CN1530741A - Silver halide emulsion and silver halide camera photosensitive material - Google Patents

Silver halide emulsion and silver halide camera photosensitive material Download PDF

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Publication number
CN1530741A
CN1530741A CNA2003101205725A CN200310120572A CN1530741A CN 1530741 A CN1530741 A CN 1530741A CN A2003101205725 A CNA2003101205725 A CN A2003101205725A CN 200310120572 A CN200310120572 A CN 200310120572A CN 1530741 A CN1530741 A CN 1530741A
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emulsion
silver
silver halide
row
layer
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佐藤忠伸
人
大岛直人
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Fujifilm Corp
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Fujifilm Corp
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Abstract

To provide a silver halide color photographic light-sensitive material having higher sensitivity and higher contrast and free of reciprocity failure over a wide range of exposure illuminance, A silver halide emulsion comprising a silver halide grain containing at least two metal comp10exes each giving an average electron releasing time of 10<-5 >to 3 seconds, the ratio in the average electron releasing time between these two metal complexes being at least 3 times or more and in these metal complexes, the content of the metal complex having a shorter average electron releasing time being 3 times or more as the molar ratio to the content of the metal complex having a longer average electron releasing time.

Description

Silver emulsion and silver halide photographic sensitive material
Technical field
The invention relates to silver emulsion and silver halide photographic sensitive material, particularly about the silver halide photographic sensitive material of the ISO of using the adulterant technology, high gradation, no reciprocity law abnormality.
Background technology
As with the silver halide particle modification, improve the silver halide photographic sensitive material overall performance to reach one of technology of desired state, the technology that adds the material (adulterant) beyond silver ion and the halogen ion is arranged, i.e. doping techniques.Particularly for the doping techniques of transition metal ion, people have carried out a large amount of research.It is generally acknowledged, when in silver halide particle, mixing transition metal ion,, also can change the photosensitive performance effectively even its addition is few.
People also know in addition, in order more effectively to improve the photosensitive performance of silver emulsion, not only can the containing transition metal ion in silver halide particle, and can the containing transition metal coordination compound.As the performance of improved silver emulsion by containing transition metal coordination compound in silver halide particle, can enumerate light sensitivity (ISOization), reciprocity law abnormality (low-light (level) reciprocity law abnormality, high illumination reciprocity law abnormality), gradation (vigourization), especially can improve high illumination reciprocity law abnormality for high silver chloride emulsion, be a crucial technology therefore.In order to improve high illumination reciprocity law abnormality, in most of the cases be to use iridium complex compound.The example that discloses doped iridium coordination compound in silver halide particle in following patent literature has: the spy opens flat 1-285941, spy and opens flat 3-118583, spy and open flat 4-213449, spy and open flat 4-278940, spy and open flat 5-66511, spy and open flat 5-313277, spy and open flat 6-82947, spy and open flat 6-235995, spy and open flat 7-72569, spy and open flat 7-72576, spy and open flat 11-202440, spy and open flat 11-295841 number etc. in the communique, dentate as iridium complex compound, the most frequently used is chlorion, can use fluorine ion, bromide ion, H in addition 2O, cryanide ion, nitrosyl radical, sulfo-nitrosyl radical.In addition, disclose among the US5360712, disclose [IrCl as the adulterant that improves high illumination reciprocity law abnormality with the adulterant technology of organic compound as dentate 5(thia)] 2-(thia=thiazole).
On the other hand, in disclosed a lot of examples,, mix with the VIII family metal complex of 6 cryanide ions as dentate in order to obtain the emulsion of ISO.In the public clear 48-35373 communique of spy, as the adulterant that contains cryanide ion, six cyano group iron (II) coordination compoundes and six cyano group iron (III) coordination compoundes are disclosed.In addition, the example that six cyano group iron (II) coordination compoundes that mix obtain high-sensitivity emulsion also has a lot, for example opens disclosed content in flat 5-66511 communique, the US5132203 instructions etc. referring to the spy.Except iron complex compound, also know the high-sensitivity emulsion that doping cyanogen coordination compound obtains, open in the flat 2-20853 communique the spy, obtain the silver emulsion of ISO when disclosing in chlorosulfonylation silver the coordination compound that mixes based on rhenium, ruthenium, osmium, iridium.In addition, for the emulsion that obtains high gradation also uses doping techniques, in EP033642, EP0606895, the EP0610670 instructions use nitrosyl radical is disclosed for example or sulfo-nitrosyl, as the dentate technology of transition metal complex compound.At this moment, use ruthenium or osmium as central metal.In order to obtain the emulsion of vigour; not only use nitrosyl radical or sulfo-nitrosyl radical; using six ruthenic chlorides, six radium chlorides, chlordene rhenium also is effectively, opens clear 63-184740, spy the spy and opens that flat 1-285941, spy open flat 2-20852, the spy opens in the flat 2-20855 communique on the books.
In recent years, also disclosing some mixes with the technology of organic compound as the coordination compound of dentate in silver halide particle in order to use independent adulterant further to improve performance.US5360712, US5457021, US5462849, EP0709724 instructions, spy open flat 7-72569, the spy opens and discloses many uses in the flat 8-179452 communique with the example of organic compound as the coordination compound of dentate, have particularly put down in writing doping [(NC) 5Fe (m-4,4 '-bipyridine) Fe (CN) 5] 6-The time, the effect of ISOization is bigger.Above-mentioned doping [IrCl 5(thia)] 2-Technology, be intended to use independent adulterant to improve the part of the technology of emulsion performance.In addition, the spy opens and discloses doping [Fe (CO) in the flat 11-24194 communique 4(P (Ph) 3)] 0, [Fe (CO) 3(P (Ph) 2)] 0And obtaining the emulsion that ISO, reciprocity law abnormality are enhanced, the spy opens and discloses among the flat 11-102042 at [M (CN) 5L] 3-(M=Fe 2+, Ru 2+, Ir 3+), [Fe (CO) 4L] 0, [M ' (CN) 3L] -(M '=Pd 2+, Pt 2+), [IrCl 5L] 2-In the coordination compound of type, L uses 2-mercaptobenzimidazole, 5-methyl-s-triazolo (1.5-A) pyrimidin-7-ol, 2-sulfydryl-1,3, obtains the technology of high-sensitivity emulsion during the 4-oxadiazole, disclose in the Te Kaiping 10-293377 communique, used [the RuCl that mixed 5L '] 2-The emulsion of (L '=imidazoles, benzimidazole and derivant thereof) is observed tangible vigourization, and the light sensitivity of this moment is compared with the emulsion that used desensitization vigour adulterant in the past and increased substantially.
These adulterants use separately and just can improve the photosensitive characteristic effectively, when using multiple adulterant simultaneously, and the emulsion that can be had the character of each adulterant simultaneously.For ISO and the less emulsion of reciprocity law, open flat 2-125425 (patent documentation 1), spy as the spy and open flat 3-132647 (patent documentation 2), spy and open described in the flat 3-188437 (patent documentation 3) etc., can by and realize with six cyano group coordination compoundes and iridium complex compound.The good emulsion of the unusual characteristic of vigour, low-light (level) and/or high illumination reciprocity law; open described in flat 4-51233 (patent documentation 6) number communique as US5474888 (patent documentation 4), US500335 (patent documentation 5) instructions, spy, can be by being the ruthenium of dentate or osmium coordination compound and iridium complex compound and with the nitrosyl radical with obtaining.In addition; disclose in US5480771 (patent documentation 7), EP0606893 (patent documentation 8), EP0606894 (patent documentation 9), EP0606895 (patent documentation 10), EP0610670 (patent documentation 11) instructions; in order to obtain the emulsion of ISO, vigour, will use nitrosyl radical to be the iron complex compound of dentate or the technology of ruthenium complex and usefulness as the ruthenium complex of the dentate of coordination compound or osmium coordination compound with cryanide ion.In addition, and can obtain ISO with 3 kinds of adulterants, vigour, the emulsion that reciprocity law is unusual less, open flat 8-314043 (patent documentation 12) the spy, Te Kaiping 8-328182 (patent documentation 13), Te Kaiping 8-211529 (patent documentation 14), disclose in Te Kaiping 8-211530 (patent documentation 15) number communique and US5480771 (patent documentation 16) instructions, use six cyanogen to close ruthenium (II) as the high photosensitivity adulterant, use the pentachloro-nitrosyl to close osmium as the vigour adulterant, use pentachloro-to close iridium (III or IV) and improve adulterant, obtain vigour as the reciprocity law abnormality, ISO, the emulsion that reciprocity law is unusual less.In addition, the spy opens the example of also having put down in writing the emulsion that uses 3 kinds of adulterants in flat 11-282114 (patent documentation 17) number communique.In this example, close that osmium, chlordene close iridium, pentachloro-(thiazole) closes iridium simultaneously and with the pentachloro-nitrosyl, obtain that under the exposure illumination of wide region reciprocity law abnormality is less, the emulsion of vigour.
But, for improving performance that each adulterant gives and the prior art that further improves performance by the technology of multiple adulterant and usefulness, also wish to develop light sensitivity and inferior other performance of Hue layer are not produced baneful influence, the low-light (level) from about 10 seconds time shutter is exposed to 10 -6About the wide region illumination of high illumination exposure under further improve the technology of reciprocity law abnormality (in this scope, making the light sensitivity unanimity).
Patent documentation 1: the spy opens flat 2-125425 communique
Patent documentation 2: the spy opens flat 3-132647 communique
Patent documentation 3: the spy opens flat 3-188437 communique
Patent documentation 4: No. 5474888 instructions of United States Patent (USP)
Patent documentation 5: No. 5500335 instructions of United States Patent (USP)
Patent documentation 6: the spy opens flat 4-51233 communique
Patent documentation 7: No. 5480771 instructions of United States Patent (USP)
Patent documentation 8: No. 0606893 instructions of European patent
Patent documentation 9: No. 0606894 instructions of European patent
No. 00606895 instructions of patent documentation 10:EP
Patent documentation 11: No. 0610670 instructions of European patent
Patent documentation 12: the spy opens flat 8-314043 communique
Patent documentation 13: the spy opens flat 8-328182 communique
Patent documentation 14: the spy opens flat 8-211529 communique
Patent documentation 15: the spy opens flat 8-211530 communique
Patent documentation 16: No. 5480771 communique of United States Patent (USP)
Patent documentation 17: the spy opens flat 8-282114 communique
Summary of the invention
The objective of the invention is, ISO is provided more, under the exposure illumination of wide region, does not have the reciprocity law abnormality, the silver halide photographic sensitive material of ISO, vigour more.
Above-mentioned purpose is resolved by following measure.
(1) a kind of silver emulsion is characterized in that, contains 2 kinds of metal complexes in silver halide particle at least, and described metal complex is included in and can makes it to have 10-5 second above, average electronics below 3 seconds in the silver halide particle and put the time slowly.
(2) silver emulsion described in (1) is characterized in that above, and at least 2 kinds of metal complexes that contain in the contained silver halide particle in emulsion, at least a kind is to make to have 10 -5Second above, less than 10 -3The average electronics of second is put the metal complex of time slowly, and at least a kind is to make to have 10 -3Average electronics is put the metal complex of time slowly more than second, below 3 seconds.
(3) above (1) or (2) described in silver emulsion, it is characterized in that the time of putting is 10 to average electronics contained in the silver halide particle slowly -5Second, the metal complex to 3 seconds was to be selected from the metal complex shown in the following general formula (I).
General formula (I)
[IrX (6-0)L n] m
X: halogen ion or class halogen ion
L: any dentate different with X
The integer of n:1 to 6
M:-4 is+4 integer extremely
(4) silver emulsion described in (3) is characterized in that above, also contains the metal complex by following general formula (II) expression in the emulsion in the contained silver halide particle.
General formula (II)
[MX’ (6-q)L’ q] r
M：Cr、Mo、Mn、Re、Fe、Ru、Os、Co、Rh、Ir、Pd、Pt、Cu
X ': halogen ion
L ': mineral compound or organic compound arbitrarily
The integer of q:0-6 (under the situation of Ir, being 0 wherein)
R:-5 is+4 integer extremely
(5) silver emulsion described in (3) is characterized in that above, also contains the metal complex of being represented by following general formula (III) in the contained silver halide particle in the emulsion.
General formula (III)
[M’X” (6-y)L” y] z
M’：Mg、Ca、Ti、Zr、V、Cr、Mo、Mn、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Zn、Cd
X ": halogen ion or cryanide ion
L ': mineral compound or organic compound arbitrarily
The integer of y:0-6 (under the situation of Ir, being 0 wherein)
Z:-5 is+4 integer extremely
(6) silver emulsion described in (3) is characterized in that above, contains the metal complex shown in above-mentioned general formula (II) and the general formula (III) simultaneously.
(7) silver emulsion described in (3) is characterized in that the X in the general formula (I) is selected from chloride ion or bromide ion above.
(8) above (3) or (7) described in silver emulsion, it is characterized in that the L in the general formula (I) is the dentate that is selected from SCN, OCN or the heterogeneous ring compound.
(9) above (3) or (7) described in silver emulsion, it is characterized in that the L in the general formula (I) is the heterogeneous ring compound of 5 Yuans rings, have at least 2 nitrogen-atoms and at least 1 sulphur atom in the ring.
(10) silver emulsion described in (9) is characterized in that above, has little substituting group of the ratio methyl of combination on the ring skeleton of the L in general formula (I) and the substituting group bigger than chlorine atom.
(11) silver emulsion described in (4) is characterized in that the M in the general formula (II) is the transition metal ion that is selected among Cr, Ru, Os, the Rh above.
(12) above (4) or (11) described in silver emulsion, it is characterized in that the L ' in the general formula (II) is selected from halogen ion, H 2O, SCN, OCN, NO, NS and heterogeneous ring compound.
(13) silver emulsion described in (5) is characterized in that the M ' in the general formula (III) is selected from Ti, Zr, Fe, Ru, Co, Ni, Pd, Pt, Cu and Zn above.
(14) silver emulsion described in (5) is characterized in that the M ' in the general formula (III) is selected from Fe or Ru above.
(15) above (5) or (14) described in silver emulsion, it is characterized in that the X in the general formula (III) " be cryanide ion.
(16) above (5) or (14) described in silver emulsion, it is characterized in that the L in the general formula (III) " be cryanide ion, SCN, OCN or heterogeneous ring compound.
(17) each described silver emulsion in (1)～(16) is characterized in that above, and the silver halide particle in the emulsion forms the chlorine silver bromide phase below the Br containing ratio 30% (mole) in the particle.
(18) each described silver emulsion in (1)～(17) is characterized in that the silver halide particle in the emulsion contains the I of 5% (mole) above -
(19) contain the silver chloride sensitive photographic material of each described emulsion in top (1)～(18).
Embodiment
Explain the present invention below.
The high illumination reciprocity law abnormality of silver halide photographic emulsions, be since when the exposure of high illumination silver halide produce due to a large amount of photoelectrons causes that sub-image disperses.Therefore, high illumination reciprocity law abnormality can improve the function of temporarily avoiding being discharged into again in the conduction band behind conduction band, the stagnation certain hour because of a large amount of photoelectrons that produce of high illumination exposure by making to have in the silver halide particle.Situation in silver halide particle when this just is equivalent to the exposure of high illumination identical situation when changing over and exposing with low-light (level).This function that makes photoelectron temporarily avoid and waiting for is promptly temporarily caught photoelectronic function, can realize (such adulterant is called as electronics and puts adulterant or illumination conversion adulterant slowly) by the containing transition metal coordination compound.Transition metal complex compound as improving high illumination reciprocity law abnormality used chlordene to close iridium in the past always.Using chlordene to close under the situation of iridium, the photoelectron that exposure is produced is captured on the lowest unoccupied molecular orbital of central metal iridium, after being detained certain hour on this track, be discharged into once more (will be that electronics is put the time slowly) on the conduction band by the timing definition that exposes to discharging the electronics of catching once more.Like this, chlordene closes iridium just to have the photoelectron that makes a large amount of generations and temporarily avoids the excellent properties waited for, but it is because longer in the hold-up time of the electron capture energy utmost point, though improved high illumination abnormality, but the light sensitivity that depends on the time from exposing to developing increases (sub-image sensitizing), and it is unstable that photographic property becomes.That is,, must in reasonable time, electronics be discharged on the conduction band once more by the iridium center of having caught the electronics on the conduction band in order under the stable situation of photographic property, to obtain good high illumination reciprocity law abnormality.If exposure light source is certain, can use and give the adulterant of only putting the time slowly corresponding to the electronics of a certain exposure illumination, even but different exposure light sources will seek out under the situation of the emulsion of giving identical photographic property, need in silver halide particle, import and have the suitable electronics corresponding and put the adulterant of time slowly with each exposure light source illumination.
Slowly the time of putting can adopt reciprocity law curve or two flash of light conduction method to determine to electronics.Average electronics among the present invention time that puts is slowly adopted the value of determining by two flash of light conduction methods, and the time of putting is confirmed this value slowly to utilize the electronics of being determined by the reciprocity law curve.The electronics that utilizes two flash of light conduction methods to obtain is put the time slowly, can adopt microwave light conduction method or radio glistening light of waves conduction method to measure.Carry out primary short time exposure with two flash of light conduction methods, through carrying out secondary short time exposure behind the certain hour.When exposing for the first time, electronics is caught by the electronics trap in the silver halide crystal, when exposing the second time of and then carrying out, the electronics of catching when the electronics trap is exposed for the first time fills up, in the electronics trap not at trapped electrons, the electron number of conduction band is not reducing, thereby observed smooth conducted signal increases when exposing for the second time.Relative therewith, between double exposure, reserve enough intervals, under the d/d situation of electronics of being caught by the electronics trap when exposing for the first time, can observe secondary smooth conducted signal and roughly return to original signal intensity.If change the interval between the double exposure, investigate the dependence of secondary smooth conducted signal intensity and exposure interval, can observe along with exposure interval increases secondary smooth conducted signal intensity and reduce.The situation that photoelectron slowly discharges is represented in the variation of sort signal intensity from the electronics trap, by obtaining the averaging time that produces signal attenuation, can characterize average electronics and put the time slowly.On the other hand, reciprocity law curve " change decide description engineering basis-silver salt description compile-" that can write according to (society) Japan description association is depicted described in P.297.Common silver emulsion is silver chloride emulsion particularly, is to be top high photographic sensitivity near the middle illumination, produces desensitization in low-light (level) one side and high illumination one side, draws out protruding curve downwards.Relative therewith, slowly put the emulsion that adulterant has improved high illumination reciprocity law abnormality by the doping electronics, desensitization is not taking place in its reciprocity law curve in the high illumination side scope of a certain exposure illumination, produce the straight zone that does not have light sensitivity to change, and is different with unadulterated reciprocity law curve.To begin to become straight exposure illumination, and promptly produce time shutter under the exposure illumination of difference and be defined as electronics and put the time slowly with unadulterated family curve.The effect that electronics is put (photoelectronic emit) is slowly again represented the effect of end exposure, and therefore, manifesting electronics when taking a picture, to put the timing definition of effect slowly be the photoelectronic time of emitting beginning again, and promptly electronics is put the time slowly.
Electronics put slowly be after exposure certain hour, carry out continuously, in order to improve high illumination reciprocity law abnormality, sub-image sensitizing does not take place, 10 -5Second observing average Xu between 3 seconds, to put time ratio better.But, use independent adulterant to be difficult to cover wide like this electronics and put the time slowly, must cover this scope with multiple adulterant.In these many adulterants, at least a kind is that the adulterant that works in high illumination range (gives 10 -5Second above, less than 10 -3The average electronics of second is put the metal complex of time slowly), at least a kind is that the adulterant that works in the low-light (level) scope (gives 10 -3Second above, the average electronics below 3 seconds is put the metal complex of time slowly).
In the present invention preferably, giving adulterant that average electronics puts the time slowly is Ir coordination compound by following general formula (I) expression.
General formula (I)
[IrX (6-0)L n] m
X: halogen ion or class halogen ion
L: any dentate different with X
The integer of n:1 to 6
M:-4 is+4 integer extremely
In the formula, X can be identical each other, also can be different, or exists under a plurality of situations at L, and a plurality of L can be identical each other, also can be different.Described halogen ion can be enumerated fluorine ion, chlorion, bromide ion or iodide ion.In following formula, described class halogen ion is the ion that has with halogen ion similarity, for example cryanide ion (CN -), thiocyanic acid radical ion (SCN -), selenocyanic acid radical ion (SeCN -), telluro cyanic acid ion (TeCN -), azido dithiocarbonic acids radical ion (SCSN 3 -), cyanic acid ion (OCN -) fulminate radical ion (ONC -), azide ion (N 3 -) etc.Described X is fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, isocyanic acid ion, thiocyanate ion, nitrate ion, nitrite ion or azide ion preferably, wherein especially preferentially selects chloride ion and bromide ion for use.Having no particular limits for L, can be mineral compound, also can be organic compound, can have electric charge, also can neutral, and preferably uncharged mineral compound or organic compound.
In the metal complex of general formula (I), preferably by the metal complex of following general formula (Ia) expression.
General formula (Ia)
[IrX a (6-0’)L a n’] m’
X a: halogen ion or class halogen ion
L a: any dentate different with X
N ': 1,2 or 3
M ' :-4 to+1 integer
X aIdentical with the X implication in the general formula (I), its preferred range is also identical.X aCan be identical each other, also can be different.L aH preferably 2O, OCN, NH 3, phosphine or CO, wherein H most preferably 2O.
L aThere are under a plurality of situations a plurality of L aCan be identical each other, also can be different.
In metal complex by general formula (I) expression, the preferred metal complex that also has by following general formula (Ib) expression.
General formula (Ib)
[IrX b (6-0”)L b n”] m”
X b: halogen ion or class halogen ion
L b: with the hydrocarbon of chain type or the ring type compound that to be a part of carbon of precursor structure or this precursor structure or hydrogen atom replaced by other atom or atomic group.
N ": 1,2 or 3
M " :-4 to+1 integer
X bThe X implication that is with general formula (I) is identical, and its preferred range is also identical.X bCan be identical each other, also can be different.L bBe hydrocarbon with chain type or the ring type compound that to be a part of carbon of precursor structure or this precursor structure or hydrogen atom replaced by other atom or atomic group, expression forms the compound of the dentate of Ir coordination compound.But, do not comprise the mineral compound that is equivalent to cryanide ion or carbonyl.Described L bHeterogeneous ring compound preferably, more preferably under the situation of heterogeneous ring compound with five-membered ring or six membered ring as dentate, under the situation of five-membered ring compounds, the compound that preferably in the ring skeleton, contains at least 1 nitrogen-atoms and at least 1 sulphur atom, under the situation of six-membered ring compounds, preferably in the ring skeleton, contain at least 1 nitrogen-atoms.Described L b, more preferably encircle and have any substituent compound on the carbon atom in the skeleton, preferably have substituting group as substituting group with the little volume of n-pro-pyl.Specifically, substituting group can be methyl, ethyl, methoxyl, ethoxy, cyano group, isocyano group, cyanato-, different cyanato-, thiocyano, isocyanide sulfenyl, formoxyl, thioformyl, hydroxyl, sulfydryl, amino, diazanyl, azido, nitro, nitroso-, hydroxyl amino, carboxyl, carbamyl, fluorine-based, chloro, bromo and iodo.At L bThere are under a plurality of situations a plurality of L bCan be identical each other, also can be different.N " can be 1,2 or 3, preferably 1 or 2, preferably 1.
In the metal complex of general formula (Ib), most preferably by the metal complex of following general formula (Ic) expression.
General formula (Ic)
[IrX c (6-0”)L c n”] m”
X c: halogen ion or class halogen ion
L c: be the heterogeneous ring compound of five-membered ring or six membered ring, contain at least 2 nitrogen-atoms and at least 1 sulphur atom in the ring skeleton, have any substituent compound on the carbon atom in the ring skeleton.
N ": 1,2 or 3
M " :-4 to+1 integer (preferably-2 to 0 integer)
X cIdentical with the X implication in the general formula (I), its preferred range is also identical.A plurality of X cCan be identical each other, also can be different.Above-mentioned L cBe that preferably thiadiazoles is the compound of skeleton, preferably on the carbon atom in the compound in conjunction with the substituting group beyond the hydrogen.Described substituting group is halogen (fluorine preferably; chlorine; bromine; iodine); methoxyl; ethoxy; carboxyl; methoxycarbonyl; acyl group; acetyl group; chloroformyl; sulfydryl; methyl mercapto; thioformyl; thiocarboxyl group; two thiocarboxyl groups; sulfino; sulfo group; sulfamoyl; methylamino; cyano group; isocyano group; cyanato-; different cyanato-; thiocyano; the isocyanide sulfenyl; hydroxyl amino; oxyimino; carbamyl; nitroso-; nitro; diazanyl; hydrazono-or azido, more preferably halogen (fluorine; chlorine; bromine; iodine); chloroformyl; sulfino; sulfo group; sulfamoyl; isocyano group; cyanato-; different cyanato-; thiocyano; the isocyanide sulfenyl; oxyimino; nitroso-; nitro or azido.Wherein, particularly preferably be chlorine, bromine, chloroformyl, isocyano group, cyanato-, thiocyano, isocyanide sulfenyl.L cThere are when a plurality of a plurality of L cCan be identical each other, also can be different.Said n " preferably 1 or 2, m " preferably-2 or-1.
Enumerate preferred object lesson below, but the invention is not restricted to these examples by the metal complex of general formula (Ia) expression.
[IrCl 5(H 2O)] 2-
[IrCl 4(H 2O) 2] -
[IrCl 5(H 2O)] -
[IrCl 4(H 2O) 2] 0
[IrCl 5(HO)] 3-
[IrCl 4(HO) 2] 2-
[IrCl 5(HO)] 2-
[IrCl 4(HO) 2] 3-
[IrCl 5(O)] 4-
[IrCl 4(O) 2] 5-
[IrCl 5(O)] 3-
[IrCl 4(O) 2] 4-
[IrBr 5(H 2O)] 2-
[IrBr 4(H 2O) 2] -
[IrBr 5(H 2O)] -
[IrBr 4(H 2O) 2] 0
[IrBr 5(OH)] 3-
[IrBr 4(OH) 2] 3-
[IrBr 5(OH)] 2-
[IrBr 5(OH) 2] 2-
[IrBr 5(O)] 4-
[IrBr 4(O) 2] 5-
[IrBr 5(O)] 3-
[IrBr 4(O) 2] 4-
[IrCl 5(OCN)] 3-
[IrBr 5(OCN)] 3-
[IrCl 5(NH 3)] 2-
[IrBr 5(NH 3)] 2-
[IrCl 5(S＝P(NH 3) 3)] 2-
[IrCl 5(S＝P(NH 3) 2(OH))] 2-
[IrCl 5(S＝P(NH 3)(OH) 2)] 2-
[IrCl 5(S＝P(OH) 3)] 2-
Above-mentioned illustrative metal complex has 10 -5Second above, 10 -3Average electronics below second is put the time slowly.
Enumerate preferred object lesson below, but the invention is not restricted to these examples by the metal complex of general formula (Ic) expression.
[IrCl 5(thiazole)] 2-
[IrCl 4(thiazole) 2] -
[IrCl 3(thiazole) 3] 0
[IrBr 5(thiazole)] 2-
[IrBr 4(thiazole) 2] -
[IrBr 3(thiazole) 3] 0
[IrCl 5(5-methylthiazol)] 2-
[IrCl 4(5-methylthiazol) 2] -
[IrBr 5(5-methylthiazol)] 2-
[IrBr 4(5-methylthiazol) 2] -
[IrCl 5(5-chlorine dithiazole)] 2-
[IrCl 4(5-chlorine dithiazole) 2] -
[IrBr 5(5-chlorine dithiazole)] 2-
[IrBr 4(5-chlorine dithiazole) 2] -
Preferred object lesson as the metal complex of being represented by general formula (Ic) also has compound described below.
[changing 1]
In these object lessons, particularly preferably be [IrCl 5(S-methyl thiourea)] 2-, [IrCl 5(5-methylthiazol)] 2-Perhaps [IrCl 5(5-chlorine dithiazole)] 2-
The object lesson of the metal complex of above-mentioned general formula (Ic) has 10 -3Second above, 3 seconds average electronics of less than is put the time slowly.
Not only enumerate the illumination conversion adulterant of these object lessons, and vigour adulterant and high photosensitivity adulterant also can discuss slowly by means of electronics the time of putting.The vigour adulterant utilizes doped portion to catch the photoelectron that exposure produces, no longer emit or behind the trapped electrons through for a long time after (several hours to several years) with its release, turn usefulness into thereby produce vigour.On the other hand, the high photosensitivity adulterant of six cyano group iron and so on, as Bulgarian Chem.Commun., 20 (1993) 350-368, Radiat.Eff.Defects Solids 135 (1995) 101-104, J.Phys.:CondensMatter, described in 9 (1997) 3227-3240 etc., by in silver halide particle, importing the shallow electronics trap that causes by the Coulomb field, doped portion has Xu who is exceedingly fast and puts the time, carries out photoelectronic catching-discharge repeatedly, to time that silver ion between lattice is supplied to or to the apparent non-inactivation of going up of the time that silver ion between lattice moves, photoelectron can be trapped on the conduction band, produces high photosensitivityization.General formula among the present invention (II) and general formula (III) are equivalent to vigour adulterant and high photosensitivity adulterant respectively, the following describes their preferred compound.
The metal complex of preferably selecting for use among the present invention by following general formula (II) expression below is described.
General formula (II)
[MX’ (6-q)L’ q] r
M：Cr、Mo、Mn、Re、Fe、Ru、Os、Co、Rh、Ir、Pd、Pt、Cu
X ': halogen ion
L ': mineral compound or organic compound arbitrarily
The integer of q:0-6 (wherein, under the situation of Ir, be 0, preferably the integer of 0-2)
The integer of r:-5 to+4 (preferably-4 to-1 integer)
X ' is fluoride ion, chloride ion, bromide ion or iodide ion, wherein preferably chlorion and bromide ion.X ' can be identical each other, also can be different.L ' can be a mineral compound, also can be organic compound, can have electric charge, also can neutral, and preferably uncharged mineral compound.L ' is H preferably 2The heterogeneous ring compound of O, NO, NS or five-membered ring or six membered ring.L ' exists when a plurality of, and L ' can be identical each other, also can be different.
In the metal complex of general formula (II), preferably by the metal complex of following general formula (IIa) expression.
General formula (IIa)
[M IIX a’ (6-q’)L a’ q’] r’
M II：Re、Ru、Os、Rh
X A ': the halogen ion
L A ': H 2The heterogeneous ring compound of O, NO, NS or five-membered ring or six membered ring
Q ': 0,1,2 or 3 (the preferably integers of 0-2)
R ' :-4 to 1 integer (preferably-4 to-1 integer)
X A 'Identical with the implication of X ' in the general formula (II), its preferred range is also identical.X A 'Can be identical each other, also can be different.L A 'Preferably, work as M IIDuring for Ru, be NO, NS, H 2The heterogeneous ring compound of O or five-membered ring or six membered ring is worked as M IIDuring for Os, be NO or NS, work as M IIDuring for Rh, be H 2O.At M IIDuring for Ru in the preferred heterogeneous ring compound; preferentially select imidazoles for use; pyridine or pyrazine; preferably they on the ring skeleton in conjunction with substituting group arbitrarily, described substituting group is halogen (fluorine preferably; chlorine; bromine; iodine); methoxyl; ethoxy; carboxyl; the methoxyl carboxyl; acyl group; acetyl group; chloroformyl; sulfydryl; methyl mercapto; thioformyl; thiocarboxyl group; two thiocarboxyl groups; sulfino; sulfo group; sulfamoyl; methylamino; cyano group; isocyano group; cyanato-; different cyanato-; thiocyano; the isocyanide sulfenyl; hydroxyl amino; oxyimino; carbamyl; nitroso-; nitro; diazanyl; hydrazono-or azido.L A 'There is when a plurality of L A 'Can be identical each other, also can be different.
Enumerate preferred object lesson below, but the invention is not restricted to these examples by the metal complex of general formula (II) expression.
[ReCl 6] 2-
[ReCl 5(NO)] 2-
[RuCl 6] 2-
[RuCl 6] 3-
[RuCl 5(NO)] 2-
[RuCl 5(NS)] 2-
[RuBr 5(NS)] 2-
[OsCl 6] 4-
[OsCl 5(NO)] 2-
[OsBr 5(NS)] 2-
[RhCl 6] 3-
[RhCl 5(H 2O)] 2-
[RhCl 4(H 2O) 2] -
[RhBr 6] 3-
[RhBr 5(H 2O)] 2-
[RhBr 4(H 2O) 2] -
[PdCl 6] 2-
[PtCl 6] 2-
Wherein, particularly preferably be [OsCl 5(NO)] 2-Or [RhBr 6] 3-
In the metal complex of general formula (III), preferably by the metal complex of following general formula (IIIa) expression.
General formula (IIIa)
[M’X” (6-y)L” y] z
M’：Mg、Ca、Ti、Zr、Fe、Ru、Co、Ni、Cu、Zn
X ": halide ion or cyanide ion (under the situation of Ru, being cryanide ion wherein)
L ": mineral compound or organic compound arbitrarily
The integer of y:0-6
The integer of z:-5 to+4 (preferably-4 to 0 integer)
Specifically, as general formula (IIIa) [MgCl preferably 6] 4-, [Mg (imidazoles) 6] 4-, [CaCl 6] 4-, [TiCl 4(imidazoles) 2] -, [ZrCl 4(imidazoles) 2] -, [Fe (CN) 6] 4-, [Fe (CN) 5(SCN)] 4-, [Fe (CN) 5(OCN)] 4-, [Fe (CN) 5(dimethyl sulfoxylate (dimethylsulfoxyside))] 3-, [Fe (CN) 5(pyrazine)] 3-, [Fe (CN) 5(4,4 '-two pyridines)] 3-, [Ru (CN) 6] 4-, [Ru (CN) 5(pyrazine)] 3-, [Ru (CN) 5(4,4 ' two pyridines)] 3-, [Co (CN) 6] 4-, [CoCl 2(imidazoles) 2] 0, [CoCl 2(glyoxal ethyline 2) 0, [Co (imidazoles) 6] 4-, [NiCl 2(pyridine) 2] 3-, [CuCl 2(pyridine) 2] 3-And [Zn (imidazoles) 6] 4-
At the above metal complex of enumerating is under the anionic situation, during with salt forming cation, preferentially selects the kation that easily is dissolved in water for use as this counter cation.Specifically can be alkali metal ions such as sodion, potassium ion, ruthenium ion, cesium ion and lithium ion, preferably ammonium ion and alkyl phosphate ion.These metal complexes except water, can also be dissolved in the mixed solvent of water and the suitable organic solvent that can mix with it (for example alcohols, ethers, glycols, ketone, ester class, amide-type etc.) and use.By the metal complex of general formula (I) expression, preferably in the particle forming process, press per 1 moles of silver 1 * 10 -10Mole is to 1 * 10 -3The amount of mole is added, preferably by per 1 moles of silver 1 * 10 -8Mole is to 1 * 10 -5The amount of mole is added.By the metal complex of general formula (II) expression, can in the particle forming process, press per 1 moles of silver 1 * 10 -11Mole is to 1 * 10 -6The amount of mole is added, preferably by 1 * 10 -9Mole is to 1 * 10 -7The amount of mole is added.By the metal complex of general formula (III) expression, preferably in the particle forming process, press per 1 moles of silver 1 * 10 -8Mole is to 1 * 10 -2The amount of mole is added, more preferably by 1 * 10 -6Mole is to 5 * 10 -4The amount of mole is added.
In the present invention, above-mentioned metal complex can directly add in the reaction solution when forming silver halide particle, perhaps, add in the halide solution that is used to form silver halide particle or in other the solution, form in the reaction solution by adding particle to, preferably it is added in the silver halide particle.In addition, in the particle of also can in advance metal complex being packed into, with the slaking of gained particulate physics, then in the silver halide particle of packing into.In addition, can also preferably these methods be used in combination, make silver halide particle contain metal complex.
When packing into these metal complexes in the silver halide particle, can make it in the inner evenly existence of particle, also can open flat 4-208936, spy as the spy opens flat 2-125245, spy open described in the flat 3-188437, make in its superficial layer that is present in particle, can also make coordination compound only be present in particle inside, on particle surface, apply the layer that does not contain coordination compound.In addition, described in US5252451 and US5256530 instructions, also coordination compound can be added in the particle, with the slaking of gained particulate physics, with the modification of particle surface phase.In addition, these methods can also be used in combination, multiple coordination compound is joined in 1 silver halide particle.
Silver emulsion of the present invention contains specific silver halide particle.The shape of particle has no particular limits, and has basically preferably that { crystalline particle of the crystalline particle of the cube of 100} face, 14 bodies (summits of these particles), 8 bodies, first type surface are by { 100} face or { the tabular particle of aspect ratio more than 3 that the 111} face constitutes.So-called aspect ratio is meant the diameter of a circle suitable with projected area divided by the resulting value of particle thickness.
The silver chloride containing ratio must be considered from the angle of fast processing, preferably more than 93% (mole), preferably more than 95% (mole) more than 90% (mole).Consider that from vigour, good latent-image stability angle the silver bromide containing ratio is advisable at 0.1-7% (mole), preferably 0.5-5% (mole).Consider that from the angle of high photosensitivity and vigour under high illumination exposure the silver iodide containing ratio is advisable at 0.02-1% (mole), preferably 0.05-0.50% (mole), preferably 0.07-0.40% (mole).Specific silver halide particle among the present invention, chlorine iodine silver bromide particle preferably, the chlorine iodine silver bromide particle that preferably above-mentioned halogen is formed.
Specific silver halide particle in the silver emulsion of the present invention preferably has phase that contains silver bromide and/or the phase that contains silver iodide.Here the said phase that contains silver bromide or contain silver iodide is meant high position around the concentration ratio of silver bromide or silver iodide.Containing the phase of silver bromide or contain the phase of silver iodide and the composition of halogen on every side, can be continually varying, also can be jumpy.Containing silver bromide or containing the phase of silver iodide like this can form the layer that concentration roughly has certain amplitude in certain part place in particle, also can be the maximal point with expansion.The silver bromide containing ratio of part that contains the phase of silver bromide is advisable more than 5% (mole), preferably 10-80% (mole), preferably 15-50% (mole).The silver iodide containing ratio of part that contains the phase of silver iodide is advisable more than 0.3% (mole), preferably 0.5-8% (mole), preferably 1-5% (mole).In addition, such phase that contains silver bromide or contain silver iodide also can be stratiform and have a plurality ofly in each particle, and silver bromide separately or silver iodide containing ratio can be different, contain phase but must minimumly respectively have 1.
The phase that contains silver bromide of silver emulsion of the present invention or contain the phase of silver iodide is stratiform and surrounds each particle, and this point is most important.Be stratiform and surround particle and phase that contains silver bromide that forms or the phase that contains silver iodide, the peripheral direction along particle in every has uniform CONCENTRATION DISTRIBUTION, and this is a preferred scheme.But, be stratiform surround the phase that contains silver bromide of particle or contain silver iodide mutually in, also can on the peripheral direction of particle, have the maximal point or the minimal point of silver bromide or silver iodide concentration, have CONCENTRATION DISTRIBUTION.For example, be stratiform and surround the phase that contains silver bromide of particle or contain under the situation of phase of silver iodide having near the particle surface, the silver bromide of particle corner angle or edge or silver iodide concentration form the concentration different with first type surface sometimes.In addition, be the phase that contains silver bromide that stratiform surrounds particle and contain silver iodide mutually, also can exist fully isolatedly, have phase that contains silver bromide of not surrounding particle or the phase that contains silver iodide at the privileged site of particle surface.
Contain at silver emulsion of the present invention under the situation of phase of silver bromide, this phase that contains silver bromide preferably forms stratiform, has the silver bromide peak concentration in the inside of particle.In addition, contain at silver emulsion of the present invention under the situation of phase of silver iodide, this phase that contains silver iodide preferably forms stratiform, has the silver iodide peak concentration on the surface of particle.The phase that contains silver bromide like this or contain the phase of silver iodide, consider from the angle that improves local concentration with less silver bromide or agi content, preferably the silver amount more than 3%, below 30% with particle volume constitutes, and preferably constitutes with the silver amount more than 3%, below 15%.
Silver emulsion of the present invention, the phase that preferably contains silver bromide simultaneously with contain silver iodide mutually both.In this case, the phase that contains silver bromide with contain silver iodide can be in same position in the particle mutually, also can be in different positions, the angle that calm particle easy to control forms is considered, preferably is in different positions.In addition, contain silver bromide mutually in also can contain silver iodide, otherwise, contain silver iodide mutually in also can contain silver bromide.In general, the iodide that add in forming high-silver chloride particle process are exuded on the particle surface than bromide is easier, thereby contain forming easily mutually of silver iodide near particle surfaces.Therefore, under the phase that contains silver bromide and the situation that is in different parts in the particle mutually that contains silver iodide, the inboard in the phase that contains silver iodide that preferably contains silver bromide forms.In this case, near the outside of the phase that contains silver iodide particle surface can also be provided with other the phase that contains silver bromide.
In order to realize needed bromide sliver content of effect of the present invention such as high photosensitivity and vigourization or agi content, form along with particle is inner and to contain the phase of silver bromide or contain the phase of silver iodide and increase, the possible required above silver chloride content that reduces, the infringement fast processing.Therefore, for these functions that make the control photographic effect concentrate near surface in the particle, the phase that preferably contains silver bromide with contain the mutually adjacent of silver iodide.Consider from these angles, the phase that contains silver bromide preferably from the inboard calculate particle volume 50% to 100% the optional position form, the phase that contains silver iodide preferably forms on 85% to 100% optional position of particle volume.In addition, more preferably, contain silver bromide particle volume 70% to 95% in the optional position on form, contain silver iodide particle volume 90% to 100% in the optional position on form.
The bromide ion that is used for making silver emulsion of the present invention contain silver bromide or silver iodide or the importing of halogen ion, can add the solution of bromide salt or iodide salt separately, perhaps also can add the solution of bromide salt or iodide salt with the interpolation of silver salt solution and perchloride salt solusion.In the latter case, can add bromide salt or iodide salt solution and perchloride solution respectively, add after perhaps also can making the mixed solution of bromide salt or iodide salt and perchloride salt.Bromide salt or iodide salt are to add with the form of the dissolubility salt of the bromide salt of alkaline metal or earth alkali metal or iodide salt and so on.Perhaps also can import by dissociated-bromine ion or iodide ion from organic molecule by described in the US5389508 instructions.In addition, as other bromide ion or iodide ion source, can also use small silver bromide particle or small silver iodide particle.
The interpolation of bromide salt or iodide salt solution can be concentrated in a certain period that particle forms and be carried out, and carries out in also can be during certain.In perchloride emulsion, import the position of iodide ion, be restricted aspect the emulsion that obtains high photosensitivity, low photographic fog.The importing of iodide ion is carried out in the inside of emulsion particles, and photosensitive increase is more little, thereby, iodide salt solution be added on the 50% better of particle volume toward the outside, preferably, preferably carry out laterally from 85% from 70% laterally.In addition, the interpolation of iodide salt solution preferably finishes in 98% inboard of particle volume, preferably finishes in 96% inboard.The inboard a little end that is added on particle surface of iodide salt solution can obtain the more emulsion of high photosensitivity, low photographic fog.
On the other hand, the interpolation of bromide salt solution is preferably carried out in the 50% past outside of particle volume, preferably carries out toward the outside 70%.
Bromide ion or iodide ion be the CONCENTRATION DISTRIBUTION on the depth direction in particle, can adopt corrosion/TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method, the TRIFTII type TOF-SIMS that for example uses Phi Evans company to make measures.About the TOF-SIMS method, can write at Japanese Surface Science in kind Co., Ltd. of " surface analysis technique selects the book secondary ion mass spectrometry with halogen labeling " ball (publishing in 1999) has detailed record.When adopting corrosion/TOF-SIMS method to analyze emulsion particles, even finish the interpolation of iodide salt solution in the inboard of particle, iodide ion also can be exuded on the particle surface, thereby can analyze.Emulsion of the present invention preferably, when adopting corrosion/TOF-SIMS method to analyze, iodide ion has peak concentration at particle surface, the concentration of iodide ion decays to the inside gradually, bromide ion has peak concentration in particle inside.If bromide sliver content is high to a certain degree, also can adopt X-ray diffraction method to measure the local concentration of silver bromide.
In this manual, the ball equivalent diameter is represented with the diameter of the ball with the volume that equates with the volume of each particle.Emulsion of the present invention is that monodispersed particle constitutes by particle size distribution preferably.The coefficient of alteration of the ball equivalent diameter of all particles of the present invention is being advisable below 20%, preferably below 15%, preferably below 10%.The coefficient of alteration of described ball equivalent diameter is to represent with respect to the percent of the mean value of ball equivalent diameter with the standard deviation of the ball equivalent diameter of various particles.At this moment,, can in one deck, blending use above-mentioned single emulsion that disperses in order to obtain wide exposure latitude, also can the above-mentioned single emulsion that disperses of lamination coating.
The present invention is used to have the silver halide emulsion layer that contains uranidin and be formed into toner, contains silver halide emulsion layer that pinkish red pigment is formed into toner, contains silver halide emulsion layer that cyanine is formed into toner at least under the situation of the silver halide colour photographic sensitive material of each one deck, contain the ball equivalent diameter of silver emulsion that uranidin is formed into the silver halide emulsion layer of toner and below 0.6 μ m, be advisable.Contain pinkish red pigment and be formed into the silver halide emulsion layer of toner and contain the ball equivalent diameter of silver emulsion that cyanine is formed into the silver halide emulsion layer of toner and below 0.5 μ m, be advisable, preferably below the 0.4 μ m.In this manual, the ball equivalent diameter is to represent with the diameter of the ball with the volume that equates with the volume of each particle.The particle of ball equivalent diameter 0.6 μ m is equivalent to the cube particle of the about 0.48 μ m of the length of side, the particle of ball equivalent diameter 0.5 μ m is equivalent to the cube particle of the about 0.40 μ m of the length of side, the particle of ball equivalent diameter 0.4 μ m is equivalent to the cube particle of the about 0.32 μ m of the length of side, and the particle of ball equivalent diameter 0.3 μ m is equivalent to the cube particle of the about 0.24 μ m of the length of side.In silver emulsion of the present invention, also can contain the silver halide particle that silver emulsion contained (the being specific silver halide particle) silver halide particle in addition that defines among the present invention.But, the silver emulsion that defines among the present invention, the total projection area of all particles must be the silver halide particle that defines among the present invention more than 50%, preferably more than 80%, preferably more than 90%.
Specific silver halide particle in the silver emulsion of the present invention except the iridium complex compound by general formula (I) expression, can also contain the iridium complex compound that whole 6 dentates are made of Cl, Br or I.In this case, Cl, Br or I also can mix existence in 6 coordination compoundes.Have Cl, Br or I as the iridium complex compound of dentate be comprised in contain silver bromide mutually in can obtain the tone of vigour under high illumination exposure, thereby be particularly preferred scheme.
Enumerate the object lesson of the iridium complex compound that whole 6 dentates are made of Cl, Br or I below, but the invention is not restricted to these examples.
[IrCl 6] 2-
[IrCl 6] 3-
[IrBr 6] 2-
[IrBr 6] 3-
[IrI 6] 3-
In the present invention, except above-mentioned metal complex, other metallic ion can also mix on the inside of silver halide particle and/or surface.Employed metallic ion is preferably selected transition metal ion for use.More preferably, these metallic ions have dentate, use with the form of 6 coordination octahedral build coordination compoundes.Using under the situation of mineral compound as dentate; can use cyanide ion, halogen ion, thiocyanic acid, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl radical ion or sulfo-nitrosyl radical ion; can also on any metallic ions such as iron, ruthenium, osmium, lead, cadmium and zinc, coordination use, also can in 1 coordination compound molecule, use multiple dentate.In addition, using under the situation of organic compound as dentate, can enumerate the heterogeneous ring compound of the carbon number of main chain as preferred organic compound at the chain compound below 5 and/or 5 Yuans rings or 6 Yuans rings.Preferred organic compound is the compound that has nitrogen-atoms, phosphorus atoms, oxygen atom or sulphur atom in molecule as the coordination atom to metal, particularly preferably be furans, thiophene, oxazole, isoxazole, thiazole, isothiazole, imidazoles, pyrazoles, triazole, furazan, pyrans, pyridine, pyridazine, pyrimidine, pyrazine, preferably be basic framework, in these compounds, import substituent compound with these compounds.
The combination of metallic ion and dentate, the preferably combination of ferric ion and ruthenium ion and cryanide ion.In the present invention, preferably with above-mentioned metal complex and these compounds and usefulness.In these compounds, preferably cryanide ion accounts for over halfly in the coordination number to center metallic iron or ruthenium, and remaining coordination position is by thiocyanate radical, ammonia, water, nitrosyl radical ion, dimethyl sulfoxide, pyridine, pyrans or 4, and 4 '-two pyridines occupy.Preferably, 6 coordination positions of central metal are all occupied by cryanide ion, form six cyano group iron complex compounds or six cyano group ruthenium complexes.These are the coordination compound of dentate with the cryanide ion, press per 1 moles of silver 1 * 10 in the particle forming process -8Mole is to 1 * 10 -2The amount of mole is added to, preferably by 1 * 10 -6Mole is to 5 * 10 -4The amount of mole is added.
The silver emulsion that uses among the present invention is preferably selected the silver emulsion of the golden sensitizing of enforcement as known in the art for use.This be because, by implementing golden sensitizing, can make the emulsion high photosensitivityization, when carrying out scan exposure, can reduce the fluctuation of photographic property with laser etc.In order to implement golden sensitizing, gold (I) compound that can use various inorganic gold compounds or have gold (I) coordination compound of inorganic dentate and have the organic coordination base.Described inorganic gold compound, for example can use gold chloride or its salt, described gold (I) coordination compound with inorganic dentate for example can use two thiosulfuric acid gold compounds such as two sulfo-hydracid gold compounds such as dithiocyanic acid gold (I) potassium and two gold aurothiosulfates (I) trisodium.
Described gold (I) compound with organic coordination base (organic compound), two gold (I) intermediate ion heterocyclic that can use the spy to open to put down in writing in the flat 4-267249 communique, for example two (1,4,5-trimethyl-1,2,4-triazole father-in-law-3-mercaptide) oleate (I) tetrafluoroborate; Organic sulfydryl gold (I) coordination compound of putting down in writing in Te Kaiping 11-218870 number number communique, for example two (1-[3-(2-sulfonation benzamido) phenyl]-5-mercapto-tetrazole sylvite) potassium oleate (I) 5 hydrates; Gold (I) compound of the nitrogen compound anion binding of putting down in writing in the Te Kaiping 4-268550 communique, for example two (1-methyl hydantoin acetate) gold (I) sodium salt tetrahydrate.These have gold (I) compound of organic coordination base, use compound synthetic in advance, segregation, in addition, the organic coordination base can also be mixed with Au compound (for example gold chloride or its salt), directly add in the emulsion without segregation.In addition, can also in emulsion, add organic dentate and Au compound (for example gold chloride or its salt) respectively, in emulsion, generate gold (I) compound with organic coordination base.
In addition, can also use gold (I) the thiol salinization compound of putting down in writing in the US3503749 communique, and special open that flat 8-69074, spy open flat 8-69075, the spy opens the compound of putting down in writing in the flat 9-269554 communique, the compound of putting down in writing in US5620841, US5912112, US5620841, US5939245, the US5912111 number number communique.The addition of these compounds can according to circumstances change in wide scope, generally is per 1 mole of silver halide 5 * 10 -7-5 * 10 -3Mole, preferably 5 * 10 -6-5 * 10 -4Mole.
In addition, can also use the colloid aurosulfo, its manufacture method is at ReserchDisclosure, 37154, Solid State Ionics the 79th volume, 60-66 page or leaf, nineteen ninety-five publishes, and Compt.Rend.Hebt.Seances Acad.Sci.Sect.B the 263rd volume, 1328 pages, be documented in the publication in 1966 etc.In above-mentioned ReserchDisclosure communique, put down in writing the method for when making the colloid aurosulfo, using the thiocyanates ion, but also can replace sulfide compounds such as using methionine or sulphur diethanol.Described colloid aurosulfo can use the various sizes size, and mean grain size is better below 50nm, preferably below the mean grain size 10nm, preferably below the mean grain size 3nm.Particle size can be measured by the TEM photo.In addition, the composition of colloid aurosulfo can be Au 2S 1, also can be Au 2S 1-Au 2S 2The composition of such sulphur surplus, the preferably composition of sulphur surplus, preferably Au 2S 1.1-Au 2S 1.8The composition analysis of colloid aurosulfo for example can take out the aurosulfo particle earlier, adopts analytical approachs such as ICP or iodometry to obtain the content of gold and the content of sulphur respectively then.Be dissolved in gold ion in the liquid phase, sulphion (comprising sulfuretted hydrogen or its salt) if be present in the aurosulfo colloid, can exert an influence, therefore isolate the aurosulfo particle, and then analyze by methods such as ultrafiltration for the composition analysis of aurosulfo particle.The addition of aurosulfo colloid can according to circumstances change in wide scope, and in general with respect to 1 mole of silver halide, gold atom is 5 * 10 -7～5 * 10 -3Mole, preferably 5 * 10 -6～5 * 10 -4Mole.
Can in a part, carry out sulphur sensitizing with golden sensitizing, can use to discharge AuCh -Molecule.In the formula, Au represents Au (I), and Ch represents sulphur atom, selenium atom, tellurium atom.Describedly can discharge AuCh -Molecule, for example can enumerate the gold compound of representing by AuCh-L.Wherein, L represents to combine with AuCh and constitutes the atomic group of molecule.For Au, with the Ch-L more than one dentate of coordination again.In addition, the feature of the gold compound of being represented by AuCh-L is, when reacting in solvent under the silver ion coexistence, at Ch is under the situation of S, generates the AgA United States Patent (USP) easily, is under the situation of Se at Ch, generating AgA United States Patent (USP) e easily, is under the situation of Te at Ch, generates AgauTe easily.It is acylated compound that such compound can be enumerated L, can enumerate the compound by the chemical formula (AuCh 1) shown in following, (AuCh 2), (AuCh 3) expression in addition.
Formula (AuCh 1) R 1-X 1-M 1-ChAu
In the formula, Au represents Au (I), and Ch represents sulphur atom, selenium atom, tellurium atom, M 1Expression replaces or unsubstituted methylene, X 1Expression oxygen atom, sulphur atom, selenium atom, NR 2, R 1Expression and X 1In conjunction with the atomic group (for example organic groups such as alkyl, aryl, heterocyclic radical) that constitutes molecule, R 2Expression hydrogen atom and substituting group (for example organic groups such as alkyl, aryl, heterocyclic radical).R 1And M 1Also can be bonded to each other and form ring.
Preferably, Ch is sulphur atom and selenium atom, X in by the compound of chemical formula (AuCh 1) expression 1Be oxygen atom, sulphur atom, R 1Be alkyl, aryl.Can enumerate as the example of compound more specifically; the Au of thiosugar (I) salt (aurothioglucose such as α aurothioglucose, gold are crossed acetyl group thioglucose, golden sulphur mannose, golden sulphur galactose, golden sulphur arabinose etc.); the Au of seleno sugar (I) salt (gold is crossed acetyl group seleno glucose, gold is crossed acetyl group seleno mannose etc.), the Au of telluro sugar (I) salt etc.Wherein, the anomer position hydroxyl of thiosugar, seleno sugar, telluro sugar expression sugar is respectively by the compound of SH base, SeH base, the replacement of TeH base.
Formula (AuCh 2) W 1W 2C=CRChAu
In the formula, Au represents Au (I), and Ch represents sulphur atom, selenium atom, tellurium atom, R 3And W 2Expression substituting group (for example organic groups such as hydrogen atom, halogen atom and alkyl, aryl, heterocyclic radical), W 1The special substituent constant σ of expression Hamann p value be on the occasion of electron withdraw group.R 3And W 1, R 3And W 2, W 1And W 2Also can be bonded to each other and form ring.
Preferably, Ch is sulphur atom and selenium atom, R in by the compound of chemical formula (AuCh 2) expression 3Be hydrogen atom and alkyl, W 1And W 2Be that the special substituent constant σ of Hamann p value is the electron withdraw group more than 0.2.Can enumerate (NC) as the example of compound more specifically 2C=CHSAu, (CH 3OCO) 2C=CHSAu, CH 3CO (CH 30CO) C=CHSAu etc.
(AuCh3)??W 3-E-ChAu
In the formula, Au represents Au (I), and Ch represents sulphur atom, selenium atom, tellurium atom, and E represents to replace or unsubstituted ethylidene W 3Expression be the special substituent constant σ of Hamann p value be on the occasion of electron withdraw group.
Preferably, Ch is sulphur atom and selenium atom in by the compound of chemical formula (AuCh3) expression, E be have the special substituent constant σ of Hamann p value be on the occasion of the ethylidene of electron withdraw group, W 3Be that the special substituent constant σ of Hamann p value is the electron withdraw group more than 0.2.The addition of these compounds can according to circumstances change in wide scope, and normally per 1 mole of silver halide is 5 * 10 -7～5 * 10 -3Mole, preferably 3 * 10 -6～3 * 10 -4
In the present invention, can also or use combinations such as noble metal sensitizing beyond the gold compound, particularly preferably be and sulphur sensitizing, the combination of selenium sensitizing above-mentioned golden sensitizing and other sensitizing rule such as sulphur sensitizing, selenium sensitizing, tellurium sensitizing, reduction sensitization.
In order to prevent to produce photographic fog in manufacturing process, preservation process or the photograph processing procedure at photosensitive material, perhaps, can in silver emulsion of the present invention, add all cpds or their precursor in order to make the photographic property stabilization.The object lesson of these compounds can adopt the spy to open the compound of putting down in writing in the 39-72 page number communique of clear 62-215272 communique, especially preferentially select the 5-arylamino of putting down in writing in EP0447647 number number communique-1 for use, 2,3,4-thiatriazole compound (having an electron withdraw group on this aromatic yl residue at least).
In addition, in the present invention, in order to improve the retention of silver emulsion, can also use: the spy opens the hydroxamic acid derivant of putting down in writing in the flat 11-109576 communique communique, put down in writing in the Te Kaiping 11-327094 communique communique, with the carbonyl adjacency, two ends have the ring-type ketone (ketone of being represented by general formula (S1) particularly of two keys that amino or hydroxyl replace, the 0036-0071 paragraph of the document can be taken in this instructions as a reference), catechol that the sulfo group put down in writing in the Te Kaiping 11-143011 communique communique replaces and hydroquinones (for example 4,5-dihydroxy-1, the 3-benzenedisulfonic acid, 2,5-dihydroxy-1, the 4-benzenedisulfonic acid, 3, the 4-dihydroxy benzenes sulfonic acid, 2, the 3-dihydroxy benzenes sulfonic acid, 2, the 5-dihydroxy benzenes sulfonic acid, 3,4,5-trihydroxy benzene sulfonic acid and their salt etc.), (record of the 56th row-Di 11 hurdles, US5556741 instructions the 4th hurdle the 22nd row is particularly suitable for the present invention to the hydroxyl amine of being represented by general formula (A) in the US5556741 instructions, this part can be taken in this instructions as a reference), the spy opens in the flat 11-102045 communique the water-soluble reductive agent by general formula (I)-(III) expression.
In addition, show photosensitive so-called spectrum sensitivity, in silver emulsion of the present invention, can also contain the beam split sensitizing coloring matter in order to give in desirable optical wavelength range.As at the employed beam split sensitizing coloring matter of beam split sensitizing blue, green, red scope, for example can enumerate F.M.Harmer work Heterocyclic compounds-Cyanine dyes and related compounds (John Wiley﹠amp; Sns[New York, London] company published in 1964) pigment put down in writing in number communique.Concrete compound and beam split sensitizing method can adopt above-mentioned spy to open the content of putting down in writing in the 22nd page of upper right hurdle-Di 38 page number communiques of clear 62-215272 communique.In addition, the red property of sense beam split sensitizing coloring matter as the high silver halide emulsion particles of silver chloride containing ratio, consider from the temperature dependency equal angles of stability, adsorption strength, exposure, especially preferentially select for use the spy to open the beam split sensitizing coloring matter of putting down in writing in the flat 3-123340 communique communique.
The addition of these beam split sensitizing coloring matters can according to circumstances change in wide scope, generally is that per 1 mole of silver halide is 0.5 * 10 -6～1.0 * 10 -2Mole, preferably 1.0 * 10 -6～5.0 * 10 -3
Silver halide colour photographic sensitive material of the present invention (following be called for short sometimes " photosensitive material "), be the silver halide colour photographic sensitive material that on supporting mass, has following each one deck at least: contain silver halide emulsion layer that uranidin is formed into toner, contain silver halide emulsion layer that pinkish red pigment is formed into toner, contain the silver halide emulsion layer that cyanine is formed into toner, it is characterized in that having at least one deck to contain silver emulsion of the present invention in the described silver halide emulsion layer.In the present invention, above-mentionedly contain the effect that silver halide emulsion layer that uranidin is formed into toner plays yellow color layer, above-mentionedly contain the effect that silver halide emulsion layer that pinkish red pigment is formed into toner plays the magenta color layer, above-mentionedly contain the effect that silver halide emulsion layer that cyanine is formed into toner plays the cyan color layer.The silver emulsion that contains separately in above-mentioned yellow color layer, magenta color layer and the cyan color layer has photonasty for the light (for example light of blue spectrum, green fields and red color range) of the wavelength coverage that differs from one another.
Photosensitive material of the present invention except above-mentioned yellow color layer, magenta color layer and cyan color layer, can also have following hydrophilic colloid layer, antihalation layer, middle layer and dyed layer as required.
In photosensitive material of the present invention, can use known in the past photosensitive material and adjuvant.
For example, the supporting mass as photograph usefulness can use transmission-type supporting mass and reflection-type supporting mass.Described transmission-type supporting mass, can use transparent cushion compounds such as cellulose nitrate substrate or polyethylene terephthalate, preferentially select for use 2, the supporting mass of information recording layer such as magnetosphere is set on the polyester of 6-naphthalene dicarboxylic acids (NDCA) and ethylene glycol (EG) or the polyester of NDCA and terephthalic acid (TPA) and EG etc.Described reflection-type supporting mass can use by a plurality of polyethylene layers and polyester layer lamination, contains the reflection supporting mass of Chinese whites such as titanium dioxide in one deck at least of such water-resistant resin layer (laminate layers).
As the reflection-type supporting mass of preferentially selecting for use among the present invention, can enumerate the supporting mass of the polyolefin layer that on the paper substrate body that silver halide emulsion layer one side is set, has the band micro-pore.Polyolefin layer also can be made of multilayer, in this case preferably, do not have micro-pore (for example polypropylene, tygon) with the polyolefin layer of the gelatin layer adjacency of silver halide emulsion layer side, and be polyolefin (for example polypropylene, tygon) with micro-pore near paper substrate body one side.The density of these multilayers between paper substrate body and photograph formation layer or the polyolefin layer of one deck is advisable at 0.40-1.0g/ml, preferably 0.50-0.70g/ml.The thickness of these multilayers between paper substrate body and photograph formation layer or the polyolefin layer of one deck is advisable at 10-100 μ m, preferably 15-70 μ m.In addition, polyolefin layer is advisable at 0.05-0.2 with the ratio of the thickness of paper substrate body, preferably 0.1-0.15.
In addition, consider from the angle that improves reflection supporting mass rigidity, preferably polyolefin layer is set, in this case in a side (back side) opposite with the photograph formation layer of above-mentioned paper substrate body, the polyolefin layer at the back side is the tygon or the polypropylene of surface dulling preferably, preferably polypropylene.The polyolefin layer at the back side is 5-50 μ m preferably, 10-30 μ m preferably, and in addition, density is 0.7-1.1g/ml preferably.In reflection supporting mass of the present invention, the optimal way that is arranged on the polyolefin layer on the paper substrate body can be enumerated the spy and open flat 10-333277, spy and open that flat 10-333278, spy open flat 11-52513, the spy opens the example of being put down in writing in flat 11-65024 communique, EP0880065 and the EP0880066 instructions.
Preferably contain fluorescer in the above-mentioned water-resistant resin layer.In addition, also can form the hydrophilic colloid layer that disperses to contain above-mentioned fluorescer by other approach.Described fluorescer can use Ben Bing oxazole class, Coumarins, pyrazolines etc., preferably benzoxazolyl naphthalene class and phenylpropyl alcohol oxazolyl stilbene fluorescent bleaches.Its consumption has no particular limits, preferably 1～100mg/m 2Under the situation in being mixed into water-resistant resin, it is with respect to the mixing ratio of resin preferably 0.0005～3% (quality), preferably 0.001～0.5% (quality).
As the reflection-type supporting mass, also can on transmission-type supporting mass or above-mentioned reflection-type supporting mass, be coated with the hydrophilic colloid layer that contains Chinese white.In addition, the reflection-type supporting mass also can be the supporting mass with metal surface of specular reflective or second kind of scattered reflection.
In addition, as the employed supporting mass of photosensitive material of the present invention, can also use white polyester class supporting mass or the supporting mass of the layer contain Chinese white is set on the supporting mass with silver halide emulsion layer one side.In order further to improve sharpness, preferably be coated with and prevent the halation layer at the silver halide emulsion layer coated side of supporting mass or the back side.Particularly, for no matter be adopt reflected light also in transmitted light can both watch the image of demonstration, preferably the transmission density of supporting mass is set in 0.35～0.8 the scope.
In photosensitive material of the present invention, in order to improve the purpose of image vividness, can in the hydrophilic colloid floor, add the process of putting down in writing in EP0337490A2 instructions the 27th～76 page number communique and handle the dyestuff (wherein preferentially selecting the oxa-cyanine type dye for use) that can decolour, the optical reflection density of photosensitive material under 680nm is reached more than 0.70, the alcohols surface-treated titanium dioxide such as (for example trimethylolethanes) that contains useful 2-4 valency in the water-resistant resin layer of supporting mass is reached more than 2% (quality), preferably more than 14% (quality).
In photosensitive material of the present invention, in order to prevent irradiation and halation or, in the hydrophilic colloid floor, can to add the process of putting down in writing in EP0337490A2 instructions the 27th～76 page number communique and handle the dyestuff (wherein preferentially selecting oxa-cyanine type dye, cyanine dye for use) that can decolour in order to improve the purposes such as security of safety lamp.In addition, can also add the dyestuff of putting down in writing in the EP0819977 instructions in the present invention.If increase use amount in these water-soluble dyes, look separates and the safety lamp security worsens sometimes.As the dyestuff that look separate to be worsened, can select for use the spy to open that flat 5-127324, spy open flat 5-127325, the spy opens the water-soluble dye of putting down in writing in the flat 5-216185 communique communique.
In the present invention, can use through processing dyed layer decolour replace water-soluble dye or with water-soluble dye usefulness also.Employedly can directly join with emulsion layer through handling the dyed layer decolour, can layer be that the middle layer is configured with what contain that processing colour mixtures such as gelatin or quinhydrones prevent agent also.This dyed layer preferably is arranged on the lower floor (supporting side) that develops the color with the emulsion layer of painted color primary colors of the same race.The dyed layer corresponding with each primary colors can all be set one by one, a part wherein also can randomly only be set.In addition, can also be provided with and carry out the painted dyed layer corresponding with a plurality of primary colors district.The optical reflection concentration of dyed layer, (in common printing machine exposure is the visible-range of 400～700nm in the employed wavelength coverage of exposure, under the situation of scan exposure the wavelength of employed scan exposure light source), the optical concentration value is being advisable more than 0.2, below 3.0 under the highest wavelength of optical concentration, preferably more than 0.5, below 2.5, preferably more than 0.8, below 2.0.
Form dyed layer and can adopt known method in the past, for example: the 8 pages of described dye well spies in the 3rd page of upper right hurdle to that open flat 2-282244 communique as the spy open the described dyestuff in hurdle, 11 pages of lower-lefts, the 3rd page of upper right hurdle to the of flat 3-7931 communique, are comprised in method in the hydrophilic colloid layer with the state of solia particle molecular dispersion; The method of mordant dyeing anionic property pigment in cationic polymer; Thereby make pigment be adsorbed on the method that is fixed in the particulates such as silver halide in the layer; The method of the use collargol of putting down in writing in the Te Kaiping 1-239544 communique communique etc.As the method for disperseing the micropowder of pigment with the solid shape, for example in the spy opens the 4th～13 page number communique of flat 2-308244 communique, put down in writing, made and contain at least water insoluble basically below the pH6 and be the method for water miscible micropowder dyestuff at least basically more than pH8.In addition, put down in writing the method for mordant dyeing anionic property pigment in cationic polymer in for example special the 18th～26 page number communique of opening flat 2-84637 communique.Preparation method about as the collargol of light absorber has detailed description in US2688601 and US3459563 instructions.In these methods, preferentially select for use to make method that contains the micropowder dyestuff and the method for using collargol.
Silver halide photographic sensitive material of the present invention can be used for colour negative, colour positive, colour reversal film, colour reversal sensitized paper, color sensitive paper etc., wherein preferably is used as color sensitive paper.Color sensitive paper preferably has yellow colour rendering silver halide emulsion layer, magenta colour rendering silver halide emulsion layer and cyan colour rendering silver halide emulsion layer each one deck at least, in general, these silver halide emulsion layers from the close-by examples to those far off are yellow colour rendering silver halide emulsion layer, magenta colour rendering silver halide emulsion layer, cyan colour rendering silver halide emulsion layer from supporting mass successively.
But, also can adopt different therewith layer structures.
The silver halide emulsion layer that contains yellow colour former can be configured in the arbitrary position on the supporting mass, but, contain under the situation that contains the dull and stereotyped particle of silver halide in the yellow colour former layer at this, preferably it is arranged on than the silver halide emulsion layer that contains the magenta colour coupler or contains one deck at least in the silver halide emulsion layer of cyan coupler apart from the farther position of supporting mass.In addition, from promote colour development, promote the desilverization, the angle that reduces the residual look that produces because of sensitizing coloring matter considers, the silver halide emulsion layer that contains yellow colour former is compared with other silver halide emulsion layer and preferably is arranged on apart from the supporting mass position farthest.In addition, consider that the silver halide emulsion layer that contains cyan coupler is the central stratum of other silver halide emulsion layer preferably, consider that the silver halide emulsion layer that contains cyan coupler is orlop preferably from reducing the angle that light fades from reducing the angle that Blix fades.In addition, each color layer of yellow, magenta and cyan also can constitute by 2 layers or 3 layers.For example, open as the spy that flat 4-75055, spy open flat 9-114035, the spy opens described in flat 10-246940 communique, the US5576159 instructions, also can form color layer not containing the color former layer of silver emulsion and silver halide emulsion layer in abutting connection with setting.
The silver emulsion that uses among the present invention and other material (adjuvant etc.) and the formation layer of taking a picture (layer configuration etc.) and the disposal route and the processing adjuvant that are used to handle this photosensitive material, can use the spy to open clear 62-215272, the spy opens the content of putting down in writing in flat 2-33144 communique, the EP0355660A2 instructions, especially preferentially selects the content of putting down in writing in the EP0355660A2 instructions for use.Can use the spy to open flat 5-34889, spy in addition opens flat 4-359249, spy and opens flat 4-313753, spy and open flat 4-270344, spy and open flat 5-66527, spy and open flat 4-34548, spy and open flat 4-145433, spy and open flat 2-854, spy and open flat 1-158431, spy and open that flat 2-90145, spy open flat 3-194539, the spy opens silver halide colour photographic sensitive material and the disposal route of putting down in writing in flat 2-93641 communique, the EP0520457A2 instructions thereof.
In the present invention, as above-mentioned reflection-type supporting mass and silver emulsion, and then the dissimilar metal ion that in silver halide particle, mixes, the preserving stabilizer of silver emulsion or anti-foggant, chemical sensitization method (sensitizer), beam split sensitizing method (branch light sensitizer), cyan, magenta, yellow colour former and emulsification dispersion method thereof, color and luster keeping quality improver (anti fouling agent and anti-stripping agent), dyestuff (dyed layer), gelatin, the layer formation of photosensitive material and the tunicle pH of photosensitive material etc. especially preferentially select the content of putting down in writing in the Patent document number communique shown in the following table 1 for use.
[table 1]
Key element Te Kaiping 7-104448 Te Kaiping 7-77775 Te Kaiping 7-301895
The reflection-type supporting mass 12 row～12 hurdles, the 7th hurdle, 19 row 43 row～44 hurdles, the 35th hurdle, 1 row 40 row～9 hurdles, the 5th hurdle, 26 row
Silver emulsion 29 row～74 hurdles, the 72nd hurdle, 18 row 36 row～46 hurdles, the 44th hurdle, 29 row 48 row～80 hurdles, the 77th hurdle, 28 row
The dissimilar metal ion The 74th hurdle 19 row～with hurdle 44 row 30 row～47 hurdles, the 46th hurdle, 5 row 29 row～81 hurdles, the 80th hurdle, 6 row
Preserving stabilizer or antifoggant The 75th hurdle 9 row～with hurdle 18 row The 47th hurdle 20 row～with hurdle 29 row 11 row～31 hurdles, the 18th hurdle, 37 row (compound)
Chemical sensitization method (chemical sensitizer) 45 row～75 hurdles, the 74th hurdle, 6 row The 47th hurdle 7 row～with hurdle 17 row The 81st hurdle 9 row～with hurdle 17 row
Beam split sensitizing method (branch light sensitizer) 19 row～76 hurdles, the 75th hurdle, 45 row 30 row～49 hurdles, the 47th hurdle, 6 row 21 row～82 hurdles, the 81st hurdle, 48 row
Cyan coupler 20 row～39 hurdles, the 12nd hurdle, 49 row 50 row～63 hurdles, the 62nd hurdle, 16 row 49 row～89 hurdles, the 88th hurdle, 16 row
Yellow colour former 40 row～88 hurdles, the 87th hurdle, 3 row The 63rd hurdle 17 row～with hurdle 30 row The 89th hurdle 17 row～with hurdle 30 row
The magenta colour coupler The 88th hurdle 4 row～with hurdle 18 row 3 row～64 hurdles, the 63rd hurdle, 11 row The 31st hurdle 34 row～77 hurdles 44 row and the 88th hurdle 32 row～with hurdle 46 row
The emulsification dispersion method of colour coupler 3 row～72 hurdles, the 71st hurdle, 11 row The 61st hurdle 36 row～with hurdle 49 row The 87th hurdle 35 row～with hurdle 48 row
Tone keeping quality improver (anti fouling agent) 50 row～70 hurdles, the 39th hurdle, 9 row 50 row～62 hurdles, the 61st hurdle, 49 row 49 row～88 hurdles, the 87th hurdle, 48 row
Anti-fading agent The 70th hurdle 10 row～
71 hurdles, 2 row
Dyestuff (colorant) 42 row～78 hurdles, the 77th hurdle, 41 row The 7th hurdle 14 row～19 hurdles 42 row and 3 row～51 hurdles, the 50th hurdle, 14 row 27 row～18 hurdles, the 9th hurdle, 10 row
Gelatin The 78th hurdle 42 row～with hurdle 48 row The 51st hurdle 15 row～with hurdle 20 row The 83rd hurdle 13 row～with hurdle 19 row
The layer of photosensitive material constitutes The 39th hurdle 11 row～with hurdle 26 row The 44th hurdle 2 row～with hurdle 35 row 38 row～32 hurdles, the 31st hurdle, 33 row
The tunicle pH of photosensitive material The 72nd hurdle 12 row～with hurdle 28 row
Scan exposure 6 row～77 hurdles, the 76th hurdle, 41 row 7 row～50 hurdles, the 49th hurdle, 2 row 49 row～83 hurdles, the 82nd hurdle, 12 row
Antioxidant in the developer solution 19 row～89 hurdles, the 88th hurdle, 22 row
The cyan of using among the present invention, magenta and yellow colour former, can also use the colour coupler of putting down in writing in the following patent literature communique: the 91st page of upper right hurdle the 4th that the spy opens clear 62-215272 communique walks to the 121st page of upper left hurdle the 6th row, the 3rd page of upper right hurdle the 14th of Te Kaiping 2-33144 communique walks to the 18th page of upper left hurdle last column and the 30th page of upper right hurdle the 6th walks to the 4th page of the 15th row～the 27 row in the 35th page of hurdle, bottom right 11 row and the EP0355660A2 instructions,～the 28 page of last column of the 5th page of the 30th row, the 45th page of the 29th row～the 31 row,～63 page of the 50th row of the 47th page of the 23rd row.
In addition, can also add among the present invention the general formula (II) of WO 98/33760 and (III), the spy opens the compound of general formula (D) expression of flat 10-221825.
Operable cyanine is formed into toner (abbreviating " cyan coupler " sometimes as) among the present invention, preferentially select pyrrolo-triazole type colour coupler for use, especially preferentially select for use the spy to open general formula (I) or (II) illustrative colour coupler in the colour coupler of the colour coupler of expression and the general formula (I) in the flat 6-347960 communique of Te Kai expression and these patents in the flat 5-313324 communique.In addition, can also use the cyan coupler of phenol, aphthols, for example special cyan coupler of opening general formula (ADF) expression in the flat 10-333297 communique.As the cyan coupler beyond above-mentioned; can use the pyrrolo-pyrazoles type cyan coupler of putting down in writing in EP0488246 and the EP0491197A1 instructions; put down in writing in the US5888716 communique 2; 5-diacylamino group phenol colour coupler; US4873183; has electron withdraw group on put down in writing in the US1926051 instructions 6; the pyrazolo pyrazoles type cyan coupler of hydrogen bond base especially preferentially selects for use the spy to open flat 8-171185; Te Kaiping 8-311360; the pyrazolo pyrazoles type cyan coupler that has carbamyl on put down in writing in No. 0 communique communique of Te Kaiping 8-33906 6.
Except the spy opens the diphenyl-imidazole class cyan coupler of putting down in writing in the flat 2-33144 communique communique, can also use the 3-pyridone class cyan coupler put down in writing in the EP0333185A2 instructions (wherein especially preferentially to select colour coupler (42) the making 4 equivalent colour couplers have chlorine cancellation base of enumerating for use and become the colour coupler of 2 equivalents as object lesson, and colour coupler (6) and (9)), the spy opens the ring-type active methylene group class cyan coupler of putting down in writing in the clear 64-32260 communique communique and (wherein especially preferentially selects the colour coupler example of enumerating as object lesson 3 for use, 8,34), the pyrrolo-pyrazoles cyan coupler of putting down in writing in the EP0456226A1 instructions, the pyrrolo-thiazoles cyan coupler of putting down in writing in the EP0484909 instructions.
In these cyan couplers, particularly preferably be the spy and open the pyrrolopyrrole class cyan coupler of putting down in writing in the flat 11-282138 communique communique by general formula (I) expression, illustrative cyan coupler (1)-(47) have been put down in writing in the 0012nd～0059 segment number communique of this patent, can be directly used in the present invention, thereby the part as this instructions is taken in this instructions in above-mentioned record.
Be formed into toner (following be called for short sometimes " magenta colour coupler ") as the pinkish red pigment that uses among the present invention, can use 5-pyrazoline ketone magenta colour coupler and the pyrazolo pyroles magenta colour coupler put down in writing in the known document number communique in the above-mentioned table, wherein, consider from color harmony picture steadiness and colour rendering equal angles, preferentially select for use the spy to open to put down in writing in the clear 61-65245 communique, 2 grades or 3 grades of alkyl straight access nodes are incorporated into 2 of Pyrazolotriazole ring, on 3 or 6 the Pyrazolotriazole colour coupler, the spy opens the pyrrolopyrrole colour coupler that the molecule of putting down in writing in the clear 61-65246 communique contains sulfonamido, the spy opens the pyrrolopyrrole colour coupler of putting down in writing in the clear 61-147254 communique with alkoxyl phenyl sulfonamido fixed base, and the pyrrolopyrrole colour coupler that has alkoxy and aryloxy group on put down in writing in EP226849A and the EP294785A instructions 6.As the magenta colour coupler, the pyrrolopyrrole colour coupler of especially preferentially selecting for use the spy to open to put down in writing in the flat 8-122984 communique by general formula (M-I) expression, the content of the 0009-0026 paragraph of this patent can be directly applied for the present invention, thereby takes in this instructions the part as this instructions.In addition, can also preferably use the pyrrolopyrrole colour coupler of putting down in writing in EP854384, the EP884640 instructions, all have sterically hindered base on 3 and 6.
In addition; be formed into toner (following be called for short sometimes " yellow colour former ") as uranidin; the compound of in top table number communique, putting down in writing; can also use and put down in writing in the EP0447969 A1 instructions; the acyl group ethanamide yellow colour former that has 3-5 person's ring texture on the acyl group; the malonyl phenyl amines yellow colour former of putting down in writing in the EP0482552A1 instructions with ring texture; EP953870A1; EP953871A1; EP953872A1; EP953873A1; EP953874A1; pyrroles who puts down in writing in the EP953875A1 instructions-2 or 3-base or indoles-2 or 3-base carbonyl acetophenone amine colour coupler, the acyl group ethanamide yellow colour former of putting down in writing in the US5118599 instructions with diox structure.Wherein, especially preferentially selecting acyl group for use is the acyl group ethanamide yellow colour former of 1-alkyl trimethylene-1-carbonyl, and a side of anilide constitutes the malonyl phenyl amines yellow colour former of dihydroindole ring.These colour couplers may be used alone, can also be used in combination.
The colour coupler that uses among the present invention, preferably the high boiling organic solvent of putting down in writing in the table number communique in the above exists and makes it the low two emulsion polymers (for example referring to the US4203716 instructions) of infiltration under (or not existing), perhaps dissolve, make it emulsification, be scattered in the hydrophilic colloid aqueous solution with polymkeric substance water insoluble and that dissolve in organic solvent.Operable water insoluble and polymkeric substance that dissolve in organic solvent can be enumerated homopolymer or the multipolymer of putting down in writing in US4857449 instructions the 7th hurdle～15 hurdles and WO88/00723 instructions the 12nd～30 page number communique.More preferably methyl acrylic ester or acrylamide copolymer are considered from the color stability angle, especially preferentially select acrylamide copolymer for use.
Can use known colour mixture to prevent agent in the present invention, wherein preferentially select for use the colour mixture of putting down in writing in the patent No. communique of enumerating below to prevent agent, for example can use the spy to open the redox compound of the high molecular of putting down in writing in the flat 5-333501 communique, 1-phenyl-3-pyrazolidone and hydrazine class compound of putting down in writing in WO89/33760, the US4923787 instructions, the spy opens flat 5-249637, the spy opens the white colour coupler of putting down in writing in flat 10-282615 communique and the DE19629142A1 instructions.In addition, under the situation of rapidization that improves the pH of developer solution, develops, can also use the redox compound of putting down in writing in DE19618786A1, EP839623A1, EP842975A1, DE19806846A1 and the FR2760460A1 instructions.
In the present invention, can use the high compound with triazine 5 valencys of molar extinction coefficient as ultraviolet light absorber, the compound of putting down in writing in for example following patent No. communique adds these compounds and can improve photosensitive layer and/or non-photosensitive layer.For example, the spy opens clear 46-3335, spy and opens clear 55-152776, spy and open flat 5-197074, spy and open flat 5-232630, spy and open flat 5-307232, spy and open flat 6-211813, spy and open flat 8-53427, spy and open flat 8-234364, spy and open flat 8-239368, spy and open flat 9-31067, spy and open that flat 10-115898, spy open flat 10-147577, the spy opens the compound of putting down in writing in the flat 8-501291 equal sign of flat 10-182621, DE19739797A, EP711804A and the Te Biao communique.
As operable cementing agent or protecting colloid in the photosensitive material of the present invention, use gelatin comparatively favourable, but also can be individually or use other hydrophilic colloid with gelatin.As preferred gelatin, the content of beavy metal impurities such as iron, copper, zinc, manganese is advisable below 5ppm, preferably below the 3ppm.In addition, the calcium content in the photosensitive material is at 20mg/m 2Below be advisable, preferably 10mg/m 2Below, 5mg/m preferably 2Below.
In the present invention, in the hydrophilic colloid layer, breed, make image deterioration, can add the spy and open antiseptic, the antimycotic agent of putting down in writing in the clear 63-271247 communique in order to prevent various moulds and bacterium.In addition, the tunicle pH of photosensitive material is advisable 4.0～7.0, and preferably 4.0～6.5.
In the present invention, the total coating weight of gelatin in the photograph formation layer is at 3g/m 2More than, 6g/m 2Below be advisable, preferably 3g/m 2More than, 5g/m 2Below.In addition, under the situation of supper-fast processing, in order to satisfy the requirement of carrying out property of development and photographic fixing bleaching property, residual look, the total film thickness that constitutes layer of taking a picture is advisable at 3-7.5 μ m, preferably 3-6.5 μ m.The assessment method of dry film thickness, can by desciccator diaphragm before and after peeling off Thickness Variation or measure with optical microscope or electron microscope observation section.In the present invention, in order to take into account develop carrying out property and rate of drying, the swelling thickness is advisable at 8-19 μ m, preferably 9-18 μ m.The mensuration of swelling thickness can adopt the photosensitive material of drying is immersed in 35 ℃ the aqueous solution, and the method for getting ready under the state that reaches abundant balance after the swelling is measured.Silver coating amount among the present invention is at 0.2g/m 2～0.5g/m 2Be advisable, preferably 0.2g/m 2～0.45g/m 2, 0.2g/m preferably 2～0.40g/m 2
In the present invention, from the coating stability that improves photosensitive material, prevent to produce static and accommodation zone electric weight equal angles is considered, can in photosensitive material, add surfactant.Described surfactant has anionic surfactant, cationic surfactant, betaines surfactant, non-ionic surfactant, for example can enumerate the spy and open the surfactant of putting down in writing in the flat 5-333492 communique.The surfactant that uses among the present invention is preferentially selected the surfactant that contains fluorine atom for use, particularly contains the surfactant of fluorine atom.The surfactant of these contain fluorine atoms can use separately, also can with known other surfactant and usefulness in the past, preferably with known other surfactant in the past and use.These surfactants want the addition in the photosensitive material to have no particular limits, and generally are 1 * 10 -5～1g/m 2, preferably 1 * 10 -5～1 * 10 -1G/m 2, preferably 1 * 10 -3～1 * 10 -2G/m 2
Photosensitive material of the present invention can be by having developing procedure to form image according to the exposure process of image information irradiates light with above-mentioned light-struck developing photosensitive material.
Photosensitive material of the present invention except the print system that is used for the negative printing machine of common use, can also be applicable to the scan exposure mode of using cathode ray (CRT).Compare with the device that uses laser, the cathode-ray tube exposure device is easier and compact, and cost is lower, and the adjustment of optical axis and color is also than being easier in addition.Be used for the cathode-ray tube of image exposure, can using the luminous various luminophors of demonstration in spectral range as required, for example can use in emitting red light body, green emitting body and the blue-light emitting body any, perhaps mixing more than 2 kinds and use.Spectral range is not limited to above-mentioned red, green and blue look, also can use at yellow, orange, purple or the luminous fluorophor of infra-red range.Particularly often use these luminophors are mixed and the cathode-ray tube of the coloured light that turns white.
The a plurality of photographic layers, the cathode-ray tube that have different spectrum sensitivities at photosensitive material also have under the situation of the luminous fluorophor that shows a plurality of spectral ranges, can be with the disposable exposure of a plurality of colors, promptly import the picture signal of a plurality of colors to cathode-ray tube, make it luminous from the pipe face, also can import the picture signal of each color successively, carry out the luminous of each color successively, the method (face exposes in turn) of exposing by the film that the color beyond this color is ended.In general, face exposes in turn and can use the cathode-ray tube of high resolution, can obtain high image quality, thereby is preferable methods.
Photosensitive material of the present invention, preferably using gases laser instrument, light emitting diode, semiconductor laser, with semiconductor laser or with semiconductor laser as the second harmonic illuminating source monochromatic high density light such as (SHG) that the solid state laser and the nonlinear optical crystal of exciting light source combines, carry out the digital scanning exposure.In order to make system compacter, more cheap, the second harmonic illuminating source (SHG) that preferably uses semiconductor laser, semiconductor laser or solid state laser and nonlinear optical crystal are combined.Particularly, for device compact to design, that cost is low and the life-span long, stability is high, preferentially select semiconductor laser for use, at least one in the exposure light source used semiconductor laser.
Under the situation of using such scan exposure light source, the very big wavelength of the spectral response of photosensitive material of the present invention can be set arbitrarily with the wavelength of light source according to employed scan exposure.The solid state laser or the semiconductor laser that use semiconductor laser as driving source are made up the SHG light source that obtains with nonlinear optical crystal, the oscillation wavelength of laser can be got half, obtain blue light and green light.Therefore, photosensitive material can have spectral response maximum value in common indigo plant, green, red 3 wavelength coverages.The time shutter of such scan exposure, if be defined as the time of the imaging element size exposure when imaging element density is 400dpi, so Shi Yi time shutter is 10 -4Below second, preferably 10 -6Below second.
When the present invention is used for silver halide colour photographic sensitive material, preferably adopt the coherent light of the blue laser of emission wavelength 420nm-460nm to carry out image exposure.In blue laser, especially preferentially select blue semiconductor laser for use.As LASER Light Source, can adopt particularly wavelength 430～450nm the cyan semiconductor laser (March calendar year 2001, the 48th applied physics lecture day inferior chemistry deliver), with the LiNbO of anti-domain structure with waveguide-shaped 3The blue laser of SHG crystal about 470nm that semiconductor laser (wave of oscillation is about 940nm) wavelength conversion is taken out, with the LiNbO of anti-domain structure with waveguide-shaped 3The green laser of SHG crystal about 530nm that semiconductor laser (wave of oscillation is about 1060nm) wavelength conversion is taken out, the red semiconductor laser of the about 685nm of wavelength (the type № HL6738MG of Hitachi), the red semiconductor laser of the about 650nm of wavelength (the type № HL6501MG of Hitachi) etc.
Silver halide photographic sensitive material of the present invention can be used in combination with exposure, the toning system put down in writing in the following known document number communique.Described toning system can be enumerated: the spy opens automatic solarization picture and the toning system of putting down in writing in the flat 10-333253 communique, the spy opens the handling apparatus for photosensitive material of putting down in writing in the 2000-10206 communique, the record system that comprises image read-out that puts down in writing in the Te Kaiping 11-215312 communique, the exposure system of putting down in writing in the flat 10-202950 communique of Te Kaiping 11-88619 and Te Kai that constitutes by the coloured image recording mode, the Digital photographic dubbing system of the remote diagnosis mode of putting down in writing in the Te Kaiping 10-210206 communique that comprises, and the photocopying system that comprises image record device that puts down in writing in the special 10-159187 of Yuanping City communique.
Scan exposure mode about being suitable in the present invention is documented in the patent documentation of listing in the superincumbent table.
When photosensitive material of the present invention is carried out the photo print apparatus exposure, preferably use the rejection filter of putting down in writing in the US4880726 instructions.Like this, can eliminate the light colour mixture, significantly improve color reproduction.In the present invention, described in EP0789370A1 and EP0789480A1 instructions, before giving image information, can also expose in advance forms yellow stipple pattern, applies and duplicates restriction.
When photosensitive material of the present invention is handled, preferentially select for use the spy to open the 26th page of hurdle, bottom right the 1st row～the 34 page of upper right hurdle the 9th row and special material and the disposal route of putting down in writing in～the 18 page of hurdle, bottom right the 20th row communique of the 5th page of upper left hurdle the 17th row of flat 4-97355 of opening of flat 2-207250.In addition, as the antioxidant that uses in the developer solution, the compound of putting down in writing in the Patent document number communique of enumerating in the table above preferentially selecting for use.
The present invention is fit to be used as the photosensitive material with fast processing.Its colour development time is below 28 seconds, preferably below 25 seconds, more than 6 seconds, preferably below 20 seconds, more than 6 seconds.Equally, the blix time was advisable below 30 seconds, preferably below 25 seconds, more than 6 seconds, and preferably below 20 seconds, more than 6 seconds.In addition, washing or stabilizing take were advisable below 60 seconds, preferably below 40 seconds, more than 6 seconds.The so-called colour development time, be meant that photosensitive material enters behind the colour developing solution to the time of the bleach-fixing liquid that enters down one treatment process.For example, under situation about handling, the time (time in the so-called liquid) that photosensitive material floods in colour developing solution is left colour developing solution, is transported to both total ascent times of time (so-called in-flight time) of the bleach-fixing liquid of treatment process to be called the colour development time in air with photosensitive material with automatic processing machine.Equally, so-called blix time is meant that photosensitive material enters in the bleach-fixing liquid back to entering follow-up washing or the time in the stabilizing solution.In addition, so-called washing or stabilizing take are meant that photosensitive material enters the time (time in the so-called liquid) in liquid before the steering stem drying process of back in washing or the stabilization liquid.
After photosensitive material exposure of the present invention, as the method for developing, except in the past use contains built-in development main ingredient in method that the developer solution of alkaline agent and development main ingredient develops and the photosensitive material, uses the wet method of developing method etc. of the activator liquid such as alkali lye that do not contain the development main ingredient, can also use without the thermal development mode for the treatment of fluid etc.Particularly, the activator method is not owing to contain the development main ingredient in the treating fluid, and the operation ratio of the management for the treatment of fluid is easier to, and the workload during liquid waste processing is less, considers it is preferable methods from the angle of environmental protection.In the activator method, as development main ingredient built-in in the photosensitive material or its precursor, for example can use the spy to open flat 8-234388, spy and open flat 9-152686, spy and open that flat 9-152693, spy open flat 9-211814, the spy opens the hydrazine compound of putting down in writing in the flat 9-160193 communique.
In addition, can also adopt the silver coating amount that reduces photosensitive material, the image amplification of use hydrogen peroxide to handle the developing method of (enhancement process).Particularly preferably be this method is used for the activator method.Specifically, can adopt the spy to open flat 8-297354, the spy opens the image forming method that the use of putting down in writing in the flat 9-152695 communique contains the activator liquid of hydrogen peroxide.In above-mentioned activator method, handle the laggard desilverization that works normal with activator liquid and handle, but also can adopt the image amplification disposal route of using low silver amount photosensitive material, omit the desilverization and handle, wash or the simple and easy method of stabilization processes.In addition, with scanner etc. by photosensitive material in the mode of reading images information, even with photosensitive material, use under the situation of photosensitive material of Gao Yinliang, also can adopt the processing mode that does not need the desilverization to handle as photography.
The processing material and the disposal route of the activator liquid that uses among the present invention, desilverization liquid (bleaching/stop bath), washing and stabilization liquid, can use technique known, preferentially select the 536th page the-the 541st page of リ サ-チ テ イ ス Network ロ-ジ ヤ-Item 36544 (in September, 1994) for use, the spy opens the content of putting down in writing in the flat 8-234388 communique.
[embodiment]
Specifically describe the present invention below by embodiment, but the invention is not restricted to these embodiment.
Embodiment 1
(preparation of emulsion B-H)
In through the aqueous gelatin solution that stirs, add silver nitrate and sodium chloride simultaneously and mix, prepare the cube high silver chloride emulsion of ball equivalent diameter 0.55 μ m, coefficient of alteration 10% in this way.Wherein, reach at 80% o'clock and begin to reach at 90% o'clock in the interpolation of silver nitrate and add potassium bromide (per 1 mole of silver halide of result is 3% (mole)) and K 4[Ru (CN) 6].Reach at 83% o'clock and begin to reach at 88% o'clock in the interpolation of silver nitrate and add K 2[IrCl 6].Interpolation at silver nitrate reaches 90% o'clock interpolation potassium iodide (per 1 mole of silver halide of result is 0.3% (mole)).Resulting emulsion is carried out desalting processing, add gelatin then and disperse again.In this emulsion, add sodium benzenethiosulfonate and sensitizing coloring matter A and sensitizing coloring matter B, use sulfo-glucose gold to carry out best maturation as sensitizer.Add 1-phenyl-5-mercapto-tetrazole and 1-(5-methylurea base phenyl)-5-mercapto-tetrazole again.With the emulsion that obtains like this as emulsion B-H.
[changing 2]
(sensitizing coloring matter A)
(sensitizing coloring matter B)
Figure A20031012057200432
(preparation of emulsion B-L)
Operate equally with the preparation of emulsion B-H, just change the interpolation speed of silver nitrate and sodium chloride, the cube high silver chloride emulsion of preparation ball equivalent diameter 0.45 μ m, coefficient of alteration 10%.With resulting emulsion as emulsion B-L.
(preparation of emulsion G-1)
In through the aqueous gelatin solution that stirs, add silver nitrate and sodium chloride simultaneously and mix, prepare the cube high silver chloride emulsion of ball equivalent diameter 0.40 μ m, coefficient of alteration 10% in this way.Wherein, till the interpolation of silver chloride reaches at 80% o'clock and begins to reach at 100% o'clock, add potassium bromide (per 1 mole of silver halide of result is 4% (mole)).Finished 90% o'clock in the interpolation of silver nitrate, add potassium iodide (per 1 mole of silver halide of result is 0.2% (mole)).Resulting emulsion is carried out desalting processing, add gelatin then and disperse again.In this emulsion, add sodium benzenethiosulfonate, use thioglucose suitably to carry out maturation as sensitizer.Add sensitizing coloring matter D, 1-phenyl-5-mercapto-tetrazole, 1-(5-methylurea base phenyl)-5-mercapto-tetrazole and potassium bromide again.With the emulsion that obtains like this as emulsion G-1.
[changing 3]
(sensitizing coloring matter D)
Figure A20031012057200441
(preparation of emulsion G-2)
Till the interpolation of silver nitrate reaches at 90% o'clock and plays at 100% o'clock, add K 2[IrCl 5(H 2O)] make that per 1 mole of silver halide Ir amount of result is 4 * 10 -6In addition mole is operated equally with emulsion G-1, preparation emulsion G-2.
(preparation of emulsion G-3)
Till the interpolation of silver nitrate reaches at 80% o'clock and begins by 90% o'clock, add K 2[IrCl 5(5-methylthiazol)] make that per 1 mole of silver halide Ir amount of result is 1 * 10 -6In addition mole is operated equally with emulsion G-1, preparation emulsion G-3.
(preparation of emulsion G-4)
Till the interpolation of silver nitrate reaches at 80% o'clock and begins by 90% o'clock, add K 2[IrCl 5(S-methylthiourea)] make that per 1 mole of silver halide Ir amount of result is 8 * 10 -7In addition mole is operated equally with emulsion G-1, preparation emulsion G-4.
(preparation of emulsion G-5)
Till the interpolation of silver nitrate reaches at 80% o'clock and begins by 90% o'clock, add K 2[IrCl 5(5-methylthiazol)] make that per 1 mole of silver halide Ir amount of result is 6 * 10 -7Mole till the interpolation of silver nitrate reaches at 90% o'clock and plays at 100% o'clock, adds K 2[IrCl 5(H 2O)] make that per 1 mole of silver halide Ir amount of result is 4 * 10 -6In addition mole is operated equally with emulsion G-1, preparation emulsion G-5.
(preparation of emulsion G-6)
Till the interpolation of silver nitrate reaches at 80% o'clock and begins by 90% o'clock, add K 2[IrCl 5(S-methylthiourea)] make that per 1 mole of silver halide Ir amount of result is 2 * 10 -7Mole till the interpolation of silver nitrate reaches at 90% o'clock and plays at 100% o'clock, adds K 2[IrCl 5(H 2O)] make that per 1 mole of silver halide Ir amount of result is 4 * 10 -6In addition mole is operated equally with emulsion G-1, preparation emulsion G-6.
(preparation of emulsion R-H)
In through the aqueous gelatin solution that stirs, add silver nitrate and sodium chloride simultaneously and mix, prepare the cube high silver chloride emulsion of ball equivalent diameter 0.35 μ m, coefficient of alteration 10% in this way.Wherein, till the interpolation of silver nitrate reaches at 80% o'clock and plays at 90% o'clock, add K 4[Ru (CN) 6].Till the interpolation of silver nitrate reaches at 80% o'clock and plays at 100% o'clock, add potassium bromide (per 1 mole of silver halide of result is 4.3% (mole)).Till reaching at 83% o'clock to play at 88% o'clock, the interpolation of silver nitrate adds K 2[IrCl 6].Finish 90% o'clock interpolation potassium iodide (per 1 mole of silver halide of result is 0.15% (mole)) in the interpolation of silver nitrate.Resulting emulsion is carried out desalting processing, add gelatin then and disperse again.In this emulsion, add sodium benzenethiosulfonate, use sodium thiosulfate 5 hydrates suitably to carry out maturation as golden sensitizer as sulphur sensitizer and two (1,4,5-trimethyl-1,2,4-triazole father-in-law-3-mercaptide) oleate (I) tetrafluoroborates of use.Add sensitizing coloring matter H, 1-phenyl-5-mercapto-tetrazole, 1-(5-methylurea base phenyl)-5-mercapto-tetrazole, Compound I and potassium bromide again.With the emulsion that obtains like this as emulsion R-H.
[changing 4]
[changing 5]
(Compound I)
Figure A20031012057200462
(preparation of emulsion R-L)
Operate equally with the preparation of emulsion R-H, just change the interpolation speed of silver nitrate and sodium chloride, the cube high silver chloride emulsion of preparation ball equivalent diameter 0.28 μ m, coefficient of alteration 10%.With resulting emulsion as emulsion R-L.
In order to investigate the photonasty of emulsion G-1 to G-6, prepare following test portion.
Two sides with polyvinyl resin lining paper, Corona discharge Treatment is carried out on the supporting mass surface that makes like this, the gelatin undercoat that contains neopelex is set then, be coated with the photosensitive layer of ground floor more successively, make the test portion of the silver halide colour photographic sensitive material of following described layer formation to layer 7.The coating fluid of each photosensitive layer usefulness is by the following stated preparation.
The preparation of ground floor coating fluid
Yellow colour former (ExY) 57g, tint stabilizer (Cpd-1) 7g, tint stabilizer (Cpd-2) 4g, tint stabilizer (cpd-3) 7g, tint stabilizer (cpd-8) 2g are dissolved among solvent (Solv-1) 21g and the ethyl acetate 80ml, this solution is put into 23.5% (quality) aqueous gelatin solution 220g that contains the 4g neopelex, carry out emulsification with high-speed stirred mulser (dissolver) and disperse, add the emulsification dispersion thing A that water is mixed with 900g.On the other hand, above-mentioned emulsification is disperseed thing A and emulsion B-H mixed dissolution, be mixed with the ground floor coating fluid by following composition.The emulsion coating weight represents to be converted into the coating weight of silver amount.
According to the coating fluid of using with the same method of the ground floor coating fluid preparation second layer to layer 7.As the gelatin hardening agent of each layer, use 1-oxygen-3,5-two chloro-s-triazine sodium salts (H-1), (H-2), (H-3).In addition, in each layer, add Ab-1, Ab-2, Ab-3 and Ab-4, make total amount separately reach 15.0mg/m 2, 60.0mg/m 2, 5.0mg/m 2And 10.0mg/m 2
[changing 6]
(H-1) hard coat agent
(gelatin is used 1.4 quality %)
(H-2) hard coat agent
(H-3) hard coat agent
[changing 7]
(Ab-1) antiseptic (Ab-2) antiseptic
(Ab-3) antiseptic
Figure A20031012057200492
(Ab-4) antiseptic
R 1R 2A-CH 3-NHCH 3B-CH 3-NH 2C-H-NH 2D-H-NHCH 3A, b, c, 1: 1: 1 of d: 1 potpourri (mol ratio)
In addition, add 1-phenyl-5-mercapto-tetrazole, be respectively per 1 mole of silver halide 1.0 * 10 for green-sensitive emulsion layer and magenta-sensitive emulsion layer -3Mole and 5.9 * 10 -4Mole.In addition, in the second layer, the 4th layer and layer 6, also add 1-phenyl-5-mercapto-tetrazole and be respectively 0.2mg/m 2, 0.2mg/m 2And 0.6mg/m 2In the magenta-sensitive emulsion layer, add copolymer latices (mass ratio 1: 1, the mean molecular weight 200000-400000) 0.05mg/m of methacrylic acid and butyl acrylate 2Add catechol-3 in the second layer, the 4th layer and layer 6, the 5-sodium disulfonate is respectively 6mg/m 2, 6mg/m 2And 18mg/m 2In addition, for anti-irradiation, add following dyestuff (expression coating weight in the parantheses).
[changing 8]
Figure A20031012057200501
(layer constitutes)
The following describes the formation of each layer.Numeral coating weight (mg/m 2).Silver emulsion represents to be converted into the coating weight of silver.
Supporting mass
The polyvinyl resin laminated paper
[contain Chinese white (TiO in the polyvinyl resin of ground floor side 2: containing ratio 10% (quality), ZnO: containing ratio 4% (quality)) and fluorescer (4,4 '-two (5-methyl benzoxazolyl) stilbene, containing ratio 0.03% (quality)), cyan dye (ultramarine)]
Ground floor (feeling blue or green emulsion layer)
Emulsion B-H 0.09
Emulsion B-L 0.10
Gelatin 1.00
Yellow colour former (Ex-Y) 0.46
Tint stabilizer (Cpd-1) 0.06
Tint stabilizer (Cpd-2) 0.03
Tint stabilizer (Cpd-3) 0.06
Tint stabilizer (Cpd-8) 0.02
Solvent (Solv-1) 0.17
The second layer (colour mixture prevents layer)
Gelatin 0.50
Colour mixture prevents agent (Cpd-4) 0.05
Tint stabilizer (Cpd-5) 0.01
Tint stabilizer (Cpd-6) 0.06
Tint stabilizer (Cpd-7) 0.01
Solvent (Solv-1) 0.03
Solvent (Solv-2) 0.11
The 3rd layer (green-sensitive emulsion layer)
Emulsion G-1 0.12
Gelatin 1.36
Magenta colour coupler (ExM) 0.15
Ultraviolet light absorber (UV-A) 0.14
Tint stabilizer (Cpd-2) 0.02
Tint stabilizer (Cpd-4) 0.002
Tint stabilizer (Cpd-6) 0.09
Tint stabilizer (Cpd-8) 0.02
Tint stabilizer (Cpd-9) 0.03
Tint stabilizer (Cpd-10) 0.01
Tint stabilizer (Cpd-11) 0.0001
Solvent (Solv-3) 0.11
Solvent (Solv-4) 0.22
Solvent (Solv-5) 0.20
The 4th layer (colour mixture prevents layer)
Gelatin 0.36
Colour mixture prevents layer (Cpd-4) 0.03
Tint stabilizer (Cpd-5) 0.006
Tint stabilizer (Cpd-6) 0.05
Tint stabilizer (Cpd-7) 0.004
Solvent (Solv-1) 0.02
Solvent (Solv-2) 0.08
Layer 5 (magenta-sensitive emulsion layer)
Emulsion R-H 0.05
Emulsion R-L 0.05
Gelatin 1.11
Cyan coupler (ExC-2) 0.13
Cyan coupler (ExC-3) 0.03
Tint stabilizer (Cpd-1) 0.05
Tint stabilizer (Cpd-6) 0.06
Tint stabilizer (Cpd-7) 0.02
Tint stabilizer (Cpd-9) 0.04
Tint stabilizer (Cpd-10) 0.01
Tint stabilizer (Cpd-14) 0.01
Tint stabilizer (Cpd-15) 0.12
Tint stabilizer (Cpd-16) 0.03
Tint stabilizer (Cpd-17) 0.09
Tint stabilizer (Cpd-18) 0.07
Solvent (Solv-5) 0.15
Solvent (Solv-8) 0.05
Layer 6 (UV-absorbing layer)
Gelatin 0.46
Ultraviolet light absorber (UV-B) 0.45
Compound (S1-4) 0.0015
Solvent (Solv-7) 0.25
Layer 7 (protective seam)
Gelatin 1.00
The propenyl modified copolymer of polyvinyl alcohol (PVA)
(modification degree 17%) 0.04
Whiteruss 0.02
Surfactant (Cpd-13) 0.01
[changing 9]
(ExY-1) yellow colour former
Figure A20031012057200541
With
Figure A20031012057200542
70: 30 potpourris (mol ratio)
[changing 10]
(ExM) magenta colour coupler
With
40: 40: 20 potpourris (mol ratio)
[changing 11]
(ExC-2) cyan coupler
(ExC-3) cyan coupler
Figure A20031012057200562
With
With
50: 25: 25 potpourris (mol ratio)
[changing 12]
(Cpd-1) tint stabilizer
Number mean molecular weight 60,000
(Cpd-2) tint stabilizer
Figure A20031012057200572
(Cpd-3) tint stabilizer
N=7～8 (mean value)
(Cpd-4) colour mixture prevents agent
Figure A20031012057200574
[changing 13]
(Cpd-5) tint stabilizer
(Cpd-6) tint stabilizer
Figure A20031012057200582
Number mean molecular weight 600m/n=10/90
(Cpd-7) tint stabilizer (Cpd-8) tint stabilizer
Figure A20031012057200583
(Cpd-9) tint stabilizer (Cpd-10) tint stabilizer
[changing 14]
(Cpd-11) tint stabilizer
(Cpd-13) surfactant
Figure A20031012057200592
With
Figure A20031012057200593
7: 3 potpourris (mol ratio)
[changing 15]
(Cpd-14)???????????????????????????????????????????????(Cpd-15)
(Cpd-19) colour mixture prevents agent
[changing 16]
(UV-1) ultraviolet light absorber (UV-2) ultraviolet light absorber
(UV-3) ultraviolet light absorber (UV-4) ultraviolet light absorber
(UV-5) ultraviolet light absorber (UV-6) ultraviolet light absorber
Figure A20031012057200613
Figure A20031012057200614
The potpourri of UV-A:UV-1/UV-2/UV-3/UV-4=4/2/2/3 (mass ratio)
The potpourri of UV-B:UV-1/UV-2/UV-3/UV-4/UV-5/UV-6=9/3/3/4/5/3 (mass ratio)
The potpourri of UV-C:UV-2/UV-3/UV-6/UV-7=1/1/1/2 (mass ratio)
[changing 17]
Figure A20031012057200622
(Solv-4)O＝P(OC 6H 13(n)) 3
[changing 18]
Figure A20031012057200631
With the above test portion that obtains as test portion 101.In order to investigate the photonasty of emulsion G-1 to G-6, operate equally with test portion 101, just the emulsion with the green-sensitive emulsion layer replaces to G-2 to G-6 respectively, makes test portion 102 to 106.
Each coating test portion is placed in 10 ℃, the environment of 30%RH, uses high illumination exposure with emulsion (the HIE type that Denso under the mountain (strain) is made), by green color filter apply that sensitometry uses 10 -4High illumination contrast exposure second.Through the test portion of overexposure, carry out colour development described below after 6 seconds in exposure and handle.
It below is treatment process.
[processing]
Handle continuously by following treatment process, reach 0.5 times of the molten amount of colour development groove until the molten amount of the additional liquid of the colour development of using.
Treatment process temperature-time magnitude of recruitment *
45.0 ℃ of 16 seconds 45ml of colour development
40.0 ℃ of 16 seconds 35ml of blix
1 40.0 ℃ of rinsings 8 seconds-
2 40.0 ℃ of rinsings 8 seconds-
40.0 ℃ of rinsing 3** 8 seconds-
4 38.0 ℃ of 8 seconds 121ml of rinsing
Dry 80.0 ℃ 16 seconds
The every 1m of (notes) * photosensitive material 2Magnitude of recruitment
* goes up at rinsing device (3) the rinsecleaning system RC50D that Fuji Photo Film Co., Ltd. makes is installed, and discharges rinsing liquid by rinsing device (3), with being pumped to reverse osmosis module (RC50D).Supply with rinsing with the infiltration water that same groove is carried, concentrate returns rinsing device (3).Adjust pump pressure, make to be transported to amount of seepage to reverse osmosis module and to keep the 50-300ml/ branch, at 10 hours every day, temperature was transferred circulation.The 4 trough counter-current modes of from (1) to (4) are taked in rinsing.
Each treating fluid composed as follows.
[colour developing solution] [tank liquor] [replenishing liquid]
Water 800ml 600ml
Fluorescer (FL-1) 5.0g 8.5g
Triisopropanolamine 8.8g 8.8g
Paratoluenesulfonic acid sodium salt 20.0g 20.0g
Ethylenediamine tetraacetic acid 4.0g 4.0g
Sodium sulphite 0.10g 0.50g
Potassium chloride 10.0g-
4,5-dihydroxy benzenes-1,3-sodium disulfonate
0.50g??????????0.50g
Disodium-N, two (sulfonation ethyl) hydramines of N-
8.5g???????????14.5g
4-amino-3-methyl-N-ethyl-N-(β-Methanesulfomide ethyl) aniline 3/2 sulfate monohydrate
10.0g??????????22.0g
Sal tartari 26.3g 26.3g
Add total amount 1000ml 1000ml behind the water
PH (25 ℃, adjust) with sulfuric acid and KOH
10.35??????????12.6
[bleach-fixing liquid] [tank liquor] [replenishing liquid]
Water 800ml 800ml
ATS (Ammonium thiosulphate) (750g/ml)
107ml???????????214ml
Succinic acid 29.5g 59.0g
Ethylenediamine tetraacetic acid iron (III) ammonium 47.0g 94.0g
Ethylenediamine tetraacetic acid 1.4g 2.8g
Nitric acid (67%) 17.5g 35.0g
Imidazoles 14.6g 29.2g
Ammonium sulfite 16.0g 32.0g
Potassium metabisulfite 23.1g 46.2g
Add total amount 1000ml 1000ml behind the water
PH (25 ℃) with nitric acid and ammoniacal liquor adjustment
6.0?????????????6.0
[rinsing liquid] [tank liquor] [replenishing liquid]
Chlorinated isocyanuric acid sodium 0.02g 0.02g
Deionized water (conductance 5 μ S/cm are following) 1000ml 1000ml
pH(25℃)?????????????????????????6.5?????????????6.5
[changing 19]
Figure A20031012057200651
Measure the magenta colour developing concentration of each test portion after handling, obtain 10 -4The family curve of high illumination exposure second.By the logarithm of the needed exposure E of generation 1.7 colour developing concentration of each test portion, read the photonasty of each emulsion.Photonasty is that the photonasty in order to emulsion G-1 is that 100 o'clock relative value is represented.This numerical value is big more, shows that photonasty is high more.The results are shown in the table 2.In addition, each coating test portion is placed in 20 ℃, the environment of 30%RH, use high illumination exposure with sensitometer (the HIE type of Denso under the mountain (strain) manufacturing) carry out that the sensitometer of grey uses 10 -6High illumination contrast exposure second.Through the test portion of overexposure, carrying out the above-mentioned colour development time in exposure after 6 seconds or after 60 seconds is 16 seconds processing.
Gained the results are shown in the table 2.Use emulsion of the present invention, obtain being suitable for adopting the high illumination photonasty of the digit explosure of laser scanning exposure, compare, be more suitable in digit explosure with the situation of independent use metal complex.In addition, under the situation of exposure beginning in back 60 seconds colour development, all samples are all very stable in the photonasty change of height colour developing concentration range.
[table 2]
Table 2
Test portion № adulterant αRelative photonasty * 1
101 (comparative examples) do not add 100
102 (comparative example) IrCl 5(H 2O) 158
103 (comparative example) IrCl 5(5-Methia) 180
104 (comparative example) IrCl 5(S-methylthiourea) 185
105 (the present invention) IrCl 5(H 2O)/IrCl 5(5-Methia) 193
106 (the present invention) IrCl 5(H 2O)/IrCl 5(S-methylthiourea) 195
αThe 5-Methia=5-methylthiazol
* 1With 10 -4The photonasty of the test portion 101 in second when exposure is that 100 relative photonasty is represented
Embodiment 2
(preparation of emulsion B-1)
In through the aqueous gelatin solution that stirs, add silver nitrate and sodium chloride simultaneously and mix, prepare the cube high silver chloride emulsion of ball equivalent diameter 0.53 μ m, coefficient of alteration 10% in this way.Wherein, till the interpolation of silver nitrate reaches at 80% o'clock and plays at 90% o'clock, add potassium bromide (per 1 mole of silver halide of result is 2% (mole)) and K 4[Ru (CN) 6].Reach at 83% o'clock and play in the interpolation of silver nitrate and ended in 88% o'clock, add K 2[IrCl 6].Finish 90% o'clock interpolation potassium iodide (per 1 mole of silver halide of result is 0.23% (mole)) in the interpolation of silver nitrate.Resulting emulsion is carried out desalting processing, add gelatin then and disperse again.In this emulsion, add sodium benzenethiosulfonate and sensitizing coloring matter A and sensitizing coloring matter B, use thioglucose suitably to carry out maturation as sensitizer.Add 1-phenyl-5-mercapto-tetrazole and 1-(5-methylurea base phenyl)-5-mercapto-tetrazole again.With the emulsion that obtains like this as emulsion B-1.
(preparation of emulsion B-2)
In through the aqueous gelatin solution that stirs, add silver nitrate and sodium chloride simultaneously and mix, prepare the cube high silver chloride emulsion of ball equivalent diameter 0.43 μ m, coefficient of alteration 10% in this way.Till the interpolation of silver nitrate reaches at 80% o'clock and plays at 90% o'clock, add potassium bromide (per 1 mole of silver halide of result is 2% (mole)) and K 4[Ru (CN) 6].Reach at 83% o'clock and play in the interpolation of silver nitrate and ended in 88% o'clock, add K 2[IrCl 6].Finish 90% o'clock interpolation potassium iodide (per 1 mole of silver halide of result is 0.23% (mole)) in the interpolation of silver nitrate.Resulting emulsion is carried out desalting processing, add gelatin then and disperse again.In this emulsion, add sodium benzenethiosulfonate and sensitizing coloring matter A and sensitizing coloring matter B, use thioglucose suitably to carry out maturation as sensitizer.Add 1-phenyl-5-mercapto-tetrazole and 1-(5-methylurea base phenyl)-5-mercapto-tetrazole again.With the emulsion that obtains like this as emulsion B-2.
(preparation of emulsion G-11)
In through the aqueous gelatin solution that stirs, add silver nitrate and sodium chloride simultaneously and mix, prepare the cube high silver chloride emulsion of ball equivalent diameter 0.38 μ m, coefficient of alteration 10% in this way.Wherein, till the interpolation of silver nitrate reaches at 80% o'clock and plays at 90% o'clock, add K 4[Ru (CN) 6].Reach at 80% o'clock and play in the interpolation of silver nitrate and only added potassium bromide (per 1 mole of silver halide of result is 3% (mole)) at 100% o'clock.Reach at 83% o'clock and play in the interpolation of silver nitrate and only added K at 88% o'clock 2[IrCl 6].Finish 90% o'clock interpolation potassium iodide (per 1 mole of silver halide of result is 0.15% (mole)) in the interpolation of silver nitrate.Resulting emulsion is carried out desalting processing, add gelatin then and disperse again.In this emulsion, add sodium benzenethiosulfonate, use thioglucose suitably to carry out maturation as sensitizer.Add sensitizing coloring matter D, 1-phenyl-5-mercapto-tetrazole, 1-(5-methylurea base phenyl)-5-mercapto-tetrazole and potassium bromide again.With the emulsion that obtains like this as emulsion G-11.
(preparation of emulsion G-12)
For emulsion G-11, do not add K 2[IrCl 6], till reaching at 80% o'clock to play at 90% o'clock, the interpolation of silver nitrate adds K 2[IrCl 5(5-methylthiazol (Methylthia))], making the Ir amount of per 1 mole of silver halide is 1 * 10 -6Mole then, adds K till the interpolation of silver nitrate reaches at 90% o'clock to play at 100% o'clock 2[IrCl 5(H 2O)], making the Ir amount of per 1 mole of silver halide is 2 * 10 -6In addition mole is operated equally with emulsion G-11, obtains emulsion G-12.
(preparation of emulsion G-13)
Till reaching at 50% o'clock to play at 80% o'clock, the interpolation of silver nitrate adds Cs 2[OsCl 5(NO)], making the Ir amount of per 1 mole of silver halide is 6 * 10 -8In addition mole is operated equally with emulsion G-12, obtains emulsion G-13.
(preparation of emulsion G-14)
Till reaching at 50% o'clock to play at 80% o'clock, the interpolation of silver nitrate adds Cs 2[OsCl 5(NO)], making the Ir amount of per 1 mole of silver halide is 6 * 10 -8Mole replaces K 2[IrCl 5(5-methylthiazol)] interpolation K 2[IrCl 5(S-methylthiourea)], making the Ir amount of per 1 mole of silver halide is 4 * 10 -7In addition mole is operated equally with emulsion G-12, obtains emulsion G-14.
(preparation of emulsion R-1)
In through the aqueous gelatin solution that stirs, add silver nitrate and sodium chloride simultaneously and mix, prepare the cube high silver chloride emulsion of ball equivalent diameter 0.38 μ m, coefficient of alteration 10% in this way.Wherein, till the interpolation of silver nitrate reaches at 80% o'clock and plays at 90% o'clock, add K 4[Ru (CN) 6].Reach at 80% o'clock and play in the interpolation of silver nitrate and only added potassium bromide (per 1 mole of silver halide of result is 3% (mole)) at 100% o'clock.Reach at 83% o'clock and play in the interpolation of silver nitrate and only added K at 88% o'clock 2[IrCl 6].Finish 90% o'clock interpolation potassium iodide (per 1 mole of silver halide of result is 0.15% (mole)) in the interpolation of silver nitrate.Resulting emulsion is carried out desalting processing, add gelatin then and disperse again.In this emulsion, add sodium benzenethiosulfonate, use sodium thiosulfate 5 hydrates suitably to carry out maturation as golden sensitizer as sulphur sensitizer and two (1,4,5-trimethyl-1,2,4-triazole father-in-law-3-mercaptide) oleate (I) tetrafluoroborates of use.Add sensitizing coloring matter H, 1-phenyl-5-mercapto-tetrazole, 1-(5-methylurea base phenyl)-5-mercapto-tetrazole, Compound I and potassium bromide then.With the emulsion that obtains like this as emulsion R-1.
(preparation of emulsion R-2)
In through the aqueous gelatin solution that stirs, add silver nitrate and sodium chloride simultaneously and mix, prepare the cube high silver chloride emulsion of ball equivalent diameter 0.28 μ m, coefficient of alteration 10% in this way.Wherein, till the interpolation of silver nitrate reaches at 80% o'clock and plays at 90% o'clock, add K 4[Ru (CN) 6].Till reaching at 80% o'clock to play at 100% o'clock, the interpolation of silver nitrate adds potassium bromide (per 1 mole of silver halide of result is 3% (mole)).Till reaching at 83% o'clock to play at 88% o'clock, the interpolation of silver nitrate adds K 2[IrCl 6].Finish 90% o'clock interpolation potassium iodide (per 1 mole of silver halide of result is 0.15% (mole)) in the interpolation of silver nitrate.Resulting emulsion is carried out desalting processing, add gelatin then and disperse again.In this emulsion, add sodium benzenethiosulfonate, use sodium thiosulfate 5 hydrates suitably to carry out maturation as golden sensitizer as sulphur sensitizer and two (1,4,5-trimethyl-1,2,4-triazole father-in-law-3-mercaptide) oleate (I) tetrafluoroborates of use.Add sensitizing coloring matter H, 1-phenyl-5-mercapto-tetrazole, 1-(5-methylurea base phenyl)-5-mercapto-tetrazole, Compound I and potassium bromide then.With the emulsion that obtains like this as emulsion R-2.
Use above emulsion to prepare following test portion.
Ground floor (feeling blue or green emulsion layer)
Emulsion B-1 0.07
Emulsion B-2 0.07
Gelatin 0.75
Yellow colour former (ExY-2) 0.34
Tint stabilizer (Cpd-1) 0.04
Tint stabilizer (Cpd-2) 0.02
Tint stabilizer (Cpd-3) 0.04
Tint stabilizer (Cpd-8) 0.01
Solvent (Solv-1) 0.13
The second layer (colour mixture prevents layer)
Gelatin 0.60
Colour mixture prevents agent (Cpd-19) 0.09
Tint stabilizer (Cpd-5) 0.007
Tint stabilizer (Cpd-7) 0.007
Ultraviolet light absorber (UV-C) 0.05
Solvent (Solv-5) 0.11
The 3rd layer (green-sensitive emulsion layer)
Emulsion G-11 0.12
Gelatin 0.73
Magenta colour coupler (ExM) 0.15
Ultraviolet light absorber (UV-A) 0.05
Tint stabilizer (Cpa-2) 0.02
Tint stabilizer (Cpd-7) 0.008
Tint stabilizer (Cpa-8) 0.07
Tint stabilizer (Cpa-9) 0.03
Tint stabilizer (Cpd-10) 0.009
Tint stabilizer (Cpa-11) 0.0001
Solvent (Solv-3) 0.06
Solvent (Solv-4) 0.11
Solvent (Solv-5) 0.06
The 4th layer (colour mixture prevents layer)
Gelatin 0.48
Colour mixture prevents agent (Cpd-4) 0.07
Tint stabilizer (Cpd-5) 0.006
Tint stabilizer (Cpd-7) 0.006
Ultraviolet light absorber (UV-C) 0.04
Solvent (Solv-5) 0.09
Layer 5 (magenta-sensitive emulsion layer)
Emulsion R-1 0.05
Emulsion R-2 0.05
Gelatin 0.59
Cyan coupler (ExC-2) 0.13
Cyan coupler (ExC-3) 0.03
Tint stabilizer (Cpd-7) 0.01
Tint stabilizer (Cpd-9) 0.04
Tint stabilizer (Cpd-15) 0.19
Tint stabilizer (Cpd-18) 0.04
Ultraviolet light absorber (UV-7) 0.02
Solvent (Solv-5) 0.09
Layer 6 (UV-absorbing layer)
Gelatin 0.32
Ultraviolet light absorber (UV-C) 0.42
Solvent (Solv-7) 0.08
Layer 7 (protective seam)
Gelatin 0.70
The propenyl sex change multipolymer of polyvinyl alcohol (PVA)
(modification degree 17%) 0.04
Whiteruss 0.01
Surfactant (Cpd-13) 0.01
Dimethyl silicone polymer 0.01
Silicon dioxide 0.003
With the above test portion that obtains as test portion 201.Change emulsion G-11 into emulsion G-12 respectively and make test portion to emulsion G-14, as test portion 202-204.
[changing 20]
In order to investigate the photosensitive performance of these test portions when the laser scanning exposure, carry out following experiment.As LASER Light Source, use the about 440nm of wavelength blue semiconductor laser (March calendar year 2001, the 48th applied physics lecture day inferior chemistry deliver), usefulness has the LiNbO of the anti-domain structure of waveguide-shaped 3The green laser of SHG crystal about 530nm that semiconductor laser (wave of oscillation is about 1060nm) wavelength conversion is taken out and the red semiconductor laser (the type № HL6501MG of Hitachi) of the about 650nm of wavelength.Utilize laser that polygonal prism makes 3 looks respectively with respect to the direction of scanning vertical moving, successively in the enterprising line scanning exposure of test portion.Owing to the light quantity change that the temperature of semiconductor laser causes, can use Po Er felt original paper that temperature is kept certain and be inhibited.Beam diameter is 80 μ m, and sweep span is 42.3 μ m (600dpi), and the mean exposure time of per 1 pixel is 1.7 * 10 -7Second.Adopt this Exposure mode, under 20 ℃, the environment of 30%RH, test portion is carried out the contrast exposure of grey colour developing.
For each test portion of exposure, the colour development of carrying out is similarly to Example 1 handled.But, the top ends of test portion is beginning colour development in about 3 seconds after exposure, and rearward end is beginning colour development in about 9 seconds after exposure.
The magenta reflection colour developing concentration of each test portion after measure handling similarly to Example 1, is read the photonasty of each emulsion by the logarithm of the needed exposure E of generation 1.7 colour developing concentration of each test portion.Photonasty is that the photonasty in order to emulsion G-11 is that 100 o'clock relative value is represented.The results are shown in the table 3.In addition, similarly to Example 1, each coating test portion is placed in 20 ℃, the environment of 30%RH, carrying out the colour development time after 6 seconds or after 60 seconds in above-mentioned exposure is 16 seconds processing.
[table 3]
Table 3
Test portion № adulterant αRelative photonasty * 1Contrast * 2
201 (comparative examples) do not add 100 2.58
202 (the present invention) IrCl 5(H 2O)/IrCl 5(5-Methia) 158 2.50
203 (comparative example) OsCl 5(NO) 180 3.67
204 (the present invention) OsCl 5(NO)/IrCl 5(H 2O)/IrCl 5
(S-methylthiourea) 185 3.60
αThe 5-Methia=5-methylthiazol
* 1With 10 -4The photonasty of the test portion 101 in second when exposure is that 100 relative photonasty is represented
* 2The contrast of each test portion is to represent with the slope between photographic fog+0.1 to photographic fog+0.5
By the result of table 3 as can be seen, test portion 203,203 can be suitable for the photonasty and the contrast of laser scanning exposure most in height colour developing concentration range, and does not depend on from exposing to the time of development treatment, can obtain stable performance.
The present invention is put the performance that adulterant is caught in this design of time by Xu, will have the adulterant appropriate combination use that Xu who adapts with the needed exposure illumination of emulsion is put the time, thereby obtains not having in whole exposure illumination scope the emulsion of reciprocity law abnormality.By this opinion being generalized to the necessary performance of emulsion (photonasty, contrast), can obtain the emulsion of reciprocity law abnormality that the exposure illumination for wide region do not have and high photosensitivity, vigour.

Claims (4)

1. a silver emulsion is characterized in that, contains 2 kinds at least and give 10 in silver halide particle -5Second above, the average electronics below 3 seconds is put the metal complex of time slowly.
2. silver emulsion according to claim 1 is characterized in that, in described at least 2 kinds of metal complexes, at least a kind is to give 10 -5Second above, less than 10 -3The average electronics of second is put the metal complex of time slowly, and at least a kind is to give 10 -3Average electronics is put the metal complex of time slowly more than second, below 3 seconds.
3. silver emulsion according to claim 1 and 2 is characterized in that, described metal complex is to be selected from the metal complex shown in the following general formula (I).
General formula (I)
[IrX (6-0)L n] m
X: halogen ion or class halogen ion
L: any dentate different with X
The integer of n:1 to 6
M:-4 is+4 integer extremely
4. a silver halide photographic sensitive material is the silver halide photographic sensitive material that has one deck silver halide emulsion layer on supporting mass at least, it is characterized in that, this silver halide emulsion layer contains each described silver emulsion among the claim 1-3.
CNA2003101205725A 2003-03-13 2003-12-12 Silver halide emulsion and silver halide camera photosensitive material Pending CN1530741A (en)

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JP2003068446 2003-03-13

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