CN1695085A - Silver halide color photosensitive material - Google Patents

Abstract

A silver halide color photosensitive material high in sensitivity and excellent in shelf life stability, latent image stability, and processing stability. The material comprising a support and further comprising, over the support, at least one red-photosensitive layer, at least one green-photosensitive layer, at least one blue-photosensitive layer, and at least one non-photosensitive layer is characterized in that at least one of the photosensitive layers contains a monodispersed silver halide emulsion having an average silver iodide content of 2.0 to 4.0 mol%, an average aspect ratio of 8.0 or more, and a dislocation line, and in that at least one photosensitive layer containing the silver halide emulsion contains 0.60 mg/m<2> or more of inhibitor.

Description

Silver halide colour photographic sensitive material

Technical field

The present invention relates to silver halide colour photographic sensitive material, relate in detail high sensitivity and the good silver halide colour photographic sensitive material of storage stability, latent-image stability and Treatment Stability.

Background technology

Silver halide colour photographic sensitive material can be described as the product of technology height maturation on the one hand, but on the other hand, desired performance relates to high sensitivity, high image quality, changes many aspects such as the performance change that causes is little with preservation condition, and then also must append the rapid processing adaptability that shortens the development treatment time from now on, the level of these requirements just constantly improves in recent years.

Particularly,,, must be suppressed at reduced levels to photographic fog, also will take into account keeping quality simultaneously in order to keep the superiority of silver halide colour photographic sensitive material along with the technical progress of nearest digital camera at the high sensitivity this respect, and further high sensitivityization.

The high sensitivity technology of silver emulsion, be that sensibilization technology relates to: the various known methods of the spectral sensitization of the manufacture method of silver emulsion, the chemical sensitization of silver emulsion, silver emulsion, the method for designing of silver halide colour photographic sensitive material, developing process of silver halide colour photographic sensitive material or the like, wherein most preferably and essential method be the inefficiency part that reduces in the photo-process of silver halide crystal, improve quantum efficiency.

As one of method that realizes high sensitivityization, high image qualityization, developed the technology of ratio of the sensitivity/particle size of per 1 silver halide particle in a kind of raising silver emulsion (the following emulsion that abbreviates as sometimes).

Known general in silver emulsion contained silver halide particle have different shape.The normal crystal silver halide particle of cube, octahedron, tetrakaidecahedron shape or have 1 twin plane or tabular silver halide particle, tetrapod shape or the bar-shaped silver halide particle etc. of a plurality of parallel twin plane for example with nonparallel twin plane.Wherein tabular silver halide particle (following abbreviate as sometimes dull and stereotyped particle) has following various advantages: as its photographic property, with respect to intrinsic sensitivity, its hyperchromic sense sensitivity is higher relatively, can realize the lifting of the distinctiveness (sharpness) of silver halide photographic sensitive material by particle shape, less by the light scattering that particle causes, can obtain the high image of resolution.

As the prior art that relates to dull and stereotyped particle, for example open manufacture method and the operation technique that discloses it in flat 6-43605 number, 6-43606 number, 6-214331 number, 6-222488 number, 6-230493 number, 6-258745 number etc. United States Patent (USP) No. 4434226, No. 4439520, No. 4414310, No. 4433048, No. 4414306, No. 4459353, special fair 4-36374 number, 5-16015 number, 6-44132 number, spy.

In order more effectively to cause the above-mentioned advantage of dull and stereotyped particle, adopting the dull and stereotyped particle of high aspect ratio is effective method.As well known in the art, because the content of silver iodide is high more, the preparation of the dull and stereotyped particle of high aspect ratio is difficult more, and therefore above-mentioned of the prior art dull and stereotyped particle is the low iodine silver bromide of silver bromide or agi content mostly.Yet, the silver halide particle that agi content is low has the activity of development, and the dull and stereotyped particle of high aspect ratio is because the factor of its shape can further promote development, therefore under the situation of same silver-colored coating amount, cause granular deterioration easily or be subjected to the influence of natural radiation line, for the high more dull and stereotyped particle of aspect ratio, the advantage that causes aforementioned dull and stereotyped particle also is difficulty more.In addition, the dull and stereotyped particle that aspect ratio is high more also exists following problem, and promptly because the deviation of particle diameter has the tendency of increase, and chemical sensitization or spectral sensitization are difficult to fully carry out, the result causes the reduction of level or the reduction of color development concentration.

Open in flat 6-230491 number the spy, disclose a kind of agi content with respect to the central area, the agi content of fringe region is its dull and stereotyped particle 1.5～50 times, aspect ratio 8～100.But this technology is by the phase configuration edge region that agi content is high, and chemical sensitization adaptability incurs loss, and causes the result that sensitivity reduces and level weakens.On the other hand, open in flat 6-235988 number the spy, disclose following a kind of dull and stereotyped particle, promptly a kind of sandwich construction particle that is formed by interior layer, middle layer and outermost layer at least has the higher zone of agi content on this middle layer, and aspect ratio is 3～100.But this technology is because to be configured in the lower outermost particulate fraction of the agi content in the higher zone outside of agi content more, and therefore the problems such as granular performance degradation that promote property to cause by the development of the dull and stereotyped particle of high aspect ratio are not resolved.

On the other hand, as the method for the photographic fog that improves silver halide colour photographic sensitive material, keeping quality etc., be known that the method that adopts inhibitor.For example open in flat 5-53234 number, 5-27360 number, 5-19395 number, 5-17540 number etc. and disclose the combination of various inhibitor, but improving photographic fog and conservatory while, reduced sensitivity, therefore can not solve whole problems the spy.As inhibitor with sulfydryl and water-soluble base, open the photographic fog that discloses dull and stereotyped particle in flat 2-837 number the spy and prevent agent and low-light (level) inefficacy improver, open the spy and disclose a kind of photographic fog for flat 4-16838 number and prevent agent for selenium sensitizing.In addition, the spy open disclose in flat 6-19024 number, 6-19026 number, 6-19037 number the reactionlessness chalcogen compound photographic fog prevent aspect effective content.

As the problem of photographic fog, be two following aspects, promptly be introduced into the photographic fog (photographic fog absolute value) that finally becomes silver emulsion self in the silver halide colour photographic sensitive material and in the photographic fog development of chemical slaking to the process of the most suitable degree.From making stable aspect, preferred photographic fog slower development, and from the angle of photographic property, think that the lower silver emulsion of photographic fog absolute value is desirable, but do not reach the degree that satisfies the two simultaneously.

On the other hand, in the treatment plant of developing on a large scale used automatic processing machine and the small-sized developing machine that in shop etc., uses, when promptly in so-called mini-lab etc., carrying out development treatment continuously, normally corresponding to the film area of handling, replenish a certain amount of each developer replenisher solution, always be in the certain treatment characteristic or the state of composition with control and treatment liquid.In addition, also have always the development activity for the treatment of fluid is monitored, carry out the method for revisal as required.If can carry out the qualitative control of development treatment liquid like this closely, then do not have problem, but for example when the film treatment capacity of unit interval more after a little while, when carrying out non-constant development treatment, at water evaporation quantities such as dry areas especially for a long time, after perhaps spacer knobs stopped development time the holiday for a long time, under the situation, the activity of development treatment liquid was in the situation of easy variation when beginning development treatment once more etc.

Under this development treatment environment, carried out making silver halide colour photographic sensitive material give various trials such as Treatment Stability, known for example has: the method that the The Nomenclature Composition and Structure of Complexes of photonasty silver halide particle is improved, formation by silver halide colour photographic sensitive material, the method that layer formation, thickness, film hardness etc. are improved for example, pass through oil soluble additive, for example the method for improving by coupling agent, DIR coupling agent etc. perhaps adopts the method for stable developing agent, development restrainer etc.Yet in the method for these raisings to the stability of development treatment, most situations are the reductions that are accompanied by other photographic property, are difficult to Treatment Stability and photographic property two aspects all favourable.

In view of the above-mentioned problems, propose inhibitor that a kind of employing has ad hoc structure and carried out photosensitive silve halide material chemical sensitization, high sensitivity and photographic fog excellent in stability (for example can with reference to patent documentation 1).In addition, also proposed a kind of employing grain spacing from the control method, comprised and make particle on the direction vertical, grow up, have the silver emulsion (for example patent documentation 2) that specific halogen is formed the tabular silver halide particle that distributes with respect to the particle principal plane of substrate emulsion grain.

Yet, though above-mentioned any method can realize high sensitivityization to a certain degree, in storage stability, latent-image stability, Treatment Stability aspect particularly, requiring under the present situation of high-qualityization, is sufficient definitely inadequately, need further improve quality.

(patent documentation 1)

The spy opens 2000-235240 communique (scope of claim)

(patent documentation 2)

The spy opens 2001-142169 communique (scope of claim)

Summary of the invention

Above-mentioned purpose of the present invention constitutes realization by following each.

(1) a kind of silver halide colour photographic sensitive material, it is characterized in that: it has 1 layer blue layer of sense red beds, green layer, sense and non-photosensitive layer at least on support, it is 2.0～4.0mol%, average aspect ratio more than 8.0 and have the monodispersed silver emulsion of dislocation line that in these photosensitive layers at least 1 layer contains average silver iodide content, and at least 1 layer the photosensitive layer that comprises this silver emulsion contains 0.60mg/m ²Above inhibitor.

(2) silver halide colour photographic sensitive material of record in (1) is characterized in that: at least a kind in the aforementioned inhibitor is the compound shown in the following general formula [I].

General formula [I]

Het-(J) _n1-(Q) _m1

[in the formula, Het is not for containing 5～6 member heterocyclic ring containing nitrogens as the sulfydryl of substituent sulfydryl or protection, and J represents the connection base of (m1+1) valency, and Q is water-soluble base.N1 represents 0～5 integer, and m1 represents the integer more than 1].

(3) silver halide colour photographic sensitive material of record in (2), it is characterized in that: the compound shown in the aforementioned formula [I] is the compound shown in following general formula [II] or the general formula [III].

General formula (II) general formula (III)

[in the general formula [II], W is oxygen atom, sulphur atom, nitrogen-atoms or C (R ₄₁), X is nitrogen-atoms or C (R ₄₁).Z is for forming the necessary atomic group of 5～6 member heterocyclic ring containing nitrogens that does not contain as the sulfydryl of substituent sulfydryl or protection.R ₄₁Be substituting group or the hydrogen atom beyond the sulfydryl of sulfydryl or protection.The situation of J, Q, n1, m1 and general formula [I] is identical.

In general formula [III], P, Q ', R, T are nitrogen-atoms or C (R ₄₁), R ₄₁R with general formula [II] ₄₁Implication is identical.The situation of J, Q, n1, m1 and general formula [I] is identical].

(4) silver halide colour photographic sensitive material of record in (1) is characterized in that: at least a kind of aforementioned inhibitor is the compound shown in the following general formula (1).

General formula (1)

[in the formula, X is N or CR ', and R ' is hydrogen atom, replacement or unsubstituted alkyl or replacement or unsubstituted aryl.R ₃And R ₄Be respectively hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl or heterocyclic radical.N2 is 0 or 1.R ₃And R ₄Be selected from-SO for directly or indirectly having at least 1 ₃H ,-COOH and-group of OH and salt thereof].

(5) silver halide colour photographic sensitive material of each record in (1)～(4) is characterized in that: in the aforementioned silver emulsion of per 1 moles of silver by 1.7 * 10 ^-4The above sensitizing coloring matter of mole carries out spectral sensitization.

(6) silver halide colour photographic sensitive material of each record in (1)～(5) is characterized in that: specific photograph sensitivity is more than 200.

Embodiment

Silver halide colour photographic sensitive material of the present invention has 1 layer of sense red beds, green layer, the blue layer of sense and non-photosensitive layer at least on support, it is characterized in that: it is 2.0～4.0mol%, average aspect ratio more than 8.0 and have the monodispersed silver emulsion of dislocation line that in these photosensitive layers at least 1 layer contains average silver iodide content, and at least 1 layer the photosensitive layer that comprises this silver emulsion contains 0.60mg/m ²Above inhibitor.

At first to the average silver iodide content among the present invention be 2.0～4.0mol%, average aspect ratio more than 8.0 and the monodispersed silver emulsion with dislocation line describe.

Silver emulsion among the present invention is an average aspect ratio at the tabular silver halide particle more than 8.0 (following abbreviate as sometimes dull and stereotyped particle), and this flat board particle classifies as twin crystal on crystallography.Twin crystal is meant, the crystallization that in a particle, has an above twin plane, about the form of twin crystal in the silver halide particle be sorted in Network ラ イ Application and モ イ ザ-57 pages of 99 pages of 99 volumes, 100 volumes of report " Photographishe Korrespondenz " in have a detailed description.Tabular silver halide particle among the present invention preferably has the twin plane more than 2 parallel to each other in particle.The face (being called principal plane) of wide area is almost parallel to these twin planes with respect to having in the plane that forms the tabular particle surface.Particularly preferred form is the situation with 2 twin planes that are parallel to principal plane among the present invention.In the present invention, the silver halide particle number with 2 twin planes that are parallel to principal plane is preferably more than 70%, more preferably more than 80%, particularly preferably in more than 90%.

Tabular silver halide particle among the present invention be the aspect ratio obtained by following method at the silver halide particle more than 8, the mean value of preferred aspect ratio is 8～500, more preferably 10～500.

The aspect ratio of silver halide particle is by following method each silver halide particle to be obtained its particle diameter and grain thickness, obtains by following formula.

Aspect ratio=particle diameter/grain thickness

Tabular silver halide particle among the present invention preferably has the tabular silver halide particle of (111) principal plane, should have 2 twin planes that are parallel to principal plane by (111) principal plane.

In tabular silver halide particle of the present invention, the mean grain size of tabular silver halide particle is preferably 0.1～50 μ m, and more preferably 0.1～20 μ m most preferably is 1.0～20 μ m.

In the present invention, with the arithmetic mean of particle diameter ri as mean grain size.Wherein significant figure are got 3, and the minimum bit numeral rounds up, and measure the particle number for indistinguishably choosing more than 1000.Here so-called particle diameter ri is meant, the diameter (projected area circle conversion particle diameter) when will the projected image when observing perpendicular to the direction of the principal plane of tabular silver halide particle being scaled the circular image of homalographic.In addition, particle diameter ri can make a video recording, print by with electron microscope silver halide particle being extended to 1～70,000 times, and the area during to particle diameter on the printout or projection is surveyed and obtained.

In silver emulsion of the present invention, preferably below 0.25 μ m, more preferably 0.005～0.20 μ m is preferably 0.005～0.10 μ m to the average thickness value of tabular silver halide particle especially.

Being used to of above-mentioned explanation calculates the projected area and the thickness of each particle of the particle diameter of silver halide particle and aspect ratio and can be obtained by following method.Coating is made sample as the latex balloon of the known particle diameter of interior target with make principal plane be parallel to the silver halide particle of substrate orientation on support, by the carbon granules projection particle is carried out projection from certain angle after, make reproduction copies by common replica method.Take the electron micrograph of this sample, obtain the projected area and the thickness of each particle with image processing apparatus etc.At this moment, calculate the projected area of particle, calculate the thickness of particle according to the projected length of interior target particle according to interior target projected area.

Tabular silver halide particle of the present invention is characterised in that monodispersity, during by following formula definition size distribution (coefficient of alteration of particle diameter), and the preferred less than 30% of size distribution, more preferably less than 15%.

Size distribution (%)=(standard deviation/mean grain size of particle diameter) * 100

Mean grain size and standard deviation are obtained by the particle diameter ri of above-mentioned definition.

In silver emulsion of the present invention, one of its feature is that the average silver iodide content of silver halide particle is 2.0～4.0 moles of %.

The agi content of above-mentioned silver halide particle can be obtained by EPMA (Electron ProbeMicro Analyzer method).Specifically, silver halide particle is fully disperseed mutually non-contiguously to make sample, arrive below-100 ℃ with cooled with liquid nitrogen, irradiating electron beam simultaneously, by obtaining the silver launched from each silver halide particle and the characteristic X ray strength of iodine, can determine the agi content of each silver halide particle.In addition, in the present invention, the silver halide particle more than 100 is calculated the agi content of obtaining these silver halide particles by said method, with its mean value as average silver iodide content.

One of feature of tabular silver halide particle among the present invention is to have dislocation line, and the form of dislocation line can suitably be selected.For example can select the dislocation line that linearly exists with respect to the specific direction of particle crystal orientation, or crooked dislocation line.Further also can select along the form of whole particle privileged site that exist or that exist only in particle, for example dislocation line exists only in the form of grain edges position (peripheral part), form or near the concentrated form in summit etc. that is present in of dislocation line that dislocation line exists only in principal plane.In tabular silver halide particle of the present invention, preferably there is dislocation line in the edge of particle at least, preferably have the dislocation line more than 10, more preferably more than 20 in the edge.

The dislocation line that silver halide particle has can pass through for example at J.F.Hamilton, Photo.Sci.Eng.11 (1967) 57 and T.Shiozawa, J.Soc.Phot.Sci, the low temperature of record uses the direct method of transmission electron microscope to observe down among the Japan35 (1972) 213.Promptly, from silver emulsion, take out silver halide particle, but notice that added pressure can not make particle misplace, the silver halide particle of this taking-up is placed on the screen cloth that electron microscope uses, under the state of cooling sample, observe, and note preventing because electron ray produces damage (printout etc.) with transmission beam method.At this moment, because particle is thick more, electron ray is difficult more to be seen through, and adopts the electron microscope of high accelerating potential type to observe more significantly.According to the photo of the particle that obtains by this method, can know the number and the position of dislocation line on each particle.

Tabular silver halide particle of the present invention preferably has the dislocation line that is positioned at edge part more than 10 with 50% of particle number proportional meter, more preferably more than 70%.In addition, the number ratio with tabular silver halide particle of edge dislocation line is preferably 50～100 number %, more preferably 60～100 number %, more preferably 70～100 number %.

So-called tabular silver halide particle has the dislocation line that is positioned at edge part and is meant among the present invention, and per 1 particle exists near the peripheral part that is positioned at dull and stereotyped particle more than 10, near the dislocation line near the crest line or the summit.Specifically, edge part is meant, when observe dull and stereotyped particle perpendicular to principal plane, with the length of line segment that links the center (center of gravity when principal plane is tieed up figures as 2) of dull and stereotyped particle principal plane and summit during as L, will distance be after the point of 0.50L couples together, be positioned at the zone in the figure outside of this formation from each summit to the center.

In the present invention, as method from dislocation line to silver halide particle that introduce, for example can use, by two spouts add contain just like the method for the aqueous solution of iodide ions such as potassium iodide and water-soluble silver salt solution or add the method for silver iodide particle, known method such as method that the method, the Ru Te that only add the solution that contains iodide ion opens the use iodide ion releasing agent of record in flat 6-11781 number, form dislocation as the dislocation line origin in the position of expectation.In these methods, preferably add the method that contains just like the aqueous solution of iodide ions such as potassium iodide and the method for water-soluble silver salt solution, the method for adding the silver iodide particle and use iodide ion releasing agent by two spouts.

So-called iodide ion releasing agent is meant among the present invention, by with the alkali shown in the following general formula (1) or the reaction of nucleopilic reagent, discharge the compound of iodide ion.

General formula (1)

R-I

In general formula (1), R represents the organic group of 1 valency.R preferably for example, alkyl, thiazolinyl, alkynyl, aryl, aralkyl, heterocyclic radical, acyl group, carbamyl, alkoxy carbonyl, aryloxycarbonyl, alkyl sulphonyl, aryl sulfonyl, sulfamoyl.The organic group of the preferred carbon number of R below 30, more preferably below 20, further preferred below 10.

In addition, R preferably has substituting group, and substituting group can further be replaced by other substituting group.As preferred this substituting group, can enumerate halogen, alkyl, thiazolinyl, alkynyl, aryl, aralkyl, heterocyclic radical, acyl group, acyloxy, carbamyl, alkoxy carbonyl, aryloxycarbonyl, alkyl sulphonyl, aryl sulfonyl, sulfamoyl, alkoxy, aryloxy group, amino, amide group, uride base, urethane groups, sulfoamido, sulfinyl, phosphoamide base, alkylthio group, arylthio, cyano group, sulfo group, carboxyl, hydroxyl, nitro etc.

As the iodide ion releasing agent shown in the general formula (1), preferred iodate paraffinic, iodate alcohol, iodate carboxylic acid, iodate acid amides and derivant thereof, more preferably iodate acid amides, iodate alcohol and derivant thereof, the iodate amide-type that further preferred heterocyclic radical replaces, most preferred example is (acetyl iodide amine) benzene sulfonate.

In the present invention, when iodide ion releasing agent and nucleopilic reagent reaction, when discharging iodide ion, as nucleopilic reagent, can use for example hydroxide ion, sulfurous acid ion, thiosulfuric acid ion, sulphite, carboxylate, ammonia, amine, alcohols, ureas, Thiourea, phenols, hydrazine class, thioether class, hydroxamic acid etc., preferred hydroxide ion, sulfurous acid ion, thiosulfuric acid ion, sulphite, carboxylate, ammonia, amine, more preferably hydroxide ion, sulfurous acid ion.

Introduce in silver emulsion of the present invention by the iodide ion releasing agent dislocation line preferred reaction conditions one for example down shown in.

Preferred 80～30 ℃ of temperature of reaction, more preferably 70～40 ℃.PAg before dislocation line is introduced is preferred more than 7.0 below 10.0, more preferably more than 7.5 below 9.5.With respect to the total silver halide amount after the particle growth end, the amount of the iodide ion releasing agent of interpolation is preferably 1～5mol%.In addition, the pH during the iodide ion release reaction is preferably the condition below 11.0 more than 7.0, more preferably more than 8.0 below 11.0.In addition, the material outside adopting hydroxide ion is during as the parentization agent, and the amount of nucleophilic reagent is more than 0.25 times below 2.0 times of amount of iodide ion releasing agent preferably, and is more preferably more than 0.5 times below 1.5 times, further preferred more than 0.8 times below 1.2 times.

Introduce in silver emulsion of the present invention by the fine grain emulsion that contains silver iodide dislocation line preferred reaction conditions one for example down shown in.

Temperature when adding the fine grain emulsion that contains silver iodide is preferably 80～30 ℃, more preferably 70～40 ℃.The amount of the fine grain emulsion that contains silver iodide that adds is in the silver iodide amount, and the total silver halide amount with respect to after the particle growth end is preferably 1～5mol%.

Silver emulsion among the present invention preferably contains at least a kind in polyvalent metal atom, polyvalent metal atom ion, polyvalent metal atom chelate or the polyvalent metal atom chelate ion on the inside of silver halide particle or surface.

As aforementioned polyvalent metal atom, the polyvalent metal atom ion, polyvalent metal atom chelate or polyvalent metal atom chelate ion, can use Fe, Co, Ni, Ru, Rh, Pd, Re, Os, Ir, Pt, Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Cu, Zn, Ga, Ge, As, Se, Sr, Y, Mo, Zr, Nb, Cd, In, Sn, Sb, Ba, La, W, Au, Hg, Tl, Pb, Bi, Ce and U etc. come from the metallic atom in the 3rd～7 cycle (prevailing was the 4th～6 cycle) of the periodic table of elements, ion, its chelate and the salt (comprising chelate salt) that contains them, other contains in their compound at least a kind, preferably selects single salt or metallo-chelate.

When selecting metallo-chelate, preferred 6 coordination chelates, 5 coordination chelates, 4 coordination chelates, 2 coordination chelates, more preferably octahedra 6 coordination chelates, plane 4 coordination chelates.

Part as constituting chelate can use CN ^-, CO, NO ₂ ^-, 1,10-phenanthroline, 2,2 '-bipyridine, SO ₃ ^-, ethylenediamine, NH ₃, pyridine, H ₂O, NCS ^-, O ₃, SO ₄ ^2-, OH ^-, N ^3-, S ^2-, F ^-, Cl ^-, Br ^-, I ^-Deng.

Make and contain polyvalent metal in the used silver emulsion of the present invention and can adopt following known technology.

For example can be applied in B.H.Carroll, " Iridium Sensitization, ALiterature Review ", Phptographic Science and Engineering, the 24th volume, No. 6,1980 11/12 month, the 265th～267 page; No. the 1951933rd, United States Patent (USP), No. 2628167, No. 3687676, No. 3761267, No. 3890154, No. 3901711, No. 3901713, No. 4173483, No. 4269927, No. 4413055, No. 4477561, No. 4581327, No. 4643965, No. 4806462, No. 4828962, No. 4835093, No. 4902611, No. 4981780, No. 4997751, No. 5057402, No. 5134060, No. 5153110, No. 5164292, No. 5166044, No. 5204234, No. 5166045, No. 5229263, No. 5252451, No. 5252530; EPO No. 0244184, No. 0488737, No. 0488601, No. 0368304, No. 0405938, No. 0509674, No. 0563946; Special hope flat 2-249588 number; The technology of putting down in writing in No. 93/02390 grade of WO.And then, can also use United States Patent (USP) No. 4847191, No. 4933272, No. 4981781, No. 5037732, No. 937180, No. 4945035, No. 5112732; EPO No. 0509674, No. 0513738; WO No. 91/10166, No. 92/16876; No. the 298320th, Deutsche Bundespatent; The technology of record in the United States Patent (USP) No. 5360712, No. 5024931 etc.

In addition, at Research Disclosure (hereinafter to be referred as RD) the 367th volume, in November, 1994, among the item 36736, the standard of selecting shallow electron trap adulterant carried out the explanation of explaining the profound in simple terms.In the present invention, preferably in being selected from polyvalent metal atom, its ion and chelate thereof, its chelate ion at least a kind, use as 6 coordination chelate ions shown in following.

[ML ₆] ⁿ

In the formula, M is the polyvalent metal ion that is full of frontal orbital, preferred Fe ²⁺, Ru ²⁺, Os ²⁺, Co ³⁺, Rh ³⁺, Ir ³⁺, Pd ⁴⁺Or Pt ⁴⁺L ₆The 6 coordination chelate parts that expression can independently be selected, wherein in the part at least 4 be anion ligand, at least 1 (preferably at least 3 and most preferably at least 4) in the part during than any halogenide part electronegativity raise; Therefore n represents 2-, 3-or 4-.

In the present invention, when using the Ir compound, K is arranged as preferred compound example ₂IrCl ₆, K ₃IrCl ₆, K ₃IrBr ₆Deng.

In the present invention, can enumerate InCl as the concrete example of other polyvalent metal compounds of preferred use ₃, K ₄Fe (CN) ₆, K ₃Fe (CN) ₆, K ₄Ru (CN) ₆, Pb (NO ₃) ₂And hydrate etc.

In the present invention, use at least a kind that is selected from polyvalent metal atom, its ion and the chelate thereof, especially preferably use each atom, its ion and chelates thereof such as Ir, Ru, Os, Fe, Rh, Co, In, Ga, Ge, Pd or Pt.

As at least a kind the concentration of using among the present invention of being selected from polyvalent metal atom, its ion and chelate thereof, its chelate ion, general suitable is with respect to per 1 mole of silver halide is 1 * 10 ^-7～1 * 10 ^-2The scope of mole, more preferably 1 * 10 ^-6～1 * 10 ^-3The scope of mole, preferred especially 2 * 10 ^-6～1 * 10 ^-4The scope of mole.

The preferred silver bromide of silver emulsion among the present invention, iodine silver bromide, iodine bromine silver chloride, preferred especially iodine silver bromide, iodine bromine silver chloride.Silver chloride content is preferably 0～50 mole of %, more preferably 0～30 mole of %, further preferred 0～10 mole of %.

As the preferred dispersion medium that can be used for silver emulsion of the present invention, can enumerate gelatin and hydrophilic colloid.As gelatin, preferably can use the alkali treated gelatin of common molecular weight about 100,000 or the gelatin of acid treatment gelatin or oxidation processes and the enzyme of the middle record of Bull.Soc.Sci.Photo.Japan.No.16.P30 (1966) to handle gelatin.As hydrophilic colloid, for example can use the protein of gelatine derivative, gelatin and other high molecular graft polymer, albumin, casein and so on; As the cellulose derivative of hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfuric acid ester class, as the derivant of mosanom, starch derivative; Multiple synthetic hydrophilic polymer material as the single or multipolymer of polyvinyl alcohol (PVA), polyvinyl alcohol (PVA) part acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethylacrylic acid, polyacrylamide, polyvinyl imidazol, polyvinyl pyrazoles.

When making silver emulsion of the present invention, the desalination operation more than 1 time is set in granuloplastic way preferably.Here so-called desalination operation is meant that the washing silver emulsion is removed the solubility salt.About this desalination operation, can preferably use inorganic salts, anionic surfactant or anionic property polymkeric substance (for example polystyrolsulfon acid) to implement with reference to No. 17643 II items of Research Disclosure (hereinafter to be referred as RD) by flocculoreaction.The desalination operation is preferably carried out with respect to the volume less than 10 volume % after the silver halide particle growth time, more preferably carries out when less than 5 volume %.

Silver emulsion among the present invention can be reduced sensitizing.Reduction sensitization can add reductive agent in the protecting colloid aqueous solution that silver halide particle is grown up; perhaps make protecting colloid aqueous solution that silver halide particle grows up under the low pAg condition below the pAg7.0; perhaps under the high pH condition more than the pH7.0, carry out the growth of the slaking of silver halide particle or particle and implement.These methods also can suitably make up.

In the manufacturing of silver emulsion of the present invention, the formation of silver halide particle can be adopted the whole bag of tricks of knowing in this area.Promptly can use single jet method, two spout method, three spout methods or silver halide particle supply method etc. in combination in any ground.In addition, also can be used in combination the control method that the pH, the pAg that make in the liquid phase that generates silver halide cooperate the growth rate of silver halide.The formation of silver halide particle can carried out near under the condition of critical growth rate.

In the manufacturing of silver emulsion of the present invention, can use kind of an emulsion.When emulsion was planted in use, the silver halide particle in this kind emulsion can have the crystalline texture as the rule of cube, octahedron, the tetrakaidecahedron, also can have as spherical and tabular irregular crystal habit.Can use that the ratio of (100) face and (111) face is the particle of any ratio in the particle here.

In addition, though can be the compound of these crystal habits, also can be the mixing of the particle of various crystal habits, the silver halide particle in the preferred kind emulsion that uses be the twin crystal silver halide particle with twin plane, especially preferably has the twin crystal silver halide particle of the parallel twin plane of two subtends.

In the manufacturing of silver emulsion of the present invention, can use ag halide solvent as known in the art, if possible, when the dull and stereotyped particle of substrate forms, be preferably in the operation the slaking after karyomorphism becomes and avoid using ag halide solvent.

In the manufacturing of silver emulsion of the present invention, can use any one method in acid process, neutral method, the ammonia process, preferred acidic method or neutral method.

In the manufacturing of silver emulsion of the present invention, can mix halide ion and silver ion simultaneously, also can under the situation that either party exists, mix the opposing party.In addition, consider the critical growth rate of silver halide crystal, can pAg, the pH that mix in the mixing kettle in halide ion and the silver be controlled, add one by one or side by side.Also can adopt conversion method in any operation that silver halide forms, the halogen that changes silver halide particle is formed.

In the present invention, when using silver halide grains, this silver halide grains can be prepared before preparation silver halide particle of the present invention in advance, also can prepare simultaneously with the preparation of this silver halide particle.Under the situation about in the latter, preparing, can open as shown in flat 1-183417 number, 2-44335 number etc. as the spy, adopt the mixer of establishing in addition outside the reaction vessel that carries out silver halide particle formation in the present invention to make, this mixer preferably is provided with other preparation container, at random the silver halide grains of once preparing by mixer is prepared therein, so that the interior growth environment of reaction vessel of silver halide particle preparation is carried out in its adaptation, be fed to again in this reactor.

In the manufacturing of silver emulsion of the present invention, preferably at least a portion of growth operation, carry out the concentration operation of silver emulsion by ultrafiltration.Owing to making as during dull and stereotyped emulsion that this aspect ratio of silver emulsion of the present invention is higher, preferred diluted ambient in order to improve productivity, preferably adopts ultrafiltration.When adopting ultrafiltration to carry out the concentration operation of silver emulsion, preferably can adopt the spy to drive the manufacturing equipment of disclosed silver emulsion in the flat 10-339923 communique.

In the manufacturing of silver emulsion of the present invention, about the condition beyond above-mentioned, can open XV item of the I item of clear 61-6643 number, 61-14630 number, 61-112142 number, 62-157024 number, 62-18556 number, 63-92942 number, 63-151618 number, 63-163451 number, 63-220238 number, 63-311244 number, RD38957 and III item, RD40145 etc. with reference to the spy, select suitable condition.

The silver emulsion that is made of above-mentioned specific factor of the present invention can carry out chemical sensitization by known method.

Chemical sensitizer as being used for the present invention has no particular limits, and can use known chalcogen sensitizer, golden sensitizer.

As the selenium sensitizer that uses among the present invention, preferred especially use can generate the unstable selenide of silver selenide precipitation with the silver nitrate reaction in aqueous solution.It for example is documented in United States Patent (USP) No. 1574944, No. 1602592, No. 1623499; The spy opens clear 60-150046 number; In Te Kaiping 4-25832 number, 4-109240 number, 4-147250 number etc.

As useful selenium sensitizer, can enumerate the electroselenium metal, different selenium cyanate (for example different selenium cyanic acid allyl ester), selenourea class (N for example, N-dimethyl selenourea, N, N, N '-triethyl selenourea, N, N, N '-trimethyl-N '-seven fluorine selenourea, N, N, N '-trimethyl-N '-seven fluoropropyl carbonyl selenourea, N, N, N '-trimethyl-N '-4-nitrobenzophenone carbonyl selenourea etc.), selenium ketone (the third selenium ketone, benzene second selenium ketone etc.), selenium acid amides (selenium acetamide for example, N, N-dimethyl-selenide benzamide etc.), selenium carboxylic acids and selenium ester class (2-selenium propionic acid for example, 3-selenium methyl butyrate etc.), selenium phosphoric acid ester (for example seleno tri-p-cresyl phosphate etc.), selenide class (selenium dimethyl for example, the selenizing triphenyl phasphine, selenizing pentafluorophenyl group-diphenylphosphine, selenizing three furyl phosphines, selenizing three pyridine radicals phosphines etc.).Particularly preferred selenium sensitizer is selenourea, selenium acid amides, selenide class.

Preferably use the sulphur sensitizer in the present invention.Preferred concrete example has, and 1, thiourea derivative, Rhodanine derivant, aminodithioformic acid class, polysulfide organic compound, thiosulfate, sulphur monomers etc. such as 3-rhenocure CA, triethyl thiocarbamide, 1-ethyl-3-(2-thiazolyl) thiocarbamide.In addition, as the sulphur monomer, preferably belong to rhombic α-sulphur.In addition, each instructions that also can use United States Patent (USP) No. 1574944, No. 2410689, No. 2278947, No. 2728668, No. 3501313, No. 3656955 etc.; No. the 1422869th, West Germany application open (OLS), spy open the sulphur sensitizer of record in clear 56-24937 number, 55-45016 number etc.

In the present invention, preferably use precious metal salts such as the gold put down in writing in No. 307105 grades of RD the 307th volume, platinum, palladium, indium, wherein especially preferably use golden sensitizer together with above-mentioned each sensitizer.As useful golden sensitizer, except that chlorination auric acid, gold aurothiosulfate, thiocyanic acid gold etc., for example can enumerate, open disclosed organic gold compound in flat 1-147537 number, 4-70650 number etc. at United States Patent (USP) No. 2597856, No. 5049485, special public clear 44-15748 number, spy.In addition, when using the sensitizing method of golden chelate, as assistant, the golden part that preferred combination is used thiosulfate, thiocyanate, thioether etc. especially preferably uses thiocyanate.

Of the present inventionly can carry out spectral sensitization by known method by the above-mentioned specific silver emulsion that constitutes.

As the spectral sensitization pigment that can be used for the present invention, known compound be can use, anthocyanidin, part cyanines pigment, compound flower cyanine, compound part of cyanines pigment, ホ ロ ボ-ラ-anthocyanidin, half cyanines pigment, styrene pigment and half oxonols (hemi oxonol) pigment comprised.Useful especially pigment is the pigment that belongs to anthocyanidin, part cyanines pigment and compound part of cyanines pigment.These pigments go for normally used any nuclear.Promptly can examine with pyrrolin, oxazoline nuclear, thiazoline nuclear, pyrrole nucleus, oxazole nuclear, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazolium nuclear, pyridine nucleus, the nuclear that these nuclears and aliphatic hydrocarbon ring merge, i.e. indolenine nuclear, benzo indolenine nuclear, indole nucleus, benzoxazole nuclear, Nai Bing oxazole nuclear, benzothiazole nucleus, aphthothiazoles nuclear, benzo selenazole nucleus, benzimidazole nucleus, quinoline nuclei etc.The carbon atom of these nuclears can be substituted.

As the nuclear that has ketone methine structure in part cyanines pigment and the compound part cyanines pigment, can examine with pyrazolin-5-one, thio-hydantoin nuclear, 2-Liu Dai oxazolidine-2,4-diketone nuclear, thiazoline-2,5～6 yuan of heteronucleus such as 4-diketone nuclear, rhodanine nuclear, thiobarbituric acid.

The patent of putting down in writing these contents has, for example No. the 929080th, Deutsche Bundespatent, United States Patent (USP) No. 2231658, No. 2493748, No. 2503776, No. 2519001, No. 2912329, No. 3655394, No. 3656959, No. 3672897, No. 3649217, No. the 1242558th, BrP, spy public clear 44-14030 number.

In the present invention, with per 1 moles of silver calculate by the specific silver emulsion that constitutes of the present invention by 1.7 * 10 ^-4The above sensitizing coloring matter of mole carries out spectral sensitization, and more preferably 1.7 * 10 ^-4～1.0 * 10 ^-3Mole, further preferred 1.7 * 10 ^-4～5.0 * 10 ^-4Mole.

Below inhibitor of the present invention is described.

One of feature of silver halide colour photographic sensitive material of the present invention is, at least 1 layer the photosensitive layer that contains by the specific tabular silver emulsion of the present invention that constitutes of above-mentioned explanation contains 0.60mg/m ²Above inhibitor, preferred 0.60～3.00mg/m ², more preferably 0.60～2.00mg/m ²

So-called inhibitor is meant antifoggant among the present invention, photographic fog prevents agent or stabilizing agent etc., as operable inhibitor, have no particular limits, can enumerate for example purine class, azole, benzothiazolium salt for example, the nitro indazole class, the nitrobenzimidazole class, the chloro-benzimidazole class, the bromo benzimidazole, the thyroidan class, the mercaptobenzimidazole class, the aminotriazole(ATA) class, benzotriazole, the nitrobenzene and triazolam class, mercapto-tetrazole class (particularly 1-phenyl-5-mercapto-tetrazole) etc., also has sulfhydryl miazines, the thione compounds of mercapto-triazine class Li such as oxazolidone and so on also has benzene sulfo-sulfinic acid, benzene sulfo-sulfonamide, hydroquinone derivatives, p-aminophenol derivative, gallic acid-derivate, ascorbic acid derivates.

Silver halide colour photographic sensitive material of the present invention is in above-mentioned inhibitor, and preferably at least a kind of inhibitor is the compound shown in the aforementioned formula [I], more preferably the compound shown in aforementioned formula [I] or the general formula [III].

In the compound shown in aforementioned formula [I], [II] or [III], the sulfydryl of described protection is meant, can be when development treatment the protecting group cracking and become sulfydryl base, as the concrete example of this protecting group, can enumerate acyl group, sulfonyl, cyanoethyl etc.As the nitrogenous heterocyclic concrete example that Het in the general formula [I] represents, can enumerate heterocycle such as pyrrolidine, piperidines, morpholine, thiomorpholine, pyrroles, pyridine, pyrimidine, pyrazine, triazine, imidazoles, pyrazoles, oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazolium, thiadiazoles, oxadiazole and with the condensation lopps of phenyl ring.

What the connection base that the J among general formula [I], [II] or [III] represents specifically can be enumerated has, by alkylidene, arlydene, heteroarylidene ,-SO ₂-,-SO-,-O-,-S-,-N (R ₂₃The base of 1 valency that)-alone or in combination constitutes.R wherein ₂₃Expression alkyl, aryl, hydrogen atom.J is preferably arlydene, most preferably phenylene.N1 is preferably 0 or 1.

The water-soluble base that Q among general formula [I], [II] or [III] represents is meant, can be in developer solution anionization base, specifically can enumerate sulfoamido, sulfamoyl, phenol hydroxyl, carboxyl, sulfo group and salt thereof.Preferred carboxyl, sulfo group.M1 is preferably 1 or 2.

In general formula [II], as 5～6 yuan of nitrogenous heteroaromatics that constitute by Z, can enumerate pyridine, pyrimidine, pyrazine, triazine, imidazoles, pyrazoles, oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazolium, thiadiazoles, oxadiazole each ring and with the condensation lopps of phenyl ring.Preferred triazole, tetrazolium.

As the R in the general formula [II] ₄₁The substituting group of expression; specifically can enumerate halogen atom (chlorine atom for example; bromine atoms etc.); alkyl (methyl for example; ethyl; isopropyl; hydroxyethyl; methoxy; trifluoromethyl; the tert-butyl group etc.); naphthenic base (cyclopentyl for example; cyclohexyl etc.); aralkyl (benzyl for example; 2-phenethyl etc.); aryl (phenyl for example; naphthyl; p-methylphenyl; rubigan etc.); aryloxy group (phenoxy group for example; naphthoxy etc.); alkoxy (methoxyl for example; ethoxy; isopropoxy; n-butoxy etc.); aryloxy group (for example phenoxy group etc.); cyano group; acyl amino (acetyl-amino for example; propiono amino etc.); alkylthio group (methyl mercapto for example; ethylmercapto group; positive butylthio etc.); arylthio (for example thiophenyl etc.); sulfuryl amino (mesyl amino for example; benzenesulfonyl amino etc.); uride base (3-methyl uride for example; 3; 3-dimethyl uride; 1,3-dimethyl uride etc.); sulfonamide amido (for example dimethylamino sulfoamido etc.); carbamyl (methyl sulfonamide for example; the ethyl sulfonamide; dimethylamino sulphonyl etc.); sulfamoyl (ethyl sulfamoyl for example; dimethylamino sulfonyl etc.); alkoxy carbonyl (methoxycarbonyl for example; ethoxy carbonyl etc.); aryloxycarbonyl (for example phenyloxycarbonyl etc.); sulfonyl (mesyl for example; the fourth sulfonyl; benzenesulfonyl etc.); acyl group (acetyl group for example; propiono; bytyry etc.); hydroxyl; nitro; nitroso-; oxidation amido (for example oxy picolinate base); imino group (for example phthalimide-based etc.); disulfide group (curing phenyl for example; curing-2-[4-morpholinodithio base etc.); carboxyl; sulfo group; heterocyclic radical (pyridine radicals for example; benzimidazolyl; benzothiazolyl benzoxazolyl etc.).

3 in general formula [III] among preferred P, Q ', R, the T is nitrogen-atoms, and preferred especially P, Q ', R are the situation of nitrogen-atoms.

The compound shown in general formula [I], [II] or [III]-(J) _N1-(Q) _M1Also can have substituting group on the position of substitution of heterocycle in addition,, can enumerate above-mentioned substituting group as its concrete example.

Below enumerate the object lesson of the compound shown in formula of of the present invention [I], [II] or [III], but it not a limitation of the present invention.

I-1????????????????I-2????????????I-3

I-4??????????????????I-5

I-7????????????????????????I-8????????????????I-9

I-10?????????????????????????????????????I-12

I-13???????????????????????????I-14???????????????I-15

I-16?????????????????????I-17??????????????I-18

I-19?????????I-20????????I-21

I-22????????????????????????????????????????I-23

I-25

I-26???????????????????????I-27

Compound shown in general formula of the present invention [I], [II] or [III] can be by for example, and at ジ ヤ Na Le Off ア プ ラ ス テ イ ッ シ エ ケ ミ [2], the method for putting down in writing in the known documents such as 124,286 is easily synthetic.

Below be the synthetic of example compound I-1.

＜synthesis example 〉

The synthetic method of example compound I-1

1-(4-the carboxyl phenyl)-tetrazolium that adds 4.5g in 20ml methyl alcohol adds the 5ml strong aqua it is dissolved fully.Add the 2ml35% hydrogen peroxide then, at room temperature stirred 12 hours.The hydrochloric acid that adds 1 mole/L becomes acid back and filters the crystallization of separating out, and by recrystallizing methanol, obtains 3.7g example compound I-1 (yield 96%).

In addition, in silver halide colour photographic sensitive material of the present invention, at least a kind inhibitor is the compound shown in the aforementioned formula (1) in the preferred above-mentioned inhibitor.

In aforementioned formula (1), X is N or CR ', and R ' is hydrogen atom, replacement or unsubstituted alkyl or replacement or unsubstituted aryl.R ₃And R ₄Be respectively hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl or heterocyclic radical.N2 is 0 or 1.R ₃And R ₄Be selected from-SO for directly or indirectly having at least 1 ₃H ,-COOH and-group of OH and salt thereof.

In general formula (1), as R ₃And R ₄The alkyl of expression for example can be enumerated methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group, amyl group, cyclopentyl, hexyl, cyclohexyl, octyl group, each base of dodecyl.These alkyl can be further by halogen atom (chlorine for example, bromine, fluorine etc.), alkoxy (methoxyl for example, ethoxy, 1,1-dimethyl ethoxy, own oxygen base, cyclohexyl oxygen base, octyloxy, each base such as dodecyloxy), aryloxy group (phenoxy group for example, each base such as naphthoxy), alkoxy carbonyl (methoxycarbonyl for example, ethoxy carbonyl, butoxy carbonyl, each base such as 2-ethylhexyl carbonyl), aryloxycarbonyl (phenyloxycarbonyl for example, each base such as naphthoxy carbonyl), thiazolinyl (vinyl for example, each base such as allyl), heterocyclic radical (2-pyridine radicals for example, the 3-pyridine radicals, the 4-pyridine radicals, morpholinyl, piperidyl, piperazinyl, the selenazoles base, the sulfolane base, ピ ペ リ ジ ニ Le, tetrazole radical, thiazolyl oxazolyl, imidazole radicals, thienyl, pyrrole radicals, pyrazinyl, pyrimidine radicals, pyridazinyl, pyrimidine radicals, pyrazolyl, furyl etc.), alkynyl (for example propinyl etc.), amino (for example amino, N, the N-dimethylamino, anilino-etc.), hydroxyl, cyano group, sulfo group, carboxyl, sulfoamido (sulfonyloxy methyl amino for example, the ethyl sulfonamido, the butyl sulfonamido, the octyl group sulfonamido, phenyl sulfonamido etc.) replacement such as.

As R ₃And R ₄The thiazolinyl of the expression of expression, can enumerate for example vinyl, allyl etc., as alkynyl, can enumerate for example propinyl, in addition, as aryl, can enumerate for example phenyl, naphthyl etc., and then, can enumerate for example pyridine radicals (for example each base such as 2-pyridine radicals, 3-pyridine radicals, 4-pyridine radicals), thiazolyl, oxazolyl, imidazole radicals, furyl, thienyl, pyrrole radicals, pyrazinyl, pyrimidine radicals, pyridazinyl, selenazoles base, sulfolane base, piperidyl, pyrazolyl, tetrazole radical etc. as heterocyclic radical.

Any one of above-mentioned thiazolinyl, alkynyl, aryl and heterocyclic radical can by with R ₃And R ₄Shown alkyl and replace as the basic identical group shown in the substituting group of alkyl.

Below show the instantiation of compound shown in the general formula (1), but the invention is not restricted to these examples.

1-1

1-2

1-3

1-4

1-5

1-6

1-7

1-8

1-9

1-10

1-11

1-12

1-13

1-14

1-15

1-16

1-17

1-18

1-19

1-20

1-21

1-22

1-23

The preferred specific photograph sensitivity of silver halide colour photographic sensitive material of the present invention is more than 200, and more preferably 200～3200, more preferably 200～1600, be preferably 200～800 especially.

The specific photograph sensitivity of so-called silver halide colour photographic sensitive material is meant among the present invention, the test method of being formulated according to ISO sensitometry method of stipulating in JIS K 7614-1981 and definite photograph sensitivity.

(1) test condition: test is to carry out in the indoor of 20 ± 5 ℃ of temperature, relative humidity 60 ± 10%, and the photosensitive material of test is being placed back use more than 1 hour under this state.

(2) exposure: on the plane of exposure shown in relative minute following the stating of light energy distribution of reference light.

Wavelength nm branch luminous energy (1*) wavelength nm relatively divides luminous energy relatively

360????????????2???????????????370???????????8

380????????????14??????????????390???????????23

400????????????45??????????????410???????????57

420????????????63??????????????430???????????62

440????????????81??????????????450???????????93

460????????????97??????????????470???????????98

480????????????101?????????????490???????????97

500????????????100?????????????540???????????102

550????????????103?????????????560???????????100

570????????????97??????????????580???????????98

590????????????90??????????????600???????????93

610????????????94??????????????620???????????92

630????????????88??????????????640???????????89

650????????????86??????????????660???????????86

670????????????89??????????????680???????????85

690????????????75??????????????700???????????77

Annotate (1*): with the value of 560nm as 100 benchmarks and definite value.

Illumination change on the plane of exposure adopts wedge to carry out, and used wedge adopts in the wavelength coverage of 360～700nm, is in 10% in the variation of beam split penetrating concentration on any part in the zone of not enough 400nm, is in 5% in the zone more than the 400nm.Time shutter is 1/100 second.

(3) development treatment

Begin to the development treatment from exposure, the photosensitive material of test remain on 20 ± 5 ℃ of temperature, relative humidity 60 ± 10% state under.

Development treatment exposure back more than 30 minutes 6 hours with interior end.

Development treatment is carried out British Journal of PhotographyAnnual 1988, and P.196-198 the C-41 of Ji Zai イ-ス ト マ Application コ ダ Star Network corporate system handles.

(4) concentration determination

Concentration is with log ₁₀(φ 0/ φ) expression.φ 0 is for being used for the illuminating bundle of concentration determination, and φ is the transmitted beam of determined part.The geometric condition of concentration determination is, illuminating bundle is the parallel beam of normal direction, uses as transmitted beam transmission and the full light beam that spreads in semispace to be benchmark, during assay method beyond adopting it, carries out revisal according to the normal concentration sheet.In addition, during mensuration, make emulsion face and infrared rays receiver side opposite.Indigo plant, green, red Status M concentration are got in concentration determination, and dichroism forms value that the spy opens record in the flat 6-67350 communique paragraph numbering [0036] as the overall characteristic of the light source that uses in the thermometer, optical system, optical filter, infrared rays receiver.

(5) specific photograph sensitivity determines

The result with concentration determination is handled in employing under the condition shown in (1)～(4), determine specific photograph sensitivity according to following step.With respect to each blue, green, red Cmin, the exposure of corresponding 0.15 high concentration shows that with the lux stopwatch note is made HB, HO, HR respectively.HB, a side (side that sensitivity is low) that the HR intermediate value is bigger are as HS.

Specific photograph sensitivity S is according to following calculating.

S＝(2/HG×HS) ^1/2

Then, about other formation of the photosensitive layer of silver halide colour photographic sensitive material of the present invention, see the following description.

About the preparation of the silver emulsion among the present invention, can adopt the method for putting down in writing in projects of in ResearchDisclosure (hereinafter to be referred as RD) No.308119, putting down in writing.Below show the record position.

The page number of project RD308119

The iodine degree is formed 993 I-A items

Manufacture method 993 I-A items and 994 E items

The normal crystal 993 I-A items of crystal flaw

Crystal flaw twin crystal 993 I-A items

Extension 993 I-A items

Halogen is formed identical 993 I-B items

Halogen is formed different 993 I-B items

The halogen 994 I-C items that reverse

Halogen replaces 994 I-C items

Containing metal 994 I-D items

Single 995 I-F items that disperse

Add solvent 995 I-F items

Sub-image forms surface of position 995 I-G items

Sub-image forms the inner 995 I-G items in position

Be suitable for silver halide photographic sensitive material egative film 995 I-H items

Positivity (containing inner photographic fog particle) 995 I-H items

Be mixed with emulsion 995 I-J items

Desalination 995 II-A items

In the present invention, use the physics slaking relevant, chemical slaking and beam split sensitizing to handle with silver emulsion.The adjuvant that uses in these operations is documented among RD No.17643, No.18716 and the No.308119.

Below show the record position.

The page number RD17643 RD18716 of project RD308119

Chemical sensitizer 996 III-A items 23 648

Branch light sensitizer 996 IV-A-A,

B、C、D?????????????23-24????????648-649

H, I, J item

Rich shade sensitizer 996 IV-A-E, J item 23-24 648-649

Antifoggant 998 VI 24-25 649

Stabilizing agent 998 VI 24-25 649

Spendable known photograph also is documented among the above-mentioned RD with adjuvant in silver halide colour photographic sensitive material of the present invention.Below show related record position.

The page number RD17643 RD18716 of project RD308119

Look muddy inhibitor 1002VII-I item 25 650

Pigment image stabilizing agent 1001VII-I item 25

Whitening agent 998V 24

Ultraviolet light absorber 1003VIII-I item,

XIII-C item 25-26

Light absorber 1003VIII 25-26

Light scattering agent 1003VIII

Colour filter dyestuff 1003VIII 25-26

Cementing agent 1003IX 26 651

Antistatic agent 1006XIII 27 650

Hardener 1004X 26 651

Plasticiser 1006XII 27 650

Lubricant 1006XII 27 650

Activating agent, coating additive 1005XI 26-27 650

Matting agent 1007XVI

Developer is (at silver-halide color 1001XXB item

Contain in the sensitive photographic material)

Can use various coupling agents in photosensitive layer of the present invention, its instantiation is documented among the above-mentioned RD.Below show related record position.

The page number RD17643 of project RD308119

Yellow colour former 1001VII-D item VIIC-G item

Magenta colour coupler 1001VII-D item VIIC-G item

Cyan coupler 1001VII-D item VIIC-G item

Colour former agent 1002VII-G item VIIG item

DIR colour coupler 1001VII-F item VIIF item

BAR colour coupler 1002VII-F item

The release 1001VII-F item of other useful residues

Coupling agent

The solvable coupling agent 1001VII-E of alkali item

Above-mentioned various adjuvant can add by process for dispersing of putting down in writing among the RD308119XIV etc.

In silver halide colour photographic sensitive material of the present invention, also can be arranged on the auxiliary layer in the colour filter put down in writing in the above-mentioned RD308119VII-K item or middle layer etc.

Silver halide colour photographic sensitive material of the present invention can have various layer structure such as the suitable layer of above-mentioned RD308119VII-K item record, contrary layer, cellular construction.

When silver halide colour photographic sensitive material of the present invention is carried out development treatment, can use known developer of record in the 4th edition 291-334 page or leaf of The Theory of The Photographyic Process of the work of T.H. ジ エ system ズ for example and Journal of the American Chemical Society the 73rd volume, No.3, the 100th page (1951).In addition, also can carry out development treatment according to the usual method of putting down in writing among the 28-29 page or leaf of above-mentioned RD17643, RD18716 615 pages and the RD308119XIX.

By the following examples the present invention is carried out more specific description, but the invention is not restricted to these embodiments.

Embodiment 1

The preparation of＜silver emulsion 〉

[preparation of tabular silver emulsion Em-1]

(preparation of tabular kind emulsion 1)

By following step, prepare flat kind of emulsion 1.

[karyogenesis operation]

In reaction vessel, remain on 15 ℃ 28.3L contain the aqueous solution of 162.8g low molecular weight gelatine (mean molecular weight 1.5 ten thousand) and 23.6g potassium bromide, adopt the special mixed stirring device high-speed stirred of putting down in writing in the clear 62-160128 communique of opening on one side, with the sulfuric acid of 0.5 mole/L, adjust pH to 1.90 on one side.Then, in 1 minute, add following S-01 liquid and following X-01 liquid with certain flow, carry out adding following G-01 liquid in the karyomorphism one-tenth with two spout methods.

The silver nitrate aqueous solution of the 1.25 moles/L of S-01 liquid: 205.7ml

The kbr aqueous solution of the 1.25 moles/L of X-01 liquid: 205.7ml

G-01 liquid: 2921ml contains the aqueous solution of methanol solution of 10 quality % of 120.5g alkali treatment inertia gelatin (mean molecular weight 100,000) and the following surfactant A of 8.8ml

Surfactant A: HO (CH ₂CH ₂O) _m[CH (CH ₃) CH ₂O] ₂₀(CH ₂CH ₂O) _nH (m+n=10)

[curing step]

After the karyogenesis operation finishes, be warmed up to 60 ℃, adjustment pAg to 9.2 with 45 minutes.Then add the aqueous solution and the potassium hydroxide aqueous solution of the ammonia that contains 0.136 mole, adjust pH to 9.3, keep after 6 minutes, adjust pH to 6.1 with the nitric acid of 1 mole/L.

[growth operation]

After curing step finished, pAg remained on 9.2, with two spout methods, when quickening flow (during beginning and the interpolation throughput ratio when finishing be about 5 times) on one side, Yi Bian in 20 minutes following S-02 liquid of interpolation and following X-02 liquid.

The silver nitrate aqueous solution of the 1.25 moles/L of S-02 liquid: 2620ml

The kbr aqueous solution of the 1.25 moles/L of X-02 liquid: 2620ml

After having added above-mentioned each solution, carry out desalination, washing processing, add the gelatin that appends and fully disperse according to usual method.The emulsion that as above obtains is the tabular emulsion of the coefficient of alteration 14.2% of cube conversion mean grain size 0.27 μ m, average aspect ratio 12.0, particle diameter.With it as tabular kind emulsion 1.

(preparation of Em-1)

Carry out the follow-up growth of tabular kind emulsion 1 by following step, make Em-1 as the tabular silver emulsion.

[formation of A phase]

1% aqueous gelatin solution that 15L contains the 10 quality % methanol solutions of the tabular kind emulsion 1 that is equivalent to 0.21 mole and 1.0ml aforementioned surfactants A maintains the temperature at 60 ℃, pAg is 8.9, with two spout methods, when on one side quickening flow (during beginning and the interpolation throughput ratio when finishing be about 10 times), add following S-11 liquid and following X-11 liquid formation A on one side mutually.Average aspect ratio after A forms mutually is 18.4.

The silver nitrate aqueous solution of the 3.5 moles/L of S-11 liquid: 2059ml

The aqueous solution of the potassium bromide that contains 3.45 moles/L of X-11 liquid: 2059ml and the potassium iodide of 0.05 mole/L

[formation of B phase]

After A forms mutually, add following I-11 liquid and following Z-11 liquid, after adjusting pH to 9.7 and keep 6 minutes with potassium hydroxide aqueous solution, adjust pH to 5.0, adjust pAg to 9.8 with kbr aqueous solution with acetic acid aqueous solution.Then, when quickening on one side to add flow (during beginning and the interpolation throughput ratio when finishing be about 2.2 times), add following S-12 liquid and following X-12 liquid formation B on one side mutually.

I-11 liquid: contain the aqueous solution of 57.7g to acetyl iodide amine benzene sulfonic acid sodium salt

Z-11 liquid: the aqueous solution that contains the 20.0g sodium sulphite

The silver nitrate aqueous solution of the 3.5 moles/L of S-12 liquid: 726ml

The aqueous solution of the potassium bromide that contains 3.36 moles/L of X-12 liquid: 726ml and the potassium iodide of 0.14 mole/L

[foreign minister's formation]

After B forms mutually, Yi Bian when quickening flow (during beginning and the interpolation throughput ratio when finishing be about 1.4 times), form foreign minister Yi Bian add following S-13 liquid and following X-13 liquid.

The silver nitrate aqueous solution of the 1.25 moles/L of S-13 liquid: 509ml

The kbr aqueous solution of the 1.25 moles/L of X-13 liquid: 509ml

After foreign minister forms end,, carry out desalination and washing is handled, add gelatin and fully disperse according to the method for record in Tong Tekaiping 5-72658 number.Adjust pH to 5.8 at 40 ℃, adjust pAg to 8.1, obtain tabular silver emulsion Em-1.

Em-1 as the tabular silver emulsion is analyzed, and the result shows that it is: mean grain size 1.0 μ m, the average aspect ratio that cube converts is 13.3, the coefficient of alteration 14% of particle diameter, the average silver iodide content of particle are the tabular particle of 3.4 moles of %.In addition, in Em-1 as the tabular silver emulsion, confirm on each limit, to exist respectively the tabular particle of 5 above dislocation lines be present in whole projected area 82% in.

[preparation of tabular silver emulsion Em-2]

In the preparation of above-mentioned tabular silver emulsion Em-1, except the X-12 liquid of using following X-12 ' liquid replacement use in B forms mutually, all the other prepare tabular silver emulsion Em-2 after the same method.

The aqueous solution of the potassium bromide that contains 3.25 moles/L of X-12 ' liquid: 726ml and the potassium iodide of 0.25 mole/L

Em-2 as the tabular silver emulsion is analyzed, and the result shows that it is: mean grain size 1.0 μ m, the average aspect ratio that cube converts is 12.9, the coefficient of alteration 15% of particle diameter, the average silver iodide content of particle are the tabular particle of 4.2 moles of %.In addition, in Em-2 as the tabular silver emulsion, confirm on each limit, to exist respectively the tabular particle of 5 above dislocation lines be present in whole projected area 77% in.

[preparation of tabular silver emulsion Em-3]

In the preparation of above-mentioned tabular silver emulsion Em-1, to remove and be used for I-11 liquid and the Z-11 liquid that B forms mutually, all the other prepare tabular silver emulsion Em-3 after the same method.

Em-3 as the tabular silver emulsion is analyzed, and the result shows that it is: mean grain size 1.0 μ m, the average aspect ratio that cube converts is 12.3, the coefficient of alteration 15% of particle diameter, the average silver iodide content of particle are the tabular particle of 3.4 moles of %.In addition, in Em-3, there is not tabular particle with dislocation line as the tabular silver emulsion.

[preparation of tabular silver emulsion Em-4]

In the preparation of above-mentioned tabular silver emulsion Em-1, except suitably being adjusted at A phase, B mutually and the pAg of top layer when forming, so that average aspect ratio reaches beyond 6.8, all the other prepare tabular silver emulsion Em-4 after the same method.

Em-4 as the tabular silver emulsion is analyzed, and the result shows that it is: mean grain size 1.0 μ m, the average aspect ratio that cube converts is 6.8, the coefficient of alteration 18% of particle diameter, the average silver iodide content of particle are the tabular particle of 3.4 moles of %.In addition, in Em-4 as the tabular silver emulsion, confirm on each limit, to exist respectively the tabular particle of 5 above dislocation lines be present in whole projected area 76% in.

The chemical sensitization of＜silver emulsion is handled 〉

Use as above each silver emulsion of preparation, carry out chemical sensitization and spectral sensitization, the green-sensitive emulsion that preparation is handled through sensitizing by following method.

(preparation of green-sensitive emulsion G-1)

The tabular silver emulsion of a part is heated to 55 ℃ of heating for dissolving, and per 1 mole of silver halide adds 1.0 * 10 ^-4Mole sensitizing coloring matter SD-4,4.6 * 10 ^-5Mole SD-5,7.8 * 10 ^-6Mole SD-6, added as 1.1 * 10 of chemical sensitizer after 20 minutes at interval 55 ℃ of maintenances in 2 minutes ^-5Molar sulphur sodium thiosulfate five water salt, 3.2 * 10 ^-5Mole gold chloride and 3.5 * 10 ^-4The mixed solution of molar sulphur potassium cyanate carries out slaking so that its 1/100 second sensitivity reaches optimal degree.Add stabilizing agent ST-1 when slaking finishes, add inhibitor according to the addition of putting down in writing in the aftermentioned table, cooling makes its cooling curing obtain green-sensitive emulsion G-1.In addition, SD-4, SD-5, SD-6 and ST-1 about using in the above-mentioned preparation see aftermentioned for details.

(preparation of green-sensitive emulsion G-2～G-13)

In the preparation of above-mentioned green-sensitive emulsion G-1, except the total addition level according to the kind of the kind of the content changing silver emulsion of putting down in writing in the aftermentioned table, inhibitor and addition and sensitizing coloring matter, all the other obtain green-sensitive emulsion G-2～G-13 after the same method.

As above the feature of Pei Zhi each silver emulsion is as follows.

[silver emulsion]

The numbering of silver emulsion	Average silver iodide content (mol%)	Aspect ratio	Dislocation line has or not	Remarks
					?Em-1 ?Em-2 ?Em-3 ?Em-4	??3.4 ??4.2 ??3.4 ??3.4	????13.3 ????12.9 ????12.3 ????6.8	Have or not	Comparative example comparative example comparative example of the present invention

Then, as above the feature of each green-sensitive emulsion of preparation is as follows.

[silver emulsion]

The green-sensitive emulsion numbering	The emulsion numbering	Inhibitor addition inhibitor I-6	????(mg/m 2) inhibitor 1-4	Total sensitizing coloring matter amount mole/silver mole)	Remarks
						????G-1 ????G-2 ????G-3 ????G-4 ????G-5 ????G-6 ????G-7 ????G-8 ????G-9 ????G-10 ????G-11 ????G-12 ????G-13	????Em-1 ????Em-1 ????Em-1 ????Em-1 ????Em-1 ????Em-1 ????Em-1 ????Em-2 ????Em-3 ????Em-4 ????Em-2 ????Em-3 ????Em-4	????- ????0.80 ????- ????0.40 ????0.40 ????0.60 ????1.00 ????- ????- ????- ????0.40 ????0.40 ????0.40	????0.45 ????- ????0.80 ????0.40 ????0.40 ????0.60 ????1.00 ????0.45 ????0.45 ????0.45 ????0.40 ????0.40 ????0.40	??1.84×10 -4??1.84×10 -4??1.84×10 -4??1.84×10 -4??1.50×10 -4??1.84×10 -4??1.84×10 -4??1.84×10 -4??1.84×10 -4??1.84×10 -4??1.84×10 -4??1.84×10 -4??1.84×10 -4	Comparative example comparative example comparative example comparative example of the present invention of the present invention comparative example comparative example comparative example

In addition, the addition of each inhibitor is every 1m when being used for high sensitivity green layer described later (the 9th layer) with the green-sensitive emulsion that will contain this inhibitor ²Scale show.

The making of＜silver halide colour photographic sensitive material 〉

[preparation of sample 101]

On the tri acetyl cellulose film support of the thick 125 μ m that are provided with prime coat, each layer from supporting the side to begin to form to form shown in following successively is made as the sample 101 of silver-halide color photoelement.

The addition of following each raw material is with every 1m ²The gram numerical table show.In addition, silver halide and collargol be scaled silver scale show that sensitizing coloring matter (representing with SD) is used with respect to the molal quantity of per 1 moles of silver and represented.

(the 1st layer: (g/m anti-halo layer) ²)

Black collargol 0.13

UV-1??????????????????????0.30

CM-1??????????????????????0.11

OIL-1?????????????????????0.23

Gelatin 1.20

(the 2nd layer: the middle layer)

OIL-3?????????????????????0.267

Gelatin 0.89

(the 3rd layer: low sensitivity sense red beds)

Iodine silver bromide emulsion a 0.31

Iodine silver bromide emulsion c 0.22

SD-1??????????????????????1.28×10 ^-4

SD-2??????????????????????1.78×10 ^-5

SD-3??????????????????????8.40×10 ^-5

C-1???????????????????????0.324

CC-1??????????????????????0.056

D-1??????????????????????????0.014

AS-2?????????????????????????0.002

OIL-2????????????????????????0.320

Gelatin 1.06

(the 4th layer: middle sensitivity sense red beds)

Iodine silver bromide emulsion b 0.08

Iodine silver bromide emulsion d 0.40

SD-1?????????????????????????2.56×10 ^-4

SD-2?????????????????????????3.50×10 ^-5

SD-3?????????????????????????1.72×10 ^-4

C-1??????????????????????????0.219

CC-1?????????????????????????0.044

D-1??????????????????????????0.024

D-3??????????????????????????0.002

AS-2?????????????????????????0.002

OIL-2????????????????????????0.001

Gelatin 0.84

(the 5th layer: high sensitivity sense red beds)

Iodine silver bromide emulsion g 0.48

SD-1?????????????????????????7.11×10 ^-5

SD-2?????????????????????????9.78×10 ^-6

SD-3?????????????????????????4.72×10 ^-5

C-1??????????????????????????0.046

C-2??????????????????????????0.041

CC-1?????????????????????????0.019

D-3??????????????????????????0.003

AS-2?????????????????????????0.001

OIL-2????????????????????????0.088

Gelatin 0.84

(the 6th layer: the middle layer)

AS-1???????????????????????0.20

OIL-1??????????????????????0.25

Gelatin 0.91

(the 7th layer: low sensitivity green layer)

Iodine silver bromide emulsion b 0.23

Iodine silver bromide emulsion c 0.10

SD-4???????????????????????1.17×10 ^-4

SD-5???????????????????????1.28×10 ^-5

SD-6???????????????????????1.61×10 ^-5

M-1????????????????????????0.275

CM-1???????????????????????0.085

D-2????????????????????????0.004

AS-2???????????????????????0.001

X-2????????????????????????0.069

AS-3???????????????????????0.033

OIL-1??????????????????????0.410

Gelatin 1.14

(the 8th layer: middle sensitivity green layer)

Iodine silver bromide emulsion c 0.09

Iodine silver bromide emulsion d 0.33

SD-4???????????????????????3.83×10 ^-4

SD-5???????????????????????4.00×10 ^-5

SD-6???????????????????????5.00×10 ^-5

M-1????????????????????????0.101

CM-1???????????????????????0.039

D-2????????????????????????0.001

D-3????????????????????????0.012

AS-2???????????????????????0.001

X-2???????????????????????????0.014

AS-3??????????????????????????0.007

OIL-1?????????????????????????0.280

Gelatin 1.06

(the 9th layer: the high sensitivity green layer)

Green-sensitive emulsion G-1 0.50

SD-4??????????????????????????1.00×10 ^-4

SD-5??????????????????????????3.50×10 ^-5

SD-6??????????????????????????6.00×10 ^-6

M-1???????????????????????????0.058

CM-1??????????????????????????0.029

AS-2??????????????????????????0.001

X-2???????????????????????????0.015

AS-3??????????????????????????0.007

OIL-1?????????????????????????0.141

Gelatin 1.11

(the 10th layer: yellow colour filter)

Yellow colloidal silver 0.06

AS-1??????????????????????????0.07

OIL-1?????????????????????????0.009

Gelatin 0.90

(11th layer: the blue layer of low sensitivity sense)

Iodine silver bromide emulsion b 0.11

Iodine silver bromide emulsion d 0.17

Iodine silver bromide emulsion e 0.17

SD-7??????????????????????????2.78×10 ^-4

SD-8??????????????????????????7.17×10 ^-5

Y-1???????????????????????????0.925

AS-2??????????????????????????0.003

OIL-1????????????????????????????0.371

Gelatin 1.91

(the 12nd layer: the blue layer of high sensitivity sense)

Iodine silver bromide emulsion e 0.03

Iodine silver bromide emulsion h 0.25

SD-7?????????????????????????????2.78×10 ^-5

SD-8?????????????????????????????1.83×10 ^-5

Y-1??????????????????????????????0.078

AS-2?????????????????????????????0.001

D-4??????????????????????????????0.038

OIL-1????????????????????????????0.047

Gelatin 0.61

(the 13rd layer: the 1st protective seam)

Iodine silver bromide emulsion i 0.22

UV-1?????????????????????????????0.10

UV-2?????????????????????????????0.06

X-1??????????????????????????????0.04

AF-6?????????????????????????????0.003

Gelatin 0.70

(the 14 layer: the 2nd protective seam)

PM-1?????????????????????????????0.10

PM-2?????????????????????????????0.018

WAX-1????????????????????????????0.02

SU-1?????????????????????????????0.003

Gelatin 0.55

In addition, beyond above-mentioned composition, can suitably add coating auxiliary agent SU-2, SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizing agent ST-1, weight-average molecular weight: 10000 and weight-average molecular weight: 100000 2 kinds of polyvinyl pyrrolidones (AF-1, AF-2), lime chloride, inhibitor AF-3, AF-4, AF-5, AF-6, AF-7, hardener H-1, H-2 and antiseptic Ase-1.

In the making of above-mentioned sample 101, use the feature of green-sensitive emulsion G-1 each iodine silver bromide emulsion in addition as shown in the table.In addition, the mean grain size of iodine silver bromide emulsion c, d, e, g, h, is represented with a cubical edge lengths (mean value) for iodine silver bromide emulsion a, b, i with diameter of a circle (mean value) expression that is equivalent to equate with projected area.

Iodine silver bromide emulsion	Mean grain size (μ m)	Average iodine content (mole %)	Average aspect ratio (mean grain size/thickness)
				Iodine silver bromide emulsion a iodine silver bromide emulsion b iodine silver bromide emulsion c iodine silver bromide emulsion d iodine silver bromide emulsion e iodine silver bromide emulsion g iodine silver bromide emulsion h iodine silver bromide emulsion i	????0.27 ????0.28 ????0.61 ????0.89 ????0.95 ????1.50 ????1.23 ????0.043	???????2.0 ???????2.0 ???????3.1 ???????3.7 ???????8.0 ???????3.1 ???????7.9 ???????1.9	??????- ??????- ??????5.43 ??????6.10 ??????3.07 ??????6.60 ??????2.85 ??????-

Each emulsion except green-sensitive emulsion G-1, iodine silver bromide i adds sodium thiosulfate, gold chloride, potassium rhodanide etc. after having added each sensitizing coloring matter of above-mentioned record, carry out chemical sensitization, so that the relation of photographic fog sensitivity reaches the most suitable.

In addition, measuring the result that specific photograph sensitivity obtains by the method for stipulating among the JIS JIS K 7614-1981 that formulates according to aforesaid international standard ISO sensitivity is 200.

Below at length listed compound used in the manufacturing of above-mentioned sample 101.

Y-1

M-1

C-1

C-2

CC-1

CM-1

D-1??????????????????????????????????????????????????D-2

D-3

D-4

SD-1

SD-2

SD-3

SD-4

SD-5

SD-6

SD-7

SD-8

AS-1

AS-2

AS-3

OIL-1???????????????????????????UV-1

OIL-2??????????????????????????OIL-3

H ₉C ₄OOC (CH ₂) ₈COOC ₄H ₉Whiteruss

UV-2

V-1

N: the degree of polymerization

Ase-1 (following 3 mixture of ingredients)

(composition A) (composition B) (composition C)

Composition A: composition B: composition C=50: 46: 4 (mol ratio)

H-1

CH ₂＝CHSO ₂-CH ₂CONHC ₂H ₄NHCOCH ₂-SO ₂CH＝CH ₂

H-2

X-2

ST-1

AF-1，2

AF-1 Mw 10,000AF-2 Mw 100,000n: the degree of polymerization

AF-3

AF-7

X-1

SU-2

SU-1

SU-3

SU-4

WAX-1

Mw＝3,000

PM-1

x∶y∶z＝3∶3∶4

PM-2

N: the degree of polymerization

[manufacturing of sample 102～113]

In the manufacturing of above-mentioned sample 101, except the green-sensitive emulsion G-1 that the green-sensitive emulsion G-2～G-13 with aforementioned preparation replaces using in the 9th layer the high sensitivity green layer, make sample 102～113.

[exposure of each sample, development and evaluating characteristics]

(exposure and development)

According to JIS K 7614-1981, after more than each sample of Zhi Zaoing exposes by wedge, open the developing method of putting down in writing in paragraph numbering [0220]～[0227] of flat 10-123652 communique by the spy and carry out colored color development development treatment.

(evaluating characteristics)

To carry out each sample of colored color development development treatment by said method, with the infiltration type densimeter of X-rite corporate system, carry out the mensuration that respectively sees through Status M concentration of yellow, magenta, cyan, make each photograph D-LogE family curve.

The mensuration of＜green layer sensitivity 〉

Use on the characteristic pinkish red concentration family curve of D-LogE in above-mentioned photograph of making, will realize being defined as sensitivity, obtain relative sensitivity as 100 with the sensitivity of sample 101 from the inverse of the required exposure of the concentration of Cmin+0.10.

＜conservatory evaluation 〉

Prepare each sample of 2 parts of above-mentioned making, under 23 ℃, the environment of 50%RH, preserved 7 days for 1 part, as baseline sample 1, in addition 1 part pressure degradation treatment of under 40 ℃, the environment of 80%RH, similarly carrying out for 1 week, with it as forcing deterioration sample 1.

Carry out above-mentioned each sample of handling and adopt with aforementioned same method and expose and development treatment, obtain the poor Δ dmin (Dmin of the Dmin-baseline sample 1 of pressure deterioration sample 1) of minimum separately pinkish red concentration (Dmin), with it as conservatory yardstick.

The evaluation of＜latent-image stability 〉

Prepare each sample of 2 parts of above-mentioned making, 1 part carry out above-mentioned exposure after, directly carry out development treatment and with it as baseline sample 2.In addition 1 part after carrying out above-mentioned exposure, under 40 ℃, the environment of 50%RH, carried out for 1 week and force to carry out development treatment after the deterioration, with it as forcing deterioration sample 2.

To each sample through developing, measure each sensitivity by said method, the sensitivity of the baseline sample 2 of each sample as 100, is obtained the sensitivity of sensitivity (100)-pressure deterioration sample 2 of poor Δ S{ baseline sample 2 of the sensitivity of pressure deterioration sample 2 on the other side }.Δ S value is more little, and the expression latent-image stability is good more.

The evaluation of＜development treatment stability 1 〉

After each sample carried out wedge exposure, with the benchmark development time, with respect to the processing time of the time after second variation of benchmark development time ± 30 as color development developing procedure in the aforesaid benchmark development treatment, carry out each development treatment, at the exposure station place corresponding to the concentration point of the pinkish red concentration 1.0 under the benchmark development time, measuring development time be this concentration D of the sample of processing in+30 seconds _G(+30 seconds) and development time are this concentration D of the sample of processing in-30 seconds _G(30 seconds) obtain this concentration difference (Δ D _G).Δ D _GMore for a short time, show that the development treatment stability that changes for development time is good more.

The evaluation of＜stable developing 2 〉

After each sample carried out wedge exposure,,, handle (pipeline processes) continuously, carry out the evaluation of development treatment stability according to the additional liquid of processing area supplementary provisions amount with automatic development treatment machine.

In aforesaid benchmark development treatment, measure the developer solution that uses when handling beginning and handle the green sensitivity S of sense that each sample obtains _G0With each sample that carries out after the 1/2 round-robin pipeline processes is handled the green sensitivity S of the sense that obtains _G1/2, obtain sensitivity rate of change S according to following formula ₀S ₀Value more near 1.0, represent outstanding more.

S _G＝S _G1/2/S _G0

In addition, above-mentioned continuous processing adopts that Konica company makes takes picture with scenes randomly as the セ Application チ ユ リ ア 100 of colour negative and セ Application チ ユ リ ア 400 and carries out.In addition, the semi-invariant that so-called 1/2 circulation is meant color development developer solution magnitude of recruitment among the present invention arrives moment of 1/2 of the treatment trough volume of this color development developer solution.In addition, feeling green sensitivity represents with the inverse of the required exposure of the concentration that reaches Cmin+0.3.

The result who more than obtains is as shown in following table.

Sample number	Relative sensitivity	[evaluation result]				Remarks
							Keeping quality	Latent-image stability	Development treatment stability
		??1∶ΔD0	????2∶S0
				101 102 103 104 105 106 107 108 109 110 111 112 113	????100 ????112 ????118 ????126 ????116 ????128 ????129 ????84 ????84 ????82 ????87 ????86 ????84				????+0.13 ????+0.07 ????+0.06 ????+0.03 ????+0.05 ????+0.03 ????+0.02 ????+0.16 ????+0.15 ????+0.18 ????+0.13 ????+0.13 ????+0.14	????-28 ????-14 ????-13 ????-09 ????-13 ????-09 ????-10 ????-35 ????-35 ????-38 ????-31 ????-30 ????-32	????0.08 ????0.04 ????0.04 ????0.02 ????0.03 ????0.02 ????0.02 ????0.10 ????0.11 ????0.12 ????0.08 ????0.09 ????0.10	????0.94 ????0.98 ????1.01 ????1.00 ????0.99 ????1.00 ????1.01 ????0.93 ????0.94 ????0.91 ????0.95 ????0.94 ????0.93	Comparative example comparative example comparative example comparative example of the present invention of the present invention comparative example comparative example comparative example

Utilizability on the industry

As mentioned above, by with formation of the present invention, can provide a kind of high sensitivity, and the good silver halide colour photographic sensitive material of storage stability, latent-image stability and Treatment Stability.

Claims (6)

1. silver halide colour photographic sensitive material, it is characterized in that: it has 1 layer blue layer of sense red beds, green layer, sense and non-photosensitive layer at least on support, it is 2.0～4.0mol%, average aspect ratio more than 8.0 and have the monodispersed silver emulsion of dislocation line that in these photosensitive layers at least 1 layer contains average silver iodide content, and at least 1 layer the photosensitive layer that comprises this silver emulsion contains 0.60mg/m ²Above inhibitor.

2. the silver halide of claim 1 record silver colour photographic sensitive material, it is characterized in that: at least a kind in the aforementioned inhibitor is the compound shown in the following general formula [I]:

General formula [I]

Het-(J) _n1-(Q) _m1

[in the formula, Het is not for containing 5～6 member heterocyclic ring containing nitrogens as the sulfydryl of substituent sulfydryl or protection, and J represents the connection base of (m1+1) valency, and Q is water-soluble base; N1 represents 0～5 integer, and m1 represents the integer more than 1].

3. the silver halide of claim 2 record silver colour photographic sensitive material, it is characterized in that: the compound shown in the aforementioned formula [I] is the compound shown in following general formula [II] or the general formula [III]:

General formula (II) general formula (III)

[in the general formula [II], W is oxygen atom, sulphur atom, nitrogen-atoms or C (R ₄₁), X is nitrogen-atoms or C (R ₄₁); Z is for forming the necessary atomic group of 5～6 member heterocyclic ring containing nitrogens that does not contain as the sulfydryl of substituent sulfydryl or protection; R ₄₁For the situation of the substituting group beyond the sulfydryl of sulfydryl or protection or hydrogen atom J, Q, n1, m1 and general formula [I] identical;

In general formula [III], P, Q ', R, T are nitrogen-atoms or C (R ₄₁), R ₄₁R with general formula [II] ₄₁Implication is identical; The situation of J, Q, n1, m1 and general formula [I] is identical].

4. the silver halide of claim 1 record silver colour photographic sensitive material, it is characterized in that: at least a kind of aforementioned inhibitor is the compound shown in the following general formula (1).

General formula (1)

[in the formula, X is N or CR ', and R ' is hydrogen atom, replacement or unsubstituted alkyl or replacement or unsubstituted aryl; R ₃And R ₄Be respectively hydrogen atom, alkyl, thiazolinyl, alkynyl, aryl or heterocyclic radical; N2 is 0 or 1; R ₃And R ₄Be selected from-SO for directly or indirectly having at least 1 ₃H ,-COOH and-group of OH and salt thereof].

5. the silver halide of each record silver colour photographic sensitive material in the claim 1～4 is characterized in that: in the aforementioned silver emulsion of per 1 moles of silver by 1.7 * 10 ^-4The above sensitizing coloring matter of mole carries out spectral sensitization.

6. the silver halide of each record silver colour photographic sensitive material in the claim 1～5, it is characterized in that: specific photograph sensitivity is more than 200.