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Patent US6107018 - High chloride emulsions doped with combination of metal complexes - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA radiation-sensitive emulsion is disclosed comprised of silver halide grains (a) containing greater than 50 mole percent chloride, based on silver, (b) having greater than 50 percent of their surface area provided by {100} crystal faces, and (c) having a central portion accounting for from 95 to 99...http://www.google.com/patents/US6107018?utm_source=gb-gplus-sharePatent US6107018 - High chloride emulsions doped with combination of metal complexesAdvanced Patent SearchPublication numberUS6107018 APublication typeGrantApplication numberUS 09/250,200Publication dateAug 22, 2000Filing dateFeb 16, 1999Priority dateFeb 16, 1999Fee statusPaidAlso published asEP1030215A1Publication number09250200, 250200, US 6107018 A, US 6107018A, US-A-6107018, US6107018 A, US6107018AInventorsEric L. Bell, Michael S. Graham, Jerzy Z. MydlarzOriginal AssigneeEastman Kodak CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (26), Referenced by (14), Classifications (17), Legal Events (7) External Links: USPTO, USPTO Assignment, EspacenetHigh chloride emulsions doped with combination of metal complexesUS 6107018 AAbstract A radiation-sensitive emulsion is disclosed comprised of silver halide grains (a) containing greater than 50 mole percent chloride, based on silver, (b) having greater than 50 percent of their surface area provided by {100} crystal faces, and (c) having a central portion accounting for from 95 to 99 percent of total silver and containing two dopants selected to satisfy each of the following class requirements: (i) a hexacoordination metal complex which satisfies the formula (I)
wherein n is zero, -1, -2, -3 or -4; M is a filled frontier orbital polyvalent metal ion, other than iridium; and L.sub.6 represents bridging ligands which can be independently selected, provided that least four of the ligands are anionic ligands, and at least one of the ligands is a cyano ligand or a ligand more electronegative than a cyano ligand; and (ii) an iridium coordination complex containing a thiazole or substituted thiazole ligand. A photographic recording element comprising a support and at least one light sensitive silver halide emulsion layer comprising silver halide grains as described above is also disclosed, as well as an electronic printing method which comprises subjecting a radiation sensitive silver halide emulsion layer of a recording element to actinic radiation of at least 10.sup.-4 ergs/cm.sup.2 for up to 100μ seconds duration in a pixel-by-pixel mode, wherein the silver halide emulsion layer is comprised of silver halide grains as described above.
What is claimed is: 1. A radiation-sensitive emulsion comprised of silver halide grains(a) containing greater than 50 mole percent chloride, based on silver, (b) having greater than 50 percent of their surface area provided by {100} crystal faces, and (c) having a central portion accounting for from 95 to 99 percent of total silver and containing two dopants selected to satisfy each of the following class requirements:(i) a hexacoordination metal complex which satisfies the formula: [ML.sub.6 ].sup.n                                          (I) wherein n is zero, -1, -2, -3 or -4; M is a filled frontier orbital polyvalent metal ion, other than iridium; and L.sub.6 represents bridging ligands which can be independently selected, provided that at least four of the ligands are anionic ligands, and at least one of the ligands is a cyano ligand or a ligand more electronegative than a cyano ligand; and(ii) an iridium coordination complex containing a thiazole or substituted thiazole ligand. 2. A radiation-sensitive emulsion according to claim 1, wherein the iridium coordination complex of class (ii) satisfies the formula: [IrL.sup.1.sub.6 ].sup.n'                                  (II) wherein n' is zero, -1, -2, -3 or -4; and L.sup.1.sub.6 represents six bridging ligands which can be independently selected, provided that at least four of the ligands are anionic ligands, each of the ligands is more electropositive than a cyano ligand, and at least one of the ligands comprises a thiazole or substituted thiazole ligand. 3. A radiation-sensitive emulsion according to claim 2 wherein at least one of the ligands of the class (ii) dopant is a halide ligand.
7. A radiation-sensitive emulsion according to claim 2 wherein M represents an Fe.sup.+2, Ru.sup.+2, Os.sup.+2, Co.sup.+3, Rh.sup.+3, Pd.sup.+4, or Pt.sup.+4 ion.
15. A radiation-sensitive emulsion according to claim 2 wherein the class (i) dopant is located within the central portion of grains in an interior region surrounding at least 50 percent of the total silver forming the grains and is present in a concentration of from 10.sup.-8 to 10.sup.-3 mole per mole of silver, and the class (ii) dopant is located within the central portion of the grains in a sub-surface shell region surrounding at least 50 percent of the total silver forming the grains and is present in a concentration of from 10.sup.-9 to 10.sup.-4 mole per mole of silver.
17. A radiation-sensitive emulsion according to claim 16 wherein the class (i) dopant is present in a concentration of from 10.sup.-6 to 5
19. A radiation-sensitive emulsion according to claim 2 wherein the class (ii) dopant is present in a concentration from 10.sup.-8 to 10.sup.-5 mole per silver mole.
22. An electronic printing method which comprises subjecting a radiation sensitive silver halide emulsion layer of a recording element to actinic radiation of at least 10.sup.-4 ergs/cm.sup.2 for up to 100μ seconds duration in a pixel-by-pixel mode, wherein the silver halide emulsion layer is comprised of silver halide grains(a) containing greater than 50 mole percent chloride, based on silver, (b) having greater than 50 percent of their surface area provided by {100} crystal faces, and (c) having a central portion accounting for from 95 to 99 percent of total silver and containing two dopants selected to satisfy each of the following class requirements:(i) a hexacoordination metal complex which satisfies the formula: [ML.sub.6 ].sup.n                                          (I) wherein n is zero, -1, -2, -3 or -4; M is a filled frontier orbital polyvalent metal ion, other than iridium; and L.sub.6 represents bridging ligands which can be independently selected, provided that at least four of the ligands are anionic ligands, and at least one of the ligands is a cyano ligand or a ligand more electronegative than a cyano ligand; and(ii) an iridium coordination complex containing a thiazole or substituted thiazole ligand. 23. A method according to claim 22 wherein the pixels are exposed to actinic radiation of about 10.sup.-3 ergs/cm.sup.2 to 10.sup.2 ergs/cm.sup.2.
25. A method according to claim 22 wherein the duration of the exposure is up to 0.5.mu. seconds.
26. A method according to claim 22 wherein the duration of the exposure is up to 0.05.mu. seconds.
EMULSION PRECIPITATIONS Emulsion A A reaction vessel contained 6.92 L of a solution that was 3.8% in regular gelatin and contained 1.71 g of a Pluronic� antifoam agent. To this stirred solution at 46 soon after 28.3 mL of dithiaoctanediol solution was poured into the reactor. A half minute after addition of dithiaoctanediol solution, 104.5 mL of a 2.8 M AgNO.sub.3 solution and 107.5 mL of 3.0 M NaCl were added simultaneously at 209 mL/min for 0.5 minute. The vAg set point was chosen equal to that observed in the reactor at this time. Then the 2.8 M silver nitrate solution and the 3.0 M sodium chloride solution were added simultaneously with a constant flow at 209 mL/min over 20.75 minutes. The resulting silver chloride emulsion had a cubic shape that was 0.38 μm in edge length. The emulsion was then washed using an ultrafiltration unit, and its final pH and pCl were adjusted to 5.6 and 1.8, respectively.
Emulsion B This emulsion was precipitated exactly as Emulsion A, except that 16.54 milligrams per silver mole of K.sub.4 Ru(CN).sub.6 was added during precipitation during to 80 to 85% of grain formation.
Emulsion C This emulsion was precipitated exactly as Emulsion A, except that 0.16 milligrams per silver mole of K.sub.2 IrCl.sub.5 (Thiazole) was added during precipitation during to 90 to 95% of grain formation.
Emulsion D This emulsion was precipitated exactly as Emulsion A, except that 16.54 milligrams per silver mole of K.sub.4 Ru(CN).sub.6 was added during precipitation during to 80 to 85% of grain formation and 0.16 milligrams per silver mole of K.sub.2 IrCl.sub.5 (Thiazole) was added during precipitation during to 90 to 95% of grain formation.
Emulsion E This emulsion was precipitated exactly as Emulsion A, except that 0.164 milligrams per silver mole of K.sub.2 IrCl.sub.5 (5-Methyl-Thiazole) was added during precipitation during to 90 to 95% of grain formation.
Emulsion F This emulsion was precipitated exactly as Emulsion A, except that 16.54 milligrams per silver mole of K.sub.4 Ru(CN).sub.6 was added during precipitation during to 80 to 85% of grain formation and 0.164 milligrams per silver mole of K.sub.2 IrCl.sub.5 (5-Methyl-Thiazole) was added during precipitation during to 90 to 95% of grain formation.
Emulsion G A reaction vessel contained 8.65 L of a solution that was 3.97% in regular gelatin and contained 1.75 g of a Pluronic antifoam agent. To this stirred solution at 46.1.degree. C. 79.8 mL of 3.0 M NaCl was dumped, and soon after 25.7 mL of dithiaoctanediol solution was poured into the reactor. A half minute after addition of dithiaoctanediol solution, 133.1 mL of a 2.8 M AgNO.sub.3 solution and 129.9 mL of 3.0 M NaCl were added simultaneously at 128.2 mL/min for 0.75 minute. The vAg set point was chosen equal to that observed in the reactor at this time. Then the 2.8 M silver nitrate solution and the 3.0 M sodium chloride solution were added simultaneously with a constant flow at 128.2 mL/min over 22.3 minutes. The resulting silver chloride emulsion had a cubic shape that was 0.29 μm in edge length. The emulsion was then washed using an ultrafiltration unit, and its final pH and pCl were adjusted to 5.6 and 1.8, respectively.
Emulsion H This emulsion was precipitated exactly as Emulsion G, except that 16.54 milligrams per silver mole of K.sub.4 Ru(CN).sub.6 was added during precipitation during to 80 to 85% of grain formation.
Emulsion I This emulsion was precipitated exactly as Emulsion G, except that 0.1656 milligrams per silver mole of K.sub.2 IrCl.sub.5 (5-Methyl-Thiazole) was added during precipitation during to 90 to 95% of grain formation.
Emulsion J This emulsion was precipitated exactly as Emulsion G, except that 16.54 milligrams per silver mole of K.sub.4 Ru(CN).sub.6 was added during precipitation during to 80 to 85% of grain formation and 0.1656 milligrams per silver mole of K.sub.2 IrCl.sub.5 (5-Methyl-Thiazole) was added during precipitation during to 90 to 95% of grain formation.
Emulsion K This emulsion was precipitated exactly as Emulsion G, except that 0.3312 milligrams per silver mole of K.sub.2 IrCl.sub.5 (5-Methyl-Thiazole) was added during precipitation during to 90 to 95% of grain formation.
Emulsion L This emulsion was precipitated exactly as Emulsion G, except that 16.54 milligrams per silver mole of K.sub.4 Ru(CN).sub.6 was added during precipitation during to 80 to 85% of grain formation and 0.3312 milligrams per silver mole of K.sub.2 IrCl.sub.5 (5-Methyl-Thiazole) was added during precipitation during to 90 to 95% of grain formation.
SENSITIZATION OF EMULSIONS The emulsions were each optimally sensitized by the customary techniques using two basic sensitization schemes. The sequence of chemical sensitizers, spectral sensitizers, and antifoggants addition are the same for each finished emulsion. Both colloidal gold sulfide or gold(I) (as disclosed in copending, commonly assigned U.S. Ser. No. 08/965,507 filed Nov. 6, 1997) and Na.sub.2 S.sub.2 O.sub.3 were used for chemical sensitization. Detailed procedures are described in the Examples below.
PHOTOGRAPHIC COMPARISONS Coatings were exposed through a step wedge with 3000 K tungsten source at high-intensity short exposure times (10.sup.-2 to 10.sup.-4 second for red sensitized emulsions and 10.sup.-3 to 10.sup.-5 second for green sensitized emulsions) or low-intensity, long exposure time of 10 to 0.1 second for red sensitized emulsions and 1 to 10.sup.-2 second for green sensitized emulsions. The total energy of each exposure was kept at a constant level. Speed is reported as relative log speed (RLS) at specified level above the minimum density as presented in the following Examples. In relative log speed units a speed difference of 30, for example, is a difference of 0.30 log E, where E is exposure in lux-seconds. These exposures will be referred to as "Optical Sensitivity" in the following Examples.
Example 1 This example compares effects of K.sub.4 Ru(CN).sub.6 and K.sub.2 IrCl.sub.5 (Thiazole) synergy on shoulder reciprocity failure. In each case, silver chloride cubic emulsions sensitized for red color record were used. The sensitization details are as follows:
Part 1.1: A portion of silver chloride Emulsion A was optimally sensitized by the addition of p-glutaramidophenyl disulfide (GDPD) followed by addition of stilbene, followed by the optimum amount of Na.sub.2 S.sub.2 O.sub.3 followed by addition of gold(I). The emulsion was then heated to 65 addition of 1-(3-acetamidophenyl)-5-mercaptotetrazole followed by addition of Lippmann bromide and followed by addition of Spectral Sensitizing dye B. Then the emulsion was cooled to 40
Example 2 This example compares effects of K.sub.4 Ru(CN).sub.6 and K.sub.2 IrCl.sub.5 (Thiazole) synergy on shoulder reciprocity failure. In each case, silver chloride cubic emulsions sensitized for red color record were used. The sensitization details are as follows:
Part 2.1: A portion of silver chloride Emulsion A was optimally sensitized by the addition of GDPD followed by addition of a stilbene compound, followed by a heat ramp up to 65 added followed by addition of the optimum amount of Na.sub.2 S.sub.2 O.sub.3, followed by addition of gold(I), and subsequent addition of 1-(3-acetamidophenyl)-5-mercaptotetrazole. Then the emulsion was cooled to 40
Example 3 This example compares effects of K.sub.4 Ru(CN).sub.6 and K.sub.2 IrCl.sub.5 (Thiazole) synergy on shoulder reciprocity failure. In each case, silver chloride cubic emulsions sensitized for red color record were used. The sensitization details are as follows:
Part 3.1: A portion of silver chloride Emulsion A was optimally sensitized by the addition of Lippmann bromide doped with iridium hexachloride. The emulsion was then heated to 65 10 minutes with subsequent addition of p-glutaramidophenyl disulfide (GDPD) followed by the optimum amount of gold(I) followed by addition of Na.sub.2 S.sub.2 O.sub.3 with subsequent addition stilbene followed by addition of Spectral Sensitizing Dye B followed by addition of 1-(3-acetamidophenyl)-5-mercaptotetrazole. Then the emulsion was cooled to 40
TABLE III__________________________________________________________________________           Optical Sensitivity     Digital Sensitivity    mg    mg    HIRF        LIRF              Contrast @  Coating K.sub.4 Ru(CN).sub.6 / K.sub.2 IrCl.sub.5 (Tz)/ 10.sup.-2                                         s-10.sup.-4 s 10 s-0.1 s                                         Speed @ Dmin + 0.2ID  Ag mole     Ag mole           Dmin + 1.3                 Dmin + 1.95                       Dmin + 1.3                             Dmin + 1.95                                   Dmin + 1.9                                         &amp; Dmin + 1.8__________________________________________________________________________Part 3.1    --    --    37.6  45.9  3.7   3.4   45    1.329  Part 3.2 16.54 -- 37.5 42.9 3.9 3.2 68 1.382  Part 3.3 -- 0.16 16.1 26.5 2.0 2.8 72 1.607  Part 3.4 16.54 0.16 -3.7 -1.7 0.9 0.7 108  1.875__________________________________________________________________________
Example 4 This example compares effects of K.sub.4 Ru(CN).sub.6 and K.sub.2 IrCl.sub.5 (Thiazole) synergy on shoulder reciprocity failure. In each case, silver chloride cubic emulsions sensitized for red color record were used. The sensitization details are as follows:
Part 4.1: A portion of silver chloride Emulsion A was optimally sensitized by the addition of p-glutaramidophenyl disulfide (GDPD), followed by the optimum amount of Na.sub.2 S.sub.2 O.sub.3 followed by addition of gold(I). The emulsion was then heated to 60 temperature for 28 minutes with subsequent addition of 1-(3-acetamidophenyl)-5-mercaptotetrazole followed by addition of Lippmann bromide and followed by addition of Spectral Sensitizing dye B. Then the emulsion was cooled to 40
TABLE IV__________________________________________________________________________           Optical Sensitivity     Digital Sensitivity    mg    mg    HIRF        LIRF              Contrast @  Coating K.sub.4 Ru(CN).sub.6 / K.sub.2 IrCl.sub.5 (Tz)/ 10.sup.-2                                         s-10.sup.-4 s 10 s-0.1 s                                         Speed @ Dmin + 0.2ID  Ag mole     Ag mole           Dmin + 1.3                 Dmin + 1.95                       Dmin + 1.3                             Dmin + 1.95                                   Dmin + 1.9                                         &amp; Dmin + 1.8__________________________________________________________________________Part 4.1    --    --    55.8  59.8  12.4  14.9  21    1.245  Part 4.2 16.54 -- 45.7 50.5 10.4 9.5 32 1.513  Part 4.3 -- 0.16 27.6 37.2  3.1 3.1 46 1.546  Part 4.4 16.54 0.16 -0.2  5.6  1.0 1.5 98 2.109__________________________________________________________________________
Example 5 This example compares effects of K.sub.4 Ru(CN).sub.6 and K.sub.2 IrCl.sub.5 (5-Methyl-Tz) synergy on shoulder reciprocity failure. In each case, silver chloride cubic emulsions sensitized for red color record were used. The sensitization details are as follows:
TABLE V__________________________________________________________________________     mg    Optical Sensitivity     Digital Sensitivity    mg    K.sub.2 IrCl.sub.5 (5-           HIRF        LIRF              Contrast @  Coating K.sub.4 Ru(CN).sub.6 / Methyl-Tz)/ 10.sup.-2 s-10.sup.-4 s 10                                         s-0.1 s Speed @ Dmin = 0.2ID  Ag mole     Ag mole           Dmin + 1.3                 Dmin + 1.95                       Dmin + 1.3                             Dmin + 1.95                                   Dmin + 1.9                                         &amp; Dmin + 1.8__________________________________________________________________________Part 5.1    --    --    37.6  45.9  3.7   3.4   45    1.329  Part 5.2 16.54 -- 37.5 42.9 3.9 3.2 68 1.382  Part 5.3 -- 0.164 24.2 29.9 2.9 2.8 69 1.440  Part 5.4 16.54 0.164 -1.5  1.5 1.6 1.2 98 1.938__________________________________________________________________________
Example 6 This example compares effects of K.sub.4 Ru(CN).sub.6 and K.sub.2 IrCl.sub.5 (5-Methyl-Tz) synergy on shoulder reciprocity failure. In each case, silver chloride cubic emulsions sensitized for red color record were used. The sensitization details are as follows:
TABLE VI__________________________________________________________________________     mg    Optical Sensitivity     Digital Sensitivity    mg    K.sub.2 IrCl.sub.5 (5-           HIRF        LIRF              Contrast @  Coating K.sub.4 Ru(CN).sub.6 / Methyl-Tz)/ 10.sup.-2 s-10.sup.-4 s 10                                         s-0.1 s Speed @ Dmin + 0.2ID  Ag mole     Ag mole           Dmin + 1.3                 Dmin + 1.95                       Dmin + 1.3                             Dmin + 1.95                                   Dmin + 1.9                                         &amp; Dmin + 1.8__________________________________________________________________________Part 6.1    --    --    55.8  59.8  12.4  14.9  21    1.245  Part 6.2 16.54 -- 45.7 50.5 10.4 9.5 32 1.311  Part 6.3 -- 0.164 32.5 45.8 9.6 8.2 41 1.315  Part 6.4 16.54 0.164 12.8 31.3 -1.8 1.1 72 1.738__________________________________________________________________________
Example 7 This example compares effects of K.sub.4 Ru(CN).sub.6 and K.sub.2 IrCI.sub.5 (5-Methyl-Tz) synergy on shoulder reciprocity failure. In each case, silver chloride cubic emulsions sensitized for green color record were used. The sensitization details are as follows:
Part 7.1: A portion of silver chloride Emulsion G was optimally sensitized by the addition of gold sulfide. The emulsion was then heated to 55 addition Lippmann bromide, followed by addition of Spectral Sensitizing Dye C followed by addition of 1-(3-acetamidophenyl)-5-mercaptotetrazole. Then the emulsion was cooled to 40
TABLE VII__________________________________________________________________________     mg    Optical Sensitivity     Laser Sensitivity    mg    K.sub.2 IrCl.sub.5 (5-           HIRF        LIRF              Contrast @  Coating K.sub.4 Ru(CN).sub.6 / Methyl-Tz)/ 10.sup.-3 s-10.sup.-5 s 1                                         s-10.sup.-2 s Speed @ Dmin                                         + 0.2ID  Ag mole     Ag mole           Dmin + 1.3                 Dmin + 1.95                       Dmin + 1.3                             Dmin + 1.95                                   Dmin + 1.9                                         &amp; Dmin + 1.8__________________________________________________________________________Part 7.1    --    --    39.8  61.8  14.2  13.8  40    1.709  Part 7.2 16.54 -- 31.6 56 9.4 11.2 58 1.892  Part 7.3 -- 0.1656  7.2 24.1 7.6 8.8 62 1.911  Part 7.4 16.54 0.1656  2.4 5.3 1.1 -0.5 96 2.354__________________________________________________________________________
Example 8 This example compares effects of K.sub.4 Ru(CN).sub.6 and K.sub.2 IrCl.sub.5 (5-Methyl-Tz) synergy on shoulder reciprocity failure. In each case, silver chloride cubic emulsions sensitized for green color record were used. The sensitization details are as follows:
TABLE VIII__________________________________________________________________________     mg    Optical Sensitivity     Digital Sensitivity    mg    K.sub.2 IrCl.sub.5 (5-           HIRF        LIRF              Contrast @  Coating K.sub.4 Ru(CN).sub.6 / Methyl-Tz)/ 10.sup.-3 s-10.sup.-5 s 1                                         s-10.sup.-2 s Speed @ Dmin                                         + 0.2ID  Ag mole     Ag mole           Dmin + 1.3                 Dmin + 1.95                       Dmin + 1.3                             Dmin + 1.95                                   Dmin + 1.9                                         &amp; Dmin + 1.8__________________________________________________________________________Part 8.1    --    --    39.8  61.8  14.2  13.8  40    1.709  Part 8.2 16.54 -- 31.6 56 9.4 11.2 58 1.892  Part 8.3 -- 0.3312  3.2 6.2 4.9 7.1 64 1.931  Part 8.4 16.54 0.3312  1.1 1.6 -0.9 --0.5 102  2.426__________________________________________________________________________
Example 9 This example compares effects of K.sub.4 Ru(CN).sub.6 and K.sub.2 IrCl.sub.5 (5-Methyl-Tz) synergy on shoulder reciprocity failure. In each case, silver chloride cubic emulsions sensitized for green color record were used. The sensitization details are as follows:
Part 9.1: A portion of silver chloride Emulsion G was optimally sensitized by the addition of Spectral Sensitizing Dye C followed by the optimum amount of gold sulfide. The emulsion was then heated to 60 held at this temperature for 34 minutes. Then the emulsion was cooled to 40 addition of 1-(3-acetamidophenyl)-5-mercaptotetrazole.
TABLE IX__________________________________________________________________________     mg    Optical Sensitivity     Digital Sensitivity    mg    K.sub.2 IrCl.sub.5 (5-           HIRF        LIRF              Contrast @  Coating K.sub.4 Ru(CN).sub.6 / Methyl-Tz)/ 10.sup.-3 s-10.sup.-5 s 1                                         s-10.sup.-2 s Speed @ Dmin                                         + 0.2ID  Ag mole     Ag mole           Dmin + 1.3                 Dmin + 1.95                       Dmin + 1.3                             Dmin + 1.95                                   Dmin + 1.9                                         &amp; Dmin + 1.8__________________________________________________________________________Part 9.1    --    --    32.6  48.6  14.5  14.9  60    1.880  Part 9.2 16.54 -- 32.4 45.6 7.2 11.1 74 2.114  Part 9.3 -- 0.1656  8.3 18 7.7  9.4 80 2.160  Part 9.4 16.54 0.1656  3.2 4.7 0.5  1.8 114  2.620__________________________________________________________________________
Example 10 This example compares effects of K.sub.4 Ru(CN).sub.6 and K.sub.2 IrCl.sub.5 (5-Methyl-Tz) synergy on shoulder reciprocity failure. In each case, silver chloride cubic emulsions sensitized for green color record were used. The sensitization details are as follows:
TABLE X__________________________________________________________________________     mg    Optical Sensitivity     Digital Sensitivity    mg    K.sub.2 IrCl.sub.5 (5-           HIRF        LIRF              Contrast @  Coating K.sub.4 Ru(CN).sub.6 / Methyl-Tz)/ 10.sup.-3 s-10.sup.-5 s 1                                         s-10.sup.-2 s Speed @ Dmin                                         + 0.2ID  Ag mole     Ag mole           Dmin + 1.3                 Dmin + 1.95                       Dmin + 1.3                             Dmin + 1.95                                   Dmin + 1.9                                         &amp; Dmin + 1.8__________________________________________________________________________Part    --    --    32.6  48.6  14.5  14.9  60    1.880  10.1  Part 16.54 -- 32.4 45.6 7.2 11.1 74 2.114  10.2  Part -- 0.3312  4.5  7.0 4.8  7.1 82 2.423  10.3  Part 16.54 0.3312  1.3  1.9 1.4  0.3 118  2.648  10.4__________________________________________________________________________
Budz et al U.S. Pat. No. 5,451,490 discloses an improved electronic printing method which comprises subjecting a radiation sensitive silver halide emulsion layer of a recording element to actinic radiation of at least 10.sup.-4 ergs/cm.sup.2 for up to 100μ seconds duration in a pixel-by-pixel mode. The radiation sensitive silver halide emulsion layer contains a silver halide grain population comprising at least 50 mole percent chloride, based on silver, forming the grain population projected area. At least 50 percent of the grain population projected area is accounted for by tabular grains that are bounded by {100} major faces having adjacent edge ratios of less than 10, each having an aspect ratio of at least 2. The substitution of a high chloride tabular grain emulsion for a high chloride cubic grain emulsion was demonstrated to reduce high intensity reciprocity failure (HIRF). Budz et al discloses among conventional alternatives (a) dopants and (b) low methionine gelatino-peptizer. Treatment of gelatino-peptizer with an oxidizing agent to lower methionine is disclosed by Research Disclosure, Vol. 389, September 1996, Item 38957, II. Vehicles, vehicle extenders, vehicle-like addenda and vehicle related addenda, A. Gelatin and hydrophilic colloid peptizers, paragraph (3).
It has become increasing clear that with the continuing development of a variety of high intensity digital printing devices that photographic print materials with performance invariant to exposure time is increasingly important. When exposure times are reduced below one second to very short intervals (e.g., 10.sup.-5 second or less), higher exposure intensities must be employed to compensate for the reduced exposure times. High intensity reciprocity failure (hereinafter also referred to as HIRF) occurs when photographic performance is noted to depart from the reciprocity law when such shorter exposure times are employed. Print materials which traditionally suffer speed or contrast losses at short exposure times (high intensity exposures) will fail to reproduce detail with high resolution. Text will appear blurred. Through-put of digital print devices will suffer as well. Accordingly, print materials with reduced HIRF are desired in order to produce excellent photographic prints in a wide variety of digital printers.
wherein n is zero, -1, -2, -3 or -4; M is a filled frontier orbital polyvalent metal ion, other than iridium; and L.sub.6 represents bridging ligands which can be independently selected, provided that least four of the ligands are anionic ligands, and at least one of the ligands is a cyano ligand or a ligand more electronegative than a cyano ligand; and (ii) an iridium coordination complex containing a thiazole or substituted thiazole ligand.
In another aspect, this invention is directed to an electronic printing method which comprises subjecting a radiation sensitive silver halide emulsion layer of a recording element to actinic radiation of at least 10.sup.-4 ergs/cm.sup.2 for up to 100μ seconds duration in a pixel-by-pixel mode, wherein the silver halide emulsion layer is comprised of silver halide grains as described above.
DESCRIPTION OF PREFERRED EMBODIMENTS In one embodiment, the present invention represents an improvement on the electronic printing method disclosed by Budz et al, cited above and here incorporated by reference. Specifically, this invention in one embodiment is directed to an electronic printing method which comprises subjecting a radiation sensitive silver halide emulsion layer of a recording element to actinic radiation of at least 10.sup.-4 ergs/cm.sup.2 for up to 100μ seconds duration in a pixel-by-pixel mode. The present invention realizes an improvement in reciprocity failure by modifying the radiation sensitive silver halide emulsion layer. While certain embodiments of the invention are specifically directed towards electronic printing, use of the emulsions and elements of the invention is not limited to such specific embodiment, and it is specifically contemplated that the emulsions and elements of the invention are also well suited for conventional optical printing.
M is a filled frontier orbital polyvalent metal ion, other than iridium, preferably Fe.sup.+2, Ru.sup.+2, Os.sup.+2, Co.sup.+3, Rh.sup.+3, Pd.sup.+4 or Pt+.sup.4, more preferably an iron, ruthenium or osmium ion, and most preferably a ruthenium ion;
Class (i) dopant can be employed in any conventional useful concentration. A preferred concentration range is from 10.sup.-8 to 10.sup.-3 mole per silver mole, most preferably from 10.sup.-6 to 5 silver mole.
Emulsions demonstrating the advantages of the invention can be realized by modifying the precipitation of conventional high chloride silver halide grains having predominantly (&gt;50%) {100} crystal faces by employing a combination of class (i) and (ii) dopants as described above.
In another improved form the high chloride grains can take the form of tabular grains having {100} major faces. Preferred high chloride {100} tabular grain emulsions are those in which the tabular grains account for at least 70 (most preferably at least 90) percent of total grain projected area. Preferred high chloride {100} tabular grain emulsions have average aspect ratios of at least 5 (most preferably at least &gt;8). Tabular grains typically have thicknesses of less than 0.3 μm, preferably less than 0.2 μm, and optimally less than 0.07 μm. High chloride {100} tabular grain emulsions and their preparation are disclosed by Maskasky U.S. Pat. Nos. 5,264,337 and 5,292,632, House et al U.S. Pat. No. 5,320,938, Brust et al U.S. Pat. No. 5,314,798 and Chang et al U.S. Pat. No. 5,413,904, the disclosures of which are here incorporated by reference.
The quantity or level of high energy actinic radiation provided to the recording medium by the exposure source is generally at least 10.sup.-4 ergs/cm.sup.2, typically in the range of about 10.sup.-4 ergs/cm.sup.2 to 10.sup.-3 ergs/cm.sup.2 and often from 10.sup.-3 ergs/cm.sup.2 to 10.sup.2 ergs/cm.sup.2. Exposure of the recording element in a pixel-by-pixel mode as known in the prior art persists for only a very short duration or time. Typical maximum exposure times are up to 100μ seconds, often up to 10μ seconds, and frequently up to only 0.5.mu. seconds. Single or multiple exposures of each pixel are contemplated. The pixel density is subject to wide variation, as is obvious to those skilled in the art. The higher the pixel density, the sharper the images can be, but at the expense of equipment complexity. In general, pixel densities used in conventional electronic printing methods of the type described herein do not exceed 10.sup.7 pixels/cm.sup.2 and are typically in the range of about 10.sup.4 to 10.sup.6 pixels/cm.sup.2. An assessment of the technology of high-quality, continuous-tone, color electronic printing using silver halide photographic paper which discusses various features and components of the system, including exposure source, exposure time, exposure level and pixel density and other recording element characteristics is provided in Firth et al., A Continuous-Tone Laser Color Printer, Journal of Imaging Technology, Vol. 14, No. 3, June 1988, which is hereby incorporated herein by reference. As previously indicated herein, a description of some of the details of conventional electronic printing methods comprising scanning a recording element with high energy beams such as light emitting diodes or laser beams, are set forth in Hioki U.S. Pat. No. 5,126,235, European Patent Applications 479 167 A1 and 502 508 A1, the disclosures of which are hereby incorporated herein by reference.
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