent particle size, reduces the solubleness of particle, control chemical sensitization, and the layout of control dyestuff.

For example the layer placement technique, silver emulsion, dye forming coupler, the function colour coupler is the DIR colour coupler for example, various adjuvants, with the development that can be used for emulsion of the present invention and the technical description of sensitive photographic material that uses this emulsion in European patent No.0565096A1 (open day on October 13rd, 1993) and the patent wherein quoted, its full content is incorporated herein by reference.Each project and corresponding part outline as follows.

1. layer is arranged: the 61st page, 23-35 is capable, and the 61st page, 62 pages of the 41st row-Di, the 14th row

2. middle layer: the 61st page, 36-40 is capable

3. (interimage) effect gives layer between image: the 62nd page, 15-18 is capable

4. the silver halide halogen is formed: the 62nd page, 21-25 is capable

5. silver halide particle crystal habit: the 62nd page, 26-30 is capable

6. silver halide particle size: the 62nd page, 31-34 is capable

7. method of preparing emulsion: the 62nd page, 35-40 is capable

8. silver halide particle size distribution: the 62nd page, 41-42 is capable

9. flat particle: the 62nd page, 43-46 is capable

10. the inner structure of particle: the 62nd page, 47-53 is capable

11. the emulsion latent image forms type: the 62nd page, 63 pages of the 54th row-Di, the 5th row

12. the physics slaking of emulsion. chemical slaking: the 63rd page, 6-9 is capable

13. the use of emulsion mixture: the 63rd page, 10-13 is capable

14. the emulsion of photographic fog: the 63rd page, 14-31 is capable

15. non-photosensitive emulsion: the 63rd page, 32-43 is capable

16. silver-colored coating weight: the 63rd page, 49-50 is capable

17. photograph adjuvant: be described in Research Disclosure (RD) 17643 (in Dec, 1978), RD item 18716 (in November, 1979) and RD item 307105 (in November, 1989).Each and corresponding part are shown in following table:

	Adjuvant	RD17643	RD18716
				1.	Chemical sensitizer	The 23rd page	The 648th page, right hurdle
2.	The photonasty improving agent		On logical
				3.	Divide light sensitizer, the rich shade sensitizer	The 23-24 page or leaf	The 648th page, 649 pages on right hurdle to the, right hurdle
4.	Whitening agent	The 24th page	The 647th page, right hurdle
				5.	Anti-photographic fog agent and stabilizing agent	The 24-25 page or leaf	The 649th page, right hurdle
6.	Light absorber, filter membrane dyestuff, ultraviolet absorber	The 25-26 page or leaf	The 649th page, 650 pages on right hurdle to the, left hurdle
				7.	Color spot prevents agent	The 25th page, right hurdle	The 650th page, the left-to-right hurdle
8.	The pigment image stabilizing agent	The 25th page	The 650th page, left hurdle
				9.	Rigidizer	The 26th page	The 651st page, left hurdle
10.	Bonding agent	The 26th page	The 651st page, left hurdle
				11.	Plastifier, lubricant	The 27th page	The 650th page, right hurdle
12.	Coating additive, surfactant	The 26-27 page or leaf	The same
				13.	Antistatic agent	The 27th page	The same
14.	Delusterant

	Adjuvant	RD307105
			1.	Chemical sensitizer	The 866th page
2.	The photonasty improving agent
			3.	Divide light sensitizer, the rich shade sensitizer	The 866-868 page or leaf
4.	Whitening agent	The 868th page
			5.	Anti-photographic fog agent and stabilizing agent	The 868-870 page or leaf
6.	Light absorber, filter membrane dyestuff, ultraviolet absorber	The 873rd page
			7.	Color spot prevents agent	The 872nd page
8.	Pigment portrait stabilizing agent	The 872nd page
			9.	Rigidizer	The 874-875 page or leaf
10.	Bonding agent	The 873-874 page or leaf
			11	Plastifier, lubricant	The 876th page
12.	Coating additive, surfactant	The 875-876 page or leaf
			13.	Antistatic agent	The 876-877 page or leaf
14.	Delusterant	The 878-879 page or leaf

18. formaldehyde scavenger: the 64th page, 54-57 is capable

19. the anti-photographic fog agent based on sulfydryl: the 65th page, 1-2 is capable

20. reagent is emitted, for example photographic fog agent: the 65th page, 3-7 is capable

21. dyestuff: the 65th page, 7-10 is capable

22. general colour former agent: the 65th page, 11-13 is capable

23. yellow, magenta, and cyan colour coupler: the 65th page, 14-25 is capable

24. polymkeric substance colour coupler: the 65th page, 26-28 is capable

25. diffusivity dye forming coupler: the 65th page, 29-31 is capable

26. colour former agent: the 65th page, 32-38 is capable

27. general utility functions colour coupler: the 65th page, 39-44 is capable

28. bleach boosters-be released into toner: the 65th page, 45-48 is capable

29. development accelerant-be released into toner: the 65th page, 49-53 is capable

30. other DIR colour coupler: the 65th page, 66 pages of the 54th row-Di, the 4th row

31. colour coupler process for dispersing: the 66th page, 5-28 is capable

32. antiseptic, mildewproof agent: the 66th page, 29-33 is capable

33. sense material type: the 66th page, 34-36 is capable

34. photographic layer thicknesses of layers and speed of expansion: the 66th page, 67 pages of the 40th row-Di, the 1st row

35. backing layer: the 67th page, 3-8 is capable

36. general development treatment: the 67th page, 9-11 is capable

37. developer solution and developer: the 67th page, 12-30 is capable

38. developer solution adjuvant: the 67th page, 31-44 is capable

39. counter-rotating is handled: the 67th page, 45-56 is capable

40. treating fluid aperture opening ratio: the 67th page, 68 pages of the 57th row-Di, the 12nd row

41. development time: the 68th page, 13-15 is capable

42. bleaching-photographic fixing, bleaching, and photographic fixing: the 68th page, 69 pages of the 16th row-Di, the 31st row

43. automatic processing machine: the 69th page, 32-40 is capable

44. washing, immersion and stable: the 69th page, 70 pages of the 41st row-Di, the 18th row

45. treating fluid replenishes, using: the 70th page, 19-23 is capable

46. developer is compound in the intensifying material: the 70th page, 24-33 is capable

47. development temperature: the 70th page, 34-38 is capable

48. use lens on rete: the 70th page, 39-41 is capable

Also can preferably use the liquid lime chloride that is described in European patent No.602600, it contains 2-Pyridinecarboxylic Acid or 2, dipicolimic acid 2, molysite, ferric nitrate for example, persulfuric acid iron.When using this liquid lime chloride, preferably between colour development step and blanching step, insert one and stop step and a washing step, and use organic acid, acetate for example, succinic acid, or maleic acid is as stopping body lotion.And for pH regulator and bleaching photographic fog, liquid lime chloride preferably contains the organic acid of 0.1 to 2mol/ liter (hereinafter will rise writing " L "), acetate for example, succinic acid, maleic acid, glutaric acid, perhaps hexane diacid.

When silver halide photographic sensitive material of the present invention is preferably used as color sensitive material, that the order of arrangement of layer is generally from the supporting layer side is red-, green-and indigo plant-photosensitive material.But, can reverse according to this arrangement order of predetermined purposes, perhaps can use a kind of like this arrangement order, wherein, different photographic layers is inserted in between a kind of color sensitive layer.Between the light-sensitive silver halide layer, can form non-photographic layer, and as the superiors and orlop.They can contain, for example, and colour coupler hereinafter described, DIR compound and color mix inhibitor.Silver halide emulsion layer as each photographic layer unit of a plurality of formations, preferred arrangement a kind of high-and the double-decker of low-fast emulsion layer, thereby photonasty is reduced in order on the direction of supporting layer, as DE No.1,121,470 or GBNo.923,045 is described, and its content is incorporated herein by reference.And, as JP-A ' s-57-112751,62-200350,62-206541 and 62-206543 are described, its content is incorporated herein by reference, and to the arrangement of each layer the low velocity emulsion layer is formed on the one side away from supporting layer, and two high-speed emulsion layers form on the face near supporting layer.

Specifically, is that low velocity sense blu-ray layer (BL)/is at a high speed felt blu-ray layer (BH)/high-speed green-light-sensing layer (GH)/low velocity green-light-sensing layer (GL)/high-speed red-light-sensing layer (RH)/low velocity red-light-sensing layer (RL) to the arrangement of each layer from the order away from the face of supporting layer, and order be that BH/BL/GL/GH/RH/RL or order are BH/BL/GH/GL/RL/RH.

In addition, as described in JP-B-55-34932, its content is incorporated herein by reference, and the arrangement of each layer is sense blu-ray layer/GH/RH/GL/RL from the order away from the face of supporting layer.

And as described in JP-A-56-25738 and JP-A-62-63936, its content is incorporated herein by reference, and the arrangement of each layer is sense blu-ray layer/GL/RL/GH/RH from the order away from the face of supporting layer.

As described in JP-B-49-15495, its content is incorporated herein by reference, three layers are arranged, be that the silver halide emulsion layer with high photosensitivity is arranged to the upper strata, have the photosensitive silver halide emulsion layer that is lower than this upper strata and be arranged to the middle layer, and will have the photosensitive silver halide emulsion layer that is lower than this middle layer and be arranged to lower floor; That is to say to have different photosensitive layers and arrange, photonasty is reduced in order on the direction of supporting layer.Even in layer structure is above-mentioned to have different photosensitive layers when constituting by three, a kind of to a kind of layer of color sensitive in the order of these layers begin to be arranged to medium velocity emulsion layer/high-speed emulsion layer/low velocity emulsion layer from face away from supporting layer, described in JP-A-59-202464, its content is incorporated herein by reference.

In addition, can use the order of high-speed emulsion layer/low velocity emulsion layer/medium velocity emulsion layer or low velocity emulsion layer/medium velocity emulsion layer/high-speed emulsion layer.And even when forming four or a plurality of layers, arrangement can change as mentioned above.

In order to improve color rendition, as United States Patent (USP) 4,663,271,4,705,744,4,707,436, JP-A-62-160448 and JP-A-63-89850, its content is incorporated herein by reference, described have be different from main photographic layer BL, the layer (CL) that gives of the interlayer effect of GL and RL beam split photosensitive profile preferably is placed in contiguous or near main photographic layer.

In photographic material of the present invention, preferably use non-sensitization fine particle silver halide.This non-sensitization fine particle silver halide is preferably by for obtaining not sensitization in the decent exposure process that dyestuff portrait carries out and nonvisualized basically silver halide fine particle is formed in development step.These silver halide particles preferably do not form photographic fog in advance.In this trickle silver halide particle, the content of silver bromide is 0 to 100mol%, and, can contain silver chloride and/or silver iodide if desired.This trickle silver halide particle preferably contains 0.5 to 10mol% silver iodide.The mean particle size of this trickle silver halide particle, that is, the mean value of projected area equal circle diameter is preferably 0.01 to 0.5 μ m, more preferably 0.02 to 0.2 μ m.

This trickle silver halide particle can the mode identical with common Photoactive silver-halide prepare.The surface of silver halide particle does not need to carry out optical sensibilization and does not need to carry out beam split sensitizing yet.But, before joining silver halide particle in the coating solution, preferably to wherein adding a kind of known stabilizing agent usually, for example, a kind of triazole compounds, a kind of azepine indene compound, a kind of benzothiazole compound, a kind of sulfhydryl compound, or a kind of zinc compound.Collargol can be incorporated into this contain the layer trickle silver halide particle in.

The silver-colored coating weight of photosensitive material of the present invention is preferably 10.0g/m ²Perhaps lower, 6.0g/m most preferably ²Perhaps lower.

Multiple dye forming coupler can be used in the photosensitive material of the present invention, preferred especially following colour coupler.

Yellow colour former: by EP No.502, formula among the 424A (I) and the colour coupler of (II) representing; By EPNo.513, the colour coupler (particularly the 18th page Y-28) of the formula among the 496A (1) and (2) expression; By EPNo.568, the colour coupler of the formula in the claim 1 of 037A (I) expression; By U.S. Patent No. 5,066,576 the 1st hurdles, the colour coupler of general formula (I) expression in the 45th to 55 row; Colour coupler by the expression of the formula (I) in the 0008th section of JP-A-4-274425; By EP No.498, the 40th page of described colour coupler of claim 1 among the 381A1 (particularly the 18th page D-35); By EP No.447, the colour coupler shown in the 4th page (Y) among the 969A1 (particularly Y-1 (the 17th page) and Y-54 (the 41st page)); With U.S. Patent No. B4, the colour coupler shown in the formula (II) to (IV) in 476,219 (particularly II-17, II-19 (17 hurdle), and II-24 (19 hurdle)) the 7th hurdle the 36th to 58 row, its full content is incorporated herein by reference.

Magenta colour coupler: JP-A-3-39737 (L-57 (the 11st page, the bottom right hurdle), L-68 (the 12nd page, the bottom right hurdle), and L-77 (the 13rd page, the bottom right hurdle); EP No.456, [A-4]-63 (the 134th page) in 257 and [A-4]-73 and [A-4]-75 (the 139th page); EP No.486, M-4 and M-6 (the 26th page) in 965, and M-7 (the 27th page); EPNo.571, the M-45 among the 959A (the 19th page); (M-1) among the JP-A-5-204106 (the 6th page); With the 0237th section M-22 among the JP-A-4-362631, its full content is incorporated herein by reference.

Cyan colour coupler: the CX-1 among the JP-A-4-204843, CX-3, CX-4, CX-5, CX-11, CX-12, CX-14, and CX-15 (the 14th to 16 row); C-7 among the JP-A-4-43345 and C-10 (the 35th page), C-34 and C-35 (the 37th page) and (I-1) and (I-17) (the 42nd and 43 page); With formula (Ia) in the claim 1 of JP-A-6-67385 with the colour coupler (Ib), its full content is incorporated herein by reference.

The polymkeric substance colour coupler: P-1 among the JP-A-2-44345 and P-5 (the 11st page), its content is incorporated herein by reference.

The suitable diffusible colour coupler that is used to form having of coloured dye is preferably and is described in U.S. Patent No. 4,366,237, GB No.2,125,570, EP No.96,873B, with DE No.3, the colour coupler described in 234,533, its content is incorporated herein by reference.

The colour coupler that does not need to absorb that is used to repair coloured dye is preferably the yellow color cyan colour coupler, and by being described in EP No.456, the formula (CI) among the 5th page of the 257A1 (CII), (CIII) and (CIV) is described (particularly the 84th page YC-86); Yellow color magenta colour coupler ExM-7 (the 202nd page), Ex-1 (the 249th page), and EX-7 (the 251st page) are described in EP No.456,257A1; Pinkish red colored cyan colour coupler CC-9 (8 hurdle) and CC-13 (10 hurdle) are described in U.S. Patent No. 4,833,069; (2) U.S. Patent No. 4,837,136 (8 hurdles); With the colourless colour coupler of covering, shown in the formula in the claim 1 of WO No.92/11575 (A) (the particularly example of the 36th to 45 page compound), its full content is introduced this zhang as a reference.

Thereby the example (comprising colour coupler) of compound that discharges the compound residue that can be used for taking a picture with the reaction of a kind of developer of oxidised form is as described below, and the disclosed content of these files is incorporated herein by reference.Development restrainer discharges compound: by EP No.378, and the formula (I) among the 11st page of the 236A1, (II), (III) and (IV) (T-101 (the 30th page) particularly, T-104 (the 31st page), T-113 (the 36th page); T-131 (the 45th page), T-144 (the 51st page), and T-158 (the 58th page)) shown in compound; By EP No.436, the compound shown in the formula (I) (particularly D-49 (the 51st page)) among the 7th page of the 938A2; By EP No.568, the compound of the formula among the 037A (1) (particularly (23) (the 11st page)) expression; With by EPNo.440, the formula (I) in b95A2 the 5th and 6 pages, (II) and (III) compound shown in (particularly the 29th page I-(1)).The bleaching accelerator discharges compound: by EP No.310, and the compound shown in the formula (I) among the 5th page of the 125A2 and (I ') (particularly the 61st page (60) and (61)); With the compound shown in the formula (I) (particularly (7) (the 7th page)) in the claim 1 of JP-A-6-59411.Part discharges compound: by U.S. Patent No. 4,555, and the compound that the LIG-X in 478 the claim 1 represents (particularly the 12nd hurdle, the compound of the 21st to 41 row).Leuco dye releasing compound: U.S. Patent No. 4,749, the compound 1 to 6 in 641 the 3rd to 8 hurdle.Fluorescent dye discharges compound: by U.S. Patent No. 4,774, and the compound that the COUP-DYE in 181 the claim 1 represents (the particularly compound 1 to 11 in the 7th to 10 hurdle).Development accelerator or photographic fog agent discharge compound: by U.S. Patent No. 4,656, and the formula (1) in 123 the 3rd hurdle, the compound of (2) and (3) (particularly (I-22) in the 25th hurdle) expression; With EP No.450, the 75th page of 637A2, the ExZK-2 in the 36th to 38 row.Unless discharge the compound that a kind of division does not have the dyestuff function: by U.S. Patent No. 4,857, the compound of the formula in 447 claims 1 (I) (the particularly Y-1 to Y-19 in the 25th to 36 hurdle) expression.

The preferred example of the adjuvant except colour coupler is as mentioned below, and its disclosed full content is incorporated herein by reference.

The dispersion medium of oil-soluble organic compound: the P-3 among the JP-A-62-215272, P-5, P-16, P-19, p-25, P-30, P-42, P-49, P-54, P-55, P-66, P-81, P-85, P-86, and P-93 (the 140th to 144 page).The dipping latex of oil-soluble organic compound: be described in U.S. Patent No. 4,199,363 latex.Developer oxidation product scavenger: by U.S. Patent No. 4,978,606 the 2nd hurdles, formula (I) (I-(1) particularly, I-(2), I-(6) in the 54th to 62 row, and I-(12) (the 4th and 5 hurdle)) Biao Shi compound, with U.S. Patent No. 4,923, the compound of general formula (particularly compound 1 (the 3rd the hurdle)) expression in 787 the 5th to 10 row.The color spot inhibitor: among the EP No.298321A the 4th page, the 30th to 33 row, particularly I-47, I-72, III-1, and the formula (I) shown in the III-27 (the 24th to 48 page) is to (III).Discoloration inhibitor: EP No.298, the A-6 among the 321A, A-7, A-20, A-21, A-23, A-24, A-25, A-26, A-30, A-37, A-40, A-42, A-48, A-63, A-90, A-92, A-94, and A-164 (the 69th to 118 page); U.S. Patent No. 5,122, II-1 to III-23, particularly III-10 in 444 the 25th to 38 hurdles; I-1 to III-4, particularly II-2 among the EP No.471, the 8th to 12 page of 347A; With U.S. Patent No. 5,139, A-1 to A-48, particularly A-39 and A-42 in 931 the 32nd to 40 hurdles.Reduce the material of colored improving agent or color integration inhibitor consumption: I-1 to II-15, particularly I-46 among the EP No.411, the 5th to 24 page of 324A.Fu Er Malin scavenger: SCV-1 to SCV-28, particularly SCV-8 among the EP No.477, the 24th to 29 page of 932A.H-1 among the 17th page of rete rigidizer: the JP-A-1-214845, H-4, H-6, H-8, and H-14; U.S. Patent No. 4,618, the compound (H-1 to H-54) in 573 the 13rd to 23 hurdles by formula (VII) to (XII) expression; Among the JP-A-2-214852 the 8th page, the bottom right hurdle is by the compound (H-1 to H-76), particularly H-14 of formula (6) expression; Be described in U.S. Patent No. 3,325, the compound of 287 claims 1.Development restrainer guide agent: the P-24 among the JP-A-62-168139, P-37, and P-39 (the 6th and 7 page); Be described in U.S. Patent No. 5,019, the compound of 28 and 29 in 492 claims 1, particularly the 7th hurdle.Antiseptic and mildewproof agent: U.S. Patent No. 4,923, I-1 to III-43, particularly II-1 in 790 the 3rd to 15 hurdles, II-9, II-10, II-18, and III-25.Stabilizing agent and anti-photographic fog agent: U.S. Patent No. 4,923, the I-1 in 793 the 6th to 16 hurdles is to (14), particularly I-1, I-60, (2) and (13); U.S. Patent No. 4,952, the compound 1 to 65 in 483 the 25th to 32 hurdles, particularly compound 36.Chemical sensitizer: the triphenylphosphine among the JP-A-5-40324, selenide and compound 50.A-1 to b-20, particularly a-1 among the 15th to 18 page of dyestuff: the JP-A-3-156450, a-12, a-18, a-27, a-35, a-36, and b-5, V-1 to V-23, particularly V-1 in the 27th to 29 page; F-I-1 to F-II-43, particularly F-I-11 and F-II-8 among the EP No.445, the 33rd to 55 page of 627A; III-1 to III-36, particularly III-1 and III-3 among the EP No.457, the 17th to 28 page of 153A; The crystallite dispersion of Dye-1 to Dye-124 among the 8th to 26 page of the WO No.88/04794; Compound 1 to 22 among the EP No.319, the 6th page of 999A, particularly compound 1; EP No.519, the Compound D of being represented by formula (1) to (3) among the 306A-1 is to D-87 (the 3rd to 28 page); U.S. Patent No. 4,268, the compound 1 to 22 (the 3rd to 10 hurdle) of 622 Chinese styles (I) expression; With U.S. Patent No. 4,923, compound (1) to (31) (the 2nd to 9 hurdle of 788 Chinese styles (I) expression.Ultraviolet light absorber: the compound (18b) to (18r) and 101 to 427 (the 6th to 9 page) of JP-A-46-3335 Chinese style (1) expression; EP No.520, the compound (3) to (66) (the 10th to 44 page) of 938A Chinese style (I) expression and the compound H BT-1 to HBT-10 (the 14th page) that represents by formula (III); With EP No.521, the compound (1) to (31) (the 2nd to 9 hurdle) of 823A Chinese style (1) expression.

Photographic material of the present invention can be used on the multiple color sensitive material, for example, is used for the colored negative film of general service or film, is used for the color reverse film of lantern slide and TV, colour paper, colored positive photoresist film and colour reversal photographic paper.And photographic material of the present invention is applicable to the lens of having equipped the film unit that is described in JP-B-2-32615 and the novel patent disclosure No.3-39784 of Japan's use.

Be applicable to that carrier of the present invention is described in, for example, RD.No.17643, the 28th page; RD.No.18716,648 pages the left hurdle from the 647th page right hurdle to the; And RD.No.307105, the 879th page.

In photosensitive material of the present invention, be preferably 28 μ m or lower in total film thickness, more preferably 23 μ m or lower, further preferred 18 μ m or lower, most preferably 16 μ m or lower with whole hydrophilic colloid layers on the side of emulsion layer.Film speed of expansion T _1/2Be preferably 30 seconds or lower, more preferably 20 seconds or lower.Film speed of expansion T _1/2Be defined as, when saturated film thickness be meant by 30 ℃ carry out maximum swelling film thickness that the colour development solution-treated realizes 3 minutes 15 seconds 90% the time, be used for the 1/2 needed time that film thickness reaches this saturated film thickness.Film thickness is meant that under the condition of humidity 25 ℃ and relative humidity be the film thickness that 55% (two days) record.Film speed of expansion T _1/2Can be described in A.Green etc. by use, Photogr.Sci.Eng., Vol.19, No.2, the 124th to 129 page dilatometer is measured.Film speed of expansion T _1/2Can regulate by changing aging condition as bonding agent or after coating by in gelatin, adding the film rigidizer.Expansivity is preferably 150 to 400%.Expansivity can be calculated according to the following equation from the maximum swelling film thickness that records under these conditions:

(maximum swelling film thickness-film thickness)/film thickness.

In photosensitive material of the present invention, preferably formation has the hydrophilic colloid layer (being known as " backing layer ") that 2 to 20 μ m always feel film thickness on relative side, the side with emulsion layer.This tegillum preferably contains above-mentioned light absorber, filter membrane dyestuff, ultraviolet absorber, antistatic agent, film rigidizer, bonding agent, plastifier, lubricant, coating additive and surfactant.The expansivity of backing layer is preferably 150% to 500%.

Photosensitive material of the present invention can develop by the method for routine, and these methods are described in above-mentioned RD.No.17643, the 28th and 29 page; RD.No.18716, the 651st page, the left-to-right hurdle; With RD No.307105, the 880th and 881 page.

Hereinafter use description to colored negative film Treatment Solution of the present invention.

List in the 9th page of JP-A-4-121739, upper right hurdle, the 1st row, to the 11st page, the hurdle, lower-left, the compound of the 4th row can be used in the colour development solution used in the present invention.Being used for the special preferred color developer of process fast is, for example, 2-methyl-4-[N-ethyl-N-(2-hydroxyethyl) amino] aniline, 2-methyl-4-[N-ethyl-N-(3-hydroxypropyl) amino] aniline and 2-methyl-4-[N-ethyl-N-(4-hydroxyl butyl) amino] aniline.

The consumption of these color developers is preferably 0.01 to 0.08 mole in every liter of colour development solution, more preferably 0.015 to 0.06 mole, most preferably is 0.02 to 0.05 mole.The amount of the color developer that contains in the additional liquid of this colour development solution is preferably 1.1 to 3 times corresponding to above-mentioned concentration, more preferably 1.3 of above-mentioned concentration to 2.5 times.

Azanol can be widely used as the antiseptic of colour development solution.When needs improve antiseptic property, the preferred use has substituent hydroxylamine derivative, and these substituting groups are for example alkyl, hydroxy alkyl, sulfo group alkyl and carboxyalkyl, its example comprises N, N-two (sulfo group ethyl) azanol, monomethyl azanol, dimethyl hydroxylamine, single ethyl azanol, diethyl hydroxylamine and N, N-two (carboxy ethyl) azanol.Wherein, N, N-two (sulfo group ethyl) azanol is most preferred.Though these can be used in combination with azanol, preferably use among them one or at least two members to replace azanol.

The consumption of these antiseptics is preferably 0.02 to 0.2 mole in every liter of colour development solution, more preferably 0.03 to 0.15 mole, most preferably is 0.04 to 0.1 mole.

The amount of the antiseptic that contains in the additional liquid of colour development solution is preferably 1.1 to 3 times of mother liquor (developer container solution) concentration, and is identical with color developer.

Sulphite prevents agent with the tarring that the form of oxidation is used as color developer in colour developing solution.The consumption of every kind of sulphite in colour development solution is preferably 0.01 to 0.05 mole in every liter, and more preferably 0.02 to 0.04 mole, and preferably be used to replenish in the liquid, its consumption is corresponding to 1.1 to 3 times of above-mentioned concentration.

The pH value of colour development solution is preferably 9.8 to 11.0, and more preferably 10.0 to 10.5.The pH value of replenishing liquid is higher by 0.1 to 1.0 than above-mentioned value.Common damping fluid is carbonate for example, and phosphate, sulfo group water oxygen hydrochlorate and borate can be used to stablize above-mentioned pH value.

Though the amount of the additional liquid of every square metre photosensitive material colour development solution is preferably 80 to 1300 milliliters (hereinafter using " mL " expression), from reducing the viewpoint of environmental pollution, need reduce this consumption.Specifically, the amount of replenishing liquid is preferably 80 to 600mL, and more preferably 80 to 400mL.

Though bromide ion concentration is generally 0.01 to 0.06 mole every liter in this colour development solution, preferably above-mentioned concentration is set at 0.015 to 0.03 mole every liter, keep photonasty simultaneously to suppress photographic fog, distinguish rate and graininess thereby improve.In the time of in bromide ion concentration is set at above-mentioned scope, replenishes and preferably contain the bromide ion concentration that calculates by following formula in the liquid.But, when C is negative, preferably in replenishing liquid, do not contain bromide ion.

C＝A-W/V

Wherein

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

A: the target bromide ion concentration (mol/L) in the colour development solution,

W: when 1 square metre photosensitive material is carried out colour development, from photosensitive material bleed the bromide ion the colour development solution amount (mol) and

V: the amount (L) that the colour development that every square metre photosensitive material is provided replenishes liquid.

When the amount of replenishing liquid is reduced or when having set high bromide ion concentration, the preferred development accelerator that uses, for example by 1-phenyl-3-pyrazolidone and pyrazolidone that 1-phenyl-2-methyl-the 2-hydroxymethyl-the 3-pyrazolidone is represented, with by 3,6-two sulphur-1, the thioester compound that the 8-ethohexadiol is represented is to improve photonasty.

Be described in the 4th page of JP-A-4-125558, the hurdle, lower-left, the 16th row, to the 7th page, the hurdle, lower-left, the compound of the 6th row and treatment conditions can be applicable in the Treatment Solution with bleaching power of the present invention.The preferred use has the bleaching agent of 150mV oxidation-reduction potential at least.Specifically, its suitable examples is described in JP-A-5-72694 and 5-173312, and the example of its particularly suitable is 1,3-diaminopropanetetraacetic acid and list in the iron complex of embodiment 1 compound in the 7th page of JP-A-5-173312.

In order to improve the biodegradability of bleaching agent, the preferred use listed in JP-A-4-251845, JP-A-4-268552, EP No.588,289, EP No.591,934 and JP-A-6-208213 in the iron complex salt of compound as bleaching agent.Every liter of this concentration with above-mentioned bleaching agent of solution of bleaching power is preferably 0.05 to 0.3 mole, and preferred especially 0.1 to 0.15 mole every liter, to reduce discharging to environment.When the solution with bleaching power is a kind of liquid lime chloride, wherein preferably mix bromide, incorporation is 0.2 to 1 mole every liter, more preferably 0.3 to 0.8 mole.

The every kind of component concentrations that is incorporated in the additional liquid of the solution with bleaching power is calculated by following formula basically.Can make the concentration of mother liquor keep constant like this.

CR＝CT×(V1+V2)/V1+CP

Wherein

CR: replenish every kind of component concentrations in the liquid,

CT: component concentrations in the mother liquor (container handling solution),

CP: the component concentrations that in the process of handling, consumes,

V1: the amount (mL) of the additional liquid that every square metre photosensitive material is provided with bleaching power and

V2: the amount (mL) of from previous container, carrying by 1 square metre photosensitive material.

In addition, in liquid lime chloride, preferably mix a kind of pH damping fluid, especially preferably mix a kind of rudimentary dicarboxylic acid, for example, succinic acid, maleic acid, malonic acid, glutaric acid or hexane diacid.Also preferred the use is described in JP-A-53-95630, the common bleaching accelerator of RD No.17129 and U.S. Patent No. 3,893,858.

Every square metre photosensitive material preferably adds 50 to 1000mL in liquid lime chloride, more preferably 80 to 500mL, most preferably is 100 to 300mL the additional liquid of bleaching.And liquid lime chloride is preferably ventilation

Be described in the 7th page of JP-A-4-125558, the hurdle, lower-left, the 10th walks to the 8th page, the hurdle, bottom right, the compound and the treatment conditions of the 19th row can be applied to having in the Treatment Solution of photographic fixing ability.

In order to improve fixation rate and keeping quality, particularly preferably in the compound that mixes the formula (I) among the JP-A-6-301169 in the Treatment Solution with photographic fixing ability and (II) represent, these compounds can be used singly or in combination.And, from improving conservatory viewpoint, preferably use described in the JP-A-1-224762 to the methylbenzene sulfinate, and sulfinic acid.From improving the viewpoint of bleaching power, though in having the solution of bleaching power or have in the solution of photographic fixing ability and preferably mix a kind of ammonium, preferably the amount of ammonium is reduced or do not use from the viewpoint that reduces environmental pollution as oxonium ion.

In bleaching, especially preferably be described in bleaching-photographic fixing and the photographic fixing step in the jet of JP-A-1-309059 and stir.

The amount of the additional liquid that every square metre photosensitive material provides in bleaching-photographic fixing step is 100 to 1000mL, is preferably 150 to 700mL.

Preferably reclaim silver by in bleaching-photographic fixing or photographic fixing step, any silver recovery unit being installed with online or offline mode.Handle under the situation that online installation can make the silver concentration in solution reduce, thereby can reduce the amount of replenishing liquid.Also can use off-line silver recovery, and the raffinate circulation is used as additional liquid.

In bleaching-photographic fixing and the photographic fixing step each can be carried out in a plurality of container handlings.Preferred these containers have been mounted step pipeline and multi-stage countercurrent system.From the viewpoint that the size with developing machine balances each other, a kind of 2-container stair structure is very effective.Processing time in the container in early stage is preferably 0.5: 1 to 1: 0.5, more preferably 0.8: 1 to 1: 0.8 with the ratio than the processing time in the later stage container.

From improving conservatory viewpoint, preferably there is a kind of sequestrant that does not form chelate in bleaching-photographic fixing and the photographic fixing solution with any metal.The biodegradable cheating agent that preferably using is associated with this liquid lime chloride describes is as this sequestrant.

Among the above-mentioned JP-A-4-125558 the 12nd page, the hurdle, bottom right, the 6th walks to the 13rd page, the hurdle, bottom right, the description of the 16th row can be preferably applied to washing and stabilizing step.Particularly; for stabilizing solution; be described in EP Nos.504 from preferred use of the viewpoint of protection environment; 609 and 519,190 pyrrole radicals methyl amine and the N-methyl azoles (N-methylolazoles) that is described in JP-A-4-362943 replace formaldehyde and the magenta colour coupler dimerization are advanced not contain the image stabilizing agent for example in the surfactant solution of formaldehyde.And, can preferably use the stabilizing solution that is described in JP-A-6-289559, reduce with photosensitive material on the difficult cohesive of the magnetic record layer that uses.

As long as guarantee washing and stablizing effect, from reducing the viewpoint of waste water to the influence of environment, every square metre photosensitive material washing and the magnitude of recruitment in the stabilizing solution are preferably 80 to 1000mL, and more preferably 100 to 500mL, most preferably is 150 to 300mL.In handling with above-mentioned magnitude of recruitment, the known mildewproof agent of preferred use, for example, thiabendazole, 1,2-benzisothiazole-3-ketone and 5-chloro-2-methyl isothiazoline-3-ketone, microbiotic, for example gentamicin and by using, for example, the deionized water of ion exchange resin is to prevent spreading of bacterium and mould.Use deionized water, mildewproof agent and antibiotic combination are more more effective than single use.

For the solution that places washing or stabilizing solution container, also preferably reduce magnitude of recruitment by carrying out reverse osmosis membrane processing, as JP-A-3-46652,3-53246,3-55542 is described in 3-121448 and the 3-126030.A kind of low pressure reverse osmosis film of preferred use in above-mentioned processing.

In processing of the present invention, especially preferably carry out the evaporation of Treatment Solution and proofread and correct, as described in JIII (JapanInstitute of Invention and Innovation) Joumal of Technical Disclosure No.94-4992.Specifically, according to the 2nd page formula 1, use the information of the temperature and humidity of relevant developing machine installation environment to proofread and correct.The water that uses in evaporation is proofreaied and correct is preferably taken from the washing adding container.In this case, preferably deionized water is used as the washing supplementing water.

Preferred in the present invention the 3rd page of using the open magazine of above-mentioned technology, right hurdle, the 15th walks to the 4th page, left hurdle, the treating agent at the 32nd ranks place.Be described in the 3rd page, right hurdle, the preferred described film treating agent of the 22nd to 28 row that uses in the process that developing machine of the present invention is being handled.

The preferred treating agent that uses in enforcement of the present invention, automatic processing machine and evaporation correcting process are described in the 5th page of the open magazine of technology, right hurdle, the 11st walks to the 7th page, right hurdle, last column.

The treating agent that is used for photographic material of the present invention can any form provide, for example, a kind of with use in the liquid agent of same concentrations, the perhaps preparation of Nong Suoing, particle, powder, tablet, paste or emulsion.For example, the liquid agent that is stored in a kind of container of low oxygen permeability is disclosed in JP-A-63-17453, vacuum-packed powder or particle are disclosed in JP-A-4-19655 and 4-230748, the particle that contains water-soluble polymers is disclosed in JP-A-4-221953, and tablet is disclosed in JP-A-51-61837 and 6-102628 and paste treating agent and is disclosed in the open 57-500485 of PCT country.Though can use any in these,, preferably use the liquid with same concentrations when using of prepared beforehand from viewpoint easy to use.

The container that is used to store above-mentioned treating agent is by for example tygon, polypropylene, and Polyvinylchloride, polyethylene terephthalate and any or potpourri in them are formed.Select according to the saturating property of needed oxygen level.The liquid that is used to store easy oxidation is the colour development solution material of low oxygen permeability preferably for example, and they are combined materials of polyethylene terephthalate or tygon and nylon for example.The thickness of each in these materials that preferably use in this container is 500 to 1500 μ m, is 20mL/m thereby make the saturating property of oxygen ².24hrs.atm or lower.

Hereinafter description be can be applicable to the Treatment Solution of colour reversal film of the present invention.

About the processing of colour reversal film, by the Aztek distribution, the 1st page, the 5th walks to the 10th page at Public Technology No.6 (on April 1st, 1991), and the 5th goes and the 15th page, 24 pages of eighth rows to the, and the 2nd row, its content is incorporated herein by reference.In the processing of colour reversal film, the image stabilizing agent is added in regulator solution (conditioning bath) or the final liquid (final bath).The example of the image stabilizing agent that is suitable for comprises Fu Er Malin, formaldehyde sodium sulfite and N-methyl azoles (N-methylolazoles).From the viewpoint of protection environment, formaldehyde sodium sulfite and N-methylolazoles are preferred.In N-methylolazoles, N-methyloltriazole is most preferred.In the relevant colour negative to colour development solution, liquid lime chloride, the description of photographic fixing solution and washings also is applicable to the processing of colour reversal film.

From the treating agent E-6 of Eastman Kodak with from the treating agent CR-56 of Fuji Photo Film Co., Ltd. is the preferred colour reversal film treating agent that comprises These characteristics.

The applied colour photographic sensitive material of the present invention is suitable for makes the Advanced Photo system negative film of (hereinafter being called " AP system ").It is, for example, becomes the AP system format and it is put into the tube of specific purposes by film production just, the NEXIA A of Fuji Photo Film Co., Ltd.'s (hereinafter being called " Fujiphoto ") for example, NEXIA F or NEXIA H (sequence number is that ISO 200/100/400).The tube film of this AP of being used for system is loaded into the camera that is used for the AP system of Fujiphoto production, for example, and Epion series, for example, Epion 300Z, and it is come into operation.And colour photographic sensitive material of the present invention is applicable to the lens of having equipped film, for example the Fuji color Uturundesu Super Slim that is produced by Fujiphoto.

The film of taking a picture is like this printed in a microscale experiment chamber system by following step:

(1) receive (the tube film that receives exposure from client),

(2) dismounting (will be transferred in the intermediate cylinder to develop) from the film of above-mentioned tube,

(3) film development,

(4) back contact (negative film after will developing returns in the original tube),

(5) print (on colour paper, (be preferably the Super FA8 that Fujiphoto is produced) and carry out C/H/P three types are printed and the printing automatically continuously of (index print) printed in index) and

(6) arrangement and granting (tube and index printing are proofreaded and provided with id number).

Said system is preferably Fuji Film Minilao Champion Super FA-298/FA-278/FA-258/FA-238 or Fuji Film Digital Labo System Frontier.The film treating agent of MinilaboChampion is, for example, FP922AL/FP562B/FP562B, AL/FP362B/FP3622B, AL, and the processing chemicals of recommending is Fuji Color Just ItCN-16L or CN-16Q.The printer treating agent is, for example, PP3008AR/PP3008A/PP1828AR/PP1828A/PP1258AR/PP1258A/PP728 AR/PP728A, and the processing chemicals of recommending is Fuji Color Just It CP-47L or CP-40FAII.In Frontier System, be suitable for scanning and imaging processing machine SP-1000 and laser printer and paper processor LP-1000P or Laser Printer LP-1000W.Fuji FilmDT200/DT100 and AT200/AT100 are preferably used as the back machine that contacts in demountor and the back contact procedure in the demounting procedure respectively.

This AP system can appreciate by photo appreciation system, and its center cell is Fujiphoto data imaging workstation laddin 1000.For example, the AP system tube film that develops is by the Aladdin1000 that directly packs into, perhaps negative film, positive photoresist film or print image-forming information and use 35 mm film scanner FE-550 or tack scanner PE-550 to be transfused to wherein, and the image data data that obtain can easily be made and edit.Resulting data can be exported as printing by existing testing equipment, for example, by based on the data colour printing machine of the hot colour printing of photograph fixation type system or based on the Pictrography 3000 of laser explosure thermal development transfer system or pass through film recorder.And Aladdin 1000 can perhaps output to it on CD-R by a kind of CD write device directly to floppy disk or Zip dish output data information.

On the other hand, at home, the photo projector AP-1 that only the AP system tube film that develops is packed into by Fujiphoto production can appreciate photo on TV.Its pack into Photoscanner AS-1 by Fujiphoto production can be imported the image information high-speed and continuous one by one in people's computing machine.And, can be used to a film printing or three-dimensional body input personal computer by the Photovision FV-10/FV-5 of Fujiphoto production.Moreover, be recorded in a floppy disk, Zip dish, the image information on CD-R or the hard disk is appreciated by using Fuji Film Application Soft Photofactory to carry out multiple operation on personal computer.Color digital printer NC-2/NC-2D based on the hot colour printing of the photo fixation type system that is produced by Fujiphoto can be from the printing of personal computer outputting high quality.

The preferred Fuji Color Pocket Album AP-5 Pop L that uses, AP-1 Pop L or AP-1Pop KG or Cartridge File 16 store the AP system tube film that develops.

Hereinafter embodiment of the present invention will be described.But the present invention is not limited to these embodiment.

(embodiment 1)

Gelatin-1 to the gelatin-4 that is used as dispersion medium in the emulsion preparation of describing hereinafter has following characteristic.

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

Gelatin-2: by in the aqueous solution of gelatin-1, adding phthalic anhydrides at pH 9.0, make it that chemical reaction take place, go out residual phthalic acid at 50 ℃, and the gelatin that forms of the dry product that obtains.In this gelatin chemical modification-NH ₂Ratio be 95%.

Gelatin-3: by add 1,2 at 50 ℃ at pH 9.0 in the aqueous solution of gelatin-1, the 4-benzenetricarboxylic anhydride makes it that chemical reaction take place, go out residual 1,2,4 ,-benzenetricarboxylic acid, and the gelatin that forms of the dry product that obtains.In this gelatin chemical modification-NH ₂Ratio be 95%.

Gelatin-4: thus to make its mean molecular weight be 15000 by act on gelatin-1 with enzyme, fermentoid and the dry product that obtains and the gelatin of the reduction molecular weight that forms.In this gelatin-NH ₂Not by chemical modification.

To gelatin-4 deionization, the water-soluble pH at 35 ℃ with 5% is adjusted to 6.0 with above-mentioned gelatin-1.

(preparation of emulsion A-1)

To contain the KBr of 1.0g gram and 1.1g above-mentioned gelatin-4 1, the aqueous solution of 300mL is in 35 ℃ of stirring (the formulations prepared from solutions first time).The water solution A g-1 (AgNO that contains 4.9g among the 100mL with 38mL ₃), the aqueous solution G-1 of the aqueous solution X-1 of 29mL (KBr that contains 5.2g in 100mL) and 8.5mL (the above-mentioned gelatin-4 that contains 8.0g in 100mL) adds according to triple jetting methods (adding 1) flow velocity with photographic fixing in the time in 30 seconds.After this, add the KBr of 6.5g, and temperature is increased to 75 ℃.After maturation stage is carried out 12 minutes, add the aqueous solution G-2 (the above-mentioned gelatin-1 that in 100mL, contains 12.7g) of 300mL.When falling the sensitizing processing, add 4 of 2.1g, 5-dihydroxy-1, the thiourea dioxide of 3-disodium disulfonate-hydrate and 0.002g with 1 minute intervening sequences.Whether falling sensibilization is described in the following table of present embodiment.

Then, with the water solution A g-2 (AgNO that in 100mL, contains 22.1g of 157mL ₃) and aqueous solution X-2 (KBr that in 100mL, contains 15.5g) add in 39.2 minutes time by the dual-jet method.The flow velocity of water solution A g-2 is accelerated in adition process, is that final flow rate is 3.4 times of initial flow rate.And, add aqueous solution X-2 and make the pAg of the emulsion solution in the reaction vessel remain on for 6.80 (adding 2).Then, with the water solution A g-3 (AgNO that in 100mL, contains 32.0g of 329mL ₃) and aqueous solution X-3 (in 100mL, containing the KBr of 21.5g and the KI of 1.2g) add in 74.2 minutes time by the dual-jet method.Quickening the flow velocity of water solution A g-3 in adition process, is that final flow rate is 1.6 times of initial flow rate.And, add aqueous solution X-3, make the pAg of the latex solution in the reaction vessel be maintained at for 6.80 (adding 3).And, with the water solution A g-4 (AgNO that in 100mL, contains 32.0g of 156mL ₃) and aqueous solution X-4 (KBr that in 100mL, contains 22.4g) add in 17 minutes time by the dual-jet method.The adding of water solution A g-4 is that the flow velocity in photographic fixing carries out.The adding of aqueous solution X-4 makes in the reaction vessel pAg of latex solution remain on for 7.52 (adding 4).

After this, order in 1 minute interval adds with the benzene thiosulfonic acid sodium of 0.0025g and the aqueous solution G-3 of 125mL (the above-mentioned gelatin-1 that contains 12.0g in 100mL).The KBr that adds 43.7g then is adjusted to 9.00 with the pAg of the emulsion solution in the reaction vessel.The AgI fine particle emulsion (the AgI fine particle that in 100g, contains 13.0g) that adds 73.9g with mean particle size 0.047 μ m.After two minutes, add water solution A g-4 and the aqueous solution X-4 of 249mL by the dual-jet method.The adding of water solution A g-4 is carried out in 9 minutes at the photographic fixing flow velocity.The adding of aqueous solution X-4 is only carried out originally 3.3 minutes, makes that the pAg of emulsion solution is maintained at 9.00 in the reaction vessel.In remaining 5.7 minutes, do not add aqueous solution X-4, the pAg that makes emulsion solution in the reaction vessel is final 8.4 (adding 5).After this, carry out desalination by common flocculation.Under agitation add entry, NaOH and above-mentioned gelatin-1, and pH and pAg are adjusted to 6.4 and 8.6 respectively at 56 ℃.

The emulsion that obtains is made up of the tabular silver halide particle, and the weighted mean value that it has equal circle diameter 0.99 μ m and particle volume is that the diameter of axle is than 1.5.Have the diameter of axle than be 2 or lower silver halide particle account for the total projection area 50% or higher.The mean value of the AgI content of flat particle is 3.94mol%, and its parallel interarea is (111) face.The AgI content on the silver halide particle surface of measuring by XPS is 2.0mol%.

Then, order adds the compound (these compounds are that enough addings are described in the table of embodiment hereinafter) of formula of the present invention (1) to (3), the hereinafter sensitizing dye shown in, the potassium thiocyanate, gold chloride, sodium thiosulfate, and N, N-dimethyl selenourea is to optimize the carrying out of chemical sensitization.After this, finish chemical sensitization by adding water miscible sulfhydryl compound MER-1 and MER-2 shown in hereinafter.Its ratio is 4: 1, and total amount is every mole a silver halide 3.6 * 10 ^-4Mole.When the addition of ExS-1 is an enzyme mole silver halide 3.21 * 10 ^-4During mole, the chemical sensitization of latex A-1 is for the suitableeest.

(preparation of emulsion A-2)

Preparation condition by change emulsion A-1 as described below prepares emulsion A-2.

(1) addition of the AgI fine particle emulsion that adds (add 5) preceding 2 minutes is changed and is 133.0g.

(2) in (adding 5), the joining day of water solution A g-4 was reduced to 8.37 minutes, and two do not change flow velocity, and the joining day of aqueous solution X-4 was reduced to 2.67 minutes.Resulting emulsion is made up of the tabular silver halide particle that has the equal circle diameter 0.99 μ m and the diameter of axle than being 1.5 particle volume weighted mean value.Have the diameter of axle than be 2 or lower silver halide particle account for the total projection area 50% or higher.The mean value of the AgI content of flat particle is 5.94mol%, and its parallel interarea is (111) face.The AgI content on the silver halide particle surface of measuring by XPS is 5.9mol%.Note that the addition as sensitizing dye ExS-1 is every mole of silver halide 3.21 * 10 ^-4During mole, the chemical sensitization of emulsion A-2 is for the suitableeest.

(preparation of emulsion B-1)

Preparation condition by change emulsion A-1 as described below prepares emulsion B-1.

(1) in (adding 2), change the adding flow velocity of water solution A g-2, be 33.6 minutes thereby make the joining day, and addition is remained on 157mL.Improve flow velocity, making final flow rate is 3.4 times of initial flow rate.And, add aqueous solution X-2, make that the pAg of emulsion solution remains on 7.20 in the reaction vessel.

(2) in (adding 3), change the adding flow velocity of water solution A g-3, making the joining day is 63.6 minutes, addition remains on 329mL.Improve flow velocity, make final flow rate make 1.6 times of initial flow rate.And add aqueous solution X-3, make the pAg of the emulsion solution in the reaction vessel remain on 7.20.Resulting emulsion is made up of the tabular silver halide particle that has the equal circle diameter 0.99 μ m and the diameter of axle than being 2.1 particle volume weighted mean value.Have the diameter of axle than be 2.1 or higher silver halide particle account for the total projection area 50% or higher.The mean value of the AgI content of flat particle is 3.94mol%, and its parallel interarea is (111) face.The AgI content on the silver halide particle surface of measuring by XPS is 2.0mol%.Note that the addition as sensitizing dye ExS-1 is every mole of silver halide 3.39 * 10 ^-4During mole, the chemical sensitization of emulsion B-1 is for the suitableeest.

(preparation of emulsion B-2)

Preparation condition by change emulsion B-1 as described below prepares emulsion B-2.

(1) addition of the AgI fine particle emulsion that adds (add 5) preceding 2 minutes is changed and is 133.0g.

(2) in (adding 5), the joining day of water solution A g-4 is reduced to 8.37 minutes, and does not change flow velocity, and the joining day of aqueous solution X-4 was reduced to 2.67 minutes.Resulting emulsion is made up of the tabular silver halide particle that has the equal circle diameter 0.99 μ m and the diameter of axle than being 2.1 particle volume weighted mean value.Have the diameter of axle than be 3.1 or higher silver halide particle account for the total projection area 50% or higher.The mean value of the AgI content of flat particle is 5.94mol%, and its parallel interarea is (111) face.The AgI content on the silver halide particle surface of measuring by XPS is 6.2mol%.Note that the addition as sensitizing dye ExS-1 is every mole of silver halide 3.39 * 10 ^-4During mole, the chemical sensitization of emulsion B-2 is for the suitableeest.

(preparation of emulsion B-3)

Preparation condition by change emulsion B-1 as described below prepares emulsion B-3.

(1) in (adding 2), change the adding flow velocity of water solution A g-2, be 28 minutes thereby make the joining day, and addition is remained on 157mL.Improve flow velocity, making final flow rate is 3.4 times of initial flow rate.And, add aqueous solution X-2, make that the pAg of emulsion solution remains on 7.52 in the reaction vessel.

(2) in (adding 3), change the adding flow velocity of water solution A g-3, making the joining day is 53 minutes, addition remains on 329mL.Improve flow velocity, make final flow rate make 1.6 times of initial flow rate.And add aqueous solution X-3, make the pAg of the emulsion solution in the reaction vessel remain on 7.52.Resulting emulsion is made up of the tabular silver halide particle that has the equal circle diameter 0.99 μ m and the diameter of axle than being 3.1 particle volume weighted mean value.Have the diameter of axle than be 3.1 or higher silver halide particle account for the total projection area 50% or higher.The mean value of the AgI content of flat particle is 3.94mol%, and its parallel interarea is (111) face.The AgI content on the silver halide particle surface of measuring by XPS is 2.1mol%.Note that the addition as sensitizing dye ExS-1 is every mole of silver halide 3.66 * 10 ^-4During mole, the chemical sensitization of emulsion B-3 is for the suitableeest.

(preparation of emulsion B-4)

Preparation condition by change emulsion B-3 as described below prepares emulsion B-4.

(1) addition of the AgI fine particle emulsion that adds (add 5) preceding 2 minutes is changed and is 133.0g.

(2) in (adding 5), the joining day of water solution A g-4 is reduced to 8.37 minutes, and does not change flow velocity, and the joining day of aqueous solution X-4 was reduced to 2.67 minutes.Resulting emulsion is made up of the tabular silver halide particle that has the equal circle diameter 0.99 μ m and the diameter of axle than being 3.1 particle volume weighted mean value.Have the diameter of axle than be 3.1 or higher silver halide particle account for the total projection area 50% or higher.The mean value of the AgI content of flat particle is 5.94mol%, and its parallel interarea is (111) face.The AgI content on the silver halide particle surface of measuring by XPS is 6.7mol%.Note that the addition as sensitizing dye ExS-1 is every mole of silver halide 3.66 * 10 ^-4During mole, the chemical sensitization of emulsion B-4 is for the suitableeest.

(preparation of emulsion B-5)

Preparation condition by change emulsion B-1 as described below prepares emulsion B-5.

(1) is raised to 75 ℃ and the gelatin that after maturation stage is carried out 12 minutes, adds aqueous solution G-2 in temperature and changed into gelatin-2 from gelatin-1.

(2) in (adding 2), change the adding flow velocity of water solution A g-2, be 22.4 minutes thereby make the joining day, and addition is remained on 157mL.Improve flow velocity, making final flow rate is 3.4 times of initial flow rate.And, add aqueous solution X-2, make that the pAg of emulsion solution remains on 7.83 in the reaction vessel.

(3) in (adding 3), change the adding flow velocity of water solution A g-3, making the joining day is 42.4 minutes, addition remains on 329mL.Improve flow velocity, make final flow rate make 1.6 times of initial flow rate.And add aqueous solution X-3, make the pAg of the emulsion solution in the reaction vessel remain on 7.83.Resulting emulsion is made up of the tabular silver halide particle that has the equal circle diameter 0.99 μ m and the diameter of axle than being 5.9 particle volume weighted mean value.Have the diameter of axle than be 5.9 or higher silver halide particle account for the total projection area 50% or higher.The mean value of the AgI content of flat particle is 3.94mol%, and its parallel interarea is (111) face.The AgI content on the silver halide particle surface of measuring by XPS is 2.4mol%.Note that the addition as sensitizing dye ExS-1 is every mole of silver halide 4.62 * 10 ^-4During mole, the chemical sensitization of emulsion B-5 is for the suitableeest.

(preparation of emulsion B-6)

Preparation condition by change emulsion B-5 as described below prepares emulsion B-6.

(1) addition of the AgI fine particle emulsion that adds (add 5) preceding 2 minutes is changed and is 133.0g.

(2) in (adding 5), the joining day of water solution A g-4 is reduced to 8.37 minutes, and does not change flow velocity, and the joining day of aqueous solution X-4 was reduced to 2.67 minutes.Resulting emulsion is made up of the tabular silver halide particle that has the equal circle diameter 0.99 μ m and the diameter of axle than being 5.9 particle volume weighted mean value.Have the diameter of axle than be 5.9 or higher silver halide particle account for the total projection area 50% or higher.The mean value of the AgI content of flat particle is 5.94mol%, and its parallel interarea is (111) face.The AgI content on the silver halide particle surface of measuring by XPS is 7.5mol%.Note that the addition as sensitizing dye ExS-1 is every mole of silver halide 4.62 * 10 ^-4During mole, the chemical sensitization of emulsion B-6 is for the suitableeest.

(preparation of emulsion C-1)

Preparation condition by change emulsion A-1 as described below prepares emulsion C-1.

(1) is raised to 75 ℃ and the gelatin that after maturation stage is carried out 12 minutes, adds aqueous solution G-2 in temperature and changed into gelatin-3 from gelatin-1.

(2) in (adding 2), change the adding flow velocity of water solution A g-2, be 14 minutes thereby make the joining day, and addition is remained on 157mL.Improve flow velocity, making final flow rate is 3.4 times of initial flow rate.And, add aqueous solution X-2, make that the pAg of emulsion solution remains on 8.30 in the reaction vessel.

(3) in (adding 3), change the adding flow velocity of water solution A g-3, making the joining day is 27 minutes, addition remains on 329mL.Improve flow velocity, make final flow rate make 1.6 times of initial flow rate.And add aqueous solution X-3, make the pAg of the emulsion solution in the reaction vessel remain on 8.30.Resulting emulsion is made up of the tabular silver halide particle that has the equal circle diameter 0.99 μ m and the diameter of axle than being 12.5 particle volume weighted mean value.Have the diameter of axle than be 12.5 or higher silver halide particle account for the total projection area 50% or higher.The mean value of the AgI content of flat particle is 3.94mol%, and its parallel interarea is (111) face.The AgI content on the silver halide particle surface of measuring by XPS is 2.6mol%.Note that the addition as sensitizing dye ExS-1 is every mole of silver halide 6.43 * 10 ^-4During mole, the chemical sensitization of emulsion C-1 is for the suitableeest.

(preparation of emulsion C-2)

Preparation condition by change emulsion C-1 as described below prepares emulsion C-2.

(1) addition of the AgI fine particle emulsion that adds (add 5) preceding 2 minutes is changed and is 93.7g.

(2) in (adding 5), the joining day of water solution A g-4 is reduced to 8.80 minutes, and does not change flow velocity, and the joining day of aqueous solution X-4 was reduced to 3.10 minutes.Resulting emulsion is made up of the tabular silver halide particle that has the equal circle diameter 0.99 μ m and the diameter of axle than being 12.5 particle volume weighted mean value.Have the diameter of axle than be 12.5 or higher silver halide particle account for the total projection area 50% or higher.The mean value of the AgI content of flat particle is 4.61mol%, and its parallel interarea is (111) face.The AgI content on the silver halide particle surface of measuring by XPS is 4.4mol%.Note that the addition as sensitizing dye ExS-1 is every mole of silver halide 6.43 * 10 ^-4During mole, the chemical sensitization of emulsion C-2 is for the suitableeest.

(preparation of emulsion C-3)

Preparation condition by change emulsion C-1 as described below prepares emulsion C-3.

(1) addition of the AgI fine particle emulsion that adds (add 5) preceding 2 minutes is changed and is 113.2g.

(2) in (adding 5), the joining day of water solution A g-4 is reduced to 8.58 minutes, and does not change flow velocity, and the joining day of aqueous solution X-4 was reduced to 2.88 minutes.Resulting emulsion is made up of the tabular silver halide particle that has the equal circle diameter 0.99 μ m and the diameter of axle than being 12.5 particle volume weighted mean value.Have the diameter of axle than be 12.5 or higher silver halide particle account for the total projection area 50% or higher.The mean value of the AgI content of flat particle is 5.27mol%, and its parallel interarea is (111) face.The AgI content on the silver halide particle surface of measuring by XPS is 6.1mol%.Note that the addition as sensitizing dye ExS-1 is every mole of silver halide 6.43 * 10 ^-4During mole, the chemical sensitization of emulsion C-3 is for the suitableeest.

(preparation of emulsion C-4)

Preparation condition by change emulsion C-1 as described below prepares emulsion C-4.

(1) addition of the AgI fine particle emulsion that adds (add 5) preceding 2 minutes is changed and is 133.0g.

(2) in (adding 5), the joining day of water solution A g-4 is reduced to 8.37 minutes, and does not change flow velocity, and the joining day of aqueous solution X-4 was reduced to 2.67 minutes.Resulting emulsion is made up of the tabular silver halide particle that has the equal circle diameter 0.99 μ m and the diameter of axle than being 12.5 particle volume weighted mean value.Have the diameter of axle than be 12.5 or higher silver halide particle account for the total projection area 50% or higher.The mean value of the AgI content of flat particle is 5.94mol%, and its parallel interarea is (111) face.The AgI content on the silver halide particle surface of measuring by XPS is 8.0mol%.Note that the addition as sensitizing dye ExS-1 is every mole of silver halide 6.43 * 10 ^-4During mole, the chemical sensitization of emulsion C-4 is for the suitableeest.

(preparation of emulsion C-5)

Preparation condition by change emulsion C-1 as described below prepares emulsion C-5.

(1) addition of the AgI fine particle emulsion that adds (add 5) preceding 2 minutes is changed and is 167.0g.

(2) in (adding 5), the joining day of water solution A g-4 is reduced to 8.03 minutes, and does not change flow velocity, and the joining day of aqueous solution X-4 was reduced to 2.32 minutes.Resulting emulsion is made up of the tabular silver halide particle that has the equal circle diameter 0.99 μ m and the diameter of axle than being 12.5 particle volume weighted mean value.Have the diameter of axle than be 12.5 or higher silver halide particle account for the total projection area 50% or higher.The mean value of the AgI content of flat particle is 7.01mol%, and its parallel interarea is (111) face.The AgI content on the silver halide particle surface of measuring by XPS is 11.0mol%.Note that the addition as sensitizing dye ExS-1 is every mole of silver halide 6.43 * 10 ^-4During mole, the chemical sensitization of emulsion C-5 is for the suitableeest.

Use the transmission electron microscope of 400-kV under liquid nitrogen temperature, to observe above-mentioned emulsion A-1, A-2, B-1 to B-6 and C-1 to C-5.As a result, 10 or more displacement line have been found in the nearly neighboring area of each flat particle.

And, these emulsion A-1, A-2, B-1 to B-6 and C-1 to C-5 are the red-light-sensing silver halide emulsion, and they have maximum beam split photonasty at the 652nm wavelength, because in the chemical sensitization step of above-mentioned emulsion preparation, added sensitizing dye ExS-1, to carry out beam split sensitizing.

The cellulose triacetate film emulsion A-1 that will have a kind of down coating, A-2, B-1 to B-6 and C-1 to C-5 are coated with being shown under the coating condition of table 1.

Table 1 emulsion coating condition

(1) emulsion layer

● emulsion ... various emulsions

(silver 1.63 * 10 ^-2Mol/m ²)

● colour coupler (2.26 * 10 ^-3Mol/m ²)

● tricresyl phosphate (1.32g/m ²)

● gelatin (3.24g/m ²)

(2) protective seam

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

● gelatin (1.80g/m ²)

Form sample 101 to 126 by changing the emulsion that to use, shown in hereinafter table 2.At 40 ℃, relative humidity is carried out film sclerosis 14 hours for 70% time with these samples.After this, the gelatin filter that these films are produced by Fuji Photo Film Co., Ltd. (long wavelength light with cutoff wavelength 500nm sees through optical filter) and one carve continuously and exposed 1/100 second.Measure the blackness of the sample that carries out following development by a kind of green color filter, to assess their photographic property.

Development is by using a kind of processor FP-362B by Fujiphoto production to carry out as described below.

A treatment step treatment solution compositions is as described below.

(treatment step)

Step	Time	Temperature	Supplementary rate *	Container volume
					Colour development	3 minutes 5 seconds	38℃	15mL	10.3L
Bleaching	50 seconds	38℃	5mL	3.6L
					Photographic fixing (1)	50 seconds	38℃	-	3.6L
Photographic fixing (2)	50 seconds	38℃	7.5mL	3.6L
					Stable (1)	30 seconds	38℃	-	1.9L
Stable (2)	20 seconds	38℃	-	1.9L
					Stable (3)	20 seconds	38℃	30mL	1.9L
Dry	1 minute 30 seconds	60℃	-	-

^*Supplementary rate is per 1.1 meters wide photosensitive material of 35-mm (equaling a 24Ex.1)

Stabilizing agent is the order adverse current with (3) → (2) → (1), and fixer also links to each other by reverse stream pipe from (2) to (1).And the container solution of stabilizing agent (2) provides to fixer (2) with the amount of additional speed with 15mL.In addition, as developer, a kind of color developer (A) and the additional liquid of a kind of color developer (B) with following composition are replenished with the amount of 12mL and 3mL respectively, that is, total amount is 15mL, rate as a supplement.Note that from developer liquid lime chloride and fixer are carried into blanching step, the wide photosensitive material 2.0mL of the 35mm that the amount of photographic fixing step and washing step is respectively per 1.1 meters.Note that also each intersection time is 6 seconds, this time was included in the processing time of each previous step.

Treatment Solution composed as follows.

(color developer (A))

	Container solution	Replenish liquid
			Diethylene triamine pentacetic acid (DTPA)	2.0g	4.0g
4,5-dihydroxy benzenes-1,3-sodium disulfonate	0.4g	0.5g
			Disodium-N, two (the 2-sulfonate ethyl) azanols of N-	10.0g	15.0g
Sodium sulphite	4.0g	9.0g
			Hydroxylamine sulfate	2.0g	-
Potassium bromide	1.4g	-
			Diethylene glycol	10.0g	17.0g
Ethylidene-urea	3.0g	5.5g
			2-methyl-4-[N-ethyl-N-(beta-hydroxyethyl) amino] the aniline sulfuric ester	4.7g	11.4g
Sal tartari	39g	59g
			Add water to	1.0L	1.0L
PH (by sulfuric acid and KOH control)	10.05	10.50

Above-mentioned container solution is represented the composition of following substances mixing back (color developer (B)).

(color developer (B))

	Container solution	Replenish liquid
			Hydroxylamine sulfate	2.0g	4.0g
Add water to	1.0L	1.0L
			PH (by sulfuric acid and KOH control)	10.05	4.0

Said vesse solution represents that above-mentioned material mixes the composition of back (color developer (A)).

(liquid lime chloride)

	Container solution	Replenish liquid
			Iron ammonium 1,3-diaminopropanetetraacetic acid salt monohydrate	120g	180g
Ammonium bromide	50g	70g
			Succinic acid	30g	50g
Maleic acid	40g	60g
			Imidazoles	20g	30g
Add water to	1.0L	1.0L
			PH (by ammoniacal liquor and nitric acid control)	4.6	4.0

(fixer)

	Container solution	Replenish liquid
			ATS (Ammonium thiosulphate) (750g/L)	280mL	1000mL
Two sulphur aqueous ammoniums (72%)	20g	80g
			Imidazoles	5g	45g
1-sulfydryl-2-(N, N-dimethyl aminoethyl)-tetrazolium	1g	3g
			Ethylenediamine tetraacetic acid	8g	12g
Add water to	1L	1L
			PH (by ammoniacal liquor and nitric acid control)	7.0	7.0

(stabilizing agent)

	Container solution and additional liquid phase are together
		To methyl sodium benzene sulphinate	0.03g
To Nonylphenoxy poly epihydric alcohol (the diglycidyl average degree of polymerization is 10)	0.4g
		Disodium ethylene diamine tetraacetate	0.05g
1,2, the 4-triazole	1.3g
		1, two (1,2, the different methyl of the 4-triazole-1-) piperazines of 4-	0.75g
1, the 2-benzisothiazole-3-ketone	0.10g
		Add water to	1.0g
PH	8.5

Hereinafter table 2 shows the result who assesses by said method.Photonasty is to add 0.2 expression by the relative value of inverse of exposure that need reach the blackness of photographic fog blackness, and the photonasty of supposing sample 101 is 100.

Table 2

Sample number into spectrum	The emulsion that uses in the specimen preparation						The compound that adds emulsion		Photographic property		Remarks
												The emulsion numbering	Length diameter ratio	Photosensitizing dye addition (moles/mole silver)	The content of AgI on the emulsion surface (mole %)	Whether the existence of 10 or more a plurality of displacement lines in each particle	Enhanced sensitivity falls	Compound number	Addition (moles/mole silver)	Photonasty *1)	Blackness exposes
	101	A-1	1.5	3.21×10 -4	2.0	Exist	Do not carry out	No	-	100												0.25	The comparative example
102											A-1	1.5	3.21×10 -4	2.0	Exist	Do not carry out	Compound I-1	3.21×10 -5	103	0.26	The comparative example
	103	A-2	1.5	3.21×10 -4	5.9	Exist	Do not carry out	No	-	100												0.26	The comparative example
104											A-2	1.5	3.21×10 -4	5.9	Exist	Do not carry out	Compound I-1	3.21×10 -5	102	0.27	The comparative example
	lO5	B-1	2.1	3.39×10 -4	2.0	Exist	Do not carry out	No	-	103												0.28	The comparative example
106											B-1	2.1	3.39×10 -4	2.0	Exist	Do not carry out	Compound I-1	3.39×10 -5	122	0.26	The present invention
	107	B-2	2.1	3.39×10 -4	6.2	Exist	Do not carry out	No	-	104												0.27	The comparative example
108											B-2	2.1	3.39×10 -4	6.2	Exist	Do not carry out	Compound I-1	3.39×10 -5	119	0.26	The present invention
	109	B-3	3.1	3.66×10 -4	2.1	Exist	Do not carry out	No	-	110												0.28	The comparative example
110											B-3	3.1	3.66×10 -4	2.1	Exist	Do not carry out	Compound I-1	3.66×10 -5	135	0.27	The present invention
	111	B-4	3.1	3.66×10 -4	6.7	Exist	Do not carry out	No	-	111												0.26	The comparative example
112											B-4	3.1	3.66×10 -4	6.7	Exist	Do not carry out	Compound I-1	3.66×10 -5	132	0.29	The present invention
	113	B-5	5.9	3.62×10 -4	2.4	Exist	Do not carry out	No	-	135												0.27	The comparative example

^*1) each photonasty is that the photonasty of supposition sample 101 is that 100 relative value is represented

Table 2 is continuous

Sample number into spectrum	The emulsion that uses in the specimen preparation						The compound that adds emulsion		Photographic property		Remarks
												The emulsion numbering	Length diameter ratio	Photosensitizing dye addition (moles/mole silver)	The content of AgI on the emulsion surface (mole %)	Whether the existence of 10 or more a plurality of displacement lines in each particle	Enhanced sensitivity falls	Compound number	Addition (moles/mole silver)	Photonasty *1)	Blackness exposes
	114	B-5	5.9	4.62×10 -4	2.4	Exist	Do not carry out	Compound I-1	4.62×10 -5	165												0.28	The present invention
115											B-6	5.9	4.62×10 -4	7.5	Exist	Do not carry out	No	-	l33	0.26	The comparative example
	116	B-6	5.9	4.62×10 -4	7.5	Exist	Do not carry out	Compound I-1	4.62×10 -5	163												0.27	The present invention
117											C-1	12.5	6.43×10 -4	2.6	Exist	Do not carry out	No	-	160	0.25	The comparative example
	118	C-1	12.5	6.43×10 -4	2.6	Exist	Do not carry out	Compound I-1	6.43×10 -5	215												0.26	The present invention
119											C-2	12.5	6.43×10 -4	4.4	Exist	Do not carry out	No	-	162	0.27	The comparative example
	120	C-2	12.5	6.43×10 -4	4.4	Exist	Do not carry out	Compound I-1	6.43×10 -5	215												0.25	The present invention
121											C-3	12.5	6.43×10 -4	6.1	Exist	Do not carry out	No	-	159	0.27	The comparative example
	122	C-3	12.5	6.43×10 -4	6.1	Exist	Do not carry out	Compound I-1	6.43×10 -5	207												0.26	The present invention
123											C-4	12.5	6.43×10 -4	8.0	Exist	Do not carry out	No	-	158	0.28	The comparative example
	124	C-4	12.5	6.43×10 -4	8.0	Exist	Do not carry out	Compound I-1	6.43×10 -5	204												0.29	The present invention
125											C-5	12.5	6.43×10 -4	11.0	Exist	Do not carry out	No	-	159	0.25	The comparative example
	126	C-5	12.5	6.43×10 -4	11.0	Exist	Do not carry out	Compound I-1	6.43×10 -5	194												0.26	The present invention

^*1) each photonasty is that the photonasty of supposition sample 101 is that 100 relative value is represented

Table 2 has shown following content.The diameter of axle is than being in 1.5 the emulsion therein, and it is very little that the photonasty of compound of the present invention improves effect.Diameter of axle ratio is greater than in 2 the emulsion therein, and the adding of compound of the present invention has improved photosensitive raising effect, and does not improve the photographic fog blackness.The diameter of axle is higher than more, and effect is obvious more.On the other hand, shown in sample 117 to 126, the lip-deep AgI content of emulsion is preferably 10mol% or lower, more preferably 5mol% or lower.

(embodiment 2)

(emulsion C-6, C-7 ， ﹠amp; The preparation of C-8)

Preparation condition by the emulsion C-1 among the change embodiment 1 as described below prepares emulsion C-6.Emulsion C-6 has equal circle diameter 0.99 μ m, and average diameter of axle ratio is 12.5, and the AgI content on the silver halide surface that records by XPS is 2.6mol%.

(1) in (adding 5), do not add AgI fine particle emulsion.

(2) in (adding 4) and (adding 5), aqueous solution X-4 is changed the aqueous solution for the KI of KBr that contains 21.8g in 100mL and 0.81g.

Preparation condition by the emulsion C-2 among the change embodiment 1 as described below prepares emulsion C-7.Emulsion C-7 has equal circle diameter 0.99 μ m, and average diameter of axle ratio is 12.5, and the AgI content on the silver halide surface that records by XPS is 4.4mol%.

(1) in (adding 5), do not add AgI fine particle emulsion.

(2) in (adding 4) and (adding 5), aqueous solution X-4 is changed the aqueous solution for the KI of KBr that contains 21.4g in 100mL and 1.37g.

Preparation condition by the emulsion C-3 among the change embodiment 1 as described below prepares emulsion C-8.Emulsion C-8 has equal circle diameter 0.99 μ m, and average diameter of axle ratio is 12.5, and the AgI content on the silver halide surface that records by XPS is 6.1mol%.

(1) in (adding 5), do not add AgI fine particle emulsion.

(2) in (adding 4) and (adding 5), aqueous solution X-4 is changed the aqueous solution for the KI of KBr that contains 21.0g in 100mL and 1.91g.

Use the transmission electron microscope of 400-kV under liquid nitrogen temperature, to observe above-mentioned emulsion C-6 to C-8.As a result, found to be less than 10 displacement line in the nearly neighboring area of each flat particle; Basically there is not displacement line.

Under the coating condition identical, form sample 201 to 212, shown in hereinafter table 3 by change emulsion to be used with embodiment 1.Develop in the mode identical, assess its photographic property (photonasty of the sample 101 in embodiment 1 is assumed that 100) with embodiment 1.

Table 3

Sample number into spectrum	The emulsion that uses in the specimen preparation						The compound that adds emulsion		Photographic property		Remarks
												The emulsion numbering	Length diameter ratio	Photosensitizing dye addition (moles/mole silver)	The content of AgI on the emulsion surface (mole %)	The number of each particle top offset line	Enhanced sensitivity falls	Compound number	Addition (moles/mole silver)	Photonasty *1)	Blackness exposes
	201	C-1	12.5	6.43×10 -4	2.6	10 or more	Do not carry out	No	-	160												0.25	The comparative example
202											C-1	12.5	6.43×10 -4	2.6	10 or more	Do not carry out	Compound I-1	6.43×10 -5	215	0.26	The present invention
	203	C-6	12.5	6.43×10 -4	2.6	Be less than 10	Do not carry out	No	-	70												0.29	The comparative example
204											C-6	12.5	6.43×10 -4	2.6	Be less than 10	Do not carry out	Compound I-1	6.43×10 -5	72	0.28	The comparative example
	205	C-2	12.5	6.43×10 -4	4.4	10 or more	Do not carry out	No	-	162												0.27	The comparative example
206											C-2	12.5	6.43×10 -4	4.4	10 or more	Do not carry out	Compound I-1	6.43×10 -5	215	0.25	The present invention
	207	C-7	12.5	6.43×10 -4	4.4	Be less than 10	Do not carry out	No	-	66												0.24	The comparative example
208											C-7	12.5	6.43×10 -4	4.4	Be less than 10	Do not carry out	Compound I-1	6.43×10 -5	69	0.25	The comparative example
	209	C-3	12.5	6.43×10 -4	6.1	10 or more	Do not carry out	No	-	159												0.27	The comparative example
210											C-3	12.5	6.43×10 -4	6.1	10 or more	Do not carry out	Compound I-1	6.43×10 -5	207	0.26	The present invention
	211	C-8	12.5	6.43×10 -4	6.1	Be less than 10	Do not carry out	No	-	62												0.29	The comparative example
212											C-8	12.5	6.43×10 -4	6.1	Be less than 10	Do not carry out	Compound I-1	6.43×10 -5	63	0.27	The comparative example

^*1) each photonasty is that the photonasty of the sample 101 of supposition among the embodiment 1 is that 100 relative value is represented

Result in the table 3 shows following content.From sample 201 to 212 as can be seen, displacement line is less than in 10 the latex therein, and by formula of the present invention (1), it is very little that the photonasty of the compound of (2) or (3) expression improves effect.But, therein the number of displacement line be 10 or more emulsion in, these compounds have improved photonasty and have improved effect, and do not improve the photographic fog blackness.

(embodiment 3)

Under the coating condition identical, form sample 301 to 320 by type and the addition of using emulsion B-1 and changing compound of the present invention with embodiment, as shown in table 4.Develop assessment photographic property (photonasty of the sample 101 among the embodiment 1 is assumed that 100) with the step identical with embodiment 1.

Table 4

Sample number into spectrum	The emulsion that uses in the specimen preparation						The compound that adds emulsion		Photographic property		Remarks
												The emulsion numbering	Length diameter ratio	Photosensitizing dye addition (moles/mole silver)	The content of AgI on the emulsion surface (mole %)	Whether the existence of 10 or more a plurality of displacement lines in each particle	Enhanced sensitivity falls	Compound number	Addition (mol%) with respect to sensitizing dye	Photonasty *1)	Blackness exposes
	301	B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-1	-	137												0.29	The comparative example
302											B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-1	1	195	0.25	The present invention
	303	B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-1	2	210												0.27	The present invention
304											B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-1	5	218	0.27	The present invention
	305	B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-1	15	217												0.28	The present invention
306											B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-1	25	206	0.26	The present invention
	307	B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-1	35	191												029	The present invention
308											B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-2	10	218	0.25	The present invention
	309	B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-3	10	216												0.26	The present invention
310											B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-6	10	212	0.28	The present invention

^*1) each photonasty is that the photonasty of supposition sample 101 is that 100 relative value is represented

Table 4

Sample number into spectrum	The emulsion that uses in the specimen preparation						The compound that adds emulsion		Photographic property		Remarks
												The emulsion numbering	Length diameter ratio	Photosensitizing dye addition (moles/mole silver)	The content of AgI on the emulsion surface (mole %)	Whether the existence of 10 or more a plurality of displacement lines in each particle	Enhanced sensitivity falls	Compound number	Addition (mol%) with respect to sensitizing dye	Photonasty *1)	Blackness exposes
	311	B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-12	10	209												0.29	The present invention
312											B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-14	10	207	0.26	The present invention
	313	B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-16	10	213												0.25	The present invention
314											B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-4	10	192	0.26	The present invention
	315	B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-7	10	190												0.27	The present invention
316											B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-8	10	199	0.26	The present invention
	317	B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-9	10	190												0.28	The present invention
318											B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-11	10	195	0.25	The present invention
	319	B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-13	10	198												0.26	The present invention
320											B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-18	10	197	0.24	The present invention

^*1) each photonasty is that the photonasty of supposition sample 101 is that 100 relative value is represented

Table 4 result displayed has illustrated following problem.From sample 301 to 307 as can be seen, the addition of compound of the present invention is preferably 1 to 25mol% with respect to sensitizing dye, and more preferably 2 to 15mol%.From sample 308 to 320 as can be seen, be used for compound of the present invention, the compound of formula (3) is most preferred.

(embodiment 4)

With the coating condition identical with embodiment 1, by carrying out/do not fall sensitizing, use emulsion B-1 and B-2 and change by formula of the present invention (1), the existence of the compound of (2) or (3) expression/do not exist to form sample 401 to 408, as shown in table 5.Development is to carry out according to the mode identical with embodiment 1, and photographic property is assessed (photonasty of the sample 101 among the embodiment 1 is assumed that 100).

Table 5

Sample number into spectrum	The emulsion that uses in the specimen preparation						The compound that adds emulsion		Photographic property		Remarks
												The emulsion numbering	Length diameter ratio	Photosensitizing dye addition (moles/mole silver)	The content of AgI on the emulsion surface (mole %)	Whether the existence of 10 or more a plurality of displacement lines in each particle	Enhanced sensitivity falls	Compound number	Addition (moles/mole silver)	Photonasty *1)	Blackness exposes
	401	B-5	5.9	4.62×10 -4	2.4	Exist	Do not carry out	No	-	135												0.27	The comparative example
402											B-5	5.9	4.62×10 -4	2.4	Exist	Do not carry out	Compound I-1	4.62×10 -5	165	0.28	The present invention
	403	B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	No	-	137												0.29	The comparative example
404											B-5	5.9	4.62×10 -4	2.4	Exist	Carry out	Compound I-1	4.62×10 -5	220	0.28	The present invention
	405	B-6	5.9	4.62×10 -4	7.5	Exist	Do not carry out	No	-	133												0.26	The comparative example
406											B-6	5.9	4.62×10 -4	7.5	Exist	Do not carry out	Compound I-1	4.62×10 -5	163	0.27	The present invention
	407	B-6	5.9	4.62×10 -4	7.5	Exist	Carry out	No	-	136												0.28	The comparative example
408											B-6	5.9	4.62×10 -4	7.5	Exist	Carry out	Compound I-1	4.62×10 -5	209	0.27	The present invention

^*1) each photonasty is that the photonasty of supposition sample 101 is that 100 relative value is represented

The result who is shown in table 5 has shown following content.From sample 401 to 408 as can be seen, preferably by formula of the present invention (1), the compound of (2) or (3) expression can make up with falling sensitizing emulsion, and the AgI content on emulsion surface is 5mol% or lower.

(embodiment 5)

Use the salt compound described in the present invention's " background technology " that known patent has been carried out complementary testing.Prepared JP-A-61-43740, the emulsion that the embodiment 1 among JP-A-6-242534 and the JP-A-10-83040 describes.In the chemical sensitization step, added formula of the present invention (1), the compound shown in (2) or (3), and by adding sensitizing dye ExS-1 in proper order, potassium rhodanide, gold chloride, sodium thiosulfate, and N, N-dimethyl selenourea carries out chemical sensitization, as described in embodiment 1.Whether compound of the present invention adds specific sample is listed in hereinafter table 6.After this, by finishing chemical sensitization with identical water-soluble sulfhydryl compound MER-1 and MER-2 among 4: 1 the ratio adding embodiment 1.Under liquid nitrogen temperature, observe displacement line by using the 400kV transmission electron microscope.

Under the coating condition identical, form sample 501 to 512, just carried out above-mentioned variation with embodiment 1.Develop in the mode identical, and photographic property is assessed with embodiment 1.The photonasty of supposing the sample of the every kind of emulsion that does not wherein use compound of the present invention is 100, and the effect that adds compound of the present invention is assessed.

Table 6

Sample number into spectrum	The emulsion that uses in the specimen preparation			The compound that adds emulsion		Photographic property		Remarks
									The emulsion numbering	Whether the existence of 10 or more displacement line on each particle	Length diameter ratio	Compound number	Addition (mole %) with respect to the enhanced sensitivity dyestuff	Photonasty *1)	Blackness exposes
	501	Emulsion B-1 of the present invention (having carried out falling enhanced sensitivity)	Exist	2.1	No	-	100									0.27	The comparative example
502								Emulsion B-1 of the present invention (having carried out falling enhanced sensitivity)	Exist	2.1	Compound I-1	10	118	0.28	The present invention
	503	Emulsion B-1 of the present invention (having carried out falling enhanced sensitivity)	Exist	2.1	Compound I-1	25	117									0.27	The present invention
504								Emulsion B-1 of the present invention (having carried out falling enhanced sensitivity)	Exist	2.1	Compound I-1	100	114	0.29	The present invention
	505	The emulsion of describing among the embodiment 1 of JP-A-61-43740	Do not exist	1.0	No	-	100									0.29	The comparative example
506								The emulsion of describing among the embodiment 1 of JP-A-61-43740	Do not exist	1.0	Compound I-1	10	101	0.28	The comparative example
	507	The emulsion of describing among the embodiment 1 of JP-A-61-43740	Do not exist	1.0	Compound I-1	25	102									0.26	The comparative example
508								The emulsion that the embodiment 1 of JP-A-61-43740 describes	Do not exist	1.0	Compound I-1	100	108	0.25	The comparative example
	509	The emulsion A that describes among the embodiment 1 of JP-A-6-242534	Do not exist	1.0	No	-	100									0.25	The comparative example
510								The emulsion A that describes among the embodiment 1 of JP-A-6-242534	Do not exist	1.0	Compound I-1	10	102	0.24	The comparative example
	511	The emulsion O that describes among the embodiment 1 of JP-A-10-83040	Do not exist	1.0	No	-	100									0.22	The comparative example
512								The emulsion O that describes among the embodiment 1 of JP-A-10-83040	Do not exist	1.0	Compound I-1	10	101	0.23	The comparative example

^*1) each photonasty is that the photonasty of each sample of not adding of supposition Compound I-1 is that 100 relative value is represented

Be shown in the content that the result of table 6 shows below.

In JP-A-61-43740, shown in the table 1 of embodiment 1, when the addition of the salt compound photonasty that arrived during greater than sensitizing dye improves effect.As the data presentation of the sample of sample 501 to 508, the salt compound in the emulsion of JP-A-61-43740 has effect a little when addition is the 100mol% of sensitizing dye.But, when addition be 25mol% or when lower photonasty to improve effect very little.

As the data presentation of sample 509 to 512, more much lower than the effect in emulsion of the present invention by the photosensitive raising effect that adding salt compound in the emulsion of JP-A-6-242534 and JP-A-10-83040 obtains.

(embodiment 6)

Prepare silver emulsion D to R according to following method.

(preparation method of emulsion D)

The low-molecular-weight O-phthalic acidifying rate that will contain 31.7g is that the aqueous solution of 42.2L of KBr of the gelatin of 97% phosphorus benzene bis-acid potassiumization and 31.7g is 35 ℃ of vigorous stirring.With 1, the AgNO that contains 316.7g of 583mL ₃Aqueous solution and 1, the aqueous solution of the gelatin 4 of the KBr that contains 221.5g of 583mL and the embodiment 1 of 52.7g added by the dual-jet method in 1 minute.The KBr that after adding, adds 52.8g immediately, and with 2, the AgNO that contains 398.2g of 485mL ₃Aqueous solution and 2, the aqueous solution of the KBr that contains 291.1g of 581mL added by the dual-jet method in 2 minutes.After the adding, add the KBr of 44.8g immediately.After this, temperature is increased to 40 ℃, makes the material slaking.After the slaking, the gelatin-2 of the embodiment 1 of adding 923g and the KBr of 79.2g, and with 15,974mL's contains 5, the AgNO of 103g ₃Aqueous solution and KBr aqueous solution in 10 minutes, add by the dual-jet method, improve flow velocity simultaneously, making final flow rate is 1.4 times of initial flow rate.In adition process, the pAg of the emulsion solution in the reaction vessel is maintained at 9.90.After washing with water, add the gelatin-1 of embodiment 1, pH and pAg are adjusted to 5.7 and 8.8 respectively, and silver amount in the emulsion of per kilogram and gelatin amount are adjusted to 131.8g and 64.1g respectively, thus preparation seed emulsion.

With 1, the aqueous solution of gelatin-2 among the embodiment that contains 46g 1 of 211mL and the KBr of 1.7g is 75 ℃ of vigorous stirring.After adding the seed emulsion of 9.9g, add the polysiloxane oil (by the L7602 of Nippon Uniker K.K. manufacturing) of the modification of 0.3g.Add H ₂SO ₄, with pH regulator to 5.5, and with the AgNO that contains 7.0g of 67.6mL ₃Aqueous solution and KBr aqueous solution added by the dual-jet method in 6 minutes, improved flow velocity simultaneously, and making final flow rate is 5.1 times of initial flow rate.Gather in adition process, the pAg of the emulsion solution in the reaction vessel is maintained at 8.15.Behind the thiourea dioxide of sodium benzenethiosulfonate that adds 2mg and 2mg, with the AgNO of the 105.6g of 328mL ₃Aqueous solution and KBr solution in 56 minutes, add by the dual-jet method, improve flow velocity simultaneously, making final flow rate is 3.7 times of initial flow rate.In adition process, to have grain size be that the AgI fine particle emulsion of 0.037 μ m adds simultaneously with the flow velocity that improves with a kind of, and making agi content is 27mol%.Simultaneously, the pAg of emulsion solution is maintained at 8.60 in the reaction vessel.The AgNO that contains 45.6g with 121.3mL ₃Aqueous solution and KBr aqueous solution in 22 minutes, add by the dual-jet method.In adition process, the pAg of emulsion solution is maintained at 7.60 in the reaction vessel.Temperature is increased to 82 ℃, adds KBr, the pAg of the emulsion solution in the reaction vessel is adjusted to 8.80, and adds above-mentioned AgI fine particle emulsion, addition is 6.33g, in KI weight.After adding, in 16 minutes, add the AgNO that contains 66.4g of 206.2mL immediately ₃Aqueous solution.At 5 minutes that add, the pAg of the emulsion solution in the reaction vessel was maintained at 8.80.After washing with water, add the gelatin-1 of embodiment 1, pH and pAg are adjusted to 5.8 and 8.7 respectively, at 40 ℃, add compound 1, and temperature is increased to 60 ℃.After sensitizing dye ExS-2 and ExS-3 adding, add potassium rhodanide, gold chloride, sodium thiosulfate, and N, N-dimethyl selenourea is to optimize the carrying out of chemical sensitization.Last in this chemical sensitization effect adds hereinafter described compound 2 and compound 3." optimization sensitizing " is meant that the addition of every kind of sensitizing dye and compound is every mole of silver halide 10 ^-1To 10 ^-8Mole.

Compound 1 compound 2 compounds 3

(preparation method of emulsion E)

With 1, the aqueous solution of gelatin-4 among the embodiment that contains 0.96g 1 of 192mL and the KBr of 0.9g is 40 ℃ of vigorous stirring.The AgNO that contains 1.49g with 37.5mL ₃The aqueous solution of the KBr that contains 1.05g of aqueous solution and 37.5mL added by the dual-jet method in 30 seconds.After adding the KBr of 1.2g, temperature is increased to 75 ℃, makes the material slaking.After slaking, add the gelatin-3 of the embodiment 1 of 35g, and pH is adjusted to 7.The thiourea dioxide that adds 6mg.The AgNO that contains 29g with 116mL ₃Aqueous solution and KBr aqueous solution add by the dual-jet method, improve flow velocity simultaneously, making final flow rate is 3 times of initial flow rate.In adition process, the pAg of the emulsion solution in the reaction vessel is remained on 8.15.The AgNO that contains 110.2g with 440.6mL ₃Aqueous solution and the aqueous solution of KBr in 30 minutes, add by the dual-jet method, by improving flow velocity, making final flow rate is 5.1 times of initial flow rate.In adition process, the AgI fine particle emulsion that uses in preparation emulsion D is added with the flow velocity that improves simultaneously, and making agi content is 15.8mol%.Simultaneously, the pAg of emulsion solution is maintained at 7.85 in the reaction vessel.96.5mL the AgNO that contains 24.1g ₃Aqueous solution and KBr aqueous solution in 3 minutes, add by the dual-jet method.In adition process, the pAg of the emulsion solution in the reaction vessel is maintained at 7.85.After adding the ethylenebis dithiocarbamate sodium sulfonate of 26mg, temperature is increased to 55 ℃, adds the KBr aqueous solution, the pAg of the emulsion solution in the reaction vessel is adjusted to 9.80.Add above-mentioned AgI fine particle emulsion, addition is counted 8.5g with KI weight.After the adding, in 5 minutes, add the AgNO that contains 57g of 228mL immediately ₃Aqueous solution.In adition process, use the pAg of the emulsion solution in the KBr aqueous solution conditioned reaction container, making the pAg that adds the later stage is 8.75.The emulsion that obtains is washed with water and identical with emulsion D basically mode is carried out chemical sensitization.

(preparation method of emulsion F)

With 1, the aqueous solution of gelatin-2 among the embodiment that contains 1.02g 1 of 192mL and the KBr of 0.9g is 35 ℃ of vigorous stirring.The AgNO that contains 4.47g with 42mL ₃The aqueous solution of the KBr that contains 3.16g of aqueous solution and 42mL added by the dual-jet method in 9 seconds.After adding the KBr of 2.6g, temperature is increased to 63 ℃, makes the material slaking.After slaking, add the gelatin-3 of embodiment 1 of 41.2g and the NaCl of 18.5g, and pH is adjusted to 7.2.The dimethyamine borane that adds 8mg.The AgNO that contains 26g with 203mL ₃Aqueous solution and KBr aqueous solution add by the dual-jet method, improve flow velocity simultaneously, making final flow rate is 3.8 times of initial flow rate.In adition process, the pAg of the emulsion solution in the reaction vessel is remained on 8.65.The AgNO that contains 110.2g with 440.6mL ₃Aqueous solution and the aqueous solution of KBr in 24 minutes, add by the dual-jet method, by improving flow velocity, making final flow rate is 5.1 times of initial flow rate.In adition process, the AgI fine particle emulsion that uses in preparation emulsion D is added with the flow velocity that improves simultaneously, and making agi content is 2.3mol%.Simultaneously, the pAg of emulsion solution is maintained at 8.50 in the reaction vessel.After the 1N potassium rhodanide aqueous solution that adds 10.7mL, the AgNO that contains 24.1g of 153.5mL ₃Aqueous solution and KBr aqueous solution in 2 minutes 30 seconds, add by the dual-jet method.In adition process, the pAg of the emulsion solution in the reaction vessel is maintained at 8.05.Add the KBr aqueous solution, the pAg of the emulsion solution in the reaction vessel is adjusted to 9.25.Add above-mentioned AgI fine particle emulsion, addition is counted 6.4g with KI weight.After the adding, in 45 minutes, add the AgNO that contains 57g of 404mL immediately ₃Aqueous solution.In adition process, use the pAg of the emulsion solution in the KBr aqueous solution conditioned reaction container, making the pAg that adds the later stage is 8.65.The emulsion that obtains is washed with water and identical with emulsion D basically mode is carried out chemical sensitization.

(preparation method of emulsion G)

In the preparation of emulsion F, AgNO in nucleation process ₃Addition be enhanced 2.3 times.And, add the AgNO that contains 57g of 404mL the last time ₃Aqueous solution the time, use the KBr aqueous solution that the pAg of the latex solution in the reaction vessel is adjusted to 6.85.Basically mode identical with emulsion F except above-mentioned prepares this emulsion.

(preparation method of emulsion H)

In the preparation of emulsion C-1 in embodiment 1, (whether adding compound is shown in the following table of present embodiment) adds by formula of the present invention (1) when needed before chemical sensitization is carried out, the compound of (2) or (3) expression.And, be changed at the sensitizing dye that begins to add of chemical sensitization and be following ExS-4, the composition of ExS-5 and ExS-6.Except above-mentioned, prepare emulsion H in identical with emulsion C-3 basically mode.Note that sensitizing dye ExS-4, the use amount of the silver halide that ExS-5 and ExS-6 are every mole is respectively 5.50 * 10 ^-4Mole, 1.3 * 10 ^-4Mole and 4.65 * 10 ^-5Mole.

(preparation method of emulsion I)

With the aqueous solution of the KBr of gelatin-4 among the embodiment that contains 0.75g 1 of 1200mL and 0.9g remain on 39 ℃ and under pH1.8 vigorous stirring.The AgNO that will contain 1.85g ₃The aqueous solution of aqueous solution and the KBr that contains 1.5mol%KI added by the dual-jet method in 16 seconds.In adition process, excessive KBr concentration is held constant.Temperature is increased to 54 ℃, makes the material slaking.After slaking, add the gelatin-2 of the embodiment 1 of 20g, and pH is adjusted to 5.9, add 2.9g KBr.The AgNO that contains 27.4g with 288mL ₃Aqueous solution and KBr aqueous solution in 53 minutes, add by the dual-jet method.In adition process, the AgI fine particle emulsion that will have grain size 0.03 μ m adds simultaneously, and the content that makes silver iodide is 4.1mol%.Simultaneously, the pAg of emulsion solution is maintained at 9.40 in the reaction vessel.Behind the KBr that adds 2.5g, contain the AgNO of 87.7g ₃Aqueous solution and KBr aqueous solution in 63 minutes, add by the dual-jet method, improve flow velocity simultaneously, making final flow rate is 1.2 times of initial flow rate.In adition process, add above-mentioned AgI fine particle emulsion simultaneously, making agi content is 10.5mol%.Simultaneously, the pAg of the emulsion solution in the reaction vessel is maintained at 9.50.The AgNO that contains 41.8g with 132mL ₃Aqueous solution and the aqueous solution of KBr in 25 minutes, add by the dual-jet method.It is 8.15 adding at last that the adding of adjusting KBr makes the pAg of emulsion solution in the reaction vessel.PH is adjusted to 7.3, adds the thiourea dioxide of 1mg.Adding after the pAg of KBr with the emulsion solution in the reaction vessel be adjusted to 9.50, add above-mentioned AgI fine particle emulsion, addition counts 5.73 with KI weight.After adding, in 10 minutes, add the AgNO that contains 66.4g of 609mL immediately ₃Aqueous solution.In originally 6 minutes of adding, the pAg of the emulsion solution in the reaction vessel is remained on 9.50 by KBr solution.After washing with water, add the gelatin-1 among the embodiment 1, and pH and pAg are adjusted to 6.5 and 8.2 respectively.。The emulsion that obtains is carried out chemical sensitization in the mode identical with emulsion H.Note that sensitizing dye ExS-4, the use amount of the silver halide that ExS-5 and ExS-6 are every mole is respectively 1.08 * 10 ^-3Mole, 2.56 * 10 ^-4Mole and 9.16 * 10 ^-5Mole.

(preparation method of emulsion J)

With the gelatin-4 among the embodiment that contains 0.70g 1 of 1200mL, the KBr of 0.9g, the aqueous solution of the polysiloxane of the modification of in the preparation of emulsion D, using of the KI of 0.175g and 0.2g remain on 33 ℃ and under pH1.8 vigorous stirring.The AgNO that will contain 1.8g ₃The aqueous solution of aqueous solution and the KBr that contains 3.2mol%KI added by the dual-jet method in 9 seconds.In adition process, excessive KBr concentration is held constant.Temperature is increased to 62 ℃, makes the material slaking.After slaking, add the gelatin-3 of the embodiment 1 of 27.8g, and pH is adjusted to 6.3, add 2.9gKBr.The AgNO that contains 27.58g with 270mL ₃Aqueous solution and KBr aqueous solution in 37 minutes, add by the dual-jet method.In adition process, the AgI fine particle emulsion that will have grain size 0.008 μ m adds simultaneously, and the content that makes silver iodide is 4.1mol%.This AgI fine particle is preparation immediately before adding, and this is by gelatin-4 aqueous solution with embodiment 1, AgNO ₃Aqueous solution and KI aqueous solution are mixed in another cavity and to be carried out, and have a magnetic splash bar in this cavity, as described in JP-A-10-43570.Simultaneously, the pAg of emulsion solution is maintained at 9.15 in the reaction vessel.Behind the KBr that adds 2.6g, will contain the AgNO of 87.7g ₃Aqueous solution and KBr aqueous solution in 49 minutes, add by the dual-jet method, improve flow velocity simultaneously, making final flow rate is 3.1 times of initial flow rate.In adition process, add above-mentioned AgI fine particle emulsion before adding with the flow velocity that improves simultaneously by being mixed with immediately, making agi content is 7.9mol%.Simultaneously, the pAg of the emulsion solution in the reaction vessel is maintained at 9.30.Behind the thiourea dioxide that adds 1mg, with the AgNO that contains 41.8g of 132mL ₃Aqueous solution and the aqueous solution of KBr in 20 minutes, add by the dual-jet method.It is 7.90 adding at last that the adding of adjusting KBr makes the pAg of emulsion solution in the reaction vessel.Temperature be increased to 78 ℃ and pH is adjusted to 9.1 after, add KBr the pAg of the emulsion solution in the reaction vessel be adjusted to 8.70.Add the AgI fine particle emulsion that uses in the preparation of emulsion D, addition is counted 5.73g with KI weight.After adding, in 4 minutes, add the AgNO that contains 66.4g of 321mL immediately ₃Aqueous solution.In originally 2 minutes of adding, the pAg of the emulsion solution in the reaction vessel is remained on 8.70.The emulsion that obtains washed with water and to carry out chemical sensitization with the essentially identical mode of emulsion H.Note that sensitizing dye ExS-4, the use amount of the silver halide that ExS-5 and ExS-6 are every mole is respectively 1.25 * 10 ^-3Mole, 2.85 * 10 ^-4Mole and 3.92 * 10 ^-5Mole.

(preparation method of emulsion K)

To contain the gelatin-1 among the embodiment 1 of 17.8g, the aqueous solution of the KBr of 6.2g and the KI of 0.46g is 45 ℃ of vigorous stirring.The AgNO that will contain 11.85g ₃The aqueous solution of aqueous solution and the KBr that contains 3.8g added by the dual-jet method in 45 seconds.After temperature is increased to 63 ℃, add the gelatin-1 of the embodiment 1 of 24.1g, make the material slaking.After slaking, will contain the AgNO of 133.4g ₃Aqueous solution and KBr aqueous solution in 20 minutes, add by the dual-jet method, making final flow rate is 2.6 times of initial flow rate.In adition process, the pAg of the emulsion solution in the reaction vessel is remained on 7.60.And, adding back 10 minutes of beginning, add the K of 0.1mg ₂IrCl ₆Behind the NaCl that adds 7g, will contain the AgNO of 45.6g ₃Aqueous solution and the aqueous solution of KBr in 12 minutes, add by the dual-jet method.In adition process, the pAg of emulsion solution in the reaction vessel is remained on 6.90.And, from adding back 6 minutes of beginning, add the aqueous solution of the yellow prussiate that contains 29mg of 100mL.After adding the KBr of 14.4g, add the AgI fine particle emulsion that uses among the preparation emulsion D, addition is counted 6.3g with KI weight.After the adding, will contain the AgNO of 42.7g immediately ₃Aqueous solution and KBr aqueous solution in 11 minutes, add by the dual-jet method.In adition process, the pAg of the emulsion solution in the reaction vessel is maintained at 6.90.The emulsion that obtains washed with water and to carry out chemical sensitization with the essentially identical mode of emulsion H.Note that sensitizing dye ExS-4, the use amount of the silver halide that ExS-5 and ExS-6 are every mole is respectively 5.79 * 10 ^-4Mole, 1.32 * 10 ^-4Mole and 1.52 * 10 ^-5Mole.

(preparation method of emulsion L)

Prepare emulsion L in identical with emulsion K basically mode, just nucleation temperature change to 35 ℃.Note that sensitizing dye ExS-4 in every mole the silver halide, the use amount of ExS-5 and ExS-6 is respectively 9.66 * 10 ^-4Mole, 2.20 * 10 ^-4Mole and 2.54 * 10 ^-5Mole.

(preparation method of emulsion M)

With the aqueous solution of the KBr of gelatin-4 among the embodiment that contains 0.75g 1 of 1200mL and 0.9g remain on 39 ℃ and under pH1.8 vigorous stirring.The AgNO that will contain 0.34g ₃The aqueous solution of aqueous solution and the KBr that contains 1.5mol%KI added by the dual-jet method in 16 seconds.In adition process, excessive KBr concentration is held constant.Temperature is increased to 54 ℃, makes the material slaking.After slaking, add the gelatin-2 of the embodiment 1 of 20g, and pH is adjusted to 5.9, add 2.9g KBr.Behind the thiourea dioxide that adds 3mg, with the AgNO that contains 28.8g of 288mL ₃Aqueous solution and KBr aqueous solution in 58 minutes, add by the dual-jet method.In adition process, the AgI fine particle emulsion that will have grain size 0.03 μ m adds simultaneously, and the content that makes silver iodide is 4.1mol%.Simultaneously, the pAg of emulsion solution is maintained at 9.40 in the reaction vessel.Behind the KBr that adds 2.5g, will contain the AgNO of 87.7g ₃Aqueous solution and KBr aqueous solution in 69 minutes, add by the dual-jet method, improve flow velocity simultaneously, making final flow rate is 1.2 times of initial flow rate.In adition process, add above-mentioned AgI fine particle emulsion simultaneously, making agi content is 10.5mol%.Simultaneously, the pAg of the emulsion solution in the reaction vessel is maintained at 9.50.The AgNO that contains 41.8g with 132mL ₃Aqueous solution and the aqueous solution of KBr in 27 minutes, add by the dual-jet method.It is 8.15 adding at last that the adding of adjusting KBr makes the pAg of emulsion solution in the reaction vessel.After adding the sodium benzenethiosulfonate of 2mg, add KBr, the pAg of the emulsion solution in the reaction vessel is adjusted to 9.50, add above-mentioned AgI fine particle emulsion, addition counts 5.73 with KI weight.After adding, in 11 minutes, add the AgNO that contains 66.4g of 609mL immediately ₃Aqueous solution.In originally 6 minutes of adding, the pAg of the emulsion solution in the reaction vessel is remained on 9.50 by KBr solution.After washing with water, add gelatin, and pH and pAg are adjusted to 6.5 and 8.2 respectively, and temperature is increased to 56 ℃.Add sensitizing dye ExS-4 and sensitizing dye ExS-7.Afterwards, add potassium rhodanide, gold chloride, sodium thiosulfate, and N, N-dimethyl selenourea makes emulsion slaking and optimum chemical sensitizing.Last in chemical sensitization, add compound 3 and 4.Note that sensitizing dye ExS-4 following in every mole the silver halide and the use amount of ExS-7 are respectively 3.69 * 10 ^-4Mole and 8.19 * 10 ^-4Mole.

(preparation method of emulsion N)

With the aqueous solution of the KBr of gelatin-2 among the embodiment that contains 0.38g 1 of 1200mL and 0.9g remain on 60 ℃ and under pH2 vigorous stirring.The AgNO that will contain 1.03g ₃Aqueous solution adds by the dual-jet method in 30 seconds with the aqueous solution that contains 0.09g KI and 0.88g KBr.After slaking, add the gelatin-3 of the embodiment 1 of 12.8g, and pH is adjusted to 5.9, add 2.90g KBr and 6.2g NaCl.The AgNO that contains 27.3g with 60.7mL ₃Aqueous solution and KBr aqueous solution in 39 minutes, add by the dual-jet method.In adition process, the pAg of emulsion solution in the reaction vessel is remained on 9.05.The AgNO that will contain 65.6g ₃Aqueous solution and KBr aqueous solution in 46 minutes, add by the dual-jet method, improve flow velocity simultaneously, making final flow rate is 2.1 times of initial flow rate.In adition process, under the flow velocity that improves, add the AgI fine particle emulsion that uses in the emulsion D preparation simultaneously, making agi content is 6.5mol%.Simultaneously, the pAg of the emulsion solution in the reaction vessel is maintained at 9.05.After adding the thiourea dioxide of 1.5mg, with the AgNO that contains 41.8g of 132mL ₃Aqueous solution and the aqueous solution of KBr in 16 minutes, add by the dual-jet method.It is 7.70 adding at last that the adding of adjusting KBr makes the pAg of emulsion solution in the reaction vessel.After adding the sodium benzenethiosulfonate of 2mg, add KBr, the pAg of the emulsion solution in the reaction vessel is adjusted to 9.80, add above-mentioned AgI fine particle emulsion, addition is counted 6.2g with KI weight.After adding, in 10 minutes, add the AgNO that contains 88.5g of 300mL immediately ₃Aqueous solution.Add the KBr aqueous solution, making the pAg of emulsion solution in the reaction vessel is 7.40 what add at last.After washing with water, add the gelatin-1 among the embodiment 1, and pH and pAg are adjusted to 6.5 and 8.2 respectively, and temperature is increased to 58 ℃.Under the situation of needs, add of the present invention by formula (1), the compound of (2) or (3) expression (whether adding compound is shown in the table below the present embodiment), and add sensitizing dye ExS-8, ExS-9 and ExS-10.Afterwards, add K ₂IrCl ₆, potassium rhodanide, gold chloride, sodium thiosulfate, and N, N-dimethyl selenourea carries out optimization and learns sensitizing.Last in chemical sensitization, add compound 3 and 4.

(preparation method of emulsion O)

In the preparation of emulsion N, the AgNO that in nucleation process, adds ₃, it is 1.96,1.67 that the amount of KBr and KI is changed respectively, and 0.172g.And the chemical sensitization temperature is changed to 61 ℃ from 58 ℃.Except as mentioned above, prepare emulsion O in the mode substantially the same with emulsion N.

(preparation method of emulsion P)

The aqueous solution of the KBr of gelatin-4 among the embodiment that contains 4.9g 1 of 1200mL and 5.3g is remained on 40 ℃ and vigorous stirring.The AgNO that 27mL is contained 8.75g ₃The aqueous solution that aqueous solution and 36mL contain 6.45g KBr added by the dual-jet method in 1 minute.Temperature is increased to 75 ℃, with the AgNO that contains 6.9g of 21mL ₃Aqueous solution in 2 minutes, add.NH at 26g ₄NO ₃After adding in proper order with the 1N NaOH of 56mL with the material slaking.After slaking, with pH regulator to 4.8.The AgNO that 438mL is contained 141g ₃Aqueous solution and 458mL contain the 102.6gKBr aqueous solution and add by the dual-jet method, making final flow rate is 4 times of initial flow rate.Temperature is reduced to 55 ℃, 240mL is contained the AgNO of 7.1g ₃Aqueous solution and the aqueous solution of KI that contains 6.46g in 5 minutes, add by the dual-jet method.After adding the KBr of 7.1g, add sodium benzenethiosulfonate and and the K of 0.05mg of 4mg ₂IrCl ₆The AgNO that 177mL is contained 57.2g ₃Aqueous solution and the aqueous solution of the 223mL KBr that contains 40.2g in 8 minutes, add by the dual-jet method.The emulsion that obtains is washed with water and carry out chemical sensitization in identical with emulsion N basically mode.

(preparation method of emulsion Q and R)

Prepare emulsion Q and R respectively in identical with L with emulsion K basically mode, just chemical sensitization is carried out in identical with emulsion O basically mode.

The eigenwert of above-mentioned silver emulsion is summarized in hereinafter table 7.Can as mentioned belowly measure surface iodide content by XPS.That is to say that sample is cooled to-115 ℃ in 1 * 10 holder or lower vacuum, and carries out radiation with X-ray detector MgK α, the voltage of X-ray source is 8kV, X-ray electric current is 20mA, measures Ag3d5/2 with this, Br3d and I3d5/2 electronics.The integer intensity at the peak that records is proofreaied and correct with the sensitization factor, from the content of these sensitization rate gauging surface iodide.Note that by high-voltage electron microscope and in the silver halide particle of emulsion D to R, observe the displacement line that is described in JP-A-3-237450.

Table 7

The emulsion numbering	Equal circle diameter (μ m) variation factor (%)	Thickness (μ m) variation factor (%)	Length diameter ratio variation factor (%)	Flat property	The Shuangzi interplanar is every (μ m) variation factor (%)	In the total projection area by having (111) face as the shared ratio of the flat particle of interarea (%)	The side is the ratio (%) of (100) face	AgI content (mol%) variation factor (%)	AgCl content (mol%)	Surfaces A gI content (mol%)
											D	1.98 23	0.198 28	10 35	51	0.014 32	92	23	15 17	0	4.3
E	1.30 25	0.108 27	12 38	111	0.013 30	93	22	11 16	0	3.6
											F	1.00 27	0.083 26	12 37	145	0.012 30	93	18	4 8	1	1.8
G	0.75 31	0.075 18	10 29	133	0.010 27	91	33	4 8	2	1.9
											H	2.01 18	0.161 18	12.5 21	78	0.011 23	99	23	3.9 5	0	2.6
I	1.54 26	0.077 18	20 33	260	0.013 26	99	23	7 7	0	2.5
											J	1.08 18	0.072 15	15 19	208	0.008 22	97	23	6 5	0	2.0
K	0.44 16	0.220 13	2 9	9	0.013 18	90	38	3 6	2	1.0
											L	0.33 17	0.165 13	2 12	12	0.013 18	88	42	3 6	2	1.0

Continuous table 7

The emulsion numbering	Equal circle diameter (μ m) variation factor (%)	Thickness (μ m) variation factor (%)	Length diameter ratio variation factor (%)	Flat property	The Shuangzi interplanar is every (μ m) variation factor (%)	In the total projection area by having (111) face as the shared ratio of the flat particle of interarea (%)	The side is the ratio (%) of (100) face	AgI content (mol%) variation factor (%)	AgCl content (mol%)	Surfaces A gI content (mol%)
											M	2.25 31	0.107 19	21 34	197	0.013 33	99	20	7.2 7	0	2.4
N	2.38 20	0.138 20	17 23	125	0.013 19	98	23	5 6	1	1.6
											O	1.83 18	0.122 20	15 22	123	0.012 19	98	23	5 6	1	1.8
P	0.84 17	0.120 18	7 19	58	0.013 16	99	25	3 7	0	2.7
											Q	0.44 17	0.220 13	2 12	9	0.013 18	88	42	2 6	2	1.0
R	0.33 17	0.165 13	2 12	12	0.013 18	88	46	1 6	2	0.5
											S	0.07 ---	0.070 ---	1 ---	---	--- ---	---	---	1 ---	0	---
T	0.07 ---	0.070 ---	1 ---	---	--- ---	---	---	0.9 ---	0	---

1) carrier

The carrier that is used for present embodiment forms in the following manner.

With the tygon-2 of 100 weight portions, 6-naphthalate polymer and P.326 (made by Ciba-Geigy Co.) as the Tinuvin of 2 weight portions of ultraviolet absorber and to carry out drying 300 ℃ of fusings, and is extruded from a T-shape mould.The material that obtains is extended 3.3 times at 140 ℃ in the vertical, in direction finding, extend 3.3 times, and 250 ℃ of 6 seconds of hot photographic fixing, thereby obtain the PEN film of 90 μ m thickness at 130 ℃.Note that an amount of indigo plant of adding in this PEN film, magenta, and weld (I-1 that describes among the Journal of Technical Disclosure No.94-6023, I-4, I-6, I-24, I-26, I-27, and II-5).This PEN film is wrapped on the stainless steel core of one 20 cm diameter, and provides the heat content of 110 ℃ and 48 hours, produce carrier with high curling resistance.

2) coating of coating down

Ring of light discharge is carried out on two surfaces of carrier, UV discharge, and glow discharge.Afterwards, each surface with carrier is coated with (10cc/m with following coating solution ², use bar-shaped spreader), this lower body layer 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 ²Polyamidoamines-chloropropylene oxide polycondensation product, thereby in coating under forming after the orientation at high temperature on the face.In 115 ℃ of dryings 6 minutes (all roller and conveyers are 115 ℃ at dry section).

3) coating of backing layer

With a kind of antistatic layer with following composition, magnetic record layer and sliding layer are coated with, as backing layer with a surface of the carrier of down coating.

3-1) coating antistatic backing

With this surface 0.2g/m ²The dispersion liquid coating (secondary aggregated particle size=about 0.08 μ m) of fine particle powder, its resistivity is 5 Ω .cm, it is a kind of tin oxide-antimony oxide combined material, mean particle size is 0.005 μ m, also has 0.05g/m simultaneously ²Gelatin, 0.02g/m ²(CH ₂=CHSO ₂CH ₂CH ₂NHCO) ₂CH ₂, 0.005g/m ²Polyoxyethylene-to nonyl phenol (degree of polymerization is 10), and resorcinol.

3-2) the coating of magnetic record layer

Use a roller coat device to use 0.06g/m ²Cobalt-gamma-iron oxide (specific surface area is 43m ²/ g, main shaft 0.14 μ m, secondary axes are 0.03 μ m saturated magnetization effect 89emu/g, Fe ^{+ 2}/ Fe ^{+ 3}=6/94, handle by the aluminium oxide monox with the iron oxide of 2wt% on this surface), use poly-(degree of polymerization 15) ethylene oxide of 3--propoxyl group trimethoxy silane (15wt%), and 1.2g/m ²Diacetyl cellulose (iron oxide disperses by open kneader and husky mill) be coated with, and use 0.3g/m ²C ₂H ₅C (CH ₂OCONH-C ₆H ₃(CH ₃) NCO) ₃As rigidizer, and acetone, methyl ethyl ketone and cyclohexane give are solvent, thereby form the magnetic record layer behind the 1.2 μ m.Add 10mg/m ²Silicon oxide particle (0.3 μ m) as practicing the sulfonium agent, and add 10mg/m with poly-(degree of polymerization the is 15) ethylene oxide of 3--propoxyl group trimethoxy silane (15wt%) coating ²Aluminium oxide (0.15 μ m) as brilliant polish.115 ℃ of down dry 6 minutes (all rollers and conveyer at dry section are 115 ℃).The D of the magnetic record layer that records by X-light (blue color filter) ^BColored blackness increase to about 0.1.The saturation magnetic moment of magnetic record layer, coercive force and squareness ratio are respectively 4.2emu/g, and 7.3 * 10 ⁴A/m and 65%.

3-3) the preparation of sliding layer

Then should surface diacetyl cellulose (25mg/m 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.Note that this potpourri is to melt down at 105 ℃ in dimethylbenzene/propylene monomethyl ether (1/1), and at room temperature topple over and be dispersed in the propylene monomethyl ether (10 times).After this, the potpourri that obtains forms a kind of dispersion liquid (mean particle size is 0.01 μ m) in acetone before adding.Add 15mg/m ²Silicon oxide particle (0.3 μ m) as practicing the sulfonium agent, and add 15mg/m with poly-(degree of polymerization is 15) the oxygen ethene of 3--propoxyl group trimethoxy silane (15wt%) coating ²Aluminium oxide (0.15 μ m) as brilliant polish.115 ℃ of down dry 6 minutes (all rollers and conveyer at dry section are 115 ℃).The sliding layer that discovery obtains has excellent characteristic; Dynamic friction coefficient is 0.06 (5mm diameter stainless steel hard sphere, charging capacity is 100g, speed is 6 cm per minute), and static friction coefficient is 0.07 (sliding method).Dynamic friction coefficient between emulsion surface (hereinafter described) and sliding layer is also very good, is 0.12.

4) coating of photographic layer

Be coated with a plurality of layers on the surface away from the carrier of face of backing layer as indicated above with following composition, form the sample of the negative photosensitive material of a kind of colour, thereby prepare sample 601 to 701, its photographic property will use red optical filter and green optical filter to test respectively.

(composition of photographic layer)

The key component of using in each layer is classified as follows, still, is not limited to these in actual the use.

ExC: cyan colour coupler

UV: ultraviolet absorber

ExM: magenta colour coupler

HBS: high boiling organic solvent

ExY: yellow colour former

H: gelatin hardener

(in describing hereinafter, actual compound has the numeral that links to each other with its symbol.The general formula of these compounds will be following zhang description.)

Corresponding to the numeral coating weight of every kind of component, unit is g/m ²The coating weight of silver halide is shown by the scale of silver.

Ground floor (first antihalation 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 (second antihalation layer)

The black collargol	Silver 0.011
		Gelatin	0.407
ExM-1	0.050
		ExF-1	2.0×10 -3
HBS-1	0.074
		Solid disperse dye ExF-2	0.014
Solid disperse dye ExF-3	0.020

The 3rd layer (middle layer)

Iodine silver bromide emulsion S	0.020
		ExC-2	0.022
The polyethylene acrylate colloid	0.085
		Gelatin	0.294

The 4th layer (low velocity red-light-sensing emulsion layer)

Iodine silver bromide emulsion R	Silver 0.065
		Iodine silver bromide emulsion Q	Silver 0.258
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 (medium velocity red-light-sensing emulsion layer)

Iodine silver bromide emulsion P	Silver 0.21
		Iodine silver bromide emulsion O	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 red-light-sensing emulsion layer)

Iodine silver bromide emulsion N	Silver 1.47
		ExC-1	0.18
ExC-3	0.07
		ExC-6	0.029
ExC-7	0.010
		ExY-5	0.008
Cpd-2	0.046
		Cpd-4	0.077
HBS-1	0.25
		HBS-2	0.12
Gelatin	2.12

Layer 7 (middle layer)

Cpd-1	0.089
		Solid disperse dye ExF-4	0.030
HBS-1	0.050
		Poly-ethylacrylic acid ester gum body	0.83
Gelatin	0.84

The 8th layer (the red-light-sensing layer being given the layer of effect between image)

Iodine silver bromide emulsion M	Silver 0.560
		Cpd-3	0.020
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 velocity green-light-sensing emulsion layer)

Iodine silver bromide emulsion L	Silver 0.39
		Iodine silver bromide emulsion K	Silver 0.28
Iodine silver bromide emulsion J	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 (medium velocity green-light-sensing emulsion layer)

Iodine silver bromide emulsion I	Silver 0.45
		ExC-6	0.009
ExM-2	0.031
		ExM-3	0.029
ExY-1	0.006
		ExM-4	0.028
ExG-1	0.005
		Cpd-3	0.006
HBS-1	0.064
		HBS-3	2.1×10 -3
Gelatin	0.44

Eleventh floor (high-speed green-light-sensing emulsion layer)

Iodine silver bromide emulsion H	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-3	0.004
Cpd-4	0.007
		HBS-1	0.18
The polyethylene acrylate latex	0.099
		Gelatin	1.11

Floor 12 (Yellow filter layer)

Yellow colloidal silver	Silver 0.010
		Cpd-1	0.16
Oil-soluble dyes ExF-5	0.010
		Oil-dispersing property dyestuff ExF-6	0.020
HBS-1	0.082
		Gelatin	1.057

The 13 layer (low velocity blue-light-sensing emulsion layer)

Iodine silver bromide emulsion G	Silver 0.18
		Iodine silver bromide emulsion E	Silver 0.20
Iodine silver bromide emulsion F	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 (feeling the blue light emulsion layer at a high speed)

Iodine silver bromide emulsion D	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)

Iodine silver bromide emulsion S	Silver 0.30
		UV-1	0.21
UV-2	0.13
		UV-3	0.20
UV-4	0.025
		F-18	0.009
HBS-1	0.12
		HBS-4	5.0×10 -2
Gelatin	2.3

The 16 layer (second protective seam)

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

Except said components, in order to improve bin stability, processibility, resistance to pressure, anti-corrosive properties and mildew resistance, antistatic behaviour, and coating performance, each layer contains W-1 to W-5, B-4 to B-6, F-1 to F-18, molysite, lead salt, gold salt, platinum salt, palladium salt, iridium salt, ruthenium salt and rhodium salt.In addition by to the 8th and the coating solution of eleventh floor in every mole silver halide add 8.5 * 10 respectively ^-3G and 7.9 * 10 ^-3The calcium of the calcium nitrate aqueous solution form of g prepares sample.

The preparation of organic solid disperse dyes

Disperse ExF-2 by following method.That is to say, water with 21.7mL, 5% the aqueous solution of 3mL to Octylphenoxy Ethoxyethane sulfonic acid soda, place the pot mill of a 700mL with 5% the aqueous solution of 0.5g to Octylphenoxy polyoxyethylene ether (degree of polymerization is 10), and to the zirconium oxide bead (1 millimeter of diameter) of dyestuff ExF-2 that wherein adds 5.0g and 500mL.Inclusions was disperseed 2 hours.This dispersion is to be undertaken by the BO type vibration ball milling that uses Chuo Koki K.K. to make.Dispersion liquid is taken out and adds 12.5% aqueous gelatin solution of 8g from ball milling.Pearl is wherein leached the aqueous gelatin solution that obtains a kind of dyestuff.The mean particle size of trickle dye granule is 0.44 μ m.

Obtain solid dispersion ExF-3 with step same as described above, ExF-4, and ExF-6.The mean particle size of these trickle dye granules is respectively 0.24 μ m, 0.45 μ m and 0.52 μ m.According to EP549,489A disperses ExF-2 according to the microdeposit process for dispersing described in the embodiment 1.Mean particle size is 0.06 μ m.

By following method dispersing solid dispersion liquid ExF-6.

The aqueous solution of the 3%W-2 of the water of 4.0Kg and 376g is added 2, in the wet cake of the ExF-6 that contains 18% water of 800g, the material that obtains is stirred into a kind of ExF-6 slurries with 32% concentration.Then, the ULTRA VISCO MILL (UVM-2) that Imex K.K. is made is with 1, and 700mL has a zirconium oxide bead that mean particle size is 0.5mm.By the about 10m/ of circular velocity second and excretion 0.5L/ minute beyond should grinding carrying out 8 hours with this slurries ball milling.

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

HBS-1 three cresyl phosphates

HBS-2 di-n-butyl phthalic ester

HBS-4 three (2-ethylhexyl) phosphate

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

X/y=240/60 (weight ratio) mean molecular weight: about 20,000

Mean molecular weight: about 8,000

Mean molecular weight: about 750,000

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

Mean molecular weight: about 10,000

N=2 to 4

(formation of every kind of sample)

In preparation emulsion H and N, whether add compound of the present invention and addition is shown in the following table of present embodiment.

These samples are carried out film sclerosis 14 hours under the condition of 40 ℃ and relative humidity 70%.Afterwards, the gelatin filter SC-39 (a kind of long wavelength light sees through optical filter, and cutoff wavelength is 390nm) that sample is produced by a Fujiphoto exposed 1/100 second, and continued wedge.Use is developed by the automatic developer FP-360B of Fujiphoto production.Note that FP-360B is adjusted, the too much solution of bleaching liquid is discharged in the waste liquid cylinder fully, be not carried in the following container.This FP-360B comprises an evaporation means for correcting, described in JIII Journal of TechnicalDisclosure No.94-4992.

Treatment step and Treatment Solution are composed as follows described.

(treatment step)

Step	Time	Temperature	Supplementary rate *	Container volume
					Colour development	3 minutes 50 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	60.0℃

^*Supplementary rate is the magnitude of recruitment of per 1.1 meters 35 millimeters wide photosensitive material (equaling a 24Ex.1)

Stabilizing agent and fixer from (2) to (1) adverse current, too much washings are all introduced in the stop bath (2).Note that to be carried into blanching step, the developer solution of photographic fixing step and washing step, the amount of bleaching liquid and stop bath is respectively 2.5mL, and 2.0mL, and 2.0mL are in 35 millimeters per 1.1 meters wide photosensitive material.Note that also each intersection time is 6 seconds, this time was included in the processing time of each previous step.

For color developer, the aperture area of processor is 100cm ², be 120cm for liquid lime chloride ², for other Treatment Solution, be about 100cm ²

The composition of Treatment Solution is shown in hereinafter.

(color developer)

	Container solution (g)	Replenish liquid (g)
			Diethylene-triamine pentaacetic acid	3.0	3.0
Cathecol-3,5-disulfonic acid disodium	0.3	0.3
			Sodium sulphite	3.9	5.3
Sal tartari	39.0	39.0
			Disodium-N, two (the 2-sulphonic acid ester ethyl) azanols of N-	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-(beta-hydroxy ethyl) amino] the aniline sulfuric ester	4.5	6.5
			Add water to	1.0L	1.0L
PH (by potassium hydroxide and sulfuric acid control)	10.05	10.18

(liquid lime chloride)

	Container solution (9g)	Replenish liquid (g)
			Iron ammonium 1,3-diaminopropanetetraacetic acid salt monohydrate	113	170
Ammonium bromide	70	105
			Ammonium nitrate	14	21
Succinic acid	34	51
			Maleic acid	28	42
Add water to	1.0L	1.0L
			PH (controlling) with ammoniacal liquor	4.6	4.0

(photographic fixing (1) container solution)

The potpourri (pH6.8) of 5: 95 (volume ratio) of above-mentioned bleaching container solution and following photographic fixing container solution.

(stop bath (2))

	Container solution (g)	Replenish liquid (g)
			Thiosulfuric acid aqueous ammonium (750g/L)	240mL	720mL
Imidazoles	7	21
			Methane thiosulfonic acid ammonium	5	15
Methane sulfinic acid ammonium	10	30
			Ethylenediamine tetraacetic acid	13	39
Add water to	1.0L	1.0L
			PH (with ammoniacal liquor and acetate control)	7.4	7.45

(washings) container solution and additional liquid phase are together

Distilled water is added with H type strong acid oxonium ion exchange resin (Amberlite IR-120B: from Rohm ﹠amp; Haas Co. obtains) and a kind of OH type strong basic anion-exchange resin (Amberlite IR-400) mixed bed column of filling in, the concentration of calcium and magnesium is set in 3mg/L or lower.Then, add 20mg/L second cyanogen urea acid sodium dichloride and 150mg/L sodium sulphate.The pH of solution is 6.5 to 7.5.

(stabilizing agent)

	Container solution and additional liquid phase are with (g)
		SPTS	0.03
Polyoxyethylene-right-single nonylplenyl ether (average degree of polymerization is 10)	0.2
		1, the 2-benzisothiazole-3-ketone. sodium	0.10
Disodium EDTA	0.05
		1,2, the 4-triazole	1.3
1, two (1,2, the different methyl of the 4-triazole-1-) piperazines of 4-	0.75
		Add water to	1.0L
pH	8.5

Sensitizing falls in H with emulsion, and each particle has 10 or more a plurality of displacement line, and diameter of axle ratio is 12.5, and the lip-deep AgI content of emulsion is 2.6%.Of the present invention by formula (1), whether the compound of (2) or (3) expression adds and addition is shown in the table 8 and 9 of present embodiment.Sensitizing falls in N with emulsion, and each particle has 10 or more a plurality of displacement line, and diameter of axle ratio is 17, and the lip-deep AgI content of emulsion is 2.4%.Of the present invention by formula (1), whether the compound of (2) or (3) expression adds and addition is shown in the table 8 and 9 of present embodiment.

Prepare sample 602 to 608 in the mode identical, just changed emulsion H and N with sample 601, as shown in table 8.

Assess the photographic property of sample 601 to 608 by the blackness of measuring the sample of handling by Red lightscreening plate.The results are shown in table 8.Photonasty is (photonasty of sample 601 is assumed that 100) that is added 0.2 expression by the relative value of the inverse of the needed exposure of black poison that reaches the photographic fog blackness.

Table 8

Sample number into spectrum	High sensitivity green-light-sensing emulsion layer: emulsion H		High sensitivity red-light-sensing emulsion layer: emulsion N		Photographic property by Red lightscreening plate		Remarks
								Compound number	Addition (mol%) with respect to photosensitizing dye	Compound number	Addition (mol%) with respect to photosensitizing dye	Photonasty *1)	Blackness exposes
	601	No	-	No	-	100								0.35	The comparative example
602							No	-	Compound I-1	5	135	0.33	The present invention
	603	No	-	Compound I-25	5	129								0.32	The present invention
604							No	-	Compound I-12	5	127	0.36	The present invention
	605	No	-	Compound I-14	5	127								0.34	The present invention
606							No	-	Compound I-7	5	117	0.35	The present invention
	607	No	-	Compound I-8	5	118								0.33	The present invention
608							No	-	Compound I-15	5	119	0.36	The present invention

^*1) each photonasty is that the photonasty of supposition sample 601 is that 100 relative value is represented

As shown in table 8, the use of compound of the present invention has improved photonasty and has improved effect.Table 8 shows that the compound of formula (3) is preferred especially.

Prepare sample 702 to 708 in the mode identical, just changed emulsion H and N with sample 701, as shown in table 9.

Assess the photographic property of sample 701 to 708 by the blackness of measuring the sample of handling by green color filter.The results are shown in table 9.Photonasty is (photonasty of sample 701 is assumed that 100) that is added 0.2 expression by the relative value of the inverse of the needed exposure of black poison that reaches the photographic fog blackness.

Table 9

Sample number into spectrum	High sensitivity green-light-sensing emulsion layer: emulsion H		High sensitivity red-light-sensing emulsion layer: emulsion N		Photographic property by green color filter		Remarks
								Compound number	Addition (mol%) with respect to photosensitizing dye	Compound number	Addition (mol%) with respect to photosensitizing dye	Photonasty *1)	Blackness exposes
	701	No	-	No	-	100								0.35	The comparative example
702							Compound I-1	5	No	-	110	0.34	The present invention
	703	Compound I-25	5	No	-	109								0.36	The present invention
704							Compound I-12	5	No	-	108	0.37	The present invention
	705	Compound I-14	5	No	-	109								0.35	The present invention
706							Compound I-7	5	No	-	105	0.34	The present invention
	707	Compound I-8	5	No	-	106								0.36	The present invention
708							Compound I-15	5	No	-	105	0.33	The present invention

^*1) each photonasty is that the photonasty of supposition sample 601 is that 100 relative value is represented

As shown in table 9, of the present invention by formula (1), the use of the compound of (2) or (3) expression has strengthened photonasty and has improved effect.But be shown in the effect that the emulsion N of the red-light-sensing of table 8 obtains by use more remarkable than the effect that the emulsion H that uses the green-light-sensing that is shown in table 9 obtains.

(embodiment 7)

Sample 201 identical modes according to the embodiment 2 that is described in JP-A-9-5912 prepare multilayer silver-halide color reversal photographic photosensitive material 801 to 808 completely, have just changed the emulsion in the 6th the high-speed red-light-sensing emulsion layer.That is to say, in the chemical sensitization step of the 6th layer emulsion of preparation, begin to add formula of the present invention (1), the compound of (2) or (3) expression in the chemical sensitization step, as shown in table 10, (whether add these compounds and addition thereof and be shown in table 10).With the carve type exposure of sample by using a white light source to carry out 1/100 second that makes, and handle as described in the embodiment 1 of JP-A-9-5912, photonasty is measured.The photonasty of layer 6 is to be represented by the relative value of the inverse that reaches 2.0 the needed exposure of cyanogen blackness.The photonasty of sample 801 is assumed that 100.

Table 10

Sample number into spectrum	The 6th emulsion layer of the sample 201 among the embodiment 2 of high sensitivity red-light-sensing emulsion layer: JP-A-9-5912				Photographic property	Remarks
							Compound number	Addition (mol%) with respect to photosensitizing dye	Length diameter ratio	Whether the existence of 10 or more a plurality of displacement lines in each particle	Photonasty *1)
	801	No	-	7.1	Exist							100	The comparative example
802						Compound I-1	5	7.1	Exist	130	The present invention
	803	Compound I-25	5	7.1	Exist							128	The present invention
804						Compound I-12	5	7.1	Exist	125	The present invention
	805	Compound I-14	5	7.1	Exist							123	The present invention
806						Compound I-7	5	7.1	Exist	112	The present invention
	807	Compound I-8	5	7.1	Exist							113	The present invention
808						Compound I-15	5	7.1	Exist	114	The present invention

^*1) each photonasty is that the photonasty of supposition sample 801 is that 100 relative value is represented

As can be seen from Table 10, the use of compound of the present invention has strengthened photonasty and has improved effect.The compound of table 10 display type (3) is preferred especially.

Other advantage and change are conspicuous to those skilled in the art.Thereby the present invention is not limited to concrete description as herein described and representational embodiment.Thereby, can carry out multiple variation and do not break away from the spirit and scope of the present invention.

Claims (6)

1. silver halide photographic light-sensitivity emulsion, wherein

The total projection area of all silver halide particles 50% or highlyer occupy by flat particle, each in this flat particle has (111) face as parallel interarea, the diameter of axle is than being 2-50, and each particle comprises 10 or more a plurality of displacement line; Described silver halide is that the content of silver chloride is iodine silver bromide or the bromine silver iodochloride of 0-8mol%; And

In said emulsion, contain at least a compound: formula (1) by formula (1) or (2) expression

Formula (2)

Wherein, A represents the needed atomic group of a kind of formation nitrogen heterocyclic ring; Each B and E represent a kind of alkylidene of the 1-to 10-of being selected from carbon independently, have the arlydene of 6 carbon ,-O-,-S-,-SO ₂-,-CO ₂-and-N (R5)-in one or its group that constitutes, wherein R5 represents hydrogen atom, methyl, its condition precedent is-O-,-S-,-SO ₂-,-CO ₂-, with-N (R5)-in each respectively with the alkylidene of 1-to 10-carbon or to have an arlydene of 6 carbon adjacent and link to each other, and B not with form nitrogenous heterocyclic nitrogen-atoms simultaneously with A and combine, and it combines with carbon atom by two keys; Among R1 and the R2 each is represented the alkyl of 4-to 20-carbon or the aralkyl of 7-to 20-carbon independently; Each expression hydrogen atom among R3 and the R4, halogen atom, the alkyl of 4-to 20-carbon, the aryl of 6-to 20-carbon, or the aralkyl of 7-to 20-carbon; X represents chlorion, bromide ion, and iodide ion, nitrate ion, sulfate ion, p-methyl benzenesulfonic acid radical ion, or oxalate, its condition precedent is that X does not exist under the situation of molecule inner salt.

2. according to the described emulsion of claim 1, wherein, this silver halide particle makes its red-light-sensing by two or more cyanine dyes, and the addition of formula (1) or (2) compound is the 1-25mol% of this cyanine dye addition.

3. according to claim 1 or 2 described emulsions, wherein, the surperficial agi content of each of silver halide particle is 2-10mol%.

4. according to the described emulsion of claim 1, wherein, silver halide particle has been carried out and has fallen the sensitizing processing.

5. according to the described emulsion of claim 1, wherein, represent by following formula (3) by the compound of formula (2) expression:

Formula (3)

Wherein, D represent to be selected from down the alkylidene of group and alkylidene and-divalent group of the alternate combinations of O-: 1,3-propylidene, 1,5-pentylidene, heptamethylene, 1, the inferior nonyl of 9-,-CH ₂CH ₂OCH ₂CH ₂-,-(CH ₂CH ₂O) ₂-CH ₂CH ₂-and-(CH ₂CH ₂O) ₃-CH ₂CH ₂-; Among m and the n each represents 0,1 independently, perhaps 2; The alkyl of 4-to the 20-carbon of each expression among R6 and the R7, the aryl of 6-to a 20-carbon, the perhaps aralkyl of 7-to a 20-carbon, but when m=2 and n=2, each among R6 and the R7 can be as phenyl ring and pyridine ring formation condensed ring; X represents chlorion, bromide ion, and iodide ion, nitrate ion, sulfate ion, p-methyl benzenesulfonic acid radical ion, or oxalate, but X is unwanted under the situation of molecule inner salt.

6. silver halide photographic sensitive material, it has at least one silver halide emulsion layer on a kind of carrier, and wherein, this silver halide emulsion layer contains the described photosensitive emulsion of claim 1.