CN101900930B - Flocculating agent composition for preparing ray emulsion and desalination and concentration method - Google Patents
Flocculating agent composition for preparing ray emulsion and desalination and concentration method Download PDFInfo
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- CN101900930B CN101900930B CN 201010114123 CN201010114123A CN101900930B CN 101900930 B CN101900930 B CN 101900930B CN 201010114123 CN201010114123 CN 201010114123 CN 201010114123 A CN201010114123 A CN 201010114123A CN 101900930 B CN101900930 B CN 101900930B
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Abstract
The invention discloses a flocculating agent composition for preparing a ray emulsion and a desalination and concentration method. By widening the concentration ratio range of a primary mature emulsion, the flocculating agent composition meets the requirements of different-purpose films on the preparation of the ray emulsion. The flocculating agent composition consists of at least two polymers which accord with the requirement, or at least two polymers which are the same type according with the requirement and have different degrees of polymerization. The flocculating agent composition can perform flocculation (or precipitation) in an acid medium so as to desalt and concentrate the emulsion. Due to the silver halide emulsion high-efficiency desalination and concentration technology, the desalination and concentration method effectively reduces the content of impurity ions in the emulsion, reduces the bulk temperature for coating and drying, and improves the performance for preserving the film photographic properties.
Description
Technical field
The present invention relates to ray silver emulsion technology of preparing, more particularly, relate to a kind of emulsion desalination, concentration technique for radiation-sensitive type emulsion (hereinafter to be referred as ray emulsion) preparation process.
Background technology
The ray emulsion preparation is the important component part of radiographic film production technology.Radiographic film comprises medical x ray film (as: Chest X-rays sheet, orthopaedics sheet, dentistry plate, mammary gland sheet etc.), industrial radiographic film (as: universal type industrial radiographic film, gamma rays and high-energy ray special adhesive).That radiographic film has is easy and simple to handle, the characteristic of visual result, archives preservation, is that to be applied as the digitized video recording materials on basis with computer technology not available, is also that radiographic film is as the vitality of professional video information recording material.Although, the factors such as film processing liquid, operating process, storage condition have considerable influence to the archives preservation characteristic of radiographic film, but efficient desalination, the concentration technique in the ray emulsion preparation is the air conditioning energy consumption that guarantees film archives preservation characteristic, reduction coating drying process in the film production run, the important step that reduces ionized water consumption (environmental friendliness).
The desalination process of conventional ray emulsion preparation has: WATER-WASHING METHOD, membrane separation process, sedimentation etc.WATER-WASHING METHOD is primary mature silver halide-gelatin emulsion condensation, specialized equipment with condensed solid silver halide-gelatin emulsion slitting, soak the emulsion slitting until to detect the emulsion conductivity qualified with deionized water.Shortcoming: operational load is heavy, production efficiency is low, and emulsion is unrealized concentrated, and desalting efficiency is low and the deionized water consumption is large.Membrane separation process is that primary mature emulsion adopts high precision semi-permeable diaphragm, a large amount of flow deionized water to rinse desalination.Shortcoming: emulsion is unrealized concentrated, and water consumption is large, and high precision semi-permeable diaphragm operation and maintenance cost is high.Sedimentation, to adopt gelatin flocculating agent (or sinking agent) or modified gelatin, realize that by the pH value of adjusting primary mature emulsion emulsion is concentrated, desalination, shortcoming: adopt modified gelatin to the ray emulsion physical and chemical performance, negative interaction to be arranged, and single use gelatin flocculating agent (or sinking agent), the desalting efficiency of primary mature emulsion, concentrated when silver-colored loss can't take into account, and influential to the emulsion coating.
Technical matters to be solved by this invention is, design the operating procedure that two or more flocculating agents (or sinking agent) is combined the design coupling, realize target: efficient desalination, effectively reduce the desalination water consumption, improve primary mature emulsion cocnentration factor, reduce the air conditioner load that the high speed of a motor vehicle is coated with dry run, the silver that reduces settling process runs off, environmental friendliness.Simultaneously, enlarge the cocnentration factor scope of primary mature emulsion, to satisfy different-purpose films to the needs of ray emulsion preparation.
Summary of the invention
The present invention is achieved by following technical proposals for the preparation of the flocculating agent composition of ray emulsion, and the water-soluble flocculant (or sinking agent) that screening is applicable must meet one of following three kinds of conditions at least:
(c) condensed polymer of β naphthalene sulfonate salt and aldehydes;
(1) can be the combination of polymkeric substance more than two types among (a), (b), (c);
(2) can be the combination of same type among (a), (b), (c), different polymerization degree, two above polymkeric substance.
The present invention utilizes above-mentioned flocculating agent composition for the preparation of ray emulsion to carry out the concentrated method of desalination: flocculating agent (or sinking agent) makes up with the primary mature emulsion that contains silver halide-gelatin (or gelatin analog) and mixes, can flocculate in acid medium (or sedimentation), realize emulsion desalination, concentrated; Select water-soluble flocculant (or sinking agent) combination, mix with the primary mature emulsion that contains silver halide-gelatin (or gelatin analog), in acid medium, can carry out the flocculation (or sedimentation) of any cocnentration factor; Acid medium refers to that primary mature emulsion adds mineral acid (as sulfuric acid, phosphoric acid) or organic acid (as acetic acid, citric acid), adjust pH value to 4.5 or below; If that primary mature emulsion contains is to be removed, soluble-salt concentration is higher, primary mature emulsion flocculation (or sedimentation) desired pH value is lower, is low to moderate 3.0 most; If that primary mature emulsion contains is to be removed, soluble-salt concentration is low, primary mature emulsion flocculation (or sedimentation) desired pH value is in the 3.5-4.5 scope; The support of emulsion coating is paper substrate or other permeability base material, and emulsion only needs once flocculate (or sedimentation), can satisfy the desalination requirement; The support of emulsion coating is glass or PET sheet base, once the solids-enriched emulsion of flocculation (or sedimentation) need to be no more than in 40 ℃, alkalescent deionized water after dissolving in temperature, flocculation (or sedimentation) in acid medium again, could satisfy the requirement of emulsion desalination.
The efficient desalination technology of silver emulsion of the present invention, desalting efficiency can improve 25-50%, and namely emulsion desalination approximately 25-50% of ion discharge reduction, significantly reduce the factory effluent discharging.
Silver emulsion efficient concentration technology of the present invention improves the cocnentration factor of primary mature emulsion more than 50%, can reduce the dry air conditioner load of emulsion coating, reduces the film energy consumption.Higher (12-20g silver/the m of industrial radiographic film silver coating amount
2), and the lower (5g silver/m of medical x ray film silver coating amount
2Under), improve the emulsion cocnentration factor more remarkable to the industrial radiographic film production effect.
The efficient desalination concentration technique of silver emulsion of the present invention reduces the silver-colored number of dropouts in waste liquid in the emulsion preparation desalting process.Silver is valuable raw material in the silver emulsion preparation, and technique has not only reduced the cost consumption of emulsion preparation process, and, alleviate the processing load of producing the heavy metal in waste liquid ion.
The efficient desalination concentration technique of silver emulsion of the present invention effectively reduces impurity ion content and the dry bulk temperature of reduction coating in emulsion, has improved the retention of film camera performance.
Embodiment
The below is described further the present invention.
The present invention comprises for the preparation of the flocculating agent composition of ray emulsion: be comprised of at least two types of polymkeric substance among (a), (b), (c); Or formed by at least two polymkeric substance of same type, different polymerization degree among (a), (b), (c); Wherein:
(c) condensed polymer of β naphthalene sulfonate salt and aldehydes.
The addition of flocculating agent (or sinking agent) composition is with the gelatin dry weight basis in primary mature silver halide-gelatin (or gelatin analog) emulsion, approximately 2-20% (5-15% is better).
Flocculating agent (or sinking agent) composition adds primary mature silver halide-gelatin (or gelatin analog) emulsion, add mineral acid (as sulfuric acid, phosphoric acid) or organic acid (as acetic acid, citric acid), adjust pH value to 4.5 or below, desalination, concentrated in acid medium.
Medical radiation emulsion, that primary mature emulsion contains is to be removed, soluble-salt concentration is lower, and the desired pH value scope of flocculation (or sedimentation) agent combination is 3.5-4.5.
Industrial x-ray emulsion, that primary mature emulsion contains is to be removed, soluble-salt concentration is higher, and the desired pH value of flocculation (or sedimentation) agent combination is lower, is low to moderate 3.0 most.
Industrial x-ray primary mature emulsion adopts flocculation (or sedimentation) agent combination desalination concentrated, the highlyest can improve emulsion cocnentration factor to 50%.The dry air conditioner load of decrease film coating can improve Coating Speed 20-40%.Have efficient, energy saving.
Flocculating agent (or sinking agent) composition is to the efficient desalination of radiographic film primary mature emulsion, and the qualified needed washing of emulsion desalination is used, amount of deionized water reduces 25-50%.The discharging of waste liquid amount of whole emulsion preparation process descends 20%.Have the environmental friendliness characteristics.
Flocculating agent (or sinking agent) combination reduces in the emulsion preparation process except the silver loss 40-60% in bisulfate waste liquor the efficient desalination of radiographic film primary mature emulsion; Alleviate the processing load of heavy metal ion in the production liquid waste processing; Have the environmental friendliness characteristics.
Following routine 1-3 is usual manner, and routine 4-7 is employing composition of the present invention and desalination method for concentration, and usual manner and method of the present invention are compared explanation:
Example 1: conventional emulsifying manner prepares ammonia process silver halide radiation-sensitive emulsion.Wherein, silver halide can be pure silver bromide, or bromo-iodide (Br
-: I
-Mol ratio was greater than 80: 20; Br: the I mol ratio is better greater than 95: 5), or bromine silver iodochloride (Br
-: I
-: Cl
-Mol ratio approximately 98: 1: 1).Preparation method: end liquid (containing deionized water 150L, inertia photographic gelatin 12kg, potassium iodide 0.6kg, potassium chloride 0.3kg and ammonium bromide 44kg), under 55 ℃, constant current speed added silver-colored solution (containing deionized water 140L, silver nitrate 32kg, ammoniacal liquor 16L and ammonium nitrate 8kg) in 5 minutes; Behind interval 2 minutes, constant current speed added silver-colored solution (containing deionized water 140L, silver nitrate 32kg, ammoniacal liquor 16L and ammonium nitrate 8kg) in 15 minutes; Acetic acid is adjusted pH value to 6.5-8, and the emulsion primary mature finishes, and the silver content of primary mature emulsion is 4.5-5.5g silver/100ml emulsion approximately.
Except salt phase: add 4% (mass percent concentration) to meet flocculation (or sedimentation) agent of a structural formula, 35kg to primary mature emulsion; Acid adding is adjusted below pH value to 4.5, and the gelatin silver emulsion is standing below 20 ℃, realize a desalination concentrated (mother liquor conductivity and concentration of silver ions that detection is inclined and removed); A sedimentation medicine cake (Main Ingredients and Appearance is gelatin, silver halide and a small amount of foreign ion) adds in (being no more than 60 ℃) 200L deionized water, adjusts the above rear medicine cake of pH value to 7.5 with alkali and dissolves fully; Stir more than 10 minutes, acid adding is adjusted below pH value to 4.5 again, adds the 150L of low temperature deionized water below 20 ℃, and the gelatin silver emulsion is standing below 20 ℃, realize that the secondary desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed).The secondary settlement desalination, discharging salt bearing liquid wastes 350-400L (remaining concentration of silver ions 0.02-0.05%).
Primary mature emulsion is qualified to the conductivity of inclining except mother liquor through twice sedimentation desalination, uses altogether deionized water 350L.
After the primary mature emulsion that desalination is processed carries out conventional chemical sensitizing (being secondary ripening), obtain to meet the emulsion to be coated of coating process requirement.Emulsion silver content after secondary ripening: 4.0-5.0g silver/100ml emulsion, Coating Speed 10-12 m/min.Primary mature emulsion, according to conventional desalination technical finesse, secondary ripening emulsion is unrealized concentrated.
Example 2: the emulsion primary mature is identical with example 1 preparation method.
Except salt phase: add 6% flocculation (or sedimentation) agent that meets the b structural formula, 33kg to primary mature emulsion; Acid adding is adjusted below pH value to 4.5, and the gelatin silver emulsion is standing below 20 ℃, realize a desalination concentrated (mother liquor conductivity and concentration of silver ions that detection is inclined and removed); One time sedimentation medicine cake adds in (being no more than 60 ℃) 200L deionized water, and alkali is adjusted the above rear medicine cake of pH value to 7.5 and dissolved fully; Stir more than 10 minutes, acid adding is adjusted below pH value to 4.5 again, adds the 150L of low temperature deionized water below 20 ℃, and the gelatin silver emulsion is standing below 20 ℃, realize that the secondary desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed).The secondary settlement desalination, discharging salt bearing liquid wastes 350-400L (remaining concentration of silver ions 0.02-0.05%).
Primary mature emulsion is qualified to the conductivity of inclining except mother liquor through twice sedimentation desalination, uses altogether deionized water 350L.
After the primary mature emulsion that desalination is processed carries out conventional chemical sensitizing, obtain to meet the emulsion to be coated of coating process requirement.Emulsion silver content after secondary ripening: 4.5-5.5g silver/100ml emulsion, Coating Speed 10-12 m/min.Primary mature emulsion, according to conventional desalination technical finesse, secondary ripening emulsion is unrealized concentrated.
Example 3: the emulsion primary mature is identical with example 1 preparation method.
Except salt phase: add 4% flocculation (or sedimentation) agent that meets the c structural formula, 35kg to primary mature emulsion; Acid adding is adjusted below pH value to 4.5, and the gelatin silver emulsion is standing below 20 ℃, realize a desalination concentrated (mother liquor conductivity and concentration of silver ions that detection is inclined and removed); One time sedimentation medicine cake adds in (being no more than 60 ℃) 200L deionized water, and alkali is adjusted the above rear medicine cake of pH value to 7.5 and dissolved fully; Stir more than 10 minutes, acid adding is adjusted below pH value to 4.5 again, adds the 150L of low temperature deionized water below 20 ℃, and the gelatin silver emulsion is standing below 20 ℃, realize that the secondary desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed).The secondary settlement desalination, discharging salt bearing liquid wastes 350-400L (remaining concentration of silver ions 0.01-0.03%).
Primary mature emulsion is qualified to the conductivity of inclining except mother liquor through twice sedimentation desalination, uses altogether deionized water 350L.
After the primary mature emulsion that desalination is processed carries out conventional chemical sensitizing, obtain to meet the emulsion to be coated of coating process requirement.Emulsion silver content after secondary ripening: 4.5-6.0g silver/100ml emulsion, Coating Speed 10-12 m/min.Primary mature emulsion, according to conventional desalination technical finesse, secondary ripening emulsion realizes that concentrated ratio is minimum.
Example 4: the emulsion primary mature is identical with example 1 preparation method.
Desalination enriching stage: combined flocculation (or sedimentation) agent 35kg (n=10 in (a) type polymer wherein that adds (a), (b) two types of polymkeric substance to primary mature emulsion, (b) x=12, m=20 in type polymer); Acid adding is adjusted below pH value to 4.5, and the gelatin silver emulsion is standing below 20 ℃, realize a desalination concentrated (mother liquor conductivity and concentration of silver ions that detection is inclined and removed); One time sedimentation medicine cake adds in (being no more than 60 ℃) 200L deionized water, and alkali is adjusted the above rear medicine cake of pH value to 7.5 and dissolved fully; Stir more than 10 minutes, acid adding is adjusted below pH value to 4.5 again, and the gelatin silver emulsion is standing below 20 ℃, realize that the secondary desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed).The secondary settlement desalination, discharging salt bearing liquid wastes 200-250L (remaining concentration of silver ions 0.005-0.008%).
Primary mature emulsion is qualified to the conductivity of inclining except mother liquor through twice sedimentation desalination, uses altogether deionized water 200L, is starkly lower than the deionized water consumption of routine 1-3.
After the primary mature emulsion that desalination is processed carries out conventional chemical sensitizing, obtain to meet the emulsion to be coated of coating process requirement, emulsion silver content: 7.0-8.0g silver/100ml emulsion, Coating Speed 15-20 m/min.Primary mature emulsion is processed according to patent desalination concentration technique, and secondary ripening emulsion is concentrated approximately 50%, and Coating Speed improves approximately more than 55%.
Example 5: the emulsion primary mature is identical with example 1 preparation method.
Desalination enriching stage: combined flocculation (or sedimentation) agent that adds (a), (b), (c) three types polymkeric substance to primary mature emulsion, (n=10 in (a) type polymer wherein, (b) x=8, m=12 in type polymer); Acid adding is adjusted below pH value to 4.5, and the gelatin silver emulsion is standing below 20 ℃, realize a desalination concentrated (mother liquor conductivity and concentration of silver ions that detection is inclined and removed); One time sedimentation medicine cake adds in (being no more than 60 ℃) 180L deionized water, and alkali is adjusted the above rear medicine cake of pH value to 7.5 and dissolved fully; Stir more than 10 minutes, acid adding is adjusted below pH value to 4.5 again, and the gelatin silver emulsion is standing below 20 ℃, realize that the secondary desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed).The secondary settlement desalination, discharging salt bearing liquid wastes 200-250L (remaining concentration of silver ions 0.005-0.008%).
Primary mature emulsion is qualified to the conductivity of inclining except mother liquor through twice sedimentation desalination, amounts to deionized water 1801, is starkly lower than the deionized water consumption of routine 1-3.
After the primary mature emulsion that desalination is processed carries out conventional chemical sensitizing, obtain to meet the emulsion to be coated of coating process requirement, emulsion silver content: 7.0-8.0g silver/100ml emulsion, Coating Speed 15-20 m/min.Primary mature emulsion is processed according to patent desalination concentration technique, and secondary ripening emulsion is concentrated approximately 50%, and Coating Speed improves approximately more than 55%.
Example 6: the emulsion primary mature is identical with example 1 preparation method.
Desalination enriching stage: add the b1 (wherein x=12, m=20) of (b) type polymer different polymerization degree and b2 (x=10, m=16) to be combined as flocculation (or sedimentation) agent to primary mature emulsion; Acid adding is adjusted below pH value to 4.5, and the gelatin silver emulsion is standing below 20 ℃, realize a desalination concentrated (mother liquor conductivity and concentration of silver ions that detection is inclined and removed); One time sedimentation medicine cake adds in (being no more than 60 ℃) 200L deionized water, and alkali is adjusted the above rear medicine cake of pH value to 7.5 and dissolved fully; Stir more than 10 minutes, acid adding is adjusted below pH value to 4.5 again, and the gelatin silver emulsion is standing below 20 ℃, realize that the secondary desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed).The secondary settlement desalination, discharging salt bearing liquid wastes 200-2501 (remaining concentration of silver ions 0.005-0.008%).
Primary mature emulsion is qualified to the conductivity of inclining except mother liquor through twice sedimentation desalination, amounts to deionized water 2001, is starkly lower than the deionized water consumption of routine 1-3.
After the primary mature emulsion that desalination is processed carries out conventional chemical sensitizing, obtain to meet the emulsion to be coated of coating process requirement, emulsion silver content: 7.0-8.0g silver/100ml emulsion, Coating Speed 15-20 m/min.Primary mature emulsion is processed according to patent desalination concentration technique, and secondary ripening emulsion is concentrated approximately 50%, and Coating Speed improves approximately more than 55%.
Example 7: the emulsion primary mature is identical with example 1 preparation method.
Desalination enriching stage: add the c1 of (c) type polymer different polymerization degree and c2 to be combined as flocculation (or sedimentation) agent to primary mature emulsion; Acid adding is adjusted below pH value to 4.5, and the gelatin silver emulsion is standing below 20 ℃, realize a desalination concentrated (mother liquor conductivity and concentration of silver ions that detection is inclined and removed); One time sedimentation medicine cake adds in (being no more than 60 ℃) 180L deionized water, and alkali is adjusted the above rear medicine cake of pH value to 7.5 and dissolved fully; Stir more than 10 minutes, acid adding is adjusted below pH value to 4.5 again, and the gelatin silver emulsion is standing below 20 ℃, realize that the secondary desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed).The secondary settlement desalination, discharging salt bearing liquid wastes 200-250L (remaining concentration of silver ions 0.005-0.008%).
Primary mature emulsion is qualified to the conductivity of inclining except mother liquor through twice sedimentation desalination, uses altogether deionized water 180L, is starkly lower than the deionized water consumption of routine 1-3.
After the primary mature emulsion that desalination is processed carries out conventional chemical sensitizing, obtain to meet the emulsion to be coated of coating process requirement, emulsion silver content: 7.0-8.0g silver/100ml emulsion, Coating Speed 15-20 m/min.Primary mature emulsion is processed according to patent desalination concentration technique, and secondary ripening emulsion is concentrated approximately 50%, and Coating Speed improves approximately more than 55%.
The data of example 1-7 show: the composition that adopts the present invention's flocculation (or sedimentation) agent, emulsion has highly enriched ratio, is suitable for improving Coating Speed, and desalting efficiency is high, reduce the desalination discharge of wastewater, and simultaneously, in waste liquid, concentration of silver ions significantly reduces, silver runs off minimizing.
Embodiment recited above is described the preferred embodiment for the present invention; be not that the spirit and scope of the present invention are limited; under the prerequisite that does not break away from design philosophy of the present invention; various distortion and improvement that in this area, common engineering technical personnel make technical scheme of the present invention all should belong to protection scope of the present invention.
Claims (3)
1. the flocculating agent composition for the preparation of ray emulsion, is characterized in that, is comprised of at least two polymkeric substance of same type, different polymerization degree among (b), (c); Wherein:
X=12 wherein, m=20; Or x=8, m=12; Or x=10, m=16
(c) condensed polymer of β naphthalene sulfonate salt and aldehydes.
2. one kind is utilized flocculating agent composition claimed in claim 1 to carry out the concentrated method of desalination, it is characterized in that, carry out according to following step: mix with the primary mature emulsion that contains silver halide-gelatin, described flocculating agent composition addition adds 2-20% with the gelatin dry weight basis in primary mature silver halide-gelatin emulsion; In acid medium, can carry out the flocculation of any cocnentration factor; To be removed, Soluble salt ions concentration that primary mature emulsion contains are 2.0-4.0M, and the desired pH value of primary mature emulsion flocculation is low to moderate 3.0 most; If to be removed, Soluble salt ions concentration that primary mature emulsion contains are 0.5-1.0M, the desired pH value scope of primary mature emulsion flocculation is 3.5-4.5.
3. the concentrated method of desalination according to claim 2, be used for ray primary mature emulsion desalination concentrated, and the flocculating agent composition addition is counted 5-15% with the gelatin dry weight in primary mature silver halide-gelatin emulsion.
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|---|---|---|---|
| CN 201010114123 CN101900930B (en) | 2010-02-26 | 2010-02-26 | Flocculating agent composition for preparing ray emulsion and desalination and concentration method |
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| Publication Number | Publication Date |
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| CN101900930B true CN101900930B (en) | 2013-11-06 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0638840A1 (en) * | 1993-08-10 | 1995-02-15 | Konica Corporation | Silver halide photographic lightsensitive material |
| US5411849A (en) * | 1992-12-10 | 1995-05-02 | Konica Corporation | Silver halide photographic light-sensitive material |
| CN1180847A (en) * | 1996-08-19 | 1998-05-06 | 富士胶片公司 | Photographic silver halide photosensitive material |
| CN1427296A (en) * | 2001-12-18 | 2003-07-02 | 中国乐凯胶片集团公司 | Silver halide particle and preparation method thereof |
| CN1932641A (en) * | 2005-09-16 | 2007-03-21 | 中国科学院理化技术研究所 | Tabular silver halide emulsion suitable for radiography and its preparation method and use |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6946240B2 (en) * | 2003-08-04 | 2005-09-20 | Eastman Kodak Company | Imaging material with improved scratch resistance |
-
2010
- 2010-02-26 CN CN 201010114123 patent/CN101900930B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5411849A (en) * | 1992-12-10 | 1995-05-02 | Konica Corporation | Silver halide photographic light-sensitive material |
| EP0638840A1 (en) * | 1993-08-10 | 1995-02-15 | Konica Corporation | Silver halide photographic lightsensitive material |
| CN1180847A (en) * | 1996-08-19 | 1998-05-06 | 富士胶片公司 | Photographic silver halide photosensitive material |
| CN1427296A (en) * | 2001-12-18 | 2003-07-02 | 中国乐凯胶片集团公司 | Silver halide particle and preparation method thereof |
| CN1932641A (en) * | 2005-09-16 | 2007-03-21 | 中国科学院理化技术研究所 | Tabular silver halide emulsion suitable for radiography and its preparation method and use |
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