CN1403871A - Prepn of nano granulated silver halide emulsion - Google Patents
Prepn of nano granulated silver halide emulsion Download PDFInfo
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- CN1403871A CN1403871A CN 01131451 CN01131451A CN1403871A CN 1403871 A CN1403871 A CN 1403871A CN 01131451 CN01131451 CN 01131451 CN 01131451 A CN01131451 A CN 01131451A CN 1403871 A CN1403871 A CN 1403871A
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Abstract
The present invention belongs to the field of photosensitive material technology and relates to especially the preparation of nano granulated silver halide emulsion. The preparation process includes: adding to the reactor the reaction system including gelatin, polyvinyl pyrrolidone, citric acid and water; injecting sliver nitrate solution and potassium bromide solution as well as potassium iodide at 40 deg.c; freezing, cutting into strips, water washing to eliminate salt, eliminating water, heating and regulating pAg to 8-9.5 to obtain the sliver halide emulsion.
Description
Technical field
The invention belongs to the photosensitive material technical field, specially refer to the preparation method of the nano granulated silver halide emulsion of dimensionally stable.
Background technology
The technology of preparing of ultra-fine grain silver emulsion comes into one's own always, especially for high resolving power silver halide information-recording material, its light activated element silver halide microcrystal must be enough tiny, because the resolution of material is the ability that characterizes the input optical signal fine degree that it can write down, so silver emulsion can not be offered an explanation the also meticulous details of silver-colored particle size of ratio composition image.In recent years, along with the development of holography, the resolution of hologram recording material must be more than thousands of, and this requires the silver halide microcrystal of holographic silver halide recording materials to be of a size of nanoscale.
Nano particle is meant that the particle of particle size between 10-100nm is called nano particle.The size of the silver halide particle of conventional emulsion is usually greater than 0.1 μ m.
In the silver halide photosensitive recording material, the grain size of light activated element silver halide is the main factor of decision recording materials resolution.The characteristics of the recording materials of nano particle emulsion are to have high resolution, and it can be applicable to holographic photography film (comprising the photography of general holographic photography and synthetic hologram), microfilm, ultra micron dry plate many special dimensions such as (or films).
In holography, to the resolution requirement of silver halide recording materials high (every millimeter reach several thousand lines to), and the resolution of material is the ability that characterizes the input optical signal fine degree that it can write down.As the silver emulsion recording materials of photoactive substance be impossible explanation than the also meticulous details of silver-colored particle size of forming its image, therefore as the silver halide hologram recording material, the particle size of its silver emulsion is had extremely strict requirement.The silver halide particle size must be at nanoscale, and when playback light was by hologram like this, the reduction silver granuel just can be relegated to a secondary and subordinate position to the absorption effect of light, and diffraction effect will account for main advantage.In addition; the nano-silver halide crystallite is because particle is ultra-fine; its surface area is huge; therefore surface free energy is very high; on thermodynamics, be in utmost point unsure state; in nano-silver halide emulsion preparation process (as in precipitation, physics and processes such as chemical ripening and coating); particle is easy to assemble or grow up; therefore the particle protective agent-gelatin that is adopted in general photosensitive silve halide material preparation far can not satisfy the preparation requirement of nano-silver halide crystallite emulsion, makes important sensitizing steps such as chemical ripening, spectral sensitization be difficult to normally carry out.
The existing method for preparing nano-silver halide emulsion roughly has following several: 1. document E.Valenta, Photographic in naturlichen Farben, the described Lippman emulsion of Halle (1912) method; 2. document B.H.Crawford, J.of Sci.Inst., 31,335 (1954) described Crowford double-jet methods; 3. document H.Thiry, Preparation and Properties of Ultra-fine Grain AgBrEmlsions, J.Photographic Science, 35,150 (1987) described Thiry double-jet methods; 4. document M.Iwasaki, T.Kubota, T.Tanaka, Preparation of New Ultra-Fine-GrainEmulsion for Holography, J.Photographic Science, 41,112 (1993) described Iwasaki multichannel rapid mixing methods; 5. document K.P.Johansson, et al, Am.Chem.Soc., 96,2873 (1992) described reverse micelle preparation methods etc.
There is following shortcoming in existing nano-silver halide method of preparing emulsion: 1. make it have very high surface free energy because the specific surface area of nano-scale silver halide particle is huge, cause its particle size poor stability, thereby be difficult to carry out chemical ripening, because the particle size of silver halide can change under the condition of chemical ripening.People such as Iwasaki once adopted the PVA stabilizing agent to suppress the nano-silver halide particle growth, but DeGrain, its chemical ripening only can keep 10 minutes for this reason, so the effect of sulphur+golden sensitizing is little, and light sensitivity is very low.2. silver content low (seeing Table 1) in the emulsion below only argentiferous 10 restrains in every liter of emulsion, is difficult to satisfy the requirement of modern film extrusion coated technology.3. because the intrinsic light sensitivity of nano-silver halide emulsion is low, adopt the efficient of chemical sensitization technology such as common sulphur sensitizing and golden sensitizing not high.
The silver content and the distribution of particles of the prepared emulsion of the various nano-silver halide method of preparing emulsion of table 1.
| Silver content (g/L) | Distribution of particles | Particle size range (nm) | |
| The Lippman method | ????8-10 | Wide | ????10-50 |
| The Crowford method | ????＜10 | Narrow | ????20-30 |
| The Iwasaki method | ????4-5 | Narrow | ????10-30 |
| Reverse micelle method | ????4-5 | Narrow | ????10-15 |
Summary of the invention
The objective of the invention is to overcome the silver halide particle poor dimensional stability, the difficulty that exist in the above-mentioned existing nano-silver halide method of preparing emulsion, to carry out in chemical ripening, the emulsion silver content low, be difficult to satisfy the requirement of modern film extrusion coated technology and the not high defective of efficient of sensitizing, a kind of preparation method of nano granulated silver halide (silver bromide and bromo-iodide) emulsion of dimensionally stable is provided.
The present invention adopts a kind of effective polyalkenes pyrrolidone stabilizing agent, and the method for preparation size stabilized nano silver emulsion is provided.
The preparation method of nano granulated silver halide emulsion of the present invention, by weight percentage:
(1) reaction system comprises gelatin, polyalkenes pyrrolidone, citric acid and water; Adopt double-jet method, in reactor, add reaction system; Wherein, contain the gelatin of 4-7%, the polyalkenes pyrrolidone of 0.1-1% and the citric acid of 0.08-0.1% in the system, surplus is a water;
(2) be 40 ℃ in temperature, in 1-4 minute time, in reactor, inject liquor argenti nitratis ophthalmicus and potassium bromide solution simultaneously, make in the reactor content of final silver and bromine be respectively 80-95mmol/L and 75-90mmol/L by stoichiometry;
Or in reactor, inject the mixed solution that liquor argenti nitratis ophthalmicus and potassium iodide, potassium bromide and potassium chloride are formed simultaneously by stoichiometry, final silver content is 80-95mmol/L in the reactor, and the mol ratio of potassium iodide, potassium bromide and potassium chloride is 0.05: 0.14: 0.81;
(3) reaction back cooling rapidly, and freezing below-10 ℃, slitting then, the washing desalination is removed moisture thereupon, at last emulsion is heated remelt, and the pAg value is transferred to behind the 8-9.5 freezing rapidly, obtains the silver emulsion that the nano particle diameter is 10-30nm.
It is the potassium iodide of silver content 1% that reaction system in the described step (1) further contains.
The structural formula of described polyalkenes pyrrolidone is:
R is H or alkyl, and described alkyl comprises groups such as methyl, ethyl or propyl group; N is 150-500.
The invention provides a kind of preparation size stabilized nano particle silver halide emulsifiable concentrates method, in this emulsion, added a kind of special stabilizers-polyalkenes pyrrolidone, particle size stability in the emulsion is improved greatly, and under 40-45 ℃ condition, endoparticle changed little in 2 hours.Wherein, silver chloride content 〉=80% of the nanometer silver chloroiodobromide grain emulsion of preparation.
The emulsion that utilizes the inventive method to prepare can carry out chemical sensitization, and 45 ℃ of chemical ripenings 60 minutes, particle size was constant substantially.
The present invention adopts polyalkenes pyrrolidone macromolecule stabilizer; make the method for each nano granulated silver halide emulsion; make nano-silver halide emulsion dimensional stability much effective than traditional protection agent gelatin; polyalkenes pyrrolidone macromolecule stabilizer makes the emulsion size can stability number about 40-45 ℃ hour, and gelatin only can stability number minute.
Description of drawings
Fig. 1. the size distribution plot and the mean radius of the embodiment of the invention 1 emulsion grain.
Fig. 2. the size distribution plot and the mean radius of the embodiment of the invention 2 emulsion grains.
Reaction system is gelatin, polyvinylpyrrolidone, potassium iodide, citric acid and water.Adopt double-jet method, in reactor, add entry, gelatin (gelatine content is 5.5%), polyvinylpyrrolidone (content is 0.75%), potassium iodide (content be silver content 1%) and citric acid (content 0.08%).Under 40 ℃ of conditions, inject liquor argenti nitratis ophthalmicus and potassium bromide solution simultaneously by stoichiometry in reactor, the silver nitrate of injection and potassium bromide total amount are respectively 83mmol/L and 77mmol/L, injection length 1-3 minute, the cooling rapidly of reaction back, and freezing below-10 ℃.The Size Distribution of its emulsion grain is seen Fig. 1, and average particle size particle size is 14-16mm.
With the emulsion slitting after freezing, the washing desalination is removed moisture thereupon, at last emulsion is heated remelt, and the pAg value is transferred to 8-9.5 carries out freezing then.Obtain the nanometer silver iodobromide grain emulsion.Embodiment 2. by weight percentage
Reaction system is gelatin, methyl polyethylene pyrrolidone, citric acid and water.Adopt double-jet method, in reactor, add entry, gelatin (gelatine content is 7.0%), polyvinylpyrrolidone (content is 0.6%) and citric acid (content 0.09%).Under 40 ℃ of conditions, the total amount of injecting silver nitrate by stoichiometry in reactor simultaneously is that 90mmol/L and potassium bromide are 85mmol/L, injection length 1-3 minute, reaction back is cooling rapidly, and freezing below-10 ℃, then slitting, the washing desalination, remove moisture thereupon, at last emulsion is heated remelt, and be transferred to behind the 8.0-9.5 pAg value freezing.Obtain the nano silver/silver bromide grain emulsion.
Above-mentioned emulsion adds sulphur+aurification sensitizer under 45 ℃ of constant temperature, the sulphur addition is 1-5 * 10
-3Mol/Ag mol, golden addition is 1-5 * 10
-4Mol/Ag mol, and continuing ripe 60 minutes, cryogenic freezing then.Average particle size particle size is 18-20nm.Embodiment 3. by weight percentage
Reaction system is gelatin, polyvinylpyrrolidone, potassium iodide, citric acid and water.Adopt double-jet method, in reactor, add entry, gelatin (gelatine content is 5.0%), polyvinylpyrrolidone (content is 0.9%), potassium iodide (content be silver content 1%) and citric acid (content 0.1%).The total amount of injecting silver nitrate in 40 ℃ of condition downhill reaction devices simultaneously is that 85mmol/L and potassium bromide are 80mmol/L, injection length 1-3 minute, and the cooling rapidly of reaction back, and freezing below-10 ℃.
Then with the emulsion slitting after freezing, the washing desalination is removed moisture thereupon, at last emulsion is heated remelt, and with the pAg value be transferred to carry out behind the 8-9.5 freezing.Obtain the nanometer silver iodobromide grain emulsion.
Above-mentioned emulsion adds the thiourea dioxide sensitizer under 45 ℃ of constant temperature, addition is 1-5 * 10
-3Mol/Ag mol, and continuing ripe 60 minutes, cryogenic freezing then.Average particle size particle size is 18-20nm.Embodiment 4. by weight percentage
Reaction system is gelatin, polypropylene pyrrolidone, citric acid and water.Adopt double-jet method, in reactor, add entry, gelatin (gelatine content is 4.0%), polyvinylpyrrolidone (content is 1.0%), citric acid (content 0.08%), under 40 ℃ of conditions, the total amount of injecting silver nitrate by stoichiometry in reactor simultaneously is the potassium halide (KI+KBr+KCl) of 90mmol/L and equimolar amounts, potassium iodide in the potassium halide mixed liquor, the mol ratio of potassium bromide and potassium chloride is (0.05: 0.14: 0.81), injection length 1-3 minute, reaction back is cooling rapidly, and freezing below-10 ℃, then slitting, the washing desalination, remove moisture thereupon, at last emulsion is heated remelt, and be transferred to behind the 8.5-9.5 pAg value freezing.Obtain nanometer silver chloroiodobromide grain emulsion.
Above-mentioned emulsion adds sulphur+aurification sensitizer under 45 ℃ of constant temperature, the sulphur addition is 1-5 * 10
-3Mol/Ag mol, golden addition is 1-5 * 10
-4Mol/Ag mol, and continuing ripe 60 minutes, cryogenic freezing then, its emulsion grain average-size is 20-25nm.
Claims (4)
1. the preparation method of a nano granulated silver halide emulsion by weight percentage, is characterized in that:
(1) reaction system comprises gelatin, polyalkenes pyrrolidone, citric acid and water; Adopt double-jet method, in reactor, add reaction system; Wherein, contain the gelatin of 4-7%, the polyalkenes pyrrolidone of 0.1-1% and the citric acid of 0.08-0.1% in the system, surplus is a water;
(2) be 40 ℃ in temperature, in 1-4 minute time, in reactor, inject liquor argenti nitratis ophthalmicus and potassium bromide solution simultaneously, make in the reactor content of final silver and bromine be respectively 80-95mmol/L and 75-90mmol/L by stoichiometry;
Or in reactor, inject the mixed solution that liquor argenti nitratis ophthalmicus and potassium iodide, potassium bromide and potassium chloride are formed simultaneously by stoichiometry, final silver content is 80-95mmol/L in the reactor, and the mol ratio of potassium iodide, potassium bromide and potassium chloride is 0.05: 0.14: 0.81;
(3) reaction back cooling rapidly, and freezing below-10 ℃, slitting then, the washing desalination is removed moisture thereupon, at last emulsion is heated remelt, and the pAg value is transferred to behind the 8-9.5 freezing rapidly, obtains the silver emulsion that the nano particle diameter is 10-30nm.
2. the method for claim 1, it is characterized in that: it is the potassium iodide of silver content 1% that the reaction system in the described step (1) further contains.
3. the method for claim 1, it is characterized in that: the structural formula of described polyalkenes pyrrolidone is:
R is H or alkyl; N is 150-500.
4. method as claimed in claim 3 is characterized in that: described alkyl comprises methyl, ethyl or propyl group.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301440C (en) * | 2003-03-21 | 2007-02-21 | 中国乐凯胶片集团公司 | Method of preparing nano color coupler oil emulsion |
| CN108120790A (en) * | 2016-11-29 | 2018-06-05 | 四川大学 | The low pressure of micro sulphion and chlorion anion-exchange chromatography-photometric turbidimetry in on-line analysis water sample simultaneously |
| CN112965332A (en) * | 2021-02-22 | 2021-06-15 | 北京镭思顿科技开发公司 | Laser holographic ultramicron silver salt photosensitive material and preparation method thereof |
-
2001
- 2001-09-10 CN CN 01131451 patent/CN1403871A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301440C (en) * | 2003-03-21 | 2007-02-21 | 中国乐凯胶片集团公司 | Method of preparing nano color coupler oil emulsion |
| CN108120790A (en) * | 2016-11-29 | 2018-06-05 | 四川大学 | The low pressure of micro sulphion and chlorion anion-exchange chromatography-photometric turbidimetry in on-line analysis water sample simultaneously |
| CN112965332A (en) * | 2021-02-22 | 2021-06-15 | 北京镭思顿科技开发公司 | Laser holographic ultramicron silver salt photosensitive material and preparation method thereof |
| CN112965332B (en) * | 2021-02-22 | 2021-12-28 | 北京镭思顿科技开发公司 | Laser holographic ultramicron silver salt photosensitive material and preparation method thereof |
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