CN1025378C - Method of manufacturing silver halide emulsion - Google Patents

Abstract

A method of manufacturing a silver halide emulsion, wherein reduction sensitization is performed by using at least one of ascorbic acid and derivatives thereof in a process of manufacturing a silver halide emulsion. The invention is further directed to a of manufacturing a silver halide emulsion, wherein reduction sensitization is performed by using at least one of ascorbic acid and derivatives thereof during precipitation of silver halide grains.

Description

Method of manufacturing silver halide emulsion

The invention relates to a kind of method for preparing silver halide photographic emulsions, this photographic emulsion can provide the photosensitive material with ISO and low Fog density.The present invention is also about a kind of method for preparing silver halide photographic emulsions, thereby a kind of photosensitive material that back light sensitivity and Fog density all do not have great changes of storing is provided.

Taking a picture with the required key property of silver emulsion is ISO, low Fog density and fine particle size.

In order to improve the light sensitivity of emulsion, need the photonic absorption number of (1) raising individual particle, the photoelectron that (2) raising is produced by light absorption changes into silver-colored efficient and (3) raising development activity that focuses on (latent image) and effectively utilizes the gained latent image.Improving granularity can increase the photonic absorption number of individual particle, but has fallen progressively image quality.Improving the activity of developing is to improve the effective ways of light sensitivity.But as colour development, graininess normally falls progressively under parallel development situation.Do not reduce graininess in order to improve light sensitivity, preferably improving the conversion photoelectron is the efficient of latent image, promptly improves quantum efficiency.In order to improve quantum efficiency, must reduce inefficient process such as compound and latent image chromatic dispersion.Learn that the reduction sensitization method that forms the little galactic nucleus that does not have the activity of developing on the inside or the surface of silver halide can prevent compound effectively.

The reduction sensitization method after deliberation long-time.People such as people such as CarrollLowe and Fallens are respectively at United States Patent (USP) 2,487,850 and 2,512,925 and BrP 789,823 on tin compound, polyamino compound and can be effectively with being the reduction sensitization agent based on the compound of thiourea dioxide be disclosed.Collier is at Photographic Science and Engineering " 23 copies, compared the performance of the galactic nucleus that forms with various reduction sensitization methods in 113 pages (1979).Collier has taked dimethylamine monoborane, stannous chloride, hydrazine, high pH is ripe and the method for low pAg maturation.The reduction sensitization method also is disclosed in United States Patent (USP) 2,518, and 698,3,201,254,3,411,917,3,779,777 and 3,930,867.Mean Japanese patent application at JP-B-57-33572 and JP-B-58-1410(" JP-B-" through substantive examination) on the selection of reduction sensitization agent is not only disclosed, the improvement of reduction sensitization method is also disclosed.In these publications, exemplified habitual reduction sensitization agent, comprising ascorbic acid.But, think that in these publications thiourea dioxide is better, and exemplified thiourea dioxide, silver-colored slaking and hydrazine.Thereby agent has better performance as reduction sensitization not find ascorbic acid.Meaning at JP-A-57-179835(" JP-A-" does not have substantive examination and disclosed Japanese patent application) also disclose and improved one's methods.

In order to realize the reduction sensitization effect, must solve storage stability.JP-A-57-82831 and JP-A-60-178445 disclose the technology that the bin stability to the emulsifying agent that carries out reduction sensitization improves, but the degree of improving not enough.Although carried out a large amount of research as mentioned above, the raising of light sensitivity also is not enough to compare with hydrogen sensitizing gained result, and hydrogen sensitizing process is that photosensitive material is used hydrogen treat in a vacuum.People such as Moisar are " Journal of Imging Science " 29, and 233 pages (1985) are reported to some extent.People go back the bin stability that demand is improved the photosensitive material of the emulsion that contains reduction sensitization.

The conventional reduction sensibilization technology can not satisfy recently the ISO of sensitive photographic material and the demand of high imaging quality.This is because at first when containing when the photosensitive material of the emulsifying agent of reduction sensitization is stored, great changes have taken place for light sensitivity and Fog density.Secondly, the raising of the light sensitivity that obtains by the reduction sensitization effect not enough.

First purpose of the present invention provides a kind of method for preparing emulsion, this emulsion can provide the photosensitive material with ISO and low Fog density, more particularly, a kind of method for preparing photosensitive material is provided, and this photosensitive material does not have great changes and has ISO in lay up period light sensitivity and Fog density.

Second purpose of the present invention provided a kind of color sensitive material, particularly has ISO and low Fog density and performance only has very little variation after storage colour photographic sensitive material.

Above-mentioned purpose of the present invention is to realize like this, in the process of preparation silver emulsion, use at least a ascorbic acid and derivant thereof to carry out reduction sensitization, and adopt a kind of color sensitive material, it comprises the transparent carrier that has one deck photosensitive silver halide emulsion layer thereon at least, wherein the 50%(weight of contained halogenation silver granuel in emulsion layer) or mostly are the halogenation silver granuels that constitute the silver emulsion of above-mentioned preparation.

What cut is that above-mentioned purpose of the present invention realizes by following method, a kind of method for preparing silver emulsion, and wherein the reduction sensitization effect is to use at least a ascorbic acid and derivant thereof and carry out in precipitation halogenation silver granuel process; A kind of as described in above-mentioned any method, prepare the method for silver emulsion, wherein the reduction sensitization effect is with every mole of silver halide 5 * 10 ^-5～1 * 10 ^-1Mole ascorbic acid and derivant thereof carry out; Perhaps a kind of as preparing the method for silver emulsion as described in above-mentioned any method, wherein the reduction sensitization effect is to carry out in the presence of at least a compound shown in formula (I), (II) and (III).

Wherein: R, R ¹And R ²Can be identical or different, represent aliphatic group, aromatic group or heterocyclic radical, M represents kation, the two valency bases of L representative, m represents 0 or 1.

The compound of formula (I) to (III) representative can be to contain two valency groups that the structure by formula (I) to (III) representative obtains polymkeric substance as repetitive.

The present invention will be described in detail as follows.

The preparation process of silver emulsion roughly is divided into as steps such as granulating, desalination, chemical sensitization and coatings.The granulating step can be further divided into steps such as nucleation, maturation and precipitation.These steps are not necessarily carried out according to said sequence, but are undertaken by opposite order or repeated sequence." in preparation silver emulsion process, carry out reduction sensitization " and mean reduction sensitization can in any step, carrying out basically.Reduction sensitization can be in nucleation or during the starting stage of granulating physical ripening, or in precipitating action, or carry out before or after the chemical sensitization effect.In the situation of the chemical sensitization that comprises golden sensitizing, sulphur sensitizing, selenium sensitizing or their combination, be preferably and before chemical sensitization, carry out reduction sensitization, can avoid producing undesirable photographic fog like this.Reduction sensitization preferably carries out during halogenation silver granuel precipitation.The method of carrying out reduction sensitization during precipitating is included in by physical ripening or adds water-soluble silver salt and water-soluble alkali halide makes halogenation silver granuel growing period carry out the method for reduction sensitization and the method for carrying out reduction sensitization and then particle is precipitated when the solids precipitation effect temporarily stops.

The example of ascorbic acid and derivant thereof (being designated hereinafter simply as " ascorbic acid compound ") is as follows:

(A-1) ascorbic acid

(A-2) L-sodium ascorbate

(A-3) L-potassium ascorbate

(A-4) DL-ascorbic acid

(A-5) D-sodium ascorbate

(A-6) L-ascorbic acid 6-acetate

(A-7) L-ascorbic acid 6-palmitic acid

(A-8) L-ascorbic acid 6-benzoic acid

(A-9) the L-ascorbic acid 5, the 6-oxalic acid

(A-10) the L-ascorbic acid 5, the 6-0-isopropylidene

In order to add above-mentioned ascorbic acid compound in the process for preparing silver emulsion in the present invention, can directly be dispersed in them in the emulsion, for example perhaps be dissolved in water, methyl alcohol and the alcohol solvent or be dissolved in the potpourri of above-mentioned solvent, in preparation process, add usefulness then.

The amount of the used ascorbic acid of the present invention is sharp much larger than the addition of habitual reduction sensitization agent.For example: JP-B-57-33572 is described, and " the reductive agent consumption is no more than every gram silver ion 0.75 * 10 usually ^-2Milliequivalent (8 * 10 ^-4Mol/AgXmol), every kilogram of silver nitrate 0.1-10mg(10 in many cases ^-7-10 ^-5The mol/AgXmol ascorbic acid) ascorbic acid is just enough " (above-mentioned scaled value is that the present inventor calculates).United States Patent (USP) 2,487, " tin compound can be used as the reduction sensitization agent to 850 reports, and addition is 1 * 10 ^-7～44 * 10 ^-6Mole ".It is every mole of silver halide 0.01mg-2mg thiourea dioxide or about 0.01mg-3mg stannous chloride that JP-A-57-179835 describes suitable addition.The better addition of the used ascorbic acid compound of the present invention depends on a number of factors, as the halogen component of granularity and emulsion, temperature, pH value and the pAg of preparation emulsion.Thereby the range of choice of addition is every mole of silver halide 5 * 10 ^-5Mol～1 * 10 ^-1Mol, even more preferably 5 * 10 ^-4Mol～1 * 10 ^-2Mol, preferably 1 * 10 ^-3Mol～1 * 10 ^-2Mol.

Though ascorbic acid compound of the present invention can preferably add when solids precipitation in the adding whenever of emulsion preparation process.Ascorbic acid compound can add any time when granulating, also can join in the reactor in advance.Outside a little, the reduction sensitization agent can be added in the aqueous solution of water soluble silver salt or water soluble alkali halide, to carry out granulation with this aqueous solution.Divide in the long period of particle growth that to add the reduction sensitization agent solution several times or to add continuously also be method preferably.

Though, aspect light sensitivity, Fog density and ageing stability, carry out the reduction sensitization that the reduction sensitization effect is better than habitually practising with ascorbic acid compound of the present invention, be more preferably sometimes with method of the present invention and be used in combination with other reduction sensitization method.But in this case, be preferably the supplementary means of others, and mainly be to carry out reduction sensitization with ascorbic acid compound as just the reduction sensitization effect.The method that is used in combination with the inventive method can be selected from following, and a kind of method is that known reductive agent is added in the silver emulsion; A kind of method is called silver-colored ripe method, and this method is to precipitate under pAg is the low pAg atmosphere of 1-7 or ripe; A kind of method is called the ripe method of high pH, and this method is to precipitate under the high pH atmosphere of pH8-11 or maturation.

The method that adds the reduction sensitization agent is better, because can accurately mix up the degree of reduction sensitization effect.

Known for example stannous compound, amine and polyamine, hydrazine derivate, formamidine sulfinic acid, silane compound and monoborane compound can be used as the reduction sensitization agent.But ascorbic acid compound gained result is better than the result of above-mentioned known reduction sensitization agent.

In the present invention, be preferably in preparation silver emulsion process and carry out reduction sensitization, and in preparation process, add at least a compound that is selected from formula (I), (II) and (III) with ascorbic acid compound.

Wherein: R, R ¹And R ²Can be identical or different, represent aliphatic group, aromatic group or heterocyclic radical, M represents kation, and L represents bivalent radical, and m represents 0 or 1.

Thiosulfonic acid compound shown in formula (I), (II) and (III) is more detailed description below.As R, R ¹And R ²When representing aliphatic group separately, they can be saturated or unsaturated, straight chain, branching or cyclic aliphatic alkyl, be preferably the alkyl of 1-22 carbon atom or the alkenyl or the alkynyl of 2-22 carbon atom are arranged.These groups can have substituting group.The example of alkyl is methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, 2-ethylhexyl, decyl, dodecyl, cetyl, octadecyl, cyclohexyl, isopropyl and normal-butyl.

Non-limiting examples of alkenyls is allyl and butenyl group.

The example of alkynyl group is propargyl and butynyl.

R, R ¹And R ²Aromatic group comprise monocycle or condensed ring aromatic base, 6-20 carbon atom preferably arranged.The example of this aromatic group is phenyl and naphthyl.These groups can have substituting group.

R, R ¹And R ²Heterocyclic radical include the 3-15 unit ring of at least one nitrogen, oxygen, sulphur, selenium and tellurium element and at least one carbon atom, be preferably 3-6 unit ring.The example of heterocyclic radical is pyrrolidine, piperidines, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazoles, benzothiazole, benzoxazole, benzimidazole, selenazoles, benzo selenazoles, tellurium azoles, triazole, benzotriazole, tetrazolium, oxadiazole and thiadiazoles.

At R, R ¹And R ²Going up substituent example is alkyl (as: methyl; ethyl and hexyl); alkoxy (as: methoxyl; ethoxy and octyloxy); aryl (as: phenyl; naphthyl and tolyl); hydroxyl; halogen atom (as: fluorine; chlorine; bromine and iodine); aryloxy group (as phenoxy group); alkylthio group (as: methyl mercapto and butylthio); arylthio (as thiophenyl); acyl group is (as acetyl group; propiono; bytyry and valeryl); sulfonyl (as: methyl sulphonyl and benzenesulfonyl); acylamino-(as: methane acid amides and benzamide); carboxyl; cyano group; sulfo group; amino;-SO ₂SM(M represents monovalent cation) and-SO ₂R ¹

The divalent group of L representative comprises atom or the atomic group that contains at least one C, N, S and O.The example of L be alkylidene, alkenylene, alkynylene, arlydene ,-O-,-S-,-NH-,-CO-and-SO ₂-.These divalent groups can use separately or its two or more merging is used.

L is divalent aliphatic base or divalent aromatic base even more preferably.L is that the example of divalent aliphatic base is

CH ₂

(n is 1-12) ,-CH ₂-CH=CH-CH ₂-,-CH ₂C ≡ C-CH ₂-,-CH ₂ CH ₂-and xylylene.L is that the example of divalent aromatic base is phenylene and naphthylene.

These substituting groups can also further be replaced by above-mentioned group.

M is metallic ion or organic cation even more preferably.The example of metallic ion is lithium ion, sodion and potassium ion.The organic cations example is ammonium ion (as: ammonium, tetramethyl-ammonium and TBuA), Phosphonium ion (as Si Ben Phosphonium) and a guanidine radicals.

When the compound of each representative of formula (I)-(III) was polymkeric substance, its repetitive was exemplified below:

Every kind of above-mentioned polymkeric substance can be homopolymer or with the multipolymer of other copolymerisable monomer.

The examples of compounds of formula (I), (II) or (III) representative is listed in the Table A of back, and still, compound is not limited in the Table A listed.

The compound of formula (I), (II) or (III) representative more preferably addition is every mole of silver halide 10 ^-7-10 ^-1Mole.Addition more preferably 10 ^-6-10 ^-2Mol/molAg is preferably 10 ^-5-10 ^-3Mol/molAg.

Employing adds adjuvant in photographic emulsion common method adds the compound of formula (I)-(III) representative in preparation process.For example, water-soluble compound adds with the aqueous solution form of any concentration; Water insoluble or water resistance stickiness compound dissolution adds as solution then can having photographic property in any organic solvent such as alcohols, di-alcohols, ketone, ethers and amide-type of adverse effect with water-soluble mixing.

The compound of formula (I), (II) or (III) representative can add in any time of process, as in the granulating stage of silver emulsion, or added before or after chemical sensitization.Even more preferably this compound before carrying out reduction sensitization or during add.This compound preferably adds when solids precipitation.

Though this compound can join in the reactor in advance, be preferably in the adding of any time in granulating stage.At this moment, formula (I), (II) or (III) compound can the water soluble silver salt or the aqueous solution form of water soluble alkali halide add, to carry out granulating with this aqueous solution.Dividing the solution add formula (I), (II) or (III) compound several times or continuously in the long period in granulating stage also is method preferably.

Most preferred of the present invention is formula (I) compound.

The fontanel silver of any silver bromide, iodine silver bromide, iodine chlorine silver bromide, chlorine silver bromide and silver chloride and so on all can be used in the photographic emulsion layer of the used sensitive photographic material of the present invention, more preferably silver halide is iodine silver bromide, silver bromide or chlorine silver bromide, wherein contains 30mol% or silver iodide still less.

It is optional from not comprising the regular crystal of twin plane and those are at Japan Photographic Society ed. to be used for halogenation silver granuel of the present invention, " Silver Salt Photographs; Basis of Photographic Industrius " (Corana Co., p.163) the halogenation silver granuel of existing report in,, contain parallel many twins of 2 or a plurality of parallel twin planes and contain non-parallel many twins of 2 or a plurality of non-parallel twin planes if any the single twin that contains a twin plane according to its application examples.Under the situation of regular crystal, the cubic granules that can use (100) face to form, the dodecahedron particle that the octahedra particle that (111) face is formed and (110) face are formed, these have report in JP-B-55-42737 and JP-A-60-222842.In addition, as " Journal of Imaging Science " 30,247 pages, 1986 reported have (H11) as the particle of (211) face, have (hh1) as the particle tool of (331) face at (hko) as the particle of (210) face with have (hk1) and can select to use according to being used for as the particle of (321) face.But must improve its preparation method.The particle that two kinds or polytype face arranged as tetrahedron particle with (100) and (111) face, have the particle of (100) and (110) face and have (111) and the particle of (110) face can be selected to use according to being used for.

The halogenation silver granuel can be that to have granularity be 0.1 micron or littler fine particle, or the projecting plane diameter is 10 microns a bulky grain.Emulsion can be to have the single of very narrow distribution to disperse emulsion, or the polydispersion emulsion of very wide distribution is arranged.

It is exactly that 80% or more (quantity of particle or weight) of all particles drop within average grain granularity ± 30% scope that what is called has monodisperse silver halide emulsion that narrow granularity disperses.For the requirement of satisfaction luminescent material gradation, have two kinds of the variable grain granularity or multiple monodisperse silver halide emulsion and can be coated on the individual layer in a plurality of emulsion layers with substantially the same color sensitive degree or on the lamination of different layers.In addition, two kinds or multiple polydispersion silver halide emulsion or single disperse and the potpourri of polydispersion emulsion can mix or overlapping.

Being used for photographic emulsion of the present invention can prepare with the described method of following document, for example: P.Glafkides " Chinie et Physique Photographique, " Paul Montel, 1967; Duffin, " Photographic Emulsion Chemistry ", Focal Press, 1966; With V.L.Zelikman et al., " Making and Coating Photographic Emulsion ", Focal Press, 1964.Just, photographic emulsion can prepare with for example acid system, neutralisation and ammonia process.As solvable silver salt and solvable halide reaction system, also can use the method for single mixed method, two mixed method or its two combination.Also can use so-called reverse mixed method in the presence of excessive silver ion, to form silver halide particle.As a kind of system of two mixed methods, can use so-called controlled pair of gunite, in the method, the pAg value in the liquid phase of generation silver halide keeps constant.According to the method, can make and have square crystal formation and almost be the silver emulsion of homogeneous granularity.

The silver emulsion that contains above-mentioned square crystal formation silver halide particle can be by making at granulating time control pAg and pH value.More particularly, this method is at " Photographic Science and Engineering " 6,159-165 page or leaf (1962); " Journal of Photogr--aphic Science " 12,242-251 page or leaf (1964); United States Patent (USP) 3,655,394 and BrP 1,413,748 on to some extent the report.

Length breadth ratio is that S3 or bigger flat particle also can be used for the present invention.Flat particle can prepare easily with following document institute reported method.Document for example has Cleve, " Photogra-phy Theory and Practice ", (1930) 131 pages; 14 of Gutoff " Photographic Science and Engineering ", 248-257 page or leaf (1970); United States Patent (USP) 4,434,226,4,414,310,4,433,048 and 4,439,520; With BrP 2,112,157.When using flat particle, the covering power of sensitizing pigment and color sensitizing efficient can be according to United States Patent (USP)s 4,434, and 226 methods of describing in detail are better to improve.

Flat particle can more preferentially be used for emulsion of the present invention.Particularly, the length breadth ratio of particle be the flat particle of 3-8 account for the total projection surface 50% or more mostly be.

Crystal structure can be uniformly, can form by different halogens with appearance in the inside of crystal, and perhaps can be layer structure.These emulsion grains are disclosed in as BrP 1,027, and 146, United States Patent (USP) 3,505,068 and 4,444,877 and Japanese patent application 58-248469.In addition, the silver halide with different component can be used epitaxial growth tie point keyed jointing, but perhaps is not also keyed jointing of the compound of silver halide such as silver thiocyanate or zinc paste.

Silver emulsion of the present invention even more preferably has the distribution or the structure of halogen component in its particle.Representative instance is core-shell-type or the double structure particle that different halogen components are arranged on the inside of particle and top layer, as described in JP-B-43-13162, JP-A-61-215540, JP-A-60-222845 and JP-A-61-75337.In this particle, the shape of core segment is identical with the whole particle shape of band shell sometimes, and is then different sometimes.Say that more specifically when core segment was square, the particle of band shell was square sometimes, or was octahedra sometimes.Otherwise when core segment was octahedron, the particle of band shell was square sometimes or is octahedra sometimes.In addition, when core segment was unconventional whole particle, the particle of band shell is some distortion sometimes, just not have definite shape sometimes.In addition, may not to form simple dual structure, but form triplen (as described in JP-A-60-222844), maybe can form the sandwich construction of multilayer, perhaps form silver halide thin layer with different component on the surface of core-shell dual structure particle.

Not only have above-mentioned peripheral structure in order to obtain the inner structure of particle, can to prepare, but also the particle of so-called syndeton is arranged.The example of this particle is disclosed in as JP-A-59-133540, JP-A-58-108526, EP199290A2, JP-B-58-24772 and JP-A-59-16254.The crystalline solid that has with the different compositions of host crystal can be made, and edge, corner or the surface portion of host crystal can be joined to.No matter whether host crystal is made up of or core-shell structure even halogen, all can form this joint crystal.

Connected structure can come nature to make by the combination between the silver halide.In addition, connected structure can be combined and make with silver halide by the silver salt compound that does not have the halite structure such as silver thiocyanate or silver carbonate.As long as can form connected structure, also can use non-silver salt compound such as PbO.

In iodine silver bromide grain with said structure such as core-shell particle, the content of silver iodide can be higher at core segment, and is then lower in the shell part, otherwise perhaps.Similarly, in having the particle of connected structure, agi content is higher in host crystal, and lower in engaging crystal, otherwise perhaps.

In the particle of said structure, the boundary member between the different halogen components that the crystalline mixture that is formed by different component causes may be clearly or unintelligible.In addition, also can form continuous structural change.

Be used for silver emulsion of the present invention and can make particle become circular processing, as described in EP-0096727B1 and EP-0064412B1; Perhaps carry out particle surface modification and handle, as described in DE-2306447C2 and JP-A-60-221320.

Be used for even more preferably surface latent image type of silver emulsion of the present invention.But internal latent image type emulsion can be used by described developing solution or the development conditions selected of JP-A-59-133542.In addition, the line internal latent image type emulsion that is surrounded by shell can use according to application.

The solvent that is used for silver halide can be used for promoting ripe effectively.For example, in known conventional process,, in reactor, add excessive halide ion in order to promote maturation.Thereby, obviously only in reactor, add silver halide solution and just can promote maturation.In addition, can use other maturing agent.Before silver salt and halogenide add, the total amount of these maturing agents is joined in the dispersion medium of reactor, perhaps maturing agent joins in the reactor with one or more halogenide, silver salt or deflocculant.In addition, maturing agent also can add separately in the step that adds halogenide and silver salt.

Maturing agent example beyond the halide ion is ammonia, amines and thiocyanate such as alkali metal thiocyanate, particularly sodium thiocyanate or potassium rhodanide and ammonium thiocyanate.

In the present invention, be very important by the chemical sensitization effect of sulphur sensibilization and golden sensibilization representative, because can obtain obvious effects by the chemical sensitization effect.According to emulsion grain composition, structure or shape, the perhaps application of emulsion, the position of carrying out chemical sensitization is different.That is to say, chemical sensitization nuclear or be embedded in the particle, perhaps apart from particle surface than shallow portion, or form at particle surface.Though method of the present invention is under any circumstance all effective, chemical sensitization nuclear preferably forms in the place near the surface.Just, the present invention's ratio in surface latent image type emulsion is more effective in internal latent image type emulsion.

Chemical sensitization can be finished with activity gels, as the 4th of T.H.James " The Theory of the Photographic Process ", and Macmillan, 1977, the 67-76 page or leaf is described.In addition, chemical sensitization can be 5-10 at PAg, and pH is under 5-8 and the 30-80 ℃ of temperature, potpourri with sulphur, selenium, tellurium, gold, platinum, palladium or iridium or multiple above-mentioned sensitizer carries out, as 120 of research reports (Reseach Disclosure), No.12008(1974 April), 34 of research reports, No.13452(1975 June), United States Patent (USP) 2,642,361,3,297,446,3,772,031,3,857,711,3,901,714,4,266,018 and 3,904,415, and BrP 1,315,755 is described.The chemical sensitization effect most preferably at gold compound and sulfocyanic ester compound, as United States Patent (USP) 3,857,711,4,266, carry out under 018 and 4,054,457 described sulfocompounds or the sulfocompound existence as hypo, thiourea compound and rhodanine compound and so on.Chemical sensitization also can be carried out in the presence of the chemical sensitization auxiliary agent.The example of chemical sensitization auxiliary agent is the known compound that can reduce photographic fog and super-sens in the chemical sensitization process, as a word used for translation indenes, a word used for translation pyridazine and a word used for translation pyrimidine.The modifier example of chemical sensitization auxiliary agent is at United States Patent (USP) 2,131, and 038,3,411,914,3,554,757, report to some extent on JP-A-126526 and G.F.Duffin " Photogoaphic Emulsion Chemistry " the 138-143 page or leaf.

In order to prevent in processing, store or photosensitive material taken pictures and when handling photographic fog is arranged that perhaps in order to stablize photographic property, the used photographic emulsion of the present invention can contain all cpds.The known examples of compounds that can be used as antifoggant or stabilizing agent has pyrroles such as benzothiazolium salt, nitroimidazole, nitrobenzimidazole, chloro benzimidazole, bromobenzene and imidazoles, thyroidan, mercaptobenzothiazoler, mercaptobenzimidazole, sulfydryl thiaziazoles, aminotriazole(ATA), benzotriazole, nitrobenzene and triazolam and mercapto-tetrazole (particularly 1-phenyl-5-mercapto-tetrazole); Mercaptopyrimidine; Sulfydryl triadines; Thione compounds is as oxadrinthione; The a word used for translation indenes is as three a word used for translation indenes, four a word used for translation indenes (particularly (1,3,3a, 7) four a word used for translation indenes of 4-hydroxyl replacement) and five a word used for translation indenes.Example is at United States Patent (USP) 3,954,474 and 3,982,947 and JP-B-52-28660 on describe to some extent.

Being used for photographic emulsion of the present invention can use as methine dyestuff spectral sensitization.The example of used pigment is cyanine dye, merocyanine dyes, compound cyanine dye, composite part cyanine dye, full polarity cyanine dye, half cyanine dye, styryl cyanine dye and hemioxonol dyestuff.The most effective dyestuff is those dyestuffs that belong to cyanine dye, merocyanine dyes and composite part cyanine dye.In these dyestuffs, any nuclear that is used as alkaline heteronucleus in cyanine dye usually all can use.The example of this nucleoid is pyrrolin He, oxazoline nuclear, thiazoline nuclear, pyrrole nucleus, oxazole nuclear, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazolium nuclear and pyridine nucleus; The alicyclic hydrocarbon cyclic condensation is become any nuclear of above-mentioned nuclear, become any nuclear of above-mentioned nuclear as indolenine nuclear, benzo indolenine nuclear, indole nucleus, benzoxazole to examine, naphthoxazole nuclear, benzothiazole nucleus, naphthothiazoles nuclear, benzo selenazole nucleus, benzimidazole nucleus and quinoline nuclei the aromatic hydrocarbon cyclic condensation.These are endorsed substituting group on carbon atom.

For merocyanine dyes or composite part cyanine dye, five yuan or hexa-member heterocycle nuclear as pyrazolin-5-one nuclear, thiohydantoin are examined, 2-thiazoline-2,4-diketone nuclear, thiazolidine-2,4-diketone nuclear, rhodanine nuclear and thiobarbituric acid are endorsed the nuclear that is used as ketone methylene structure.

These sensitizing pigment can use separately, or two kinds or multiple mixing use.In order to carry out the supersensitization effect, the special usually mixing of using multiple sensitizing pigment.The representative instance that this merging is used is described in United States Patent (USP) 2,688,545,2,977,229,3,397,060,3,522,052,3,527,641,3,617,293,3,628,964,3,666,480,3,672,898,3,679,428,3,703,377,3,769,301,3,814,609,3,837,862,4,026,707, BrP 1,344, and 281 and 1,507,803, JP-B-43-4936 and JP-B-53-12375, JP-A-52-110618 and JP-A-52-109925.

Except sensitizing pigment, emulsion can contain and not have the spectral sensitization effect, or does not absorb visible light basically and have the pigment of supersensitization effect.

As conventional method, pigment can be added in the emulsion at any time, as long as it is just passable to prepare emulsion effectively.Modal is to add pigment after the chemical sensitization effect is finished and before coating.But, pigment also can add simultaneously with chemical sensitizer, so that carry out spectral sensitization effect and chemical sensitization effect simultaneously, as United States Patent (USP) 3,628,969 and 4,225,666 is described, and pigment can add before the chemical sensitization effect, as described in JP-A-58-113928, thereby perhaps before the silver halide particle precipitation, add the effect of pigment beginning spectral sensitization.In addition, as United States Patent (USP) 4,225,666 is described, and above-claimed cpd can add in batches, adds part of compounds like this before the chemical sensitization effect, adds remaining part of compounds after sensibilization.Just as United States Patent (USP) 4,183,756 is described, and compound can form the phase at silver halide particle and whenever add.

Addition is every mole of fontanel silver 4 * 10 ^-6-8 * 10 ^-3Mole.Even more preferably, when the silver halide granularity is a preferred size, during as 0.1-1.2 μ m, addition is about 5 * 10 preferably ^-5-2 * 10 ^-3Mole.

Above-mentioned various adjuvant can be used for photosensitive material of the present invention.Yet, except that above-mentioned adjuvant, also can be according to being used for using various other adjuvants.

These adjuvants are narrated to some extent in 17643 sections of research reports (in Dec, 1978) and 18716 sections (in November, 1979), and below they are summarized in:

Adjuvant RD17643 money RD18716 money

1. 23 pages of 648 pages of right hurdles of chemical sensitizer

2. 648 pages of right hurdles of light sensitivity dose

3. spectral sensitizer, page right hurdle, 648 pages of right hurdles-649 of hypersensitizer 23-24 page or leaf

4. optical whitening agent is 24 pages

5. antifoggant and 649 pages of right hurdles of stabilizing agent 24-25 page or leaf

6. light absorber, page left hurdle, 649 pages of right hurdles-650 of filter dye 25-26 page or leaf

Ultraviolet light absorber

7. anti-650 pages of left hurdles, 25 pages of right hurdles of color spot agent～right hurdle

8. dyestuff imaging stabilizing agent is 25 pages

9. 26 pages of 651 pages of left hurdles of hardener

10. plastifier, 27 pages of 650 pages of right hurdles of lubricant

11. coating additive, 650 pages of right hurdles of surfactant 26-27 page or leaf

12. 27 pages of 650 pages of right hurdles of antistatic agent

In the present invention, can use various colour couplers.The instantiation of these colour couplers is disclosed in above-mentioned research report 17643, among VII-C～VII G, as the list of references of this patent.

The better example of yellow colour coupler is disclosed in as United States Patent (USP) 3,933, and 501,4,022,620,4,326,024 and 4,401,752, on JP-B-58-10739 and the BrP 1,425,020 and 1,476,760.

The better example of magenta colour coupler is 5-pyrazolone and pyrazoles azoles, and compound is disclosed in as United States Patent (USP) 4,310 preferably, 619 and 4,351,897, EP73,636, United States Patent (USP) 3,061, and 432 and 3,752,067, research report No.24220(1984 June), JP-A-60-33552, research report No.24230(1984 June), JP-A-60-34659 and United States Patent (USP) 4,500,630 and 4, on 540,654.

The example of cyan coupler is phenol and naphthols colour coupler, and colour coupler is disclosed in as United States Patent (USP) 4,052 preferably, 212,4,146,396,4,228,233,4,296,200,2,369,929,2,801,171,2,772,162,2,895,826,3,772,002,3,758,308,4,334,011 and 4,327,173, Deutsches Reichs-Patent application (OLS) No.3,329,729, EP121,365A, United States Patent (USP) 3,446,622,4,333,999,4,451,559 and 4,427,767 and EP161,626A.

Can be used to the colour coupler of the undesirable additional absorption of correcting color dyestuff, its better example is to be disclosed in research report No.17643, VII-G, United States Patent (USP) 4,163,670, JP-B-57-39413, United States Patent (USP) 4,004,929 and 4,138,258 and BrP 1,146,368 on colour coupler.

The better example that can form the colour coupler of the color pigment with suitable diffusive is to be disclosed in United States Patent (USP) 4,366, the colour coupler on 237, BrP 2,125,570, EP96,570 and Deutsches Reichs-Patent application (OLS) No.3,234,533.

The colour coupler representative instance of polymerisable formation color is to be disclosed in United States Patent (USP) 3,451,820,4,080,211 and 4,367,282 and BrP 2,102,173 on colour coupler.

The colour coupler that can discharge the useful residue of taking a picture during quality also can be used for the present invention preferably.The DIR colour coupler is that the colour coupler of released development inhibitor has narration on the above-mentioned research report No:17643 of this paper, VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248 and United States Patent (USP) 4,248,962.

Become image to discharge the colour coupler of nucleator or the better example of the development accelerant when developing is disclosed in BrP 2,097,140,2,131,188 and JP-A-59-157638 and JP-A-59-170840 on.

The colour coupler example that can be used for photosensitive material of the present invention is to be disclosed in as United States Patent (USP) 4,130,427 competition colour coupler; Be disclosed in as United States Patent (USP) 4,283,472,4,338,393 and 4,310,618 how equivalent colour coupler; Be disclosed in the colour coupler of oxygen compound also as the release DIR of JP-A-18590 and JP-A-62-24252; Discharge the colour coupler of pigment, this pigment becomes painted form again after being released, and as EP173,302A is described; Be disclosed in as R.D.No.11449 and 24241 and the colour coupler of the release bleach boosters of JP-A-61-201247; Be disclosed in as United States Patent (USP) 4,553 colour coupler of 477 release Legand.

Be used for colour coupler of the present invention and can be incorporated into photosensitive material with various known process for dispersing.

The example of the high boiling solvent that uses in oil-water dispersibility method is disclosed in as 2,322, on 027.

In oil-water dispersibility method, use, and boiling point is that 175 ℃ or higher high boiling organic solvent example are phthalic ester (as: dibutyl phthalates under normal pressure, dicyclohexyl phthalate and di-2-ethylhexyl phthalate), phosphate or phosphonate ester (as: triphenyl phosphate, tricresyl phosphate hydroxy toluene ester, phosphoric acid 2-second hexyl diphenyl ester, tricyclohexyl phosphate and tricresyl phosphate-2-Octyl Nitrite), benzoic ether (as: benzoic acid 2-Octyl Nitrite, benzoic acid dodecane ester and benzoic acid 2-ethylhexyl-to hydroxy ester), acid amides (as: N, N-diethyl dodecane acid amides, N, N-diethyl lauryl acid amides and N-four decyl pyrrolidone), alcohols or phenols are (as isostearoyl pure and mild 2, the 4-di-tert-pentyl phenol), alphatic carboxylic acid ester (as: two (2-ethylhexyl) sebacate, the dioctyl azelate, glycerin tributyrate, isostearoyl lactate and trioctylphosphine citrate), anil (as: N, N-dibutyl-2-butoxy-uncle's 5-octyl group aniline) and hydro carbons (as: paraffin, dodecyl benzene and diisopropyl naphthalene).Have about 30 ℃ or higher of boiling point, best 50 ℃-Yue 160 ℃ organic solvent can be used as cosolvent.The representative instance of cosolvent is ethyl acetate, butyl acetate, ethyl propionate, MEK, cyclohexanone, 2-ethoxyethyl group acetic acid esters and dimethyl formamide.

The step of latex process for dispersing and effect, and the case description that can carry latex is at United States Patent (USP) 4,199 are on 363 and Deutsches Reichs-Patent application (DLS) No.2,541,274 and 2,541,230.

The present invention can be used for various color sensitive materials.The example of photosensitive material is the colour negative that is used for general service or film, the colour reversal film that is used for magic lantern or TV, colour paper, colour positive and colour reversal photographic paper.

Containing transparent carrier and on carrier, having in the color sensitive material of the silver of one deck sensitization fontanelization at least emulsion layer, contained 50%(weight in the best described emulsion layer) or more silver halide particles be the silver halide particle that constitutes silver emulsion, this emulsion is to be prepared by the method for preparing silver emulsion, and wherein reduction sensitization is to carry out in the process of preparation silver emulsion with at least a ascorbic acid and derivant thereof.

When the present invention was used as photochromatic material, the present invention can be used for having the photosensitive material of various structures and has layer structure and the photosensitive material of specific color material combination.

Typical example is: a kind of photosensitive material, wherein the quality speed of colour former agent or diffusive merge mutually with layer structure, as described in JP-B-47-49031, JP-B-49-3843, JP-B-50-21248, JP-A-59-38147, JP-A-59-60437, JP-A-60-227256, JP-A-61-4043, JP-A-61-43743 and JP-A-61-42657 document; A kind of photosensitive material, wherein the single color photographic layer can be divided into two or three layers, and as JP-B-49-15495 and United States Patent (USP) 3,843,469 is described; A kind of photosensitive material, wherein high and low photographic layer or have the arranging and determine of layer of different color sensitive degree is as described in JP-B-53-37017, JP-B-53-37018, JP-A-51-49027, JP-A-54-143016, JP-A-53-97424, JP-A-53-97831, JP-A-62-200350 and JP-A-59-177551.

Be applicable to that carrier example of the present invention is disclosed in above-mentioned document RD.No.17643,28 pages and R.D.No.18716, page left hurdle, 647 pages of right hurdles-648.

The preparation of colour photographic sensitive material of the present invention is according to for example above-mentioned document

R.D.No.17643,28 pages-29 pages and R.D.No.18716,651 pages of L-R hurdles are described to carry out.

The used color developer of the development of photosensitive material of the present invention even more preferably contains the aqueous alkali that key component is an aromatic primary amido color developer.As color developer,, more preferably be to use the p-phenylenediamine (PPD) compounds though the amino-phenol based compound is effectively.The representative instance of p-phenylenediamine (PPD) compounds is 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-beta-hydroxyethyl aniline, 3-methyl-4-amino-N-ethyl-N-β-methylsulfonyl amido ethylaniline, 3-methyl-4-amino-N-ethyl-N-'beta '-methoxy ethylaniline and their hydrosulphate, hydrochloride and right-pyrovinic acid thing.These compounds can according to they application and two kinds or multiple merging are used.

Usually, color developer contains pH buffering agent such as alkali-metal carbonate, borate or phosphate, development restrainer or antifoggant such as bromide, iodide, benzimidazole, benzothiazole or sulfhydryl compound.If desired, color developer also can contain protective agent such as azanol, diethyl hydroxylamine, sulphurous acid hydrazine, phenyl-semicarbazide, triethanolamine, catechol sulfonic acid or triethylenediamine (1,4-phenodiazine two heterocycles (2,2,2) octane); Organic solvent such as 1,2 ethylene glycol or diethylene glycol; Development accelerant such as phenmethylol, polyglycol, tertiary ammonium salt or amine; Colour coupler; The competition colour coupler; Fogging agent such as sodium borohydride; Auxiliary developer such as 1-phenyl-3-pyrazolidone; Viscosity agent; With sequestrant such as aminopolycanboxylic acid, aminopolyphosphonic acid, alkyl phosphonic acid or phosphono-carboxylic acids.The example of sequestrant is inferior ethylenediamine tetraacetic acid, nitrilotriacetic acid(NTA), diethylene-triamine pentaacetic acid, 1,2-diaminocyclohexane tetraacetic acid, hydroxyethylamino-diacetic acid, 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid, nitrilo--N, N, N-trimethylene phosphonic, ethylene diamine-N, N, N ', N '-tetramethylene phosphonic acid and ethylene diamine-two (0-hydroxyphenyl acetate) and its salt.

In order to carry out discharged-area development, carry out Hei-Bai earlier and develop, carry out colour development then.As Hei-Bai developer, the Hei that knows very much-Bai developer is dihydroxy benzenes such as quinhydrones for example, 3-pyrazolidone such as 1-phenyl-3-pyrazolidone, amino-phenol such as N-methyl-p-aminophenol, these black-and-white development agent can be used separately, or two kinds or multiple merging use.

The pH value of color developer and black-and-white development is generally 9-12.Though the magnitude of recruitment of developer depends on colour photographic sensitive material to be developed, every square metre of photosensitive material of generalized case is 3 liters or still less.Along with the decline of bromide ion concentration in the make-up solution, magnitude of recruitment can be reduced to 500ml or still less.In order to reduce magnitude of recruitment, be preferably the processing jar and the surface of contact of air are reduced to avoid evaporating and to contact the back solution oxide with air.Use a kind of method of controlling bromide ion amount of savings in the developer to reduce magnitude of recruitment.

The colour development time is generally 2-5 minute.But this development time can shorten with high temperature and high pH value and with the high concentration developer.

Photographic emulsion layer generally will be bleached after colour development.Bleaching is handled and promptly can be carried out simultaneously with photographic fixing (bleaching a photographic fixing), also can carry out respectively.In addition, in order to improve process velocity, blix can carry out after bleaching.Also have, this processing procedure can be carried out in the bleaching-stop bath in two continuous jar, and according to application, photographic fixing can be carried out before bleaching-photographic fixing, perhaps bleached after bleaching-photographic fixing and carried out.The example of bleaching agent is polyvalent metal compounds such as iron (III), cobalt (III), chromium (VI) and copper (II); Superoxide; Quinone; Or nitro compound.The representative instance of bleaching agent is a ferricyanide; Dichromate; The organic complex salt of iron (III) or cobalt (III) such as aminopolycanboxylic acid's complex salt such as ethylene diaminetetraacetic acid, diethylene-triamine pentaacetic acid, 1,2-diaminocyclohexane tetraacetic acid, methylene imine oxalic acid and 1,3-diaminopropanetetraacetic acid and glycoletherdiaminotetraacetic acid, or the complex salt of citric acid, tartrate or malic acid; Persulfate; Bromide; Permanganate; And nitrobenzene.In these compounds, iron (III) complex salt and the persulfate of aminopolycanboxylic acid's iron (III) complex salt such as inferior ethylenediamine tetraacetic acid are better, because they can improve process velocity and prevent the pollution of the environment.Aminopolycanboxylic acid's iron (III) complex salt all is effective in liquid lime chloride and bleaching-photographic fixing solution.Used aminopolycanboxylic acid's the bleaching of iron (III) complex salt or the pH value of bleaching-photographic fixing solution to be generally 5.5-8.But in order to improve process velocity, these processes can be carried out under low pH value.

If desired, can in liquid lime chloride, bleaching-photographic fixing solution and their prefabricated solution, use bleach boosters.Effective case description of bleach boosters is as United States Patent (USP) 3,893, on 858.Be described in United States Patent (USP) 4,552,834 compound also is preferably.These bleach boosters can be added in the photosensitive material.These bleach boosters are effective especially in the bleaching-photographic fixing of photograph color sensitive material.

The example of fixer is thiosulfate, thiocyanate, thioether group compound, thiocarbamide and a large amount of iodide.In these compounds, thiosulfate particularly ATS (Ammonium thiosulphate) is to use in bigger range of application.As the protective agent of bleaching-photographic fixing solution, sulphite, hydrosulfite or carbonyl bisulfite adduct are preferably.

Sensitive photographic material of the present invention washs after the desilverization and/or stabilization usually.The water yield used in washing step can be selected in a big way, this depend on temperature, the water pot of application, the washings of performance (as material therefor such as the determined performance of colour coupler), the photographic material of photosensitive material quantity (how many steps), represent the additional step of drag flow or adverse current and other condition.Relation is by " Journal of the Society of Motion Picture and Television Engineers " 64 volumes between the quantity of the consumption of water and water pot in the approach of multistep adverse current, and the described method of 248-253 page or leaf (May nineteen fifty-five) is determined.

According to above-mentioned multistep adverse current approach, the water yield that is used for washing can reduce widely.Because washings rest on the long duration in the jar, still, undesirable bacterium breeds at double and unsteady material contacts with photosensitive material.In order to solve these problems in colour photographic sensitive material processing of the present invention, can use the method that reduces calcium and magnesium ion very effectively, as described in JP-A-61-131632.In addition, can use germifuge such as isothiazolone compounds and cyabendazole, described in JP-A-57-8542, the sodium isocyanurate of chlorine series bactericidal agent such as chlorination, as the benzotriazole germifuge, at Hiroshi Horignchi, " Chemistry of Antibacterial and Antifungal Agents ", Eiseigijutsu-Kad ed., " Sterilization; Antibacterial; and Antifungal Technignes for Microorganisms ", Nippon Bokin Bokabi Gakkai ed. describes on " Cyclopedia of Antibacterial and Antifungal Agents " to some extent.

The pH value of the water of washing sensitive photographic material of the present invention is 4-9, is preferably 5-8.Water temperature and wash time can change according to the performance and the application of photosensitive material.Generally speaking, wash time is under 15-45 ℃ of temperature 20 seconds to 10 minutes, even more preferably under 25 ℃ of-40 ℃ of temperature 30 seconds to 5 minutes.Available stabilizing agent is directly handled photosensitive material of the present invention, to replace washing operation.This stabilization processes is known, is described on JP-A-57-8543, JP-A-58-14834 and the JP-A-60-220345.

Stabilization processes is to carry out after washing sometimes.For example, stabilizing solution can contain the final treating fluid that preparation and surfactant are used as the photograph color sensitive material.In stabilizing solution, also can add various sequestrants or germifuge.

The overflow of the additional generation of washing and/or stabilizing solutions can reuse in other step such as desilverization step.

In order to simplify processing procedure and speed up processing, silver-halide color photoelement of the present invention can contain color developer.

Quicken colour development if desired, silver-halide color photoelement of the present invention can contain various 1-phenyl-3-pyrazolidone.The representative instance of this compound is described on JP-A-56-64339, JP-A-57-144547 and the JP-A-58-115438.

In the present invention, every kind for the treatment of fluid can use under 10 ℃ of-50 ℃ of temperature.Though common treatment temperature is 33 ℃-38 ℃, under higher temperature, can quickens processing with the shortening processing time, and can improve the stability of image quality or treating fluid at a lower temperature.In order to save the silver of photosensitive material, the available cobalt thickening is handled or is handled with the hydrogen peroxide thickening, as Deutsches Reichs-Patent 2,226, and 770 or United States Patent (USP) 3,674,499 is described.

Photosensitive silve halide material of the present invention also can be used for heat developing photo sensitive material, as United States Patent (USP) 4,500, and 626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056 and EP210,660A2 is described.

The present invention will be with following example more detailed description.

Example 1:

Two two-ling grains are used as crystal seed, this pair two-ling grain comprises the iodine silver bromide, average iodine content is 24mol%, and average bulb diameter of equal value is 0.8 μ m, with the double-jet method of controlling this crystal grain is formed emulsion in aqueous gelatin solution, this emulsion comprises the two-ling grain, this crystal grain comprises the iodine silver bromide, and average bulb diameter of equal value is 1.2 μ m, and core is 1: 2 with the shell ratio, content of iodine is 2mol% in the shell, and average iodine content is 10mol%.

After forming grain, emulsion is at 40 ℃, pAg be 8.9 and pH carry out conventional desalting/wash and dispersion again under 6.3 the condition, thereby made emulsion Em-1.With listed thiosulfuric acid compound 1-2 in the Table A, 1-6 and 1-16 join respectively in the reactor, and addition is listed in table 1-1, begins into shell after 1 minute, forms until particle, thereby makes emulsion Em-2～Em-4.

Table 1-1

The addition of every mole of Ag of emulsion thiosulfuric acid compound

Em-2 1-2 3×10 ^-5mol

Em-3 1-6 3×10 ^-5mol

Em-4 1-16 3×10 ^-5mol

Form particle according to the method identical, at this moment add reduction sensitization agent A-1(L-ascorbic acid with the listed addition of table 1-2 with Em-1) and tin chloride, begin to form shell after 1 minute, thereby make emulsion Em-5 and Em-6.

Table 1-2

The addition of every mole of Ag of emulsion reduction sensitization agent

Em-5 L-ascorbic acid 2 * 10 ^-3Mol

Em-6 tin chloride (II) 1 * 10 ^-5Mol

Form according to carrying out particle with the same procedure of Em-1, at this moment add thiosulfuric acid compound 1-2,1-6 and 1-16, begin to form shell after 1 minute, become back 1 minute at hull shape, add the preferred amounts of reduction sensitization agent L-ascorbic acid and tin chloride, thereby made contrast emulsion Em-7～Em-12 of the present invention and Comparative Examples, list in table 1-3.

Table 1-3

Every mole of Ag of every mole of Ag thiosulfuric acid of emulsion reduction sensitization agent

The addition of addition compound

Em-7 L-ascorbic acid 2 * 10 ^-3Mol 1-2 3 * 10 ^-5Mol

Em-8 L-ascorbic acid 2 * 10 ^-3Mol 1-6 3 * 10 ^-5Mol

Em-9 L-ascorbic acid 2 * 10 ^-3Mol 1-16 3 * 10 ^-5Mol

Em-10 tin chloride 1 * 10 ^-5Mol 1-2 3 * 10 ^-5Mol

Em-11 tin chloride 1 * 10 ^-5Mol 1-6 3 * 10 ^-5Mol

Em-12 tin chloride 1 * 10 ^-5Mol 1-16 3 * 10 ^-5Mol

According to the present invention of above-mentioned method preparation and the emulsion Em-1～Em-12 of Comparative Examples, carry out best gold with sodium thiosulfate and gold chloride and add sulphur sensitizing, thereby make emulsion.

Emulsion and protective seam coating with the listed consumption of table 1-4 are having on the tri acetyl cellulose membrane carrier of substrate layer.

Table 1-4

(1) emulsion layer

Emulsion layer ... emulsion 1-12 is shown in table 1-1～1-3

Colour coupler (silver: 1.7 * 10 ^-2Mol/m ²)

（1.5×10 ^-3mol/m ²）

Tricresyl phosphate (1.10g/m ²)

Gelatin (2.30g/m ²)

(2) protective seam

2,4-dichlorotriazine-6-hydroxyl-S-triazine sodium salt (0.08g/m ²)

Gelatin (1.80g/m ²)

These samples are carried out the sensitometry exposure, thereby carry out following colour development.

The sample of handling is carried out density measurement with green filter.The photographic property of gained the results are shown in table 1-5.

Under 38 ℃ of temperature, develop under the following condition.

1) colour development is 2 minutes and 45 seconds

2) bleaching is 6 minutes and 30 seconds

3) washing is 3 minutes and 15 seconds

4) photographic fixing is 6 minutes and 30 seconds

5) washing is 3 minutes and 15 seconds

6) stabilization is 3 minutes and 15 seconds

The treating fluid that is used for above-mentioned steps is composed as follows:

Color developer:

Sodium nitrilo triacetate 1.4g

Sodium sulphite 4.0g

Sodium carbonate 30.0g

Potassium bromide 1.4g

Hydroxylamine sulfate 2.4g

4-(N-ethyl-N-β-hydroxyethylamino)-2-methyl-aniline hydrosulphate 4.5g

Add water to 1 liter

Liquid lime chloride:

Sodium bromide 160.0g

Ammoniacal liquor (28%) 25.0ml

The inferior edetate trihydrate of iron (III) sodium 130g

Glacial acetic acid 14ml

Add water to 1 liter

Photographic fixing solution:

Four polyphosphonic acid sodium 2.0g

Sodium sulphite 4.0g

Sodium thiosulfate (700g/l) 175.0ml

Sodium bisulfite 4.6g

Add water to 1 liter

Stabilizing solutions:

Formalin 8.0ml

Add water to 1 liter

In such cases, normal wedge exposure was carried out 10 seconds and 1/100 second.

With filter light source being regulated color temperature is 4,800 ° of K, and blue light extracts with blue filter (trade mark is BPN42, and Fuji Photo film Co.Ltd. makes).Light sensitivity is to be that 0.2 Fog density point is compared with optical density (OD).Photonasty is listed by relative sensitivity, and relative sensitivity is that the light sensitivity with emulsion Em-1 sample is that 100(is 100 to 1/100 " and 10 ") estimate.Each Fog density value is that the value and 1/100 " with 10 " corresponding to non-exposed portion is identical.

Shown in table 1-5, every kind of emulsion of the present invention all has low Fog density and ISO (under the particularly low intensive situation).

The sample 1-12 that has been coated with emulsion 1-12 was worn out 12 months in environment, and environment temperature is 25 ℃, and humidity is 60%.Carry out the sensitometry test according to above-mentioned identical method then.The result represents with relative sensitivity, lists in table 1-6, and relative sensitivity is according to before not aging, and the light sensitivity of sample 1 is 100 to estimate.Be coated with each sample of emulsion of the present invention, the rising of aging back sensitivity decrease and Fog density is all very little, thereby has bin stability preferably.

Table 1-5

Example 1/100 " light sensitivity 10 " light sensitivity Fog density mark

1 100 100 0.20 control sample

2????83????78????0.18????″

3????81????75????0.19????″

4????75????70????0.18????″

5 121 130 0.19 the present invention

6 100 104 0.29 control sample

7 130 140 0.19 the present invention

8????128????135????0.18????″

9????126????133????0.18????″

10 120 126 0.23 control sample

11????120????126????0.22????″

12????115????120????0.26????″

Table 1-6

Example 1/100 " light sensitivity 10 " light sensitivity Fog density mark

1* 100 100 0.20 control sample

1????95????93????0.21????″

2????82????76????0.17????″

3????80????73????0.17????″

4????73????68????0.17????″

5 120 128 0.19 the present invention

6 90 95 0.45 control sample e

7 129 140 0.19 the present invention

8????128????133????0.19????″

9????124????132????0.18????″

10 101 110 0.33 control sample

11????98????105????0.34????″

12????95????103????0.36????″

* represent the result who carries out the sensitometry test immediately after the coating

When every kind of ascorbic acid compound A-2～A-10 carried out identical test, gained came to the same thing.

Example 2

Same procedure according to example 1 described preparation emulsion prepares emulsion, according to time every mole of Ag adding 2 * 10 of following adding ^-3Mol L-ascorbic acid, thus make emulsion.Simultaneously, when forming particle, begin to form shell preceding 1 minute, form behind the particle and before the washing, add every mole of Ag3 * 10 ^-5Mol thiosulfuric acid compound 1-2, thus emulsion made.

The joining day of L-ascorbic acid:

A: before beginning to form particle

B: begin to form behind the shell 1 minute

C: form behind the shell immediately

D: the effect of beginning chemical sensitization immediately before

The joining day of thiosulfuric acid compound:

A: begin to form preceding 1 minute at shell

B: hull shape becomes before back and the washing

The most handy gold of emulsion of preparation adds sulphur and carries out chemical sensitization, to make the listed emulsion 13-24 of table 2-1.

Table 2-1

Emulsion L-thiosulfuric acid joining day ascorbic acid joining day

13 a do not add

14????″????A

15????″????B

16 b do not add

17????b????A

18????″????B

19 C do not add

20????″????A

21????″????B

22 d do not add

23????″????A

24????″????B

These emulsions according to the identical method coating of example 1, carrying out sensitometry research, thereby are obtained showing the listed result of 2-2.Be similar to example 1, light sensitivity is by relative sensitivity estimation, and relative sensitivity is assumed to and is subjected to light sensitivity that gold adds the Em-1 of sulphur sensibilization is 100 to estimate.

Table 2-2

Example 1/100 " light sensitivity 10 " light sensitivity Fog density mark

13 115 120 0.21 the present invention

14????125????130????0.20????″

15????113????120????0.20????″

16????121????130????0.19????″

17????130????140????0.19????″

18????126????133????0.20????″

19????115????123????0.22????″

20 120 126 0.21 the present invention

21????120????122????0.21????″

22????110????115????0.22????″

23????116????121????0.22????″

24????115????120????0.20????″

1 100 100 0.20 control sample

In this case, the preparation of emulsion Em-16 and Em-17 is to add identical ascorbic acid and thiosulfuric acid (I-2) identical with the preparation of emulsion Em-5 and the Em-7 respectively time to carry out.Shown in table 1-5 and 2-2, emulsion Em-16 has identical light sensitivity and Fog density with Em-5 and emulsion Em-17 respectively with Em-7.Just, effect of the present invention is that good repeatability is arranged very much.As show shown in the 2-2, each emulsion of the present invention has ISO and low Fog density.When every kind of coating sample wears out according to example 1 identical method, estimate its photographic property, the result is identical with example 1 gained.

Example 3

Following dyestuff is joined in the chemical sensitization emulsion of example 1 preparation shown in the table 3-1, thereby make spectral sensitization emulsion.

The emulsion that makes is according to the same procedure coating of example 1, to carry out the sensitometry test.

The dyestuff that dye set 1(sense is red)

Sensitizing dye IX 5.4 * 10 ^-5Mol/mol Ag

Sensitizing dye II 1.4 * 10 ^-5Mol/mol Ag

Sensitizing dye III 2.4 * 10 ^-4Mol/mol Ag

Sensitizing dye IV 3.1 * 10 ^-5Mol/mol Ag

The dyestuff that dye set 2(sense is green)

Sensitizing dye V 3.5 * 10 ^-5Mol/mol Ag

Sensitizing dye VI 8.0 * 10 ^-5Mol/mol Ag

Sensitizing dye VII 3.0 * 10 ^-4Mol/mol Ag

Dye set (dyestuff that sense is blue)

Sensitizing dye VIII 2.2 * 10 ^-4Mol/mol Ag

Table 3-1

The non-sensitizing emulsion of spectral sensitization emulsion chemical sensitization and spectrum sensitizing dye group

Em-25????Em-1????1

″????26????″????2

″????27????″????3

″????28????″????1

″????29????″????2

″????30????″????3

″????31????Em-7????1

″????32????″????2

″????33????″????3

Carry out the sensitometry test according to example 1 described identical method, difference is that to add thoughts red or feel green dyestuff emulsion (trade mark is SC-52 with yellow filter, Fuji Photo film Co.Ltd. makes) exposure, replaced the used blue filter of example 1, the emulsion that is added with blue-sensitive dye exposes without filter.Table 3-2 represents the light sensitivity of Em-28～Em-33, be relative sensitivity, with the light sensitivity of the Em-25, the Em-26 that are respectively 10 seconds and 1/100 second exposure and Em-27 is 100 to estimate that every kind of Fog density is identical corresponding to non-exposed portion and 1/100 " with 10 ".

Table 3-2

Emulsion 1/100 " light sensitivity 10 " light sensitivity Fog density mark

Em-25 100 100 0.22 control sample

26????100????100????0.21????″

27????100????100????0.20????″

28 112 120 0.21 the present invention

29????115????122????0.20????″

30????120????130????0.19????″

31????115????120????0.20????″

32????120????125????0.19????″

33????125????135????0.20????″

As show shown in the 3-2, every kind of emulsion of the present invention has ISO and low Fog density behind spectral sensitization.

Example 4

The laminated coating that will have following composition is coated on the tri acetyl cellulose membrane carrier of backing layer, to make multi layer colour photosensitive material sample.

Photographic layer is formed:

Consumption g/m corresponding to each component ²Be the unit representation coated weight.The coated weight of fontanel silver is with g/m ²The unit representation of silver.The coated weight of sensitizing dye is unit representation with the molar weight with every mole of fontanel silver in one deck.

Sample:

Layer 1: antihalation layer

Black colloidal silver silver 0.18

Gelatin 1.40

Layer 2: middle layer

2,5-two uncle's valeryl quinhydrones 0.18

EX-1????0.07

EX-3????0.02

EX-12????0.002

U-1????0.06

U-2????0.08

U-3????0.10

HBS-1????0.10

HBS-2????0.02

Gelatin 1.04

3: the first magenta-sensitive emulsion layer of layer

(silver iodide are 6mol% to single dispersion iodine silver bromide emulsion, particle mean size

Be 0.6 μ m, the running parameter of granularity is 0.15) silver 0.55

Sensitizing dye I 6.9 * 10 ^-5

Sensitizing dye II 1.8 * 10 ^-5

Sensitizing dye III 3.1 * 10 ^-4

Sensitizing dye IV 4.0 * 10 ^-5

EX-2????0.350

HBS-1????0.005

EX-10????0.020

Gelatin 1.20

4: the second magenta-sensitive emulsion layer of layer

Plain film shape iodine silver bromide emulsion (silver iodide are 10mol%, and particle mean size is 0.7 μ m, and average aspect ratio is 5.5, and average thickness is 0.2 μ m) silver 1.0

Sensitizing dye I 5.1 * 10 ^-5

Sensitizing dye II 1.4 * 10 ^-5

Sensitizing dye III 2.3 * 10 ^-4

Sensitizing dye IV 3.0 * 10 ^-5

EX-2????0.400

EX-3????0.050

EX-10????0.015

Gelatin 1.30

5: the three magenta-sensitive emulsion layer of layer

The iodine silver bromide emulsion I

Silver 1.60

EX-3????0.240

EX-4????0.120

HBS-1????0.22

HBS-2????0.10

Gelatin 1.63

Layer 6: middle layer

EX-5????0.040

HBS-1????0.020

Gelatin 0.80

7: the first green-sensitive emulsion layer of layer

Plain film shape iodine silver bromide emulsion (silver iodide are 6mol%, and particle mean size is 0.6 μ m, and average aspect ratio is 6.0, and average thickness is 0.15 μ m)

Silver 0.40

Sensitizing dye V 3.0 * 10 ^-5

Sensitizing dye VI 1.0 * 10 ^-4

Sensitizing dye VII 3.8 * 10 ^-4

EX-6????0.260

EX-1????0.021

EX-7????0.030

EX-8????0.025

HBS-1????0.100

HBS-4????0.010

Gelatin 0.75

8: the second green-sensitive emulsion layer of layer

Single iodine silver bromide emulsion (silver iodide are 9mol%, and particle mean size is 0.7 μ m, and the variation factor of granularity is 0.18) that disperses

Silver 0.80

Sensitizing dye V 2.1 * 10 ^-5

Sensitizing dye VI 7.0 * 10 ^-5

Sensitizing dye VII 2.6 * 10 ^-4

EX-6????0.180

EX-1????0.008

EX-7????0.012

HBS-1????0.160

HBS-4????0.008

Gelatin 1.10

9: the three green-sensitive emulsion layer of layer

The iodine silver bromide emulsion II

Silver 1.2

EX-6????0.065

EX-11????0.030

EX-1????0.025

HBS-1????0.25

HBS-2????0.10

Gelatin 1.74

Layer 10: yellow filter layer

Yellow colloidal silver silver 0.05

EX-5????0.08

HBS-3????0.03

Gelatin 0.95

11: the first blue-sensitive emulsion layer of layer

Plain film shape iodine silver bromide emulsion (silver iodide are 6mol%, and particle mean size is 0.6 μ m, and average aspect ratio is 5.7, and average thickness is 0.15 μ m)

Silver 0.24

Sensitizing dye VIII 3.5 * 10 ^-4

EX-9????0.85

EX-8????0.12

HBS-1????0.28

Gelatin 1.28

12: the second blue-sensitive emulsion layer of layer

Single iodine silver bromide emulsion (silver iodide are 10mol%, and particle mean size is 0.8 μ m, and the variation factor of granularity is 0.16) that disperses

Silver 0.45

Sensitizing dye VIII 2.1 * 10 ^-4

EX-9????0.20

EX-10????0.015

HBS-1????0.03

Gelatin 0.46

13: the three blue-sensitive emulsion layer of layer

The iodine silver bromide emulsion III

Silver 0.77

EX-9????0.20

HBS-1????0.07

Gelatin 0.69

14: the first protective seam of layer

Iodine silver bromide emulsion (silver iodide are 1mol%, and particle mean size is 0.07 μ m)

Silver 0.5

U-4????0.11

U-5????0.17

HBS-1????0.90

Gelatin 1.00

15: the second protective seam of layer

Polymethacrylate grain (diameter is about 1.5 μ m) 0.54

S-1????0.15

S-2????0.05

Gelatin 0.72

Except said components, can add gelatin hardener H-1 and/or surfactant in every layer.

The molecular formula of compound used therefor is listed in table B.

Sample 401-403 prepares according to the same procedure that said sample prepares, and difference is the iodine silver bromide emulsion I in layer 5,9 and 13, and II and III change respectively.

These samples carry out the sensitometry exposure to carry out following colour development.

The sample of handling carries out density measurement with the red, green and blue filter.Gained the results are shown in table 4-1.

The result of photographic property is red with sense, sense is green and the relative sensitivity of the blue layer of sense is represented, relative sensitivity is that the light sensitivity with sample 401 is 100 to estimate.Disposal route:

The colour development process is to carry out with the following step under 38 ℃ of temperature.

Colour development 3 minutes and 15 seconds

Bleached 6 minutes and 30 seconds

Washed 2 minutes and 10 seconds

Photographic fixing 4 minutes and 20 seconds

Washed 3 minutes and 15 seconds

Stabilization 1 minute and 05 second

Used treating fluid component is as follows in each step:

Colour development solution

Diethylene-triamine pentaacetic acid 1.0g

1-hydroxyl ethylidene-1,1-di 2 ethylhexyl phosphonic acid 2.0g

Sodium sulphite 4.0g

Sal tartari 30.0g

Potassium bromide 1.4g

Potassium iodide 1.3mg

Hydroxylamine sulfate 2.4g

4-(N-ethyl-N-β-hydroxyethylamino)-2-methylsulfuric acid aniline 4.5g

Add water to 1 liter

pH????10.0

Bleaching liquid

Ethylene diaminetetraacetic acid iron ammonium 100.0g

Ethylidene tetraacethyl disodium 10.0g

Ammonium bromide 150.0g

Ammonium nitrate 10.0g

Add water to 1 liter

pH????6.0

Stop bath

Ethylene diaminetetraacetic acid disodium 1.0g

Sodium sulphite 4.0g

Thiosulfuric acid aqueous ammonium (70%) 175.0ml

Sodium bisulfite 4.6g

Add water to 1 liter

pH????6.6

Stabilizing solutions

Formalin (40%) 2.0ml

Polyoxyethylene-to single nonylplenyl ether (average degree of polymerization is 10) 0.3g

Add water to 1.0 liters

Shown in table 4-1, emulsion of the present invention has the effect that has improved light sensitivity, and Fog density does not increase.

After wearing out according to example 1 identical method, check photographic property, have bin stability preferably with emulsion sample of the present invention.

Example 5:

Sample 401-403 of the present invention exposes according to example 4 described identical methods with Comparative Examples, carries out following processing with automatic processing machine:

The step time-temperature

38 ℃ of colour developments 3 minutes and 15 seconds

Bleach 1 minute 00 second 38 ℃

38 ℃ of bleaching-photographic fixing 3 minutes and 15 seconds

Wash (1) 40 second 35 ℃

Wash (2) 1 minutes 00 second 35 ℃

38 ℃ of stabilizations 40 seconds

Dry 1 minute and 15 seconds 55 ℃

The treating fluid component is as described below

Colour developing solution (g)

Diethylene-triamine pentaacetic acid 1.0

1-hydroxyl ethylidene-1,1-di 2 ethylhexyl phosphonic acid 3.0

Sodium sulphite 4.0

Sal tartari 30.0

Potassium bromide 1.4

Potassium iodide 1.5mg

Hydroxylamine sulfate 2.4

4-(N-ethyl-N-(beta-hydroxyethyl) amino)-2-methylsulfuric acid aniline 4.5

Add water to 1.0 liters

pH????10.05

Bleaching liquid (g)

Ethylene diaminetetraacetic acid iron ammonium dihydrate 120.0

Ethylene diaminetetraacetic acid disodium 10.0

Ammonium bromide 100.0

Ammonium nitrate 10.0

Bleach boosters 0.005mol

Ammoniacal liquor (27%) 15.0ml

Add water to 1 liter

pH????6.3

Bleaching-stop bath (g)

Ethylene diaminetetraacetic acid iron ammonium dihydrate 50.0

Ethylene diaminetetraacetic acid disodium 5.0

Sodium sulphite 12.0

Thiosulfuric acid aqueous ammonium (70%) 240.0ml

Ammoniacal liquor (27%) 6.0ml

Add water to 1.0 liters

pH????7.2

Cleansing solution

Tap water is packed in the mixed bed column, and this post is equipped with H type strong-acid cation-exchange resin (Amberlite IR-120B, Rohm ﹠amp; Haas Co. makes) and OH type alkalescence anion-exchange resin (Amberlite IR-400), with must calcium and magnesium density be 3mg/l or still less.Then, add 20mg/l sodium isocyanurate dichloride and 0.15g/l sodium sulphate.The pH value of solution is 6.5-7.5.

Stabilizing solution (g)

Formalin (37%) 2.0ml

Polyoxyethylene-to single nonylplenyl ether (average degree of polymerization is 10) 0.3

Ethylene diaminetetraacetic acid disodium 0.05

Add water to 1 liter

pH????5.0-8.0

After carrying out above-mentioned processing, sample 402 of the present invention and 403 has with the identical good effect of example 4.

Example 6

Sample 401-403 of the present invention exposes according to example 4 identical methods with Comparative Examples, and presses following processing with automatic processing machine.

Disposal route:

The step time-temperature

40 ℃ of colour developments 2 minutes and 30 seconds

40 ℃ of bleaching-photographic fixing 3 minutes and 00 second

Wash (1) 20 second 35 ℃

Wash (2) 20 seconds 35 ℃

35 ℃ of stabilizations 20 seconds

Dry 50 seconds 65 ℃

Treating fluid is composed as follows described:

Colour developing solution (g)

Diethylene-triamine pentaacetic acid 2.0

1-hydroxyl ethylidene-1,1-di 2 ethylhexyl phosphonic acid 3.0

Sodium sulphite 4.0

Sal tartari 30.0

Potassium bromide 1.4

Potassium iodide 1.5mg

Hydroxylamine sulfate 2.4

4-(N-ethyl-N-(beta-hydroxyethyl) amino)-2-methylsulfuric acid aniline 4.5

Add water to 1 liter

pH????10.05

Bleaching-stop bath

Ethylene diaminetetraacetic acid ferrisodium dihydrate 50.0

Ethylene diaminetetraacetic acid disodium 5.0

Sodium sulphite 12.0

Thiosulfuric acid aqueous ammonium (70%) 260.0ml

Acetate (98%) 5.0ml

Bleach boosters 0.01mol

Add water to 1.0 liters

Cleansing solution

Tap water is packed in the mixed bed column, and this post is equipped with H type strong-acid cation-exchange resin (Amberlite IR-1208, Rohm ﹠amp; Haas Co. makes) and OH type alkalescence anion-exchange resin (Amberlite IR-400), to transfer to such an extent that calcium and magnesium density are 3mg/l or still less.Then, add 20mg/l sodium isocyanurate dichloride and 0.15g/l sodium sulphate.The pH value of solution is 6.5-7.5.

Stabilizing solution (g)

Formalin (37%) 2.0ml

Polyoxyethylene-to single nonylplenyl ether (average degree of polymerization is 10) 0.3

Ethylene diaminetetraacetic acid disodium 0.05

Add water to 1 liter

pH????5.0-8.0

Through after the above-mentioned processing, sample 402 of the present invention and 403 has with the identical good effect of example 4.

Example 7

To be coated on the tri cellulose acetate membrane carrier of backing layer by the following laminated coating of forming, make multi layer colour photosensitive material sample.

The composition of photographic layer

Consumption is with g/m ²Be unit.The coating amount g/m of fontanelization silver and colloid glue ²Silver be unit representation, the consumption of sensitizing dye is used in the molal quantity of every mole of fontanel silver in the identical layer and represents.

Layer 1: antihalation layer

The black collargol

Coating silver amount 0.2

Gelatin 2.2

UV-1????0.1

UV-2????0.2

Cpd-1????0.05

Solv-1????0.01

Solv-2????0.01

Solv-3????0.08

Layer 2: middle layer

Silver bromide particulate (the ball equivalent diameter is 0.07 μ m)

Coating silver consumption 0.15

Gelatin 1.0

Cpd-2????0.2

3: the first magenta-sensitive emulsion layer of layer

Iodine silver bromide emulsion (AgI is 10.0mol%, and inner high AgI type, ball equivalent diameter are 0.7 μ m, and the variation factor of ball equivalent diameter is 14%, tetrakaidecahedron shape particle)

Coating silver amount 0.26

Iodine silver bromide emulsion (AgI is 4.0mol%, and inner high AgI type, ball equivalent diameter are 0.4 μ m, and the variation factor of ball equivalent diameter is 22%, tetrakaidecahedron particle)

Coating silver amount 0.2

Gelatin 1.0

EXS-1 4.5×10 ^-4

EXS-2 1.5×10 ^-4

EXS-3 0.4×10 ^-4

EXS-4 0.3×10 ^-4

EXC-1????0.33

EXC-2????0.009

EXC-3????0.023

EXC-6????0.14

4: the second magenta-sensitive emulsion layer of layer

Iodine silver bromide emulsion (AgI is 16mol%, and inner high AgI type, ball equivalent diameter are 1.0 μ m, and the variation factor of ball equivalent diameter is 25%, plain film shape particle, diameter/thickness is 4.0)

Coating silver amount 0.55

Gelatin 0.7

EXS-1 3×10 ^-4

EXS-2 1×10 ^-4

EXS-3 0.3×10 ^-4

EXS-4 0.3×10 ^-4

EXC-3????0.05

EXC-4????0.10

EXC-6????0.08

5: the three magenta-sensitive emulsion layer of layer

Iodine silver bromide emulsion I (inner high AgI type, ball equivalent diameter are 1.2 μ m, and the variation factor of ball equivalent diameter is 28%)

Coating silver amount 0.9

Gelatin 0.6

EXS-1 2×10 ^-4

EXS-2 0.6×10 ^-4

EXS-3 0.2×10 ^-4

EXC-4????0.07

EXC-5????0.06

Solv-1????0.12

Solv-2????0.12

Layer 6: middle layer

Gelatin 1.0

Cpd-4????0.1

7: the first green-sensitive emulsion layer of layer

Iodine silver bromide emulsion (AgI is 10.0mol%, and inner high AgI type, ball equivalent diameter are 0.7 μ m, and the variation factor of ball equivalent diameter is 14%, tetrakaidecahedron particle)

Coating silver amount 0.2

Iodine silver bromide emulsion (AgI is 4.0mol%, and inner high AgI type, ball equivalent diameter are 0.4 μ m, and the variation factor of ball equivalent diameter is 22%, tetrakaidecahedron particle)

Coating silver amount 0.1

Gelatin 1.2

EXS-5 5×10 ^-4

EXS-6 2×10 ^-4

EXS-7 1×10 ^-4

EXM-1????0.41

EXM-2????0.10

EXM-5????0.03

Solv-1????0.2

Solv-5????0.03

8: the second green-sensitive emulsion layer of layer

Iodine silver bromide emulsion (AgI is 10mol%, and inner high AgI type, ball equivalent diameter are 1.0 μ m, and the variation factor of ball equivalent diameter is 25%, and the diameter/thickness ratio is 3.0)

Coating silver amount 0.4

Gelatin 0.35

EXS-5 3.5×10 ^-4

EXS-6 1.4×10 ^-4

EXS-7 0.7×10 ^-4

EXM-1????0.09

EXM-3????0.01

Solv-1????0.15

Solv-5????0.03

Layer 9: middle layer

Gelatin 0.5

10: the three green-sensitive emulsion layer of layer

Iodine silver bromide emulsion (II) (inner high AgI type, ball equivalent diameter are 1.2 μ m, and the variation factor of ball equivalent diameter is 28%)

Coating silver amount 1.0

Gelatin 0.8

EXS-5 2×10 ^-4

EXS-6 0.8×10 ^-4

EXS-7 0.8×10 ^-4

EXM-3????0.01

EXM-4????0.04

EXC-4????0.005

Solv-1????0.2

Layer 11: yellow filter layer

Cpd-3????0.05

Gelatin 0.5

Solv-1????0.1

Layer 12: middle layer

Gelatin 0.5

Cpd-2????0.1

13: the first blue-sensitive emulsion layer of layer

Iodine silver bromide emulsion (AgI is 10mol%, and inner high AgI type, ball equivalent diameter are 0.7 μ m, and the variation factor of ball equivalent diameter is 14%, tetrakaidecahedron particle)

Coating silver amount 0.1

Iodine silver bromide emulsion (AgI is 4.0mol%, and inner high AgI type, ball equivalent diameter are 0.4 μ m, and the variation factor of ball equivalent diameter is 22%, tetrakaidecahedron particle)

Coating silver amount 0.05

Gelatin 1.0

EXS-8 3×10 ^-4

EXY-1????0.53

EXY-2????0.02

Solv-1????0.15

14: the second blue-sensitive emulsion layer of layer

Iodine silver bromide emulsion (AgI is 19.0mol%, and inner high AgI type, ball equivalent diameter are 1.0 μ m, and the variation factor of ball equivalent diameter is 16%, tetrakaidecahedron particle)

Coating silver amount 0.19

Gelatin 0.3

EXS-8 2×10 ^-4

EXY-1????0.22

Solv-1????0.07

Layer 15: middle layer

Iodine silver bromide particulate (AgI is 2mol%, even type, the ball equivalent diameter is 0.13 μ m)

Coating silver amount 0.2

Gelatin 0.36

16: the three blue-sensitive emulsion layer of layer

Iodine silver bromide emulsion III (inner high AgI type, ball equivalent diameter are 1.2 μ m, and the variation factor of ball equivalent diameter is 28%)

Coating silver amount 1.0

Gelatin 0.5

EXS-8 1.5×10 ^-4

EXY-1????0.2

Solv-4????0.07

17: the first protective layer of layer

Gelatin 1.8

UV-18????0.1

UV-2????0.2

Solv-1????0.01

Solv-2????0.01

18: the second protective layer of layer

Silver bromide particulate (the ball equivalent diameter is 0.07 μ m)

Coating silver amount 0.18

Gelatin 0.7

Poly methyl methacrylate particle (diameter is 1.5 μ m) 0.2

W-1????0.02

H-1????0.4

Cpd-5????1.0

The molecular formula of compound used therefor is listed in table C.

Sample 701-703 prepares according to the identical method for making of said sample, and difference is that iodine silver bromide emulsion I, II and III have changed in layer 5,10 and 16.

These samples were placed 14 hours under 40 ℃ of temperature and 70% relative humidity, carried out the sensitometry exposure then, carried out colour development according to example 4 identical methods.

Measure the density of handling sample with the red, green and blue filter.Gained the results are shown in table 7-1.

The result of photographic property is red with sense, sense is green and the relative sensitivity of the blue layer of sense is represented, relative sensitivity is that light sensitivity with sample 701 is 100 estimations.

Shown in table 7-1, emulsion of the present invention has the effect that improves light sensitivity, and Fog density does not increase basically.

After sample is aging according to the same procedure of example 1, measure their photographic property, have photographic property preferably with the sample 702 and 703 of emulsion of the present invention.

Example 8

Laminated coating with following composition is coated on the tri acetyl cellulose membrane carrier of backing layer, makes the sample of multi layer colour photosensitive material.

The composition of photographic layer

The coating amount of silver halide and collargol g/m ²Silver is unit representation, the consumption g/m of colour coupler, adjuvant and gelatin ²Be unit representation, the amount of sensitizing dye is represented with the molal quantity of every moles of silver in the identical layer.Represent the symbol of adjuvant to have following meanings.Notice that adjuvant has multiple effect as a result, has then only represented a kind of effect.

UV: ultraviolet light absorber; Solv: high boiling organic solvent; ExF; Dyestuff; ExS: sensitizing dye; ExC: cyan coupler; ExM: magenta colour coupler: ExY: yellow colour coupler; Cpd: adjuvant.

Layer 1: antihalation layer

Black collargol 0.15

Gelatin 2.9

UV-1????0.03

UV-2????0.06

UV-3????0.07

Solv-2????0.08

EXF-1????0.01

EXF-2????0.01

Layer 2: low speed magenta-sensitive emulsion layer

Iodine silver bromide emulsion (AgI is 4mol%, even type, and the ball equivalent diameter is 0.4 μ m, the running parameter of ball equivalent diameter is 37%, plain film shape particle, the diameter/thickness ratio is 3.0)

Coating silver amount 0.4

Gelatin 0.8

EXS-1 2.3×10 ^-4

EXS-2 1.4×10 ^-4

EXS-5 2.3×10 ^-4

EXS-7 8.0×10 ^-6

EXC-1????0.17

EXC-2????0.02

EXC-3????0.13

Layer 3: middle light sensitivity magenta-sensitive emulsion layer

Iodine silver bromide emulsion (AgI is 6mol%, inner high AgI type, and core/shell ratio is 2: 1, and the ball equivalent diameter is 0.65 μ m, and the variation factor of ball equivalent diameter is 25%, plain film shape particle, the diameter/thickness ratio is 2.0)

Coating silver amount 0.65

Iodine silver bromide emulsion (AgI is 4mol%, even AgI type, and the ball equivalent diameter is 0.4 μ m, the variation factor of ball equivalent diameter is 37%, plain film shape particle, the diameter/thickness ratio is 3.0)

Coating silver amount 0.1

Gelatin 1.0

EXS-1 2×10 ^-4

EXS-2 1.2×10 ^-4

EXS-5 2×10 ^-4

EXS-7 7×10 ^-6

EXC-1????0.31

EXC-2????0.01

EXC-3????0.06

Layer 4: ISO magenta-sensitive emulsion layer

The iodine silver bromide emulsion I (inner high AgI type, core/shell ratio is 1: 2, the ball equivalent diameter is 0.75 μ m, the variation factor of ball equivalent diameter is 25%)

Coating silver amount 0.9

Gelatin 0.8

EXS-1 1.6×10 ^-4

EXS-2 1.6×10 ^-4

EXS-5 1.6×10 ^-4

EXS-7 6×10 ^-4

EXC-1????0.07

EXC-4????0.05

Solv-1????0.07

Solv-2????0.20

Layer 5: middle layer

Gelatin 0.6

UV-4????0.03

UV-5????0.04

Cpd-1????0.1

Polyethyl acrylate latex 0.08

Solv-1????0.05

Layer 6: low speed green-sensitive emulsion layer

Iodine silver bromide emulsion (AgI is 4mol%, even type, and the ball equivalent diameter is 0.7 μ m, the variation factor of equivalent spheroid diameter is 37%, plain film shape particle, the diameter/thickness ratio is 2.0)

Coating silver amount 0.18

Gelatin 0.4

EXS-3 2×10 ^-4

EXS-4 7×10 ^-4

EXS-5 1×10 ^-4

EXM-5????0.11

EXM-7????0.03

EXY-8????0.01

Solv-1????0.09

Solv-4????0.01

Layer 7: middle light sensitivity green-sensitive emulsion layer

Iodine silver bromide emulsion (AgI is 4mol%, surperficial high AgI type, and core/shell ratio is 1: 1, the equivalent sphere attitude, the ball equivalent diameter is 0.5 μ m, the variation factor of ball equivalent diameter is 20%, plain film shape particle, the diameter/thickness ratio is 4.0)

Coating silver amount 0.27

Gelatin 0.6

EXS-3 2×10 ^-4

EXS-4 7×10 ^-4

EXS-5 1×10 ^-4

EXM-5????0.17

EXM-7????0.04

EXY-8????0.02

Sovl-1????0.14

Solv-4????0.02

Layer 8: ISO green-sensitive emulsion layer

The iodine silver bromide emulsion II (inner high AgI type, core/shell ratio is 1: 2, the ball equivalent diameter is 0.75 μ m, the variation factor of equivalent spheroid diameter is 25%)

Coating silver amount 0.7

Gelatin 0.8

EXS-4 5.2×10 ^-4

EXS-5 1×10 ^-4

EXS-8 0.3×10 ^-4

EXM-5????0.1

EXM-6????0.03

EXY-8????0.02

EXC-1????0.02

EXC-4????0.01

Solv-1????0.25

Solv-2????0.06

Solv-1????0.01

Layer 9: middle layer

Gelatin 0.6

Cpd-1????0.04

Polyethyl acrylate latex 0.12

Slov-1????0.02

Layer 10: the donor layer that the sense red beds is had the middle layer effect

The iodine silver bromide (AgI is 6mol%, inner high AgI type, and core/shell ratio is 2: 1, and the ball equivalent diameter is 0.7 μ m, and the variation factor of equivalent spheroid diameter is 25%, plain film shape particle, the diameter/thickness ratio is 2.0)

Coating silver amount 0.68

Iodine silver bromide emulsion (AgI is 4mol%, even type, and the variation factor of ball equivalent diameter is 37%, plain film shape particle, the diameter/thickness ratio is 3.0)

Coating silver amount 0.19

Gelatin 1.0

EXS-3 6×10 ^-4

EXM-10????0.19

Solv-1????0.20

Layer 11: yellow filter layer

Yellow collargol 0.06

Gelatin 0.8

Cpd-2????0.13

Solv-1????0.13

Cpd-1????0.07

H-1????0.13

Layer 12: the blue breast layer of low speed sense

Iodine silver bromide emulsion (AgI is 4.5mol%, even AgI type, and the ball equivalent diameter is 0.7 μ m, the variation factor of ball equivalent diameter is 15%, plain film shape particle, the diameter/thickness ratio is 7.0)

Coating silver amount 0.3

Iodine silver bromide emulsion (AgI is 3mol%, even AgI type, and the ball equivalent diameter is 0.3 μ m, the variation factor of ball equivalent diameter is 30%, plain film shape particle, the diameter/thickness ratio is 7.0)

Coating silver amount 0.15

Gelatin 1.8

EXS-6 9×10 ^-4

EXC-1????0.06

EXC-4????0.03

EXY-9????0.14

EXY-11????0.89

Solv-1????0.42

Layer 13: middle layer

Gelatin 0.7

EXY-12????0.20

Solv-1????0.34

Layer 14: ISO blue-sensitive emulsion layer

The iodine silver bromide emulsion III (inner high AgI type, core/shell ratio is 1: 2, the ball equivalent diameter is 0.75 μ m, the variation factor of ball equivalent diameter is 25%)

Coating silver amount 0.5

Gelatin 0.5

EXS-6 1×10 ^-4

EXY-9????0.01

EXY-11????0.20

EXC-1????0.02

Solv-1????0.10

15: the first protective seam of layer

Silver bromide particulate emulsion (AgI is 2mol%, even AgI type, the ball equivalent diameter is 0.07 μ m)

Coating silver amount 0.12

Gelatin 0.9

UV-4????0.11

UV-5????0.16

Solv-5????0.02

H-1????0.13

Cpd-5????0.10

Polyethyl acrylate latex 0.09

16: the second protective seam of layer

Silver bromide particulate emulsion (AgI is 2mol%, even AgI type, the ball equivalent diameter is 0.07 μ m)

Coating silver amount 0.36

Gelatin 0.55

Polymethylmethacrylate grain (diameter is 1.5 μ m) 0.2

H-1????0.17

Except said components, the stabilizing agent Cpd-3(0.07g/m of emulsion) and surfactant Cpd-4(0.03g/m) coating aid that can be used as every layer adds.

The molecular formula of compound used therefor is listed in table D.

Emulsion Em-201 is that the average equivalent spheroid diameter of difference kind crystalline substance is 0.5 μ m, thereby the average equivalent spheroid diameter of final particle is 0.75 μ m according to the Em-1 preparation method of example 1 preparation.

Thiosulfuric acid compound and reduction sensitization agent join among the Em-201 according to the amount of table shown in the 8-1, and the adding method is as identical method as described in the example 1, thereby make emulsion 202-207.

Table 8-1

Emulsion thiosulfuric acid compound addition/mol Ag reduction sensitization agent addition/molAg

202 do not add and do not add tin chloride 1.2 * 10 ^-5Mol

203 1-2 2 * 10 ^-5Mol tin chloride 1.2 * 10 ^-5Mol

204 do not add and do not add ascorbic acid 2.1 * 10 ^-3Mol

205 1-2 2 * 10 ^-5Mol ascorbic acid 2.1 * 10 ^-3Mol

206 1-6 2 * 10 ^-5Mol ascorbic acid 2.1 * 10 ^-3Mol

207 1-16 2 * 10 ^-5Mol ascorbic acid 2.1 * 10 ^-3Mol

Zhi Bei emulsion 201-207 of the present invention and the most handy hypo of Comparative Examples and gold chloride carry out gold and add the sulphur sensibilization according to the method described above.

Same procedure according to above-mentioned example prepares sample 801-804, and difference is that iodine silver bromide emulsion I, II and III have changed respectively in layer 4,8 and 14.

In temperature is 40 ℃, and relative humidity is to place sample 14 hours 70% time, carries out the sensitometry exposure to carry out colour development according to the same procedure of example 5 then.

The sample of handling is carried out density measurement with the red, green and blue filter.

The result of photographic property is red with sense, sense is green and the relative sensitivity of the blue layer of sense comes comparison, and relative sensitivity is that the light sensitivity with sample 801 is 100 to estimate.

The result shows, sample 803 of the present invention and 804 samples 801 and 802 compared with Comparative Examples, and its light sensitivity is higher, and Fog density is lower.After sample wears out according to example 1 identical method and stores, measure their photographic property, the Fog density of sample 802 obviously increases, and its light sensitivity descends.But sample 803 of the present invention and 804 photographic property will be got well compared with Comparative Examples sample 801 and 802.

Table A

（1-1）CH ₃SO ₂SNa

（1-2）C ₂H ₅SO ₂SNa

（1-3）C ₃H ₇SO ₂SK

（1-4）C ₄H ₉SO ₂SLi

（1-5）C ₆H ₁₃SO ₂SNa

（1-6）C ₈H ₁₇SO ₂SNa

（1-8）C ₁₀H ₂₁SO ₂SNa

（1-9）C ₁₂H ₂₅SO ₂SNa

（1-10）C ₁₆H ₃₃SO ₂SNa

（1-12）t-C ₄H ₉SO ₂SNa

（1-13）CH ₃OCH ₂CH ₂SO ₂SNa

（1-15）CH ₂＝CHCH ₂SO ₂Na

（1-29）KSSO ₂（CH ₂） ₂SO ₂SK

（1-30）NaSSO ₂（CH ₂） ₄SO ₂SNa

（1-31）NaSSO ₂（CH ₂） ₄S（CH ₂） ₄SO ₂SNa

（2-1）C ₂H ₅SO ₂SCH ₃

（2-2）C ₈H ₁₇SO ₂SCH ₂CH ₃

（2-5）C ₂H ₅SO ₂SCH ₂CH ₂CN

（2-18）C ₂H ₅SO ₂SCH ₂CH ₂CH ₂CH ₂OH

（2-21）CH ₃SSO ₂（CH ₂） ₄SO ₂SCH ₃

（2-22）CH ₃SSO ₂（CH ₂） ₂SO ₂SCH ₃

（3-2）C ₂H ₅SO ₂SCH ₂CH ₂SO ₂CH ₂CH ₂SSO ₂C ₂H ₅

（3-7）C ₂H ₅SO ₂SSSO ₂C ₂H ₅

（3-8）（n）C ₈H ₁₇SO ₂SSSO ₂C ₈H ₁₇（n）

The HBS-1 tricresyl phosphate

The HBS-2 dibutyl phthalate

Two (the 2-second hexyl) phthalic esters of HBS-3

Claims (5)

1, a kind of method for preparing silver emulsion is carried out reduction sensitization with at least a ascorbic acid and derivant thereof in the process of this silver emulsion of preparation, it is characterized in that the consumption of described ascorbic acid or derivatives thereof is every mole of silver halide 5 * 10 ^-5～1 * 10 ^-1Mole.

2,, it is characterized in that when silver halide particle precipitates, carrying out reduction sensitization with described at least a ascorbic acid and derivant thereof according to the method for claim 1.

3, according to the method for claim 1, it is characterized in that reduction sensitization is to carry out in the presence of the compound shown at least a formula (I), (II) and (III),

Wherein: R, R ¹And R ²Can be identical or different, represent aliphatic group, aromatic group or heterocyclic radical, M represents kation, and L represents two valence link bases, m represents 0 or 1, and the compound of formula (I)-Shi (III) can be to contain that structure gained divalent group is the polymkeric substance of repetitive shown in formula (I)-Shi (III).

4, according to the method for claim 2, it is characterized in that the reduction sensitization effect is to carry out in the presence of at least a formula (I), (II) and (III) compound,

Wherein, R, R ¹And R ²Can be identical or different, represent aliphatic group, aromatic group or heterocyclic radical, M represents kation, and L represents two valence link bases, m represents 0 or 1, and the compound of formula (I)-Shi (III) can be to contain that structure gained divalent group is the polymkeric substance of repetitive shown in formula (I)-Shi (III).

5, a kind of color sensitive material, this material is included in one deck photosensitive silver halide emulsion layer at least on the transparent carrier, it is characterized in that has 50%(weight in the silver halide particle contained in the described emulsion layer) or mostly silver halide particle that is formation by the silver emulsion of the method preparation of claim 1.