CN102338981A - Efficient sensibilization method suitable for platy silver halides particle emulsion - Google Patents

Efficient sensibilization method suitable for platy silver halides particle emulsion Download PDF

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CN102338981A
CN102338981A CN2010102383823A CN201010238382A CN102338981A CN 102338981 A CN102338981 A CN 102338981A CN 2010102383823 A CN2010102383823 A CN 2010102383823A CN 201010238382 A CN201010238382 A CN 201010238382A CN 102338981 A CN102338981 A CN 102338981A
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emulsion
silver halide
plate shape
stabilizing agent
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CN102338981B (en
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马望京
杨新民
赵艳艳
段培成
刘霞
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention belongs to the technical field of sensitive materials, and in particular relates to an efficient sensibilization method suitable for a platy silver halides particle emulsion. The method comprises the following steps of: adding 1*10<-5> to 1*10<-1>mol/molAg oxalate serving as a sensibilization agent into the platy silver halides emulsion at the constant temperature of between 45 and 55 DEG C; sequentially adding a Na2S2O3 aqueous solution and a mixed aqueous solution which is obtained by mixing 0.0167 mass percent AuCl3 aqueous solution and 0.2 mass percent NH4SCN aqueous solution according to the volume ratio of 1:1, and curing for 70 to 110 minutes; and adding a stabilizing agent (tissue antagonist of interferon (TAI)), quickly freezing at a low temperature, and thus obtaining the jointly sensibilized platy silver halides particle emulsion. The jointly sensibilized platy silver halides particle emulsion has the sensitivity which is more than 2 times higher than that of an emulsion treated by an individual conventional sulfur-plus-gold sensibilization method, and has smaller fog.

Description

A kind of efficient process for increasing sensitivity that is applicable to the plate shape silver halide grain emulsion
Technical field
The invention belongs to the photosensitive material technical field, specially refer to a kind of efficient process for increasing sensitivity that is applicable to the plate shape silver halide grain emulsion.
Background technology
Overcome the inefficiencies that latent image forms, improving light sensitivity is the problem that the silver halide imaging system will solve all the time, and the latent image formation efficiency of modern high-sensitivity emulsion also has only 20～25%.Wherein the compound of photohole and electronics is to cause one of low main reason of latent image formation efficiency.
For avoiding photohole and electron recombination; People propose halogen-absorber method (absorption hole) in succession, crystallite are mixed iodide ion and double structure (effectively separating hole and electronics); To reduce the electron recombination loss, increase its effective rate of utilization, to reach the purpose that improves light sensitivity; But facts have proved that these methods are effective really, but effect is very limited.In recent years the someone propose " hole-electronic switch method " (Xia Peijie, state is red, Yao Linhui; Zhao Wenfang " hole in the formation process of latent image and conversion thereof ", " photographic science and photochemistry ", 2002; 20 (1): 46-59), this method is design a kind of " hole-electronic commutator ", catches the hole; Conversion electron, it is sharp changing fraud, improves the effect of light sensitivity thereby play to kill two birds with one stone.Possess this function conversion device at present and have three types: 1) silver-colored dimer; 2) carboxylic acid compound; 3) can split into the bielectron donor compound of molecule fragment.
Wherein, people such as De Keyzer in 1999 and Belloni is at patent documentation (De Keyzer R, Treguer M; Belloni-Cofler J; Hynd R.A photosensitive silver halide element with increased photosensitivity.Europe, EP 0922994 A2.1998, Nov.30) with the Nature magazine on (Belloni J; Treguer M; Remita H, de Keyzer R.Enhanced yield of photoinduced electrons in doped silver halide crystals.1999, Nature; No.402:865-867) delivered with carboxylate, replaced the effect that the silver halide microcrystal that mixes inside such as sulfate or replacement sulphurous acid has fairly obvious raising light sensitivity; This emulsion after mixing still can be proceeded chemical sensitization and spectral sensitization, and have no bad reaction.
In people's such as aforementioned De Keyzer and Belloni patent, introduced the sensitizing effect of carboxylate doped emulsion in detail, but the doping of carboxylate all is in emulsion process, to accomplish, doping position is at crystals; But it is in silver emulsion sensitizing process, to accomplish that the described oxalates of this patent mixes, and technology is simple relatively, and is easy to control.
Summary of the invention
The purpose of this invention is to provide a kind of efficient process for increasing sensitivity that is applicable to the plate shape silver halide grain emulsion, this process for increasing sensitivity can effectively improve the light sensitivity of emulsion, can reduce the developer fog of emulsion again.
The present invention adds oxalates as sensitizer with plate shape silver halide emulsion (described plate shape silver halide emulsion is tabular silver iodobromide grain emulsion) in the sensitizing stage, and the sulfur plus gold chemical sensitization mode according to routine adds Na successively then 2S 2O 3The WS, mixed Jinsui River solution [AuCl 3The WS (mass concentration is 0.0167%) and NH 4The SCN WS (mass concentration is 0.2%) 1: 1 by volume mixes], ripe certain hour adds stabilizing agent (TAI) and cryogenic freezing rapidly, obtains the plate shape silver halide grain emulsion after the associating sensitizing at last.
The efficient process for increasing sensitivity that is applicable to the plate shape silver halide grain emulsion of the present invention, it is that the employing number of patent application is the plate shape silver halide emulsion that 200510086439.1 disclosed methods prepare.In temperature is under 45～55 ℃ of constant temperature, in plate shape silver halide emulsion, adds oxalates as sensitizer, and the addition of oxalates is 1 * 10 -5～1 * 10 -1Mol/molAg, the sulfur plus gold mode according to routine adds Na successively then 2S 2O 3The WS, mix Jinsui River solution, ripe 70～110 minutes, add stabilizing agent (TAI) at last, cryogenic freezing rapidly obtains the plate shape silver halide grain emulsion after the associating sensitizing.
Described plate shape silver halide emulsion is tabular silver iodobromide grain emulsion.
Described mixed Jinsui River solution is that mass concentration is 0.0167% AuCl 3The WS and mass concentration are 0.2% NH 4The SCN WS is 1: 1 mixed liquor by volume.
Described Na 2S 2O 3The addition of the WS is the Na that adds 0.4～0.8mL in per 100 gram plate shape silver halide grain emulsions 2S 2O 3The WS; Described Na 2S 2O 3The mass concentration of the WS is 0.1%;
The addition of described mixed Jinsui River solution is the mixed Jinsui River solution that adds 1.2～1.6mL in per 100 gram plate shape silver halide grain emulsions;
The addition of described stabilizing agent is the stabilizing agent that adds 1.0～2.0mL in per 100 gram plate shape silver halide grain emulsions; The mass concentration of described stabilizing agent is 4%.
The temperature of described low temperature is 0～10 ℃.
The molecular formula of described oxalates is: M 2C 2O 4, wherein M is K or Na.
Described stabilizing agent is 4-hydroxyl-6-methyl isophthalic acid, 3, and 3a, 7-four benzazoles.
Associating process for increasing sensitivity of the present invention can make the light sensitivity ratio of plate shape silver halide grain emulsion improve more than 2 times through independent conventional sulfur plus gold process for increasing sensitivity, and photographic fog is littler.
Description of drawings
Fig. 1. tabular silver iodobromide grain emulsion comparison diagram of the identical photosensitive property of tabular silver iodobromide grain emulsion after independent sulphur aurification sensitizing in photosensitive property and the Comparative Examples 1 after potassium oxalate and sulphur gold associating sensitizing in the embodiment of the invention 1.
Fig. 2. tabular silver iodobromide grain emulsion comparison diagram of the identical photosensitive property of tabular silver iodobromide grain emulsion after independent sulphur aurification sensitizing in photosensitive property and the Comparative Examples 2 after sodium oxalate and sulphur gold associating sensitizing in the embodiment of the invention 2.
Fig. 3. tabular silver iodobromide grain emulsion comparison diagram of the identical photosensitive property of tabular silver iodobromide grain emulsion after independent sulphur aurification sensitizing in photosensitive property and the Comparative Examples 3 after sodium oxalate and sulphur gold associating sensitizing in the embodiment of the invention 3.
Embodiment
Comparative Examples 1
(1) preparation of tabular silver iodobromide grain emulsion: in the two notes appearance of micro-processor controlled reaction type; The deionized water, photographic gelatin (the quality percentage composition in potpourri is 2%), potassium iodide (the quality percentage composition in potpourri is 0.024%) and the ammonium bromide (the quality percentage composition in potpourri is 0.048%) that in reactor, add 800 milliliters obtain potpourri, under 70 ℃ of conditions; Flow velocity injection volumetric molar concentration with 5.0mL/min in reactor is the kbr aqueous solution 300mL of 2mol/L and the silver nitrate aqueous solution 300mL that volumetric molar concentration is 2mol/L; Emulsification times is 60 minutes, obtains tabular silver bromide emulsion, and its particle mean size is 1.5～2.0 μ m; After emulsification finishes; With emulsion cooling and to add mass concentration be that 10% kayexalate sinking agent 16mL and mass concentration are that 10% acetic acid 10mL makes its sedimentation, wash 4 times, add photographic gelatin then and redissolve; Glue is silver-colored in being adjusted to 1.0; Adding mass concentration and be 10% sodium carbonate, to regulate pH=6～6.5 be that 2% potassium bromide is regulated pAg=8.4～9.0 with adding mass concentration, and the emulsion remelt is stirred, and cools off subsequent use at last.
(2) sulphur aurification sensitizing: under 50 ℃ of constant temperature, it is 0.1% Na that 100 grams that obtain to step (1) add mass percentage concentration in the tabular silver iodobromide grain emulsion successively 2S 2O 3WS 0.4mL, mass percentage concentration are 0.0167% AuCl 3The WS and mass percentage concentration are 0.2% NH 4The SCN WS is 1: 1 mixed Jinsui River solution 1.2mL that mixes by volume; Ripe 70～110 minutes, add mass percentage concentration at last and be 4% stabilizing agent (4-hydroxyl-6-methyl isophthalic acid, 3; 3a; 7-four benzazoles) 1.0mL, freezing under 0 ℃ rapidly, obtain tabular silver iodobromide grain emulsion through sulphur aurification sensitizing.
Embodiment 1
Associating sensitizing: under 50 ℃ of constant temperature, in the tabular silver iodobromide grain emulsion of 100 grams that Comparative Examples 1 obtains, add potassium oxalate as sensitizer, addition is 1 * 10 -5Mol/molAg, adding mass percentage concentration successively according to the sulfur plus gold mode of routine then is 0.1% Na 2S 2O 3WS 0.4mL, mass percentage concentration are 0.0167% AuCl 3The WS and mass percentage concentration are 0.2% NH 4The SCN WS is 1: 1 mixed mixed Jinsui River solution 1.2mL by volume; Ripe 70～110 minutes, add mass percentage concentration at last and be 4% stabilizing agent (4-hydroxyl-6-methyl isophthalic acid, 3; 3a; 7-four benzazoles) 1.0mL, rapidly in 0 ℃ freezing, obtain tabular silver iodobromide grain emulsion through potassium oxalate and sulphur gold associating sensitizing.
Two emulsions of Comparative Examples 1 and embodiment 1 are coated on respectively carry out photosensitivity test on the dacron chip base, the result sees table 1 and shown in Figure 1.The computing method of light sensitivity are as benchmark with the corresponding exposure inverse in 0.1 optical density place more than the photographic fog.
The comparison of the photosensitive property of the tabular silver iodobromide grain emulsion of table 1 after sulphur aurification sensitizing and potassium oxalate and sulphur gold is united sensitizing separately
Figure BSA00000207385500041
Comparative Examples 2
Sulphur aurification sensitizing: under 50 ℃ of constant temperature, it is 0.1% Na that 100 grams that obtain to Comparative Examples 1 add mass percentage concentration in the tabular silver iodobromide grain emulsion successively 2S 2O 3WS 0.8mL, mass percentage concentration are 0.0167% AuCl 3The WS and mass percentage concentration are 0.2% NH 4The SCN WS is 1: 1 mixed Jinsui River solution 1.6mL that mixes by volume; Ripe 70～110 minutes, add mass percentage concentration at last and be 4% stabilizing agent (4-hydroxyl-6-methyl isophthalic acid, 3; 3a; 7-four benzazoles) 2.0mL, freezing under 10 ℃ rapidly, obtain tabular silver iodobromide grain emulsion through sulphur aurification sensitizing.
Embodiment 2
Associating sensitizing: under 50 ℃ of constant temperature, in the tabular silver iodobromide grain emulsion of 100 grams that Comparative Examples 1 obtains, add sodium oxalate as sensitizer, addition is 1 * 10 -1Mol/molAg, adding mass percentage concentration successively according to the sulfur plus gold mode of routine then is 0.1% Na 2S 2O 3WS 0.8mL, mass percentage concentration are 0.0167% AuCl 3The WS and mass percentage concentration are 0.2% NH 4The SCN WS is 1: 1 mixed mixed Jinsui River solution 1.6mL by volume; Ripe 70～110 minutes, add mass percentage concentration at last and be 4% stabilizing agent (4-hydroxyl-6-methyl isophthalic acid, 3; 3a; 7-four benzazoles) 2.0mL, freezing under 10 ℃ rapidly, obtain tabular silver iodobromide grain emulsion through sodium oxalate and sulphur gold associating sensitizing.
The emulsion of Comparative Examples 2 and 2 two series of embodiment is coated on respectively carries out photosensitivity test on the dacron chip base, the results are shown in Table 2 and shown in Figure 2.The computing method of light sensitivity are as benchmark with the corresponding exposure inverse in 0.1 optical density place more than the photographic fog.
The tabular silver iodobromide grain emulsion of table 2 is through the comparison of the photosensitive property of sulphur aurification sensitizing and sodium oxalate and sulphur gold associating sensitizing separately
Figure BSA00000207385500051
Comparative Examples 3
Sulphur aurification sensitizing: under 50 ℃ of constant temperature, it is 0.1% Na that 100 grams that obtain to Comparative Examples 1 add mass percentage concentration in the tabular silver iodobromide grain emulsion successively 2S 2O 3WS 0.6mL, mass percentage concentration are 0.0167% AuCl 3The WS and mass percentage concentration are 0.2% NH 4The SCN WS is 1: 1 mixed Jinsui River solution 1.4mL that mixes by volume; Ripe 70～110 minutes, add mass percentage concentration at last and be 4% stabilizing agent (4-hydroxyl-6-methyl isophthalic acid, 3; 3a; 7-four benzazoles) 1.5mL, freezing under 5 ℃ rapidly, obtain tabular silver iodobromide grain emulsion through sulphur aurification sensitizing.
Embodiment 3
Associating sensitizing: under 50 ℃ of constant temperature, in the tabular silver iodobromide grain emulsion of 100 grams that Comparative Examples 1 obtains, add sodium oxalate as sensitizer, addition is 1 * 10 -2Mol/molAg, adding mass percentage concentration successively according to the sulfur plus gold mode of routine then is 0.1% Na 2S 2O 3WS 0.6mL, mass percentage concentration are 0.0167% AuCl 3The WS and mass percentage concentration are 0.2% NH 4The SCN WS is 1: 1 mixed mixed Jinsui River solution 1.4mL by volume; Ripe 70～110 minutes, add mass percentage concentration at last and be 4% stabilizing agent (4-hydroxyl-6-methyl isophthalic acid, 3; 3a; 7-four benzazoles) 1.5mL, freezing under 5 ℃ rapidly, obtain tabular silver iodobromide grain emulsion through sodium oxalate and sulphur gold associating sensitizing.
The emulsion of Comparative Examples 3 and 3 two series of embodiment is coated on respectively carries out photosensitivity test on the dacron chip base, the results are shown in Table 3 and shown in Figure 3.The computing method of light sensitivity are as benchmark with the corresponding exposure inverse in 0.1 optical density place more than the photographic fog.
The tabular silver iodobromide grain emulsion of table 3 is through the comparison of the photosensitive property of sulphur aurification sensitizing and sodium oxalate and sulphur gold associating sensitizing separately

Claims (5)

1. efficient process for increasing sensitivity that is applicable to the plate shape silver halide grain emulsion, it is characterized in that: in temperature is under 45～55 ℃ of constant temperature, in plate shape silver halide emulsion, adds oxalates as sensitizer, the addition of oxalates is 1 * 10 -5～1 * 10 -1Mol/molAg adds Na then successively 2S 2O 3The WS, mix Jinsui River solution, ripe 70～110 minutes, add stabilizing agent at last, cryogenic freezing rapidly obtains the plate shape silver halide grain emulsion after the associating sensitizing;
Described plate shape silver halide emulsion is tabular silver iodobromide grain emulsion;
Described mixed Jinsui River solution is that mass concentration is 0.0167% AuCl 3The WS and mass concentration are 0.2% NH 4The SCN WS is 1: 1 mixed liquor by volume.
2. method according to claim 1 is characterized in that: described Na 2S 2O 3The addition of the WS is the Na that adds 0.4～0.8mL in per 100 gram plate shape silver halide grain emulsions 2S 2O 3The WS; Described Na 28 2O 3The mass concentration of the WS is 0.1%;
The addition of described mixed Jinsui River solution is the mixed Jinsui River solution that adds 1.2～1.6mL in per 100 gram plate shape silver halide grain emulsions;
The addition of described stabilizing agent is the stabilizing agent that adds 1.0～2.0mL in per 100 gram plate shape silver halide grain emulsions; The mass concentration of described stabilizing agent is 4%.
3. method according to claim 1 is characterized in that: the temperature of described low temperature is 0～10 ℃.
4. method according to claim 1 is characterized in that: the molecular formula of described oxalates is: M 2C 2O 4, wherein M is K or Na.
5. method according to claim 1 and 2 is characterized in that: described stabilizing agent is 4-hydroxyl-6-methyl isophthalic acid, 3, and 3a, 7-four benzazoles.
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Cited By (1)

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CN104536256A (en) * 2014-12-25 2015-04-22 天津美迪亚影像材料有限公司 Method for preparing tabular granular silver halide emulsion

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Publication number Priority date Publication date Assignee Title
CN104536256A (en) * 2014-12-25 2015-04-22 天津美迪亚影像材料有限公司 Method for preparing tabular granular silver halide emulsion
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