CN101900930A - 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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- CN101900930A CN101900930A CN 201010114123 CN201010114123A CN101900930A CN 101900930 A CN101900930 A CN 101900930A CN 201010114123 CN201010114123 CN 201010114123 CN 201010114123 A CN201010114123 A CN 201010114123A CN 101900930 A CN101900930 A CN 101900930A
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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 that is used 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 industrial radiographic film, gamma rays and high-energy ray special adhesive).The characteristic that radiographic film has is easy and simple to handle, visual result, archives are preserved is that to be applied as the digitized video recording materials on basis with computer technology not available, also is the vitality of radiographic film as professional video information recording material.Although, factors such as film processing soup, operating process, storage condition have considerable influence to the archives preservation characteristics 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 characteristics, 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 that primary mature silver halide-gelatin emulsion condensation, specialized equipment are with condensed solid silver halide-gelatin emulsion slitting, qualified until detecting the emulsion conductivity with deionized water immersion emulsion slitting.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 big.Membrane separation process is that primary mature emulsion adopts high precision semi-permeable diaphragm, a large amount of flow deionized water flushing desalination.Shortcoming: emulsion is unrealized concentrated, and water consumption is big, high precision semi-permeable diaphragm operation and maintenance cost height.Sedimentation, be to adopt gelatin flocculating agent (or sinking agent) or modified gelatin, realize that by the pH value of adjusting primary mature emulsion emulsion concentrates, desalination, shortcoming: adopt modified gelatin that the ray emulsion physical and chemical performance is had negative interaction, 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.
Summary of the invention
Technical matters to be solved by this invention is, design two or more flocculating agent (or sinking agent) combinations and the operating procedure of 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 the needs of different-purpose films to the ray emulsion preparation.
The present invention is used for the ray emulsion preparation, is achieved by following technical proposals, and the water-soluble flocculant (or sinking agent) that screening is suitable for 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) and (b), (c);
(2) can be the combination of same type among (a) and (b), (c), different polymerization degree, two above polymkeric substance.
Flocculating agent (or sinking agent) makes up with the primary mature emulsion that contains silver halide-gelatin (or gelatin analog) and mixes, and can flocculate in acid medium (or sedimentation) realizes the emulsion desalination, concentrates; Select water-soluble flocculant (or sinking agent) combination for use, mix, in acid medium, can carry out the flocculation (or sedimentation) of any cocnentration factor with the primary mature emulsion that contains silver halide-gelatin (or gelatin analog); Acid medium refers to that primary mature emulsion adds mineral acid (as sulfuric acid, phosphoric acid) or organic acid (as acetate, citric acid), adjust pH value to 4.5 or below; If primary mature emulsion contains waits to remove, soluble-salt concentration is high more, then primary mature emulsion flocculation (or sedimentation) desired pH value is low more, is low to moderate 3.0 most; If primary mature emulsion contains waits to remove, soluble-salt concentration is low, then 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, then once the solids-enriched emulsion of flocculation (or sedimentation) need be no more than dissolving back in 40 ℃, alkalescent deionized water, flocculation (or sedimentation) in acid medium once more in temperature, 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 promptly the emulsion desalination reduces about 25-50% with the ion water yield, reduces the factory effluent discharging significantly.
The efficient concentration technique of silver emulsion of the present invention, the cocnentration factor that improves primary mature emulsion can reduce the dry air conditioner load of emulsion coating more than 50%, reduce 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
2Down), raising emulsion cocnentration factor is more remarkable to the industrial radiographic film production effect.
The efficient desalination concentration technique of silver emulsion of the present invention reduces emulsion and prepares the silver-colored number of dropouts in the waste liquid in the desalting process.Silver is valuable raw material in the silver emulsion preparation, and this technology has not only reduced the cost consumption of emulsion preparation process, and, alleviate and produce treatment of heavy metal ions load in the waste liquid.
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 the emulsion, has improved the retention of film camera performance.
Embodiment
Below the present invention is described further.
The present invention is used to prepare the flocculating agent composition of ray emulsion, comprising: be made up of at least two types of polymkeric substance among (a) and (b), (c); Or form by at least two polymkeric substance of same type, different polymerization degree among (a) and (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, about 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 acetate, citric acid), adjust pH value to 4.5 or below, in acid medium desalination, concentrate.
Medical radiation emulsion, primary mature emulsion contains waits to remove, soluble-salt concentration is lower, and then to make up desired pH value scope be 3.5-4.5 in flocculation (or sedimentation) agent.
Industrial x-ray emulsion, primary mature emulsion contains waits to remove, soluble-salt concentration is higher, and then to make up desired pH value lower in flocculation (or sedimentation) agent, is low to moderate 3.0 most.
Industrial x-ray primary mature emulsion adopts flocculation (or sedimentation) agent combination desalination to concentrate, and the highlyest can improve emulsion cocnentration factor to 50%.Reduce the dry air conditioner load of film coating significantly, can improve coating speed of a motor vehicle 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 the silver loss 40-60% that removes in the emulsion preparation process in the bisulfate waste liquor to the efficient desalination of radiographic film primary mature emulsion; Alleviate treatment of heavy metal ions load in the production liquid waste processing; Have the environmental friendliness characteristics.
Following routine 1-3 is a 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
-About 98: 1: 1 of mol ratio).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 in 5 minutes speed adds silver-colored solution (containing deionized water 140L, silver nitrate 32kg, ammoniacal liquor 16L and ammonium nitrate 8kg); After 2 minutes, constant current in 15 minutes speed adds silver-colored solution (containing deionized water 140L, silver nitrate 32kg, ammoniacal liquor 16L and ammonium nitrate 8kg) at interval; Acetate is adjusted pH value to 6.5-8, and the emulsion primary mature finishes, the about 4.5-5.5g silver of the silver content of primary mature emulsion/100ml emulsion.
Remove salt phase: add flocculation (or sedimentation) agent that 4% (mass percent concentration) meets a structural formula, 35kg to primary mature emulsion; Add acid and adjust below the pH value to 4.5, the gelatin silver emulsion leaves standstill, realizes that a desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed) below 20 ℃; A sedimentation medicine cake (Main Ingredients and Appearance is gelatin, silver halide and small amount of impurities ion) adds in (being no more than 60 ℃) 200L deionized water, adjusts the above back of pH value to 7.5 medicine cake with alkali and dissolves fully; Stir more than 10 minutes, add acid once more and adjust below the pH value to 4.5, add the 150L of low temperature deionized water below 20 ℃, the gelatin silver emulsion leaves standstill, realizes that the secondary desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed) below 20 ℃.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 that mother liquor through twice sedimentation desalination, uses deionized water 350L altogether.
After the primary mature emulsion that desalination is handled carries out conventional chemical sensitizing (being secondary ripening), obtain to meet the emulsion to be coated of coating process requirement.Emulsion silver content behind the secondary ripening: 4.0-5.0g silver/100ml emulsion, coating speed of a motor vehicle 10-12 rice/minute.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.
Remove salt phase: add 6% flocculation (or sedimentation) agent that meets the b structural formula, 33kg to primary mature emulsion; Add acid and adjust below the pH value to 4.5, the gelatin silver emulsion leaves standstill, realizes that a desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed) below 20 ℃; One time sedimentation medicine cake adds in (being no more than 60 ℃) 200L deionized water, and alkali is adjusted the above back of pH value to 7.5 medicine cake and dissolved fully; Stir more than 10 minutes, add acid once more and adjust below the pH value to 4.5, add the 150L of low temperature deionized water below 20 ℃, the gelatin silver emulsion leaves standstill, realizes that the secondary desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed) below 20 ℃.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 that mother liquor through twice sedimentation desalination, uses deionized water 350L altogether.
After the primary mature emulsion that desalination is handled carries out conventional chemical sensitizing, obtain to meet the emulsion to be coated of coating process requirement.Emulsion silver content behind the secondary ripening: 4.5-5.5g silver/100ml emulsion, coating speed of a motor vehicle 10-12 rice/minute.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.
Remove salt phase: add 4% flocculation (or sedimentation) agent that meets the c structural formula, 35kg to primary mature emulsion; Add acid and adjust below the pH value to 4.5, the gelatin silver emulsion leaves standstill, realizes that a desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed) below 20 ℃; One time sedimentation medicine cake adds in (being no more than 60 ℃) 200L deionized water, and alkali is adjusted the above back of pH value to 7.5 medicine cake and dissolved fully; Stir more than 10 minutes, add acid once more and adjust below the pH value to 4.5, add the 150L of low temperature deionized water below 20 ℃, the gelatin silver emulsion leaves standstill, realizes that the secondary desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed) below 20 ℃.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 that mother liquor through twice sedimentation desalination, uses deionized water 350L altogether.
After the primary mature emulsion that desalination is handled carries out conventional chemical sensitizing, obtain to meet the emulsion to be coated of coating process requirement.Emulsion silver content behind the secondary ripening: 4.5-6.0g silver/100ml emulsion, coating speed of a motor vehicle 10-12 rice/minute.Primary mature emulsion, according to conventional desalination technical finesse, secondary ripening emulsion realizes that the ratio that concentrates is minimum.
Example 4: the emulsion primary mature is identical with example 1 preparation method.
The desalination enriching stage: to primary mature emulsion add two types of polymkeric substance of (a) and (b) combined flocculation (or sedimentation) agent 35kg (n=10 in (a) type polymer wherein, (b) x=12 in the type polymer, m=20); Add acid and adjust below the pH value to 4.5, the gelatin silver emulsion leaves standstill, realizes that a desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed) below 20 ℃; One time sedimentation medicine cake adds in (being no more than 60 ℃) 200L deionized water, and alkali is adjusted the above back of pH value to 7.5 medicine cake and dissolved fully; Stir more than 10 minutes, add acid once more and adjust below the pH value to 4.5, the gelatin silver emulsion leaves standstill, realizes that the secondary desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed) below 20 ℃.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 that mother liquor through twice sedimentation desalination, uses deionized water 200L altogether, is starkly lower than the deionized water consumption of routine 1-3.
After the primary mature emulsion that desalination is handled carries out conventional chemical sensitizing, obtain to meet the emulsion to be coated of coating process requirement, the emulsion silver content: 7.0-8.0g silver/100ml emulsion, coating speed of a motor vehicle 15-20 rice/minute.Primary mature emulsion is handled according to patent desalination concentration technique, and it is about 50% that secondary ripening emulsion concentrates, and the coating speed of a motor vehicle improves about more than 55%.
Example 5: the emulsion primary mature is identical with example 1 preparation method.
The desalination enriching stage: add combined flocculation (or sedimentation) agent of (a) and (b), (c) three types of polymkeric substance to primary mature emulsion, (n=10 in (a) type polymer wherein, (b) x=8 in the type polymer, m=12); Add acid and adjust below the pH value to 4.5, the gelatin silver emulsion leaves standstill, realizes that a desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed) below 20 ℃; One time sedimentation medicine cake adds in (being no more than 60 ℃) 180L deionized water, and alkali is adjusted the above back of pH value to 7.5 medicine cake and dissolved fully; Stir more than 10 minutes, add acid once more and adjust below the pH value to 4.5, the gelatin silver emulsion leaves standstill, realizes that the secondary desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed) below 20 ℃.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 that 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 handled carries out conventional chemical sensitizing, obtain to meet the emulsion to be coated of coating process requirement, the emulsion silver content: 7.0-8.0g silver/100ml emulsion, coating speed of a motor vehicle 15-20 rice/minute.Primary mature emulsion is handled according to patent desalination concentration technique, and it is about 50% that secondary ripening emulsion concentrates, and the coating speed of a motor vehicle improves about more than 55%.
Example 6: the emulsion primary mature is identical with example 1 preparation method.
The desalination enriching stage: to primary mature emulsion add (b) type polymer different polymerization degree b1 (x=12 wherein, m=20) and b2 (x=10 m=16) is combined as flocculation (or sedimentation) agent; Add acid and adjust below the pH value to 4.5, the gelatin silver emulsion leaves standstill, realizes that a desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed) below 20 ℃; One time sedimentation medicine cake adds in (being no more than 60 ℃) 200L deionized water, and alkali is adjusted the above back of pH value to 7.5 medicine cake and dissolved fully; Stir more than 10 minutes, add acid once more and adjust below the pH value to 4.5, the gelatin silver emulsion leaves standstill, realizes that the secondary desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed) below 20 ℃.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 that 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 handled carries out conventional chemical sensitizing, obtain to meet the emulsion to be coated of coating process requirement, the emulsion silver content: 7.0-8.0g silver/100ml emulsion, coating speed of a motor vehicle 15-20 rice/minute.Primary mature emulsion is handled according to patent desalination concentration technique, and it is about 50% that secondary ripening emulsion concentrates, and the coating speed of a motor vehicle improves about more than 55%.
Example 7: the emulsion primary mature is identical with example 1 preparation method.
The desalination enriching stage: the c1 from (c) type polymer different polymerization degree to primary mature emulsion and the c2 that add are combined as flocculation (or sedimentation) agent; Add acid and adjust below the pH value to 4.5, the gelatin silver emulsion leaves standstill, realizes that a desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed) below 20 ℃; One time sedimentation medicine cake adds in (being no more than 60 ℃) 180L deionized water, and alkali is adjusted the above back of pH value to 7.5 medicine cake and dissolved fully; Stir more than 10 minutes, add acid once more and adjust below the pH value to 4.5, the gelatin silver emulsion leaves standstill, realizes that the secondary desalination concentrates (mother liquor conductivity and concentration of silver ions that detection is inclined and removed) below 20 ℃.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 that mother liquor through twice sedimentation desalination, uses deionized water 180L altogether, is starkly lower than the deionized water consumption of routine 1-3.
After the primary mature emulsion that desalination is handled carries out conventional chemical sensitizing, obtain to meet the emulsion to be coated of coating process requirement, the emulsion silver content: 7.0-8.0g silver/100ml emulsion, coating speed of a motor vehicle 15-20 rice/minute.Primary mature emulsion is handled according to patent desalination concentration technique, and it is about 50% that secondary ripening emulsion concentrates, and the coating speed of a motor vehicle improves about 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 the coating speed of a motor vehicle, and desalting efficiency height, minimizing desalination discharge of wastewater, simultaneously, concentration of silver ions significantly reduces in the waste liquid, silver runs off minimizing.
Embodiment recited above is described the preferred embodiment for the present invention; be not that design of the present invention and scope are limited; under the prerequisite that does not break away from design philosophy of the present invention; common engineering technical personnel make technical scheme of the present invention in this area various distortion and improvement all should belong to protection scope of the present invention.
Claims (3)
1. a flocculating agent composition that is used to prepare ray emulsion is characterized in that, is made up of at least two types of polymkeric substance among (a) and (b), (c); Or form by at least two polymkeric substance of same type, different polymerization degree among (a) and (b), (c); Wherein:
(c) condensed polymer of β naphthalene sulfonate salt and aldehydes.
2. one kind is utilized the described flocculating agent composition of claim 1 to carry out the method that desalination concentrates, it is characterized in that, carry out according to following step: mix with the primary mature emulsion that contains silver halide-gelatin (or gelatin analog), described flocculating agent composition addition adds 2-20% with the gelatin dry weight basis in primary mature silver halide-gelatin (or gelatin analog) emulsion; In acid medium, can carry out the flocculation or the sedimentation of any cocnentration factor; If once ripe emulsion contains waits to remove, the soluble-salt ion concentration is 2.0-4.0M, then flocculation of primary mature emulsion or the desired pH value of sedimentation are low to moderate 3.0 most; If primary mature emulsion contains waits to remove, the soluble-salt ion concentration is 0.5-1.0M, then flocculation of primary mature emulsion or the desired pH value scope of sedimentation are 3.5-4.5.
3. the method that desalination according to claim 2 concentrates is used for ray primary mature emulsion desalination and concentrates, and flocculating agent (or sinking agent) composition addition is counted 5-15% with the gelatin dry weight in primary mature silver halide-gelatin (or gelatin analog) emulsion.
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Citations (6)
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 |
US20050031982A1 (en) * | 2003-08-04 | 2005-02-10 | Eastman Kodak Company | Imaging material with improved scratch resistance |
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 |
-
2010
- 2010-02-26 CN CN 201010114123 patent/CN101900930B/en not_active Expired - Fee Related
Patent Citations (6)
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 |
US20050031982A1 (en) * | 2003-08-04 | 2005-02-10 | Eastman Kodak Company | Imaging material with improved scratch resistance |
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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