CN1504825A - Cadmium sulfide nano particle sensitizer and preparation method and application thereof - Google Patents
Cadmium sulfide nano particle sensitizer and preparation method and application thereof Download PDFInfo
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- CN1504825A CN1504825A CNA021491976A CN02149197A CN1504825A CN 1504825 A CN1504825 A CN 1504825A CN A021491976 A CNA021491976 A CN A021491976A CN 02149197 A CN02149197 A CN 02149197A CN 1504825 A CN1504825 A CN 1504825A
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- emulsion
- sensitizer
- water
- cadmium sulfide
- silver
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- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 55
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 20
- 229910052709 silver Inorganic materials 0.000 claims abstract description 60
- 239000004332 silver Substances 0.000 claims abstract description 60
- -1 silver halide Chemical class 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001661 cadmium Chemical class 0.000 claims abstract description 6
- 239000000839 emulsion Substances 0.000 claims description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 66
- 230000001235 sensitizing effect Effects 0.000 claims description 64
- 239000002245 particle Substances 0.000 claims description 49
- 239000013081 microcrystal Substances 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 22
- 108010010803 Gelatin Proteins 0.000 claims description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- 229920000159 gelatin Polymers 0.000 claims description 17
- 239000008273 gelatin Substances 0.000 claims description 17
- 235000019322 gelatine Nutrition 0.000 claims description 17
- 235000011852 gelatine desserts Nutrition 0.000 claims description 17
- 229920002521 macromolecule Polymers 0.000 claims description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims description 8
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims description 5
- 239000004323 potassium nitrate Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 235000002639 sodium chloride Nutrition 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 229920000151 polyglycol Polymers 0.000 claims description 4
- 239000010695 polyglycol Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 2
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 claims description 2
- CSYKLDTVFRFMIT-UHFFFAOYSA-M [Ag]Br.[Cl] Chemical compound [Ag]Br.[Cl] CSYKLDTVFRFMIT-UHFFFAOYSA-M 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 2
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 2
- 238000005957 chlorosulfonylation reaction Methods 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 claims description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical group OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 229940045105 silver iodide Drugs 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 206010070834 Sensitisation Diseases 0.000 abstract description 29
- 230000008313 sensitization Effects 0.000 abstract description 29
- 239000000243 solution Substances 0.000 abstract description 18
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 229910052946 acanthite Inorganic materials 0.000 abstract description 5
- 229940056910 silver sulfide Drugs 0.000 abstract description 5
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 12
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 12
- 206010034960 Photophobia Diseases 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 208000013469 light sensitivity Diseases 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 238000010257 thawing Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229920006267 polyester film Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 description 5
- 238000009775 high-speed stirring Methods 0.000 description 4
- 229940059939 kayexalate Drugs 0.000 description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002344 gold compounds Chemical class 0.000 description 2
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 2
- 229940076131 gold trichloride Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 241001363516 Plusia festucae Species 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- LSMRBAGORXFPAB-UHFFFAOYSA-N gold;sulfanylidenesilver Chemical compound [Au].[Ag]=S LSMRBAGORXFPAB-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003498 tellurium compounds Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
The invention belongs to the technical field of silver halide photosensitive materials, and particularly relates to a cadmium sulfide nanoparticle sensitizer and a preparation method and application thereof. Dispersing a water-soluble cadmium salt solution and a water-soluble sulfur-containing compound solution in a water-soluble high molecular compound, mixing at the temperature of 10-100 ℃, and stirring to obtain a sensitizer consisting of cadmium sulfide nano particles, a water-soluble inorganic substance and the water-soluble high molecular compound; wherein the concentration of cadmium sulfide nano particles in the sensitizer is 0.00001-0.1 mol/L, the concentration of water-soluble inorganic matter is 0.00002-0.2 mol/L, and the weight percentage concentration of water-soluble high molecular compound is 0.1-10%. The silver sulfide sensitization spot formed by the sensitizer of the invention is easy to control, thereby reducing latent image dispersion and improving sensitivity and contrast.
Description
Technical field
The invention belongs to the photosensitive silve halide material technical field, particularly a kind of cadmium sulfide nanometer particle sensitizing agent and its production and use.
Background technology
The sensitizing of silver halide microcrystal emulsion mainly contains chemical sensitization and spectral sensitization.Chemical sensitization mainly is to improve the light sensitivity of silver halide microcrystal emulsion at its intrinsic spectral region, and spectral sensitization mainly is to improve light sensitivity by improving silver halide microcrystal in the indirect absorptivity of its extrinsic spectral region.
By chemical sensitization processes such as sulphur sensitizing, golden sensitizing, sulfur plus gold sensitizing, the silver halide microcrystal surface can form certain size, the chemical sensitization spot of some, i.e. silver sulfide spot or silver sulfide gold spot.These sensitization spots can capture light shine photoelectron or the photohole that produces in the silver halide microcrystal of back and pass through series of physical chemical process formation latent image and time latent image.
If there is too much chemical sensitization spot on a silver halide microcrystal surface, electronics that crystallite is produced after illumination and hole just may be captured by these sensitization spots respectively.Could form a latent image owing to need several light induced electrons to combine at least with the activity of developing with the gap silver ion, therefore the breaking up of the branch of sensitization spot causes single sensitization spot to capture photoelectronic probability reducing, the probability of generation latent image diminishes and latent image is disperseed, and then causes light sensitivity and contrast to reduce.So that the sensitization spot is concentrated light sensitivity and the contrast may improve silver halide microcrystal emulsion relatively.U.S. Patent number a kind of silver sulfide colloidal sol that has been 5167875 patent disclosure is used for the development layer of silver halide microcrystal emulsion sensitizing or silver salt diffusion transfer; U.S. Patent number be 5362470 patent disclosure a kind of ultra-fine silver, golden sulfide is used for the sensitizing of silver halide microcrystal emulsion, compares with common water miscible sulphur, gold compound process for increasing sensitivity, and the light sensitivity of emulsion increases, and photographic fog reduces; The U.S. Patent number solids sensitizer of several water-dispersion types that has been 5759760 patent disclosure, they are made up of water insoluble and gold compound, palladium compound, tellurium compound organic solvent respectively.
Common chemical sensitization mechanism is as follows: water miscible compound is adsorbed on the silver halide microcrystal surface with the form of molecule or ion earlier, and physics and the chemical change through a series of complexity forms the chemical sensitization spot again.But, because the activity site on silver halide microcrystal surface is a lot, and the absorption position of water miscible sensitizer compound on the silver halide microcrystal surface relatively disperseed, the sensitization spot position that particle surface generates also just relatively disperses, cause latent image to form probability and diminish and disperses, be difficult for the raising light sensitivity.
Summary of the invention
One of purpose of the present invention provides a kind of novel cadmium sulfide nanometer particle sensitizing agent that makes the sensitization spot form relatively and concentrate, distribute and be easy to control.
Two of purpose of the present invention provides a kind of preparation method of cadmium sulfide nanometer particle sensitizing agent.
Three of purpose of the present invention provides a kind of method of utilizing cadmium sulfide nanometer particle sensitizing agent of the present invention silver halide microcrystal emulsion to be carried out sensitizing.
Four of purpose of the present invention provides a kind of method of utilizing cadmium sulfide nanometer particle sensitizing agent of the present invention and water-soluble golden salt solusion silver halide microcrystal emulsion to be worked in coordination with sensitizing.
The present invention adopts the mineral compound cadmium sulfide as chemical sensitizer first, and the state of this compound is water-insoluble nano size particles.The cadmium sulphide particle that mainly consists of nano-scale of this sensitizer.Cadmium sulfide nano-particles at first attached to the silver halide microcrystal surface, partly or entirely changes into silver sulfide sensitization spot as sensitizer during sensitizing then in maturation.The silver sulfide sensitization spot that forms distributes than being easier to control like this, therefore can reduce latent image and disperse, and improves light sensitivity and contrast.
Cadmium sulfide nanometer particle sensitizing agent of the present invention is made up of cadmium sulfide nano-particles, water miscible inorganics and water miscible macromolecular compound.Wherein, the concentration of cadmium sulfide nano-particles is 0.00001～0.1 mol in the sensitizer, and water miscible mineral concentration is 0.00002～0.2 mol, and the mass percent concentration of water miscible macromolecular compound is 0.001～10%, and surplus is a water.
Described water miscible macromolecular compound is gelatin, polyglycol, polyvinyl alcohol (PVA), polyacrylic acid, poly-methyl acrylate or starch etc.
Described water miscible inorganics is sodium sulphate, glazier's salt, ammonium sulfate, sodium nitrate, potassium nitrate or ammonium nitrate etc.
The particle diameter of described cadmium sulfide nano-particles is in 1～30 nanometer.
Cadmium sulfide nanometer particle sensitizing agent of the present invention, mainly obtain by water miscible cadmium salt and the reaction of water miscible sulfocompound, except generating cadmium sulfide nano-particles, other composition is decided on used water soluble compound kind, can generate water-soluble substanceses such as sodium sulphate, glazier's salt, ammonium sulfate, sodium nitrate, potassium nitrate or ammonium nitrate respectively.
The preparation method of cadmium sulfide nanometer particle sensitizing agent of the present invention: water miscible cadmium salt soln and water miscible sulfocompound solution are dispersed in the water miscible macromolecular compound, in temperature is to mix under 10～100 ℃ of conditions, stir, obtain the sensitizer of forming by cadmium sulfide nano-particles, water soluble inorganic substance and water miscible macromolecular compound.Wherein, the concentration of the cadmium sulfide nano-particles in the sensitizer is 0.00001～0.1 mol, and the concentration of water miscible inorganics is 0.00002～0.2 mol, and the weight percent concentration of water miscible macromolecular compound is 0.1～10%.
The particle diameter of described cadmium sulfide nano-particles is in 1～30 nanometer.
Described water miscible inorganics is sodium sulphate, glazier's salt, ammonium sulfate, sodium nitrate, potassium nitrate or ammonium nitrate etc.
The described stirring reaction time is 1 minute～60 minutes.
Described water miscible macromolecular compound is gelatin, polyglycol, polyvinyl alcohol (PVA), polyacrylic acid, poly-methyl acrylate or starch etc.
Described water-soluble cadmium salt is cadmium nitrate or cadmium sulfate etc.
Described water-soluble sulfocompound is sodium sulphide, ammonium sulfide or potassium sulfide etc.
Sensitizer of the present invention is used as the sensitizer of silver halide microcrystal emulsion, or works in coordination with the sensitizing that is used as silver halide microcrystal emulsion with water-soluble golden salt solusion, and gold is 0.01～1 with the relative molar ratio of sulphur when working in coordination with sensitizing.
Described water-soluble golden salt is the gold trichloride hydrochloride.
Described water-soluble golden salt approximately uses 10-8～10-3 mole sensitizer/mole silver halide microcrystal emulsion in silver halide microcrystal emulsion.
Silver halide microcrystal emulsion of the present invention can prepare as follows: in a container of 50 liters that high-speed stirring apparatus is housed, add 5～15 premium on currency in advance, 0.05～0.5 kilogram of gelatin, be heated to 40～80 ℃, constant temperature stirs, and control pAg value is between 5～10.5, in 40～180 minutes, with 0.5～3 liter of the kbr aqueous solution of 0.5～3 liter of the silver nitrate aqueous solution of 1.0～3.0 mol and 1.0～3.0 mol, linear speed regulating adds the container reaction simultaneously.After reaction is finished, be cooled to 30～40 ℃, add the sedimentation of kayexalate aqueous solution, wash 3～4 times after, add gelatin and water again, make glue silver-colored in being between 0.5～3.0.The emulsion silver content is 20～80 gram silver/kilogram emulsions.Regulate temperature then between 30～60 ℃, constant temperature stirred 20～40 minutes, and the pAg that regulates emulsion regulates pH between 5.0～7.0 between 5.0～9.0.The preparation of silver halide microcrystal emulsion is finished.Resulting silver halide microcrystal size is between 0.1～3.5 micron.
Chemical sensitization method among the present invention can be carried out as follows: equivalent takes by weighing two parts of prepared as stated above silver halide microcrystal emulsions, places the identical container of two volumes and makes its thawing; Add the cadmium sulfide nanometer particle sensitizing agent of preparation as stated above and pre-configured sodium thiosulfate sensitizer respectively in two containers, two kinds of sensitizers press the consumption that molal quantity calculates and are equated every mole of approximately use 10 of silver halide microcrystal emulsion
-7～10
-2The mole sensitizer; Also can work in coordination with sensitizing with cadmium sulfide nanometer particle sensitizing agent and golden salt pair silver halide microcrystal emulsion.Under 40～75 ℃ water bath with thermostatic control, carried out chemical sensitization 10～200 minutes, at interval emulsion is coated on the resin sheet base at a series of different times, drying at room temperature, use special exposure instrument (5500K daylight) exposure then, in 20 ℃ D-19b developer solution, developed 5 minutes, with the photographic fixing of F-5 stop bath, carry out the photosensitive property test again after the washing and drying.
Sensitizer of the present invention can reduce latent image to be disperseed, and improves light sensitivity, intensifys, and reduces photographic fog.Sensitizer of the present invention can be applied to the silver halide microcrystal emulsion of nearly all crystalline form, for example cubic silver halide crystallite emulsion, octahedra silver halide microcrystal emulsion, T particle silver halide microcrystal emulsion, hud typed silver halide microcrystal emulsion, sandwich construction crystallite emulsion, hollow or porous crystallite emulsion or non-galactic nucleus crystallite emulsion etc., also almost be applicable to all photographic silver halide kinds, as black and white film, color film, x-ray film, Aero-Space film, lithographic film, plate making plate, holofilm, various colour or black and white photographic paper etc.
Silver halide microcrystal emulsion of the present invention comprises silver chloride crystallite emulsion, silver bromide crystallite emulsion, silver iodide crystallite emulsion, bromo-iodide crystallite emulsion, chlorosulfonylation silver micro-crystallite emulsion, chlorine silver bromide crystallite emulsion or silver chloroiodobromide crystallite emulsion etc.
The relevant photosensitive property result who draws from following concrete test as can be seen, under the sensitizer of equimolar amounts and identical sensitizing temperature conditions, the light sensitivity that adopts cadmium sulfide nanometer particle sensitizing agent sensitizing is than the height that adopts sodium thiosulfate sensitizer sensitizing; The photographic fog that produces during than the collaborative sensitizing of sodium thiosulfate and gold trichloride during the collaborative sensitizing of cadmium sulfide nanometer particle sensitizing agent and gold trichloride reduces greatly, also can improve the light sensitivity and the contrast of emulsion simultaneously.
Table one: CdS and Na
2S
2O
3Sensitizing result is (sensitizing temperature: 75 ℃) relatively
Table two: CdS+HAuCl
4And Na
2S
2O
3+ HAuCl
4Sensitizing result is (sensitizing temperature: 65 ℃) relatively
Table three. the chemical sensitization result of the cadmium sulfide nanometer particle sensitizing agent of equivalent under different temperatures is relatively
| The sensitizing temperature | Photographic fog | Relative sensitivity | Contrast |
| 65℃ | 0.16 | ?100 | ?3.1 |
| 75℃ | 0.22 | ?406 | ?3.6 |
Table four: cadmium sulfide nano-particles sensitizing result (sensitizing temperature: 75 ℃)
Table five: cadmium sulfide nano-particles sensitizing result (sensitizing temperature: 75 ℃)
Below in conjunction with embodiment technical scheme of the present invention is described further.
Embodiment
Embodiment 1
The sensitizer preparation: in the glass container of a 2.5L, add 0.7L distilled water, 20 gram gelatin make its dissolving under 50 ℃ of stirrings, add 0.31 gram Cd (NO again
3)
24H
2O makes its dissolving and stirs; In 0.3L distilled water, add 0.24 gram Na
2S9H
2O makes solution, and it is slowly added in the above-mentioned water bath with thermostatic control and the solution of high-speed stirred at 50 ℃, stirs 5 minutes after adding again, and is prepared into cadmium sulfide nanometer particle sensitizing agent, and particle diameter is in 1～30 nanometer.
Cubic silver bromide crystallite emulsion preparation: in 50 liters of containers that high-speed stirring apparatus is housed, add 10 premium on currency in advance, 0.2 kilogram gelatin, 0.0011 kilogram potassium bromide, be heated to 60 ℃, constant temperature stirs, and pAg is about 7.5 in control, in 300 minutes time, with the silver nitrate aqueous solution of 2 liter of 3.0 mol and the kbr aqueous solution linear speed regulating adding simultaneously container reaction of 2 liter of 3.0 mol.After reaction finishes, be cooled to 35 ℃, add 0.2 mass per liter percent concentration and be 5% kayexalate aqueous solution sedimentation, wash 3-4 time, add 0.6 kilogram of gelatin, adding water is 10 kilograms to the emulsion general assembly (TW), and the emulsion silver content is 0.065 kilogram of silver/kilogram emulsion.Then, about 50 ℃, constant temperature stirred 30 minutes, with the liquor argenti nitratis ophthalmicus of the potassium bromide solution of 1mol/L and 1mol/L the pAg of emulsion was adjusted to 7.3, was 10% the acetum pH regulator to 6.3 with emulsion with the sodium carbonate liquor of mass percent concentration 10% and mass percent concentration.Cooling is preserved standby in the refrigerator about 4 ℃.The preparation of cubic silver bromide crystallite emulsion is finished.
The cubic silver bromide crystallite emulsion is carried out sensitizing: accurately take by weighing two parts of 1 kilogram of cubic silver bromide crystallite emulsions, join in the container of two 1.5L respectively and make its thawing; And accurately measure the cadmium sulfide nanometer particle sensitizing agent 20mL of above-mentioned preparation, join in one of them container that fills this emulsion; Accurately measure the sodium thiosulfate 20mL of pre-configured 0.001mol/L, join in another container that fills this emulsion.Carry out chemical sensitization in 75 ℃ water bath with thermostatic control, respectively emulsion is coated on the polyester film base in the different time intervals then, the silver coating amount is 0.012 Kilograms Per Square Meter, cooling, after the drying at room temperature, expose, develop photographic fixing again with special exposure instrument, drying, test, mapping.The gained result as shown in Table 1.
Embodiment 2
Adopt the cadmium sulfide nanometer particle sensitizing agent of embodiment 1.
The cubic silver bromide crystallite emulsion is carried out sulphur, the collaborative sensitizing of gold: accurately take by weighing two parts of 1 kilogram of cubic silver bromide emulsions, join in the container of two 1.5L respectively and make its thawing; And accurately measure the cadmium sulfide nanometer particle sensitizing agent 20mL of above-mentioned preparation, join one of them fill this emulsion container in, and then measure 1 * 10
-4The gold trichloride hydrochloride solution 10mL of moL/L adds in this emulsion; Accurately measure the sodium thiosulfate 20mL of pre-configured 0.001mol/L, join in another container that fills this emulsion, and then measure 1 * 10
-4The gold trichloride hydrochloride solution 10mL of moL/L adds in this emulsion.Carry out chemical sensitization in 65 ℃ water bath with thermostatic control, respectively emulsion is coated on the polyester film base in the different time intervals then, the silver coating amount is 0.012 Kilograms Per Square Meter, cooling, after the drying at room temperature, expose, develop photographic fixing again with special exposure instrument, drying, test, mapping.The gained result as shown in Table 2.
Embodiment 3
Adopt the cadmium sulfide nanometer particle sensitizing agent of embodiment 1.
Under different temperatures, the cubic silver bromide crystallite emulsion is carried out sensitizing: accurately take by weighing two parts of 1 kilogram of cubic silver bromide crystallite emulsions, join in the container of two 1.5L and place 65 ℃ respectively, make its thawing in 75 ℃ the water bath with thermostatic control; Accurately measure two parts of the cadmium sulfide nanometer particle sensitizing agent 20mL of above-mentioned preparation, join respectively in two containers that fill this emulsion and carried out chemical sensitization 80 minutes; Respectively emulsion is coated on the polyester film base then, the silver coating amount is 0.012 Kilograms Per Square Meter, and cooling after the drying at room temperature, exposes with special exposure instrument, develops photographic fixing, drying, test again.The gained result as shown in Table 3.
Embodiment 4
The sensitizer preparation: in the glass container of a 2.5L, add 0.7L distilled water, 20 gram gelatin make its dissolving under 50 ℃ of stirrings, add 0.31 gram Cd (NO again
3)
24H
2O makes its dissolving and stirs; In 0.3L distilled water, add 0.20 gram K
2S5H
2O makes solution, and it is slowly added in the above-mentioned water bath with thermostatic control and the solution of high-speed stirred at 50 ℃, stirs 5 minutes after adding again, and is prepared into cadmium sulfide nanometer particle sensitizing agent, and particle diameter is in 1～30 nanometer
The cubic silver bromide crystallite emulsion is carried out sensitizing: accurately take by weighing 1 kilogram of cubic silver bromide crystallite emulsion portion, join in the container of a 1.5L and make its thawing; And accurately measure the cadmium sulfide nanometer particle sensitizing agent 20mL of above-mentioned preparation, join in the container that fills this emulsion; Carried out chemical sensitization 120 minutes in 75 ℃ water bath with thermostatic control, and respectively emulsion was coated on the polyester film base in the different time intervals then, the silver coating amount is 0.012 Kilograms Per Square Meter, cooling, after the drying at room temperature, expose, develop again with special exposure instrument, photographic fixing, drying, test.The gained result as shown in Table 4.
Embodiment 5
The sensitizer preparation: in the glass container of a 2.5L, add 0.7L distilled water, 20 gram gelatin make its dissolving under 50 ℃ of stirrings, add 0.28 gram CdSO again
44H
2O makes its dissolving and stirs; In 0.3L distilled water, add 0.24 gram Na
2S9H
2O makes solution, and it is slowly added in the above-mentioned water bath with thermostatic control and the solution of high-speed stirred at 50 ℃, stirs 5 minutes after adding again, and is prepared into cadmium sulfide nanometer particle sensitizing agent, and particle diameter is in 1～30 nanometer.
The cubic silver bromide crystallite emulsion is carried out sensitizing: accurately take by weighing 1 kilogram of octahedra silver bromide crystallite emulsion portion, join in the container of a 1.5L and make its thawing; And accurately measure the cadmium sulfide nanometer particle sensitizing agent 20mL of above-mentioned preparation, join in the container that fills this emulsion; Carried out chemical sensitization 120 minutes in 75 ℃ water bath with thermostatic control, and respectively emulsion was coated on the polyester film base in the different time intervals then, the silver coating amount is 0.012 Kilograms Per Square Meter, cooling, after the drying at room temperature, expose, develop again with special exposure instrument, photographic fixing, drying, test.The gained result as shown in Table 5.
Embodiment 6
The sensitizer preparation: in the glass container of a 2.5L, add 0.7L distilled water, 20 gram gelatin make its dissolving under 50 ℃ of stirrings, add 0.28 gram CdSO again
44H
2O makes its dissolving and stirs; In 0.3L distilled water, add 0.20 gram K
2S5H
2O makes solution, and it is slowly added in the above-mentioned water bath with thermostatic control and the solution of high-speed stirred at 50 ℃, stirs 5 minutes after adding again, and is prepared into cadmium sulfide nanometer particle sensitizing agent, and particle diameter is in 1～30 nanometer.
Octahedra silver bromide crystallite emulsion preparation: in 30 liters of containers that high-speed stirring apparatus is housed, add 6 premium on currency in advance, 0.2 kilogram gelatin, 0.02 kilogram potassium bromide, be heated to 70 ℃, constant temperature stirs, and pAg is about 8.8 in control, within 100 minutes time, with the silver nitrate aqueous solution of 2 liter of 3.0 mol and the kbr aqueous solution linear speed regulating adding simultaneously container reaction of 2 liter of 3.0 mol.After reaction is finished, be cooled to 35 ℃, add 0.2 mass per liter percent concentration and be 5% kayexalate aqueous solution and carry out sedimentation, wash 3-4 time, add 0.8 kilogram of gelatin, adding water is 10 kilograms to the emulsion general assembly (TW), and the emulsion silver content is 0.065 kilogram of silver/kilogram emulsion.Then, about 40 ℃, constant temperature stirred 30 minutes, with the liquor argenti nitratis ophthalmicus of the potassium bromide solution of 1mol/L and 1mol/L the pAg of emulsion was adjusted to 8, was that 10% sodium carbonate liquor and mass percent concentration are the pH to 6.5 of 10% acetum adjusting emulsion with mass percent concentration.Preserve standby in the refrigerator after the cooling about 4 ℃.Octahedra silver bromide crystallite emulsion preparation is finished.
Octahedra silver bromide crystallite emulsion is carried out sensitizing: accurately take by weighing 1 kilogram of octahedra silver bromide crystallite emulsion portion, join in the container of a 1.5L and make its thawing; And accurately measure the cadmium sulfide nanometer particle sensitizing agent 15mL of above-mentioned preparation, join in the container that fills this emulsion; Carried out chemical sensitization 120 minutes in 70 ℃ water bath with thermostatic control, and respectively emulsion was coated on the polyester film base in the different time intervals then, the silver coating amount is 0.012 Kilograms Per Square Meter, cooling after the drying at room temperature, exposes with special exposure instrument, develop photographic fixing again.
Embodiment 7
Sensitizer preparation: in the glass container of a 2.5L, add 0.7L distilled water and 20 gram gelatin, under 50 ℃ of stirrings, make its dissolving, add 0.28 gram CdSO again
44H
2O makes its dissolving and stirs; In 0.3L distilled water, add 0.07 gram (NH
4)
2Make solution behind the S and it is slowly added in the above-mentioned water bath with thermostatic control and the solution of high-speed stirred at 50 ℃, stirred 5 minutes after adding again, be prepared into cadmium sulfide nanometer particle sensitizing agent, particle diameter is in 1～30 nanometer.
T particle silver bromide crystallite emulsion preparation: in 30 liters of containers that high-speed stirring apparatus is housed, add 6 premium on currency in advance, 0.2 kilogram gelatin, 0.12 kilogram potassium bromide, be heated to 50 ℃, constant temperature stirs, and pAg is about 8.8 in control, within 50 minutes time, with the silver nitrate aqueous solution of 2 liter of 3.0 mol and the kbr aqueous solution linear speed regulating adding simultaneously container reaction of 2 liter of 3.0 mol.After reaction is finished, be cooled to 35 ℃, add 0.2 mass per liter percent concentration and be 5% kayexalate aqueous solution and carry out sedimentation, wash 3-4 time, add 0.8 kilogram of gelatin, adding water is 10 kilograms to the emulsion general assembly (TW), and the emulsion silver content is 0.064 kilogram of silver/kilogram emulsion.Then, about 40 ℃, constant temperature stirred 30 minutes, with the liquor argenti nitratis ophthalmicus of the potassium bromide solution of 1mol/L and 1mol/L the pAg of emulsion was adjusted to 8, was that 10% sodium carbonate liquor and mass percent concentration are the pH to 6.5 of 10% acetum adjusting emulsion with mass percent concentration.Cooling is preserved standby in the refrigerator about 4 ℃.The preparation of T particle silver bromide crystallite emulsion is finished.
T particle silver bromide crystallite emulsion is carried out sensitizing: accurately take by weighing 1 kilogram of T particle silver bromide crystallite emulsion portion, join in the container of a 1.5L and make its thawing; And accurately measure the cadmium sulfide nanometer particle sensitizing agent 10mL of above-mentioned preparation, join in the container that fills this emulsion; Carried out chemical sensitization 120 minutes in 70 ℃ water bath with thermostatic control, and respectively emulsion was coated on the polyester film base in the different time intervals then, the silver coating amount is 0.012 Kilograms Per Square Meter, cooling after the drying at room temperature, exposes with special exposure instrument, develop photographic fixing again.
Claims (11)
1. cadmium sulfide nanometer particle sensitizing agent, it is characterized in that: described sensitizer is made up of cadmium sulfide nano-particles, water miscible inorganics and water miscible macromolecular compound; Wherein, the concentration of cadmium sulfide nano-particles is 0.00001～0.1 mol in the sensitizer, and water miscible mineral concentration is 0.00002～0.2 mol, and the mass percent concentration of water miscible macromolecular compound is 0.001～10%, and surplus is a water;
Described water miscible inorganics is sodium sulphate, glazier's salt, ammonium sulfate, sodium nitrate, potassium nitrate or ammonium nitrate.
2. sensitizer as claimed in claim 1 is characterized in that: described water miscible macromolecular compound is gelatin, polyglycol, polyvinyl alcohol (PVA), polyacrylic acid, poly-methyl acrylate or starch.
3. sensitizer as claimed in claim 1 is characterized in that: the particle diameter of described cadmium sulfide nano-particles is in 1～30 nanometer.
4. preparation method as any described cadmium sulfide nanometer particle sensitizing agent of claim 1～3, it is characterized in that: water miscible cadmium salt soln and water miscible sulfocompound solution are dispersed in the water miscible macromolecular compound, in temperature is to mix under 10～100 ℃ of conditions, stir, obtain the sensitizer of forming by cadmium sulfide nano-particles, water soluble inorganic substance and water miscible macromolecular compound; Wherein, the concentration of the cadmium sulfide nano-particles in the sensitizer is 0.00001～0.1 mol, and the concentration of water miscible inorganics is 0.00002～0.2 mol, and the weight percent concentration of water miscible macromolecular compound is 0.1～10%;
Described water-soluble sulfocompound is sodium sulphide, ammonium sulfide or potassium sulfide;
Described water miscible inorganics is sodium sulphate, glazier's salt, ammonium sulfate, sodium nitrate, potassium nitrate or ammonium nitrate.
5. method as claimed in claim 4 is characterized in that: the particle diameter of described cadmium sulfide nano-particles is in 1～30 nanometer.
6. method as claimed in claim 4 is characterized in that: described water miscible macromolecular compound is gelatin, polyglycol, polyvinyl alcohol (PVA), polyacrylic acid, poly-methyl acrylate or starch.
7. method as claimed in claim 4 is characterized in that: described water-soluble cadmium salt is cadmium nitrate or cadmium sulfate.
8. purposes as any described cadmium sulfide nanometer particle sensitizing agent of claim 1～3, it is characterized in that: described sensitizer is as the sensitizer of silver halide microcrystal emulsion, or with the collaborative sensitizing of water-soluble golden salt solusion as silver halide microcrystal emulsion, gold is 0.01～1 with the relative molar ratio of sulphur during collaborative sensitizing; Described water-soluble golden salt is 10 in silver halide microcrystal emulsion
-8～10
-3Mole sensitizer/mole silver halide microcrystal emulsion.
9. purposes as claimed in claim 8 is characterized in that: described water-soluble golden salt is the gold trichloride hydrochloride.
10. purposes as claimed in claim 8 is characterized in that: described silver halide microcrystal emulsion comprises silver chloride crystallite emulsion, silver bromide crystallite emulsion, silver iodide crystallite emulsion, bromo-iodide crystallite emulsion, chlorosulfonylation silver micro-crystallite emulsion, chlorine silver bromide crystallite emulsion or silver chloroiodobromide crystallite emulsion.
11. purposes as claimed in claim 10 is characterized in that: the crystalline form of described silver halide microcrystal emulsion is cubic silver halide crystallite emulsion, octahedra silver halide microcrystal emulsion, T particle silver halide microcrystal emulsion, nucleocapsid silver halide microcrystal emulsion, sandwich construction crystallite emulsion, hollow or porous crystallite emulsion or non-galactic nucleus crystallite emulsion.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021491976A CN1504825A (en) | 2002-11-28 | 2002-11-28 | Cadmium sulfide nano particle sensitizer and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811731A (en) * | 2010-04-08 | 2010-08-25 | 洛阳师范学院 | Preparation method of Q-CdS nanoparticles |
| CN110981198A (en) * | 2019-11-21 | 2020-04-10 | 佛山欧神诺陶瓷有限公司 | Photochromic ceramic tile and preparation method thereof |
-
2002
- 2002-11-28 CN CNA021491976A patent/CN1504825A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811731A (en) * | 2010-04-08 | 2010-08-25 | 洛阳师范学院 | Preparation method of Q-CdS nanoparticles |
| CN101811731B (en) * | 2010-04-08 | 2011-06-15 | 洛阳师范学院 | Preparation method of Q-CdS nanoparticles |
| CN110981198A (en) * | 2019-11-21 | 2020-04-10 | 佛山欧神诺陶瓷有限公司 | Photochromic ceramic tile and preparation method thereof |
| CN110981198B (en) * | 2019-11-21 | 2022-08-16 | 佛山欧神诺陶瓷有限公司 | Photochromic ceramic tile and preparation method thereof |
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