CN1614507A - Indirect ammoniating preparation for silver halides sensitive emulsion - Google Patents
Indirect ammoniating preparation for silver halides sensitive emulsion Download PDFInfo
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- CN1614507A CN1614507A CN 200410096767 CN200410096767A CN1614507A CN 1614507 A CN1614507 A CN 1614507A CN 200410096767 CN200410096767 CN 200410096767 CN 200410096767 A CN200410096767 A CN 200410096767A CN 1614507 A CN1614507 A CN 1614507A
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Abstract
A method for preparing silver halide photosensitive emulsion is featured as adding a base in metal halide solution and adding an ammonium salt in silver salt solution, forming ammonia by reacting on base with ammonium salt at time when metal halide solution is mixed with silver salt solution in reaction. The prepared emulsion can be used for colour or black photographic material.
Description
Technical Field
The invention relates to a preparation method of a silver halide photosensitive emulsion, in particular to an indirect ammoniation preparation method of the silver halide photosensitive emulsion.
Background
To date, silver halide emulsion synthesis methods have been defined in a wide variety of ways, and many methods for synthesizing emulsions have been specified. For example: the synthesis temperature is used for defining and can be divided into a low temperature method, a normal temperature method, a high temperature method and a boiling method; the method is defined by the adding mode of materials during synthesis and can be divided into a single injection method, a double injection method and a multi-injection method; the method is defined by the flowing mode of emulsion during emulsion synthesis and can be divided into an internal circulation method and an external circulation method; defined as the concentration of ammonia ions, there are ammonia process, semi-ammonia process, and neutral process, etc.
The synthesis of the emulsion by ammonia process or semi-ammonia process is generally carried out by adding ammonia directly into silver solution, halide/gelatin solution or into other supplementary emulsion. During the process of adding ammonia liquor, firstly, silver oxide precipitate is formed, when ammonia is added to a certain quantity, the silver oxide precipitate can be dissolved, and a complex silver-ammonia complex solution can be formed. The reaction process is shown as the formulas (1) and (2):
the solubility of silver halide is improved by increasing the amount of ammonia solution, but when the amount of ammonia solution is excessive, not only the dispersion degree of silver halide particles is deteriorated, but also the stability of the emulsion is lowered and the fog is increased. Due to ammonia liquid (NH)4OH) during preparation, storage and transportation, the concentration of ammonia liquid is a variable due to the change of temperature, light, air, time and the like. Differences in emulsion properties due to unstable ammonia liquor concentrations; furthermore, the use of the above-described method of directly adding ammonia liquor during the synthesis of silver halide emulsions has some adverse effects on the emulsification: one is that a region where the ammonia ions are locally too concentrated is instantaneously generated; the concentration of ammonia in the two reactors can be changed after the introduction of the halogenating liquid, so that the concentration of ammonia ions can not be kept constant in a certain halogenating stage, thereby destroying the dispersibility of silver halide particles and having adverse effect on the performance of the emulsion.
Disclosure of Invention
The invention aims to provide a method for preparing silver halide emulsion by indirect ammoniation, which adopts indirect ammoniation to ensure that the concentration of ammonia in a reactor can be relatively constant and can also be changed linearly or nonlinearly according to requirements so as to obtain ideal silver halide emulsion.
The technical scheme of the invention is as follows:
a process for preparing silver halide emulsion by indirect ammoniation features that a metal halide solution contains a base and a silver salt solution contains an ammonium salt, and when the metal halide solution and silver salt solution are mixed together and react, the base and ammonium salt react to generate ammonia.
In a preferred embodiment, the base is sodium hydroxide or potassium hydroxide.
In a preferred embodiment, the ammonium salt is ammonium sulfate or ammonium nitrate.
The ammonium salt, the alkali and the acid alternately react to generate ammonia according to the formulas (3), (4) and (5) in the process of synthesizing the silver halide emulsion:
during the emulsification process, ammonia ions are generated in the emulsification system along with the addition of the supplementary glue or the injection of the silver liquid and the halogen liquid. The magnitude of the ammonia ion concentration can be characterized by the pH value.
The ammonia amount provided by the method for preparing the indirect ammonia method silver halide emulsion can be different in different emulsification stages, and the characteristic value pH can be in a wide variation range. However, the present invention has limitations in terms of the pH requirements of the different emulsification stages: in the nucleation stage, the pH value can be between 4 and 10; during the growth stage, the pH value can be controlled to be 6-11; in the mature stage, the pH value is consistent with that in the growth stage, and the uniformity of silver halide crystals can be influenced by too high and too low pH values.
The concentration of the ammonia ions involved in the present invention may be different at each stage of the synthesis of the silver halide crystallites. The concentration of the ammonia ions in the emulsifying system can be zero, and the pH of the emulsifying system can also be up to more than 11; the concentration can be kept constant at a certain concentration, can be increased from a certain low concentration to a certain high concentration, or can be decreased from a certain high concentration to a certain low concentration. In the whole emulsification process, the concentration of the ammonia ions can be changed in a step-type manner, a jump-type manner or a gradual-type manner.
When the method is adopted to synthesize the silver halide photosensitive emulsion, shallow electron traps can be added during emulsion synthesis to improve the sensitivity of photosensitive silver halide. The shallow electron trap may be a multivalent coordinated metal ion dopant introduced at the subsurface of the photo-emulsified silver crystal, for example: (NH)4)4[Fe(CN)6]、K4[Ru(CN)6]、[Rh(CN)5(SeCN)]-3Etc., but preferably hexa-ligand Fe+2Salts and Ru+2The salt is effective as a dopant for shallow electron traps, wherein Ru+2Is most effective, the ligand may be CN-1CO may also be used, but the preferred ligand is thiocyanate (NCS)-1) Cyanate (NCO)-1)。Ru+2The dosage of the ions should be 1 × 10-9～1×10-3The optimum amount of silver should be in the range of 1X 10 mol/mol-7～1×10-5Moles/mole silver.
In addition, iridium salt (Ir) can be added in the process of preparing silver halide+3) To further improve the sensitivity of the silver halide,meanwhile, the failure of high and low illumination reciprocity rate is improved, and the exposure latitude of the film is improved. Ir+3The dosage of the ions should be 1 × 10-8～1×10-3The optimum amount of silver should be in the range of 1X 10 mol/mol-5～1×10-6Moles/mole silver.
The invention can keep ammonia ions (NH) in an emulsion system during the synthesis of the silver halide emulsion3 +) The concentration is constant, so that the structure of each silver halide microcrystal is more consistent, and good conditions are provided for introducing the reduction sensitizer. The reduction sensitizer is mainly used for the growth stage or maturation of silver halide microcrystalsRepresentative compounds are amines, hydrazines, formamidine sulfinic acid, silanes and borane compounds as well as stannous chloride and ascorbic acid and derivatives thereof, and the like. The solvent of the above compounds can be alcohol, diol, ketone, ester, amide, water, etc. The application of the reduction sensitizer can further improve the photosensitive property of silver halide.
In addition to the above-mentioned reduction enhancers, the present invention may also use conventional gold sulfide enhancement methods. The gold sensitizer may be KAucl4Or Aucl3In an amount of 4X 10-6～2×10-5mol/molAg。
The photographic gelatin is a very complex protein collagen formed by combining a plurality of amino acids, and the function of the photographic gelatin in the synthesis of silver halide microcrystals is important because the difference of trace components in the photographic gelatin can directly influence the crystal form of the silver halide microcrystals besides the functions of protecting and supporting the silver halide microcrystals. Since methionine in gelatin contains divalent sulfur atoms and has a strong adsorption effect on the surface of the microcrystals, the content of methionine is critical for the plate-shaped microcrystal particles, and when the content of methionine is more than 15 mmol/g of gelatin, the plate-shaped microcrystals are distorted even under the same synthesis conditions, and a large amount of rod-shaped silver halide crystals are generated in severe cases, so that the synthesis of the plate-shaped microcrystal emulsion fails. The presence of a large number of rod-shaped silver halide nodules not only affects the photographic properties of the emulsion and deteriorates the detailed properties of the film, but also causes additional process burdens and even coating failures during the coating process. Therefore, the synthetic plate-like-microcrystalline emulsion should be preferably oxidized gelatin.
The preferred photographic gelatin for the synthesis of silver halide microcrystals according to the invention is oxidized gelatin, a deionized gelatin with a very low methionine content.
Advantageous effects
The method for generating ammonia by the reaction of ammonium salt and alkali can keep the ammonia concentration in the reactor relatively stable, and also avoids the defects of poor emulsion performance reproducibility and the like caused by ammonia volatilization, overhigh local ammonia concentration or unstable ammonia concentration and the like caused by directly adding ammonia in the prior art, so that the emulsion has more uniform particle size and more stable photographic performance.
Drawings
FIG. 1 Electron microscope slide of homogeneous core-shell cubic emulsion synthesized by the method
FIG. 2 Electron microscope plate of homogeneous core-shell octahedral emulsion synthesized by the method
FIG. 3 Electron microscope slide of plate-like emulsion synthesized by the method
FIG. 4 Electron microscope plate of core-shell plate-like emulsion synthesized by the method
Detailed Description
The present invention will be further illustrated by the following specific examples.
Example 1
Preparation of core-shell cubic emulsion
Firstly, injecting 137.5L of normal temperature deionized water into a reactor, slowly adding 4500g of deionized water and 1250g of KBr, slowly stirring for 15min, heating to 46 ℃, and adding (NH)4)3IrCl6(0.001%) 375ml, keeping the temperature to 46 ℃, starting stirring, and then adding the mixture containing: KBr 3570g, NaOH (4%) 10L and AgNO35000g，NH4NO3(20%) 5000ml of KBr solution and AgNO3Each 28.5L of the solution was kept at a pBr value of 3.2 in the reactor.
Injecting a second halogen solution and silver solution 2.5min later, wherein the halogen solution contains KBr 4250g and KI 250g, the initial flow rate is 1740g/min, and the acceleration is 145g/min2(ii) a The silver liquid contains AgNO36250g, its initial velocity is 1880g/min, acceleration is 156g/min2The pBr value was controlled at 3.4.
Injecting bittern and silver solution after 3.5min for 2min, wherein the bittern contains KBr 880g, initial flow rate is 1800g/min, and acceleration is 600g/min2(ii) a The silver liquid contains AgNO31250g, its initial speed is 1950g/min, and its acceleration is 650g/min2The pBr value was controlled at 2.8. After ripening for 6min, cooling and desalting.
The desalted and antiseptic emulsion is re-dissolved at 45 deg.c, and the re-dissolved emulsion has total weight of 100Kg, pH5.7, pBr3.48 and glue content of 60 g/Kg. The emulsion has high contrast and high resolution after chemical maturation by the gold sulfide sensitizer.
The inner core of the emulsion is composed of pure silver bromide, the middle layer is silver bromoiodide with uniform iodine distribution, and the outer layer is extremely thin pure silver bromide.
Example 2
Preparation of octahedral emulsion
The preparation method of the emulsion is the same as that of the example 1, the pBr value is changed from 3.2, 3.4 and 2.8 to 2.8, 3.0 and 2.8 respectively, and the octahedral silver bromoiodide emulsion with different particle sizes can be obtained.
Example 3
Preparation of platy crystal form emulsion (I)
Firstly, 188L of normal-temperature deionized water is injected into a reactor, 800g of oxidized gelatin and 700g of KBr are slowly added, and the concentration is 10 percent (NH)4)2SO4The solution (4000 ml) was stirred slowly for 15min, then the temperature was raised to 60 ℃ and the stirring was started. Adding KBr solution (containing KBr 610g) and AgNO at constant speed within 1min3Liquid (containing AgNO)3800g) 6000ml of each, ripen for 1min, and added with 32L of gelatin solution (containing 3200g of oxidized gelatin and 8000ml of KOH solution with the concentration of 4%). Ammoniating the crystal nucleus for 5min, and adding H2SO4(2%) 8000ml, and pBr was adjusted to 1.6. Equilibrate for 2min to enter the growth phase.
The reactor was maintained at pBr1.6 at 60 ℃ for 23min in a two-shot emulsion with uniform acceleration. Wherein the initial speed of KBr liquid (containing KBr 4900g) is 695g/min, and the acceleration is 46.4g/min2；AgNO3Liquid (containing AgNO)36400g) Initial speed of 720g/min and acceleration of 48g/min2. After the double injection, KI liquid 12L (containing KI320g) is injected at constant speed for 2min, and the stopping is carried out for 2 min.
A third double injection was performed maintaining pBr1.45 at 60 ℃. Initial speed of KBr liquid (containing KBr 5520g and NaOH 149g) is 1582g/min, acceleration is 90.4g/min2；AgNO3Liquid (containing AgNO)37862g HgCl28.27×10-3g NH3NO3386g) Initial velocity 1592g/min and acceleration 91g/min2. Injecting KI liquid 24L (containing KI680g) at constant speed for 2min, stopping for 4min, and adding AgNO3Adjusting pBr to 1.9 with 25% concentration, balancing for 2min,
a fourth double injection was performed maintaining pBr1.9 at 60 ℃. Initial velocity 2712g/min and acceleration 135.6g/min for KBr solution (containing KBr 10483g and NaOH 70.8g)2；AgNO3Liquid (containing AgNO)314938g HgCl21.57×10-2g NH4NO3733g) Initial velocity 2730g/min, acceleration 136.6g/min2. This double injection was carried out for 15min, and 1600ml of trivalent iridium salt of hexaligand (0.001%) was added under liquid at the time of 5min of emulsification. After ripening for 6min, desalting and redissolving.
The redissolved matter is adjusted to 170Kg with deionized water, wherein the deionized water contains 12Kg, the pH value is respectively adjusted to 6.0-6.2 by NaOH and KBr solution, and pBr is 3.0-3.1. After the gold sulfide and the sodium thiocyanate are chemically mature, the emulsion has higher contrast, moderate light sensitivity, good low-illumination reciprocity rate failure and storage stability.
Example 4
Preparation of platy Crystal form emulsion (II)
The emulsion is synthesized in two parts: the first step is to prepare silver halide seed crystal at lower temperature, and the second step is to synthesize emulsion based on the seed crystal. The silver halide microcrystals synthesized by steps have narrow distribution intervals or small particle size variation coefficients, and the projection area is larger than 95%.
1. Seed preparation
Firstly, 1500ml of deionized water, 6g of oxidized gelatin, 9.75g of KBr9 and a proper amount of defoaming agent are injected into an emulsification tank. After fully swelling, the temperature is raised to 45 ℃, and the stirring speed is raised to a normal working state.
Injecting silver liquid (containing AgNO) into the emulsion tank at a constant speed with the injection amount of 10ml/min317g，NH4NO380ml of 25% solution) and 100ml of each of bromine solution (KBr 13.3 g). Stopping for 1min after the emulsification is finished, and adding 50ml of glue solution in which 5g of oxidized gelatin and 10.5g of NaOH are dissolved. Heating at 2 deg.C/min for 10min after 1min, keeping the temperature constant, and ripeningFor 10 min. Then settling and desalting.
15g of gelatin oxide and 5% Na were added to the desalted sediment2CO35ml of the solution was added, and the total weight of the solution was adjusted to 340g with pure water, whereby the seed crystal was prepared.
2. Emulsion synthesis
(1) Preparing an emulsion:
primary glue solution
1000ml of pure water
Oxidized gelatin 15g
KBr 3g
Seed crystal 40g
Ammonia liquid
NH4NO38g
NH4OH(25％) 10ml
20ml of pure water
Acid liquor
HAc(40％) 16ml
Silver liquid
AgNO3255g
HgCI2(0.01％) 3ml
500ml of pure water
Bromine liquid
KBr 182g
500ml of pure water
Iodine solution
KI 7.5g
20ml of pure water
Ruthenium liquid
K4Ru(CN)60.001％ 6ml
Supplementary glue
Deionized Water 25g
200ml of pure water
(2) And (3) fully swelling the emulsified and chemically mature primary glue solution in an emulsifying tank, heating to 70 ℃, stirring and adjusting to a conventional working state, and starting emulsification. And injecting ammonia liquid at constant speed for 20 seconds, and injecting acid liquid at constant speed for 80 seconds after 80 seconds of intermittent stop, wherein the time is also 20 seconds.
Using silver solution and bromine solution to carry out first balanced double injection, wherein the initial speed is 1.2ml/min, and the acceleration is 0.15ml/min2And emulsifying for 21 min.
The second double injection is carried out for 40min, wherein the initial speed of the silver liquid is 3.6ml/min, and the acceleration is 0.07ml/min2(ii) a The initial speed of bromine liquid is 7.6ml/min, and the acceleration is 0.07ml/min2. Injecting iodine solution after emulsification, and balancing the system for 5 min.
The third double injection is a decorative double injection, the initial speeds of the silver solution and the bromine solution are both 6ml/min, and the acceleration is 0.075ml/min2For 3 min.
The fourth double injection is carried out for 37min, the initial speed of emulsification is 3ml/min, and the acceleration is 0.075ml/min2. Then 6min constant speed double injection is carried out, and the flow rate of the silver solution and the bromine solution is 4 ml/min. Immediately adding ruthenium solution after emulsification, and balancing the system for 4 min.
The last double injection takes 9min, and the flow rate of the silver-bromine liquid is 4 ml/min. At this point, the emulsification is complete. Adding the supplemented glue solution after ripening for 5min, cooling to 45 ℃, settling and desalting.
130g of deionized gel, KBr, NaOH, a preservative and a proper amount of pure water were added to the sediment after the desalting treatment so that the total weight was 2000g, pH6.4 and pBr3.2.
The emulsion has high optical sensitivity and spectral sensitivity after chemical sensitization by potassium thiocyanate and gold sulfide.
After the above emulsions are subjected to sample preparation, sensitization and development respectively, and detected, the photographic properties are listed as follows:
Claims (3)
1. a process for preparing silver halide emulsion by indirect ammoniation features that a metal halide solution contains a base and a silver salt solution contains an ammonium salt, and when the metal halide solution and silver salt solution are mixed together and react, the base and ammonium salt react to generate ammonia.
2. The process for the indirect ammoniation of a silver halide photographic emulsion as claimed in claim 1, wherein said alkali is sodium hydroxide or potassium hydroxide.
3. The method of claim 1, wherein the ammonium salt is ammonium sulfate or ammonium nitrate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113341642A (en) * | 2021-06-24 | 2021-09-03 | 安徽工业大学 | Silver bromide emulsion, preparation method thereof, photosensitive material and application in hydrogen micro-printing technology |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113341642A (en) * | 2021-06-24 | 2021-09-03 | 安徽工业大学 | Silver bromide emulsion, preparation method thereof, photosensitive material and application in hydrogen micro-printing technology |
| CN113341642B (en) * | 2021-06-24 | 2024-05-24 | 安徽工业大学 | Silver bromide emulsion, preparation method thereof, photosensitive material and application thereof in hydrogen micro-printing technology |
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