CN1402084A - Manganese sulfide nano particle sensitizer and preparation method and application thereof - Google Patents
Manganese sulfide nano particle sensitizer and preparation method and application thereof Download PDFInfo
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- CN1402084A CN1402084A CN 01130688 CN01130688A CN1402084A CN 1402084 A CN1402084 A CN 1402084A CN 01130688 CN01130688 CN 01130688 CN 01130688 A CN01130688 A CN 01130688A CN 1402084 A CN1402084 A CN 1402084A
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- sensitizer
- emulsion
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- silver
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- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000839 emulsion Substances 0.000 claims abstract description 94
- 229910052709 silver Inorganic materials 0.000 claims abstract description 59
- 239000004332 silver Substances 0.000 claims abstract description 59
- -1 silver halide Chemical class 0.000 claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 239000000126 substance Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 150000002696 manganese Chemical class 0.000 claims abstract description 10
- 239000013081 microcrystal Substances 0.000 claims description 33
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 20
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 20
- 108010010803 Gelatin Proteins 0.000 claims description 16
- 229920000159 gelatin Polymers 0.000 claims description 16
- 239000008273 gelatin Substances 0.000 claims description 16
- 235000019322 gelatine Nutrition 0.000 claims description 16
- 235000011852 gelatine desserts Nutrition 0.000 claims description 16
- SLJICQUROTUNOJ-UHFFFAOYSA-N acetamide;nitric acid Chemical compound CC(N)=O.O[N+]([O-])=O SLJICQUROTUNOJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 15
- 235000011152 sodium sulphate Nutrition 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 13
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 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 10
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 10
- 239000005695 Ammonium acetate Substances 0.000 claims description 10
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 10
- 235000019257 ammonium acetate Nutrition 0.000 claims description 10
- 229940043376 ammonium acetate Drugs 0.000 claims description 10
- 229920002521 macromolecule Polymers 0.000 claims description 10
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 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
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 10
- 239000001632 sodium acetate Substances 0.000 claims description 10
- 235000017281 sodium acetate Nutrition 0.000 claims description 10
- 239000004317 sodium nitrate Substances 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 229920000151 polyglycol Polymers 0.000 claims description 5
- 239000010695 polyglycol Substances 0.000 claims description 5
- 235000011056 potassium acetate Nutrition 0.000 claims description 5
- 239000004323 potassium nitrate Substances 0.000 claims description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 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
- 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
- 238000005957 chlorosulfonylation reaction Methods 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 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
- 206010034960 Photophobia Diseases 0.000 abstract description 14
- 208000013469 light sensitivity Diseases 0.000 abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 229920001477 hydrophilic polymer Polymers 0.000 abstract 1
- 206010070834 Sensitisation Diseases 0.000 description 36
- 230000008313 sensitization Effects 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000001235 sensitizing effect Effects 0.000 description 17
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 14
- 238000001035 drying Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 206010034972 Photosensitivity reaction Diseases 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000009775 high-speed stirring Methods 0.000 description 5
- 229940059939 kayexalate Drugs 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000036211 photosensitivity Effects 0.000 description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 5
- 229920006267 polyester film Polymers 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 229910052946 acanthite Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 229940056910 silver sulfide Drugs 0.000 description 4
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 150000002344 gold compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- RULQJAJONRHHFH-UHFFFAOYSA-N pentanedial;sulfurous acid Chemical compound OS(O)=O.O=CCCCC=O RULQJAJONRHHFH-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 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 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
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
The invention belongs to the technical field of silver halide photosensitive materials, and particularly relates to a manganese sulfide nanoparticle sensitizer and a preparation method and application thereof. The sensitizer is prepared from an aqueous solution of a hydrophilic high molecular compound, an aqueous solution of a water-soluble manganese salt and an aqueous solution of a water-soluble sulfur-containing compound, wherein: the molar ratio of the manganese salt to the sulfur-containing compound is 0.5: 1 to 2: 1, and the mixture is mixed and stirred at the temperature of 10-100 ℃ to obtain the sensitizer consisting of the manganese sulfide nano particles, the water-soluble inorganic substance and the water-soluble high molecular compound. The concentration of manganese sulfide nano particles in the sensitizer is 10－5～10－1Mol/l, concentration of water-soluble inorganic substance is 2X 10－5～2×10－1The weight percentage concentration of the hydrophilic polymer compound is 0.1-10% in mol/l. The sensitizer is used as a sensitizer of silver halide microcrystalline emulsion. Can reduce the dispersion of latent image, raise light sensitivity, raise contrast and reduce fog.
Description
Technical field
The invention belongs to the photosensitive silve halide material technical field, particularly a kind of manganese sulfide nanoparticle sensitizer and its production and use.
Background technology
The sensitizing of silver halide microcrystal emulsion mainly contains chemical sensitization and spectral sensitization two classes.The purpose of chemical sensitization mainly is to improve the light sensitivity of silver halide microcrystal in its intrinsic spectral absorption region, and the purpose of spectral sensitization mainly is to increase the light sensitivity of silver halide microcrystal in its extrinsic spectral absorption region.
By chemical sensitization processes such as sulphur sensitizing, golden sensitizing, sulfur plus gold sensitizing, the silver halide microcrystal surface has the chemical sensitization spot of certain size with formation, i.e. silver sulfide spot or silver sulfide gold spot.Under the irradiation of light, produce light induced electron and hole in the silver halide microcrystal, the main effect of sensitization spot is exactly the light induced electron or the hole of capturing in the silver halide microcrystal, and wherein light induced electron forms latent image and time latent image by certain photochemistry.
If many chemical sensitization spots are contained on a silver halide microcrystal surface, electronics that illumination is produced in crystallite and hole might 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 diminishes the probability of single sensitization spot trapped electron, the probability that causes generating latent image diminishes, the dispersion that is the sensitization spot may cause latent image to disperse, light sensitivity reduces, and contrast also reduces.In order to improve light sensitivity, increase contrast, except that the size of control sensitization spot size, also to make the sensitization spot concentrated relatively, preferably have only a sensitization spot on a microcrystal grain, can only form a latent image.
The chemical sensitizer that common chemical sensitization method is adopted mainly is water miscible sulphur, gold compound, as the sulphur sensitizer sodium thiosulfate, thiocarbamide etc. is arranged, and golden sensitizer has the complex compound of golden salt, gold etc.But these water-soluble sensitizers are added in the emulsion, and significant disadvantages is that the absorption position on the silver halide microcrystal surface relatively disperses, and the sensitization spot position of generation relatively disperses, thereby cause latent image to disperse.Therefore, how to make the chemical sensitization spot concentrated relatively in the distribution on silver halide microcrystal surface, more effectively improve light-sensitive silver halide degree and contrast, be the target that people seek assiduously always.
United States Patent (USP) 5604084 has been introduced the chemical sensitization method of sulfocompounds such as thiocarbonate, thiocarbamide, thioether; United States Patent (USP) 5167875 has been described a kind of preparation method of silver sulfide colloidal sol, is used for the development layer of silver halide microcrystal emulsion sensitizing or silver salt diffusion transfer; United States Patent (USP) 5362470 has prepared a kind of ultra-fine silver, golden sulfide, is used for silver halide microcrystal emulsion sensitizing, compares with the process for increasing sensitivity of routine, and the light sensitivity of its emulsion increases, and photographic fog reduces; United States Patent (USP) 5759760 has been introduced the solids sensitizer of several water-dispersion types, and they are made up of water insoluble and gold compound, tellurium compound, palladium compound organic solvent respectively; United States Patent (USP) 6100621 has been introduced the sensibilization of the potpourri of a kind of glutaraldehyde sulphite and selenium compound.
The sensitizing mode of above sensitizer mainly can be divided into two classes.One class is that compound is adsorbed on the silver halide microcrystal surface with molecular state earlier, passes through a series of physics and chemical change then, forms the chemical sensitization spot.Because the activity site on silver halide microcrystal surface is a lot, might form many sensitization spots at a particle surface, and the size heterogeneity of sensitization spot, certainly will cause latent image to disperse like this, light sensitivity is difficult for improving.Another kind of be the particulate of water dispersible attached to the silver halide microcrystal particle surface, form the chemical sensitization spot.But such water dispersible particulate is not easy and chemical reaction takes place for silver halide microcrystal surface, or is subjected to the influence of other material in the emulsion and can not be adsorbed on the silver halide particle surface effectively, because of rather than a kind of effective chemical sensitizer.
Summary of the invention
One of purpose of the present invention is to overcome above-mentioned sensitizer and forms many sensitization spots at a particle surface easily when sensitizing, and the size heterogeneity of sensitization spot, easily cause latent image to disperse, defectives such as light sensitivity is low, a kind of novel manganese sulfide nanoparticle sensitizer that provide a kind of sensitization spot size homogeneous, distributes and be easy to control.
A further object of the present invention provides a kind of preparation method of manganese sulfide nanoparticle sensitizer.
Another object of the present invention provides the purposes of manganese sulfide nanoparticle sensitizer.
The manganese sulfide particle that mainly consists of nano-scale of sensitizer of the present invention, and the state of this mineral compound manganese sulfide is water-insoluble nano size particles.Manganese sulfide nanoparticle at first attached to the silver halide microcrystal surface, partly or entirely changes into silver sulfide as sensitizer during sensitizing then in maturation, form silver sulfide sensitization spot.The sulphur sensitization spot size of Xing Chenging and all control easily that distributes like this, the manganese sulfide particle of a nano-scale just can form a sulphur sensitization spot, therefore can reduce latent image and disperse, and improves light sensitivity, intensifys, and reduces photographic fog.
Manganese sulfide nanoparticle sensitizer of the present invention is made up of the aqueous solution of manganese sulfide nanoparticle, water soluble inorganic substance and the aqueous solution of water-soluble high-molecular compound, and wherein, the concentration of the manganese sulfide nanoparticle in the sensitizer is 10
-5～10
-1Mol, the concentration of water soluble inorganic substance are 2 * 10
-5～2 * 10
-1Mol, the weight percent concentration of hydrophilic macromolecular compounds are 0.1～10%.
Described water soluble inorganic substance is different according to the composition of the manganese salt of participating in reaction and sulfocompound, is respectively sodium acetate, sodium nitrate, potassium acetate, potassium nitrate, ammonium acetate, ammonium nitrate, nitric acid acetyl ammonium, sodium sulphate, sodium sulphate and sodium acetate potpourri, sodium sulphate and sodium nitrate mixture, nitric acid acetyl ammonium and ammonium acetate potpourri or nitric acid acetyl ammonium and ammonium nitrate mixture etc.
The particle diameter of described manganese sulfide nanoparticle is less than 10 nanometers.
Described hydrophilic macromolecular compounds is gelatin, polyglycol, polyvinyl alcohol (PVA), polyacrylate, poly-methyl acrylate or starch etc.
Manganese sulfide nanoparticle sensitizer of the present invention, mainly obtain by water-soluble manganese salt and the reaction of water-soluble sulfocompound, except that generating manganese sulfide nanoparticle, other composition is decided on employed manganese salt and water-soluble sulfocompound kind, can generate sodium acetate, sodium nitrate, potassium acetate, potassium nitrate, ammonium acetate, ammonium nitrate, nitric acid acetyl ammonium, sodium sulphate, sodium sulphate and sodium acetate potpourri, sodium sulphate and sodium nitrate mixture, nitric acid acetyl ammonium and ammonium acetate potpourri or water-soluble substanceses such as nitric acid acetyl ammonium and ammonium nitrate mixture respectively.
The preparation method of manganese sulfide nanoparticle sensitizer of the present invention: with the aqueous solution of hydrophilic macromolecular compounds, the aqueous solution of water-soluble manganese salt, the aqueous solution of water-soluble sulfocompound, in temperature is to mix under 10～100 ℃ of conditions, stir, obtain the manganese sulfide nanoparticle sensitizer of forming by the aqueous solution of the aqueous solution of manganese sulfide nanoparticle, water soluble inorganic substance and water-soluble high-molecular compound; Wherein, the mol ratio of manganese salt and sulfocompound is between 0.5: 1 to 2: 1, and the weight percent concentration of hydrophilic macromolecular compounds is 0.1～10%.
The described stirring reaction time is 2～180 minutes.
Described water soluble inorganic substance is different according to the composition of the manganese salt of participating in reaction and sulfocompound, can generate sodium acetate, sodium nitrate, potassium acetate, potassium nitrate, ammonium acetate, ammonium nitrate, nitric acid acetyl ammonium, sodium sulphate, sodium sulphate and sodium acetate potpourri, sodium sulphate and sodium nitrate mixture, nitric acid acetyl ammonium and ammonium acetate potpourri or water-soluble substanceses such as nitric acid acetyl ammonium and ammonium nitrate mixture respectively.
Described hydrophilic macromolecular compounds is gelatin, polyglycol, polyvinyl alcohol (PVA), polyacrylate, poly-methyl acrylate or starch etc.
Described water-soluble manganese salt is manganese nitrate or manganese acetate.
Described water-soluble sulfocompound is sodium sulphide, ammonium sulfide, potassium sulfide, thioacetamide or sodium thiosulfate.
Manganese sulfide nanoparticle sensitizer of the present invention is as the sensitizer of silver halide microcrystal emulsion.
Silver halide microcrystal emulsion described in the present invention can prepare as follows: in 30 liters of containers that high-speed stirring apparatus is housed, add the 3-8 premium on currency in advance, 0.05-0.4 kilogram gelatin, 0～0.06 kilogram of potassium bromide or potassium chloride, be heated to 40～80 ℃, constant temperature stirs, control pAg value is between 5～10.5, in 40～180 minutes, with 1～3 liter of the kbr aqueous solution of 1～3 liter of the silver nitrate aqueous solution of 1.0～3.0 volumetric molar concentrations and 1.0～3.0 mol concentration, linear speed regulating adds the container reaction simultaneously.Reaction is cooled to 30～40 ℃ after finishing, and adds the sedimentation of kayexalate aqueous solution, washes 3～4 times, adds gelatin and water, makes glue silver than being between 0.5～3.0, and the emulsion silver content is 20～80 gram silver/kilogram emulsions.Then, between 30～60 ℃, constant temperature stirred 20～40 minutes, and the pAg that regulates emulsion is between 5.0～9.0, and pH is between 5.0～7.0.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: with two containers that volume is identical, equivalent takes by weighing two parts of prepared as stated above silver halide microcrystal emulsions; Add the manganese sulfide nanoparticle sensitizer of preparation as stated above and the sodium thiosulfate sensitizer for preparing in advance respectively in two containers, two kinds of sensitizers press the consumption that molal quantity calculates and are equated every mole of about use 10 of silver halide microcrystal emulsion
-6～10
-2The mole sensitizer.Under 40～70 ℃ of bath temperatures, carried out chemical sensitization 10～200 minutes, emulsion is coated on the polyester sheet base, drying at room temperature, with special exposure instrument exposure (5500K daylight), (D-19 developer solution then develops, 20 ℃, developed 5 minutes), photographic fixing (F-5 stop bath), dry and photosensitive property test.
Sensitizer of the present invention not only can reduce latent image to be disperseed, and improves light sensitivity, intensifys, and reduces photographic fog, and can make the light sensitivity of silver halide microcrystal emulsion improve 1～2 times, and contrast improves 0.5～1 times.Sensitizer of the present invention can be applicable to nearly all silver halide microcrystal emulsion, as cubic silver halide crystallite emulsion, octahedra silver halide microcrystal emulsion, T particle silver halide microcrystal emulsion, nucleocapsid silver halide microcrystal emulsion, sandwich construction emulsion, hollow or how empty crystallite emulsion or non-galactic nucleus crystallite emulsion or the like, and nearly all photographic silver halide kind, as black and white film, color film, x-ray film, Aero-Space film, lithographic film, plate making, holofilm, sensitive paper or the like.
Silver emulsion of the present invention comprises silver chloride emulsion, silver bromide emulsion, silver iodide emulsion, chlorine silver bromide emulsion, chlorosulfonylation silver emulsion, silver bromide emulsion or silver chloroiodobromide emulsion etc.
The relevant photosensitive property result who draws from following concrete experiment as can be seen, under the identical situation of sensitizer consumption, the light sensitivity that adopts nano-scale manganese sulfide sensitizer sensitizing is than the light sensitivity height that adopts sodium thiosulfate sensitizing; Adopt the contrast ratio of nano-scale manganese sulfide sensitizer sensitizing to adopt sodium thiosulfate sensitizing contrast to want high.Certainly, when identical light sensitivity, the sensitizing photographic fog that adopts manganese sulfide nanoparticle is than adopting the low of sodium thiosulfate.
Table 1. manganese sulfide nanoparticle sensitizer and sodium thiosulfate sensitizing result are relatively
| Photographic fog | Relative sensitivity | Contrast | |
| Sodium thiosulfate | ???0.09 | ????100 | ????3.2 |
| Manganese sulfide nanoparticle sensitizer | ???0.10 | ????208 | ????3.05 |
Table 2. manganese sulfide nanoparticle sensitizer and sodium thiosulfate sensitizing result are relatively
| Photographic fog | Relative sensitivity | Contrast | |
| Sodium thiosulfate | ????0.26 | ????100 | ????2.3 |
| Manganese sulfide nanoparticle sensitizer | ????0.26 | ????330 | ????3.4 |
Table 3. manganese sulfide nanoparticle sensitizer and sodium thiosulfate sensitizing result are relatively
| Photographic fog | Relative sensitivity | Contrast | |
| Sodium thiosulfate | ???0.30 | ????100 | ????3.7 |
| Manganese sulfide nanoparticle sensitizer | ???0.29 | ????138 | ????5.0 |
Embodiment
Embodiment 1
In 30 liters of containers that high-speed stirring apparatus is housed, add 6 premium on currency in advance, 0.2 kilogram gelatin, 0.0007 kilogram potassium bromide, be heated to 70 ℃, constant temperature stirs, and control pAg value is about 7.5, in 150 minutes time, 2 liters of the silver nitrate aqueous solutions of 2.0 mol concentration and 2 liters of isochrone deformation speed of kbr aqueous solution of 2.0 mol concentration are added the container reaction.Reaction is cooled to 35 ℃ after finishing, and adds 0.2 liter 5% kayexalate aqueous solution sedimentation, washes 3～4 times, adds 0.4 kilogram of gelatin, and adding water to the emulsion general assembly (TW) is 10 kilograms, and the emulsion silver content is 0.043 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 1M and 1M the pAg of emulsion was adjusted to 7.5, and sodium carbonate liquor with 10% and 10% acetum are with the pH regulator to 6.5 of emulsion.Cooling is preserved standby in the refrigerator about 4 ℃.The preparation of cubic silver bromide crystallite emulsion is finished.
In one 2.5 liters container, add 1 liter of distilled water, 0.1 kilogram of gelatin, 0.1 liter weight percent concentration are 70% manganese nitrate aqueous solution, 0.038 kilogram of thioacetamide, temperature is controlled at 60 ℃, and stirring reaction 30 minutes dilutes 100 times.Be prepared into manganese sulfide nanoparticle sensitizer.
Accurately take by weighing two parts of 1 kilogram of cubic silver bromide emulsions, join respectively in two 1.5 liters of containers; And accurately measure as stated above 0.02 liter of the manganese sulfide nanoparticle sensitizer of preparation, join in one of them container that fills this emulsion; Accurately measure the weight percent concentration for preparing in advance and be 0.025 liter of 0.1% hypo solution, join in another container that fills this emulsion.The control temperature is carried out chemical sensitization experiment 120 minutes at 50 ℃, respectively emulsion is coated on the polyester film base then, the silver coating amount is 0.008 Kilograms Per Square Meter, drying at room temperature, with the exposure instrument exposure of carrying out photosensitivity test specially, development then, photographic fixing, drying, test.The gained result is as shown in table 1.
Embodiment 2
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 control pAg value is about 8.8, in 100 minutes time, 2 liters of the silver nitrate aqueous solutions of 3.0 mol concentration and 2 liters of isochrone deformation speed of kbr aqueous solution of 3.0 mol concentration are added the container reaction.Reaction is cooled to 35 ℃ after finishing, and the adding weight percent concentration is 0.2 liter 5% kayexalate aqueous solution sedimentation, wash 3～4 times, add 0.8 kilogram of gelatin, adding water to the emulsion general assembly (TW) is 10 kilograms, 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 1M and 1M the pAg of emulsion was adjusted to 8, was the pH regulator to 6.5 of the acetum of 10% sodium carbonate liquor and 10% with emulsion with weight percent concentration.Cooling is preserved standby in the refrigerator about 4 ℃.The preparation of eight body silver bromide crystallite emulsions is finished.
In one 2.5 liters glass container, add 1 liter of distilled water, 0.1 kilogram of gelatin, weight percent concentration is 0.1 liter of 70% manganese nitrate aqueous solution, 0.04 kilogram of sodium sulphide, temperature is controlled at 60 ℃, and stirring reaction 50 minutes dilutes 100 times.Be prepared into manganese sulfide nanoparticle sensitizer.
Accurately take by weighing two parts of 1 kilogram of octahedra silver bromide emulsions, join respectively in two 1.5 liters of containers; And accurately measure as stated above 0.02 liter of the manganese sulfide nanoparticle sensitizer of preparation, join in one of them container that fills this emulsion; Accurately measure the weight percent concentration for preparing in advance and be 0.025 liter of 0.1% hypo solution, join in another container that fills this emulsion.The control temperature is carried out chemical sensitization experiment 120 minutes at 50 ℃, respectively emulsion is coated on the polyester film base then, the silver coating amount is 0.008 Kilograms Per Square Meter, drying at room temperature, with the exposure instrument exposure of carrying out photosensitivity test specially, development then, photographic fixing, drying, test.The gained result is as shown in table 2.
Embodiment 3
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 control pAg value is about 8.8, in 50 minutes time, 2 liters of the silver nitrate aqueous solutions of 3.0 mol concentration and 2 liters of isochrone deformation speed of kbr aqueous solution of 3.0 mol concentration are added the container reaction.Reaction is cooled to 35 ℃ after finishing, and the adding weight percent concentration is 0.2 liter 5% kayexalate aqueous solution sedimentation, wash 3～4 times, add 0.8 kilogram of gelatin, adding water to the emulsion general assembly (TW) is 10 kilograms, 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 1M and 1M the pAg of emulsion was adjusted to 8, was the pH regulator to 6.5 of the acetum of 10% sodium carbonate liquor and 10% with emulsion with weight percent concentration.Cooling is preserved standby in the refrigerator about 4 ℃.The preparation of T particle silver bromide crystallite emulsion is finished.
The preparation of manganese sulfide nanoparticle sensitizer is with embodiment 2.
Accurately take by weighing two parts of 1 kilogram of T particle silver bromide emulsions, join respectively in two 1.5 liters of containers; And accurately measure as stated above 0.02 liter of the manganese sulfide nanoparticle sensitizer of preparation, join in one of them container that fills this emulsion; Accurately measure the weight percent concentration for preparing in advance and be 0.025 liter of 0.1% hypo solution, join in another glass container that fills this emulsion.The control temperature is carried out chemical sensitization experiment 120 minutes at 50 ℃, respectively emulsion is coated on the polyester film base then, the silver coating amount is 0.008 Kilograms Per Square Meter, drying at room temperature, with the exposure instrument exposure of carrying out photosensitivity test specially, development then, photographic fixing, drying, test.
Embodiment 4
In 30 liters of containers that high-speed stirring apparatus is housed, add 6 premium on currency in advance, 0.2 kilogram gelatin, 0.045 kilogram potassium chloride, be heated to 50 ℃, constant temperature stirs, and control pAg value is about 7.9, in 60 minutes time, 2 liters of the silver nitrate aqueous solutions of 2.0 mol concentration and 2 liters of isochrone deformation speed of potassium chloride solution of 2.0 mol concentration are added the container reaction.Reaction is cooled to 35 ℃ after finishing, and the adding weight percent concentration is 0.2 liter 5% kayexalate aqueous solution sedimentation, wash 3～4 times, add 0.4 kilogram of gelatin, adding water to the emulsion general assembly (TW) is 10 kilograms, and the emulsion silver content is 0.043 kilogram of silver/kilogram emulsion.Then, about 40 ℃, constant temperature stirred 30 minutes, with the liquor argenti nitratis ophthalmicus of the Klorvess Liquid of 1M and 1M the pAg of emulsion was adjusted to 7.0, was that 10% sodium carbonate liquor and weight percent concentration are 10% the acetum pH regulator to 6.5 with emulsion with weight percent concentration.Cooling is preserved standby in the refrigerator about 4 ℃.The preparation of cube silver chloride crystallite emulsion is finished.
Manganese sulfide nanoparticle sensitizer is with embodiment 1.
Accurately take by weighing two parts of 1 kilogram of cube silver chloride emulsions, join respectively in two 1.5 liters of containers; And accurately measure as stated above 0.02 liter of the manganese sulfide nanoparticle sensitizer of preparation, join in one of them container that fills this emulsion; Accurately measure the weight percent concentration for preparing in advance and be 0.025 milliliter of 0.1% hypo solution, join in another glass container that fills this emulsion.The control temperature is carried out chemical sensitization experiment 120 minutes at 50 ℃, respectively emulsion is coated on the polyester film base then, the silver coating amount is 0.008 Kilograms Per Square Meter, drying at room temperature, with the exposure instrument exposure of carrying out photosensitivity test specially, development then, photographic fixing, drying, test.The gained result is as shown in table 3.
Embodiment 5
In one 2.5 liters glass container, add 1 liter of distilled water, 0.15 kilogram of polyglycol, 0.1 liter weight percent concentration is 70% manganese nitrate aqueous solution, 0.04 kilogram of sodium sulphide, temperature is controlled at 100 ℃, and stirring reaction 30 minutes dilutes 100 times.Be prepared into manganese sulfide nanoparticle sensitizer.
Accurately take by weighing two parts of 1 kilogram of embodiment, 4 described cube silver chloride emulsions, join respectively in two 1.5 liters of containers; And accurately measure as stated above 0.02 liter of the manganese sulfide nanoparticle sensitizer of preparation, join in one of them glass container that fills this emulsion; Accurately measure the weight percent concentration for preparing in advance and be 0.025 liter of 0.1% hypo solution, join in another container that fills this emulsion.The control temperature is carried out chemical sensitization experiment 120 minutes at 50 ℃, respectively emulsion is coated on the polyester film base then, the silver coating amount is 0.008 Kilograms Per Square Meter, drying at room temperature, with the exposure instrument exposure of carrying out photosensitivity test specially, development then, photographic fixing, drying, test.
Claims (13)
1. manganese sulfide nanoparticle sensitizer, it is characterized in that: this sensitizer is made up of the aqueous solution of manganese sulfide nanoparticle, water soluble inorganic substance and the aqueous solution of water-soluble high-molecular compound, and wherein, the concentration of the manganese sulfide nanoparticle in the sensitizer is 10
-5～10
-1Mol, the concentration of water soluble inorganic substance are 2 * 10
-5～2 * 10
-1Mol, the weight percent concentration of hydrophilic macromolecular compounds are 0.1～10%.
2. sensitizer as claimed in claim 1 is characterized in that: described water soluble inorganic substance is sodium acetate, sodium nitrate, potassium acetate, potassium nitrate, ammonium acetate, ammonium nitrate, nitric acid acetyl ammonium, sodium sulphate, sodium sulphate and sodium acetate potpourri, sodium sulphate and sodium nitrate mixture, nitric acid acetyl ammonium and ammonium acetate potpourri or nitric acid acetyl ammonium and ammonium nitrate mixture.
3. sensitizer as claimed in claim 1 is characterized in that: the particle diameter of described manganese sulfide nanoparticle is less than 10 nanometers.
4. sensitizer as claimed in claim 1 is characterized in that: described hydrophilic macromolecular compounds is gelatin, polyglycol, polyvinyl alcohol (PVA), polyacrylate, poly-methyl acrylate or starch.
5. as the preparation method of any described manganese sulfide nanoparticle sensitizer of claim 1-4, it is characterized in that: with the aqueous solution of hydrophilic macromolecular compounds, the aqueous solution of water-soluble manganese salt, the aqueous solution of water-soluble sulfocompound, in temperature is to mix under 10～100 ℃ of conditions, stir, obtain the manganese sulfide nanoparticle sensitizer of forming by the aqueous solution of the aqueous solution of manganese sulfide nanoparticle, water soluble inorganic substance and water-soluble high-molecular compound; Wherein, the mol ratio of manganese salt and sulfocompound is between 0.5: 1 to 2: 1, and the weight percent concentration of hydrophilic macromolecular compounds is 0.1～10%.
6. the preparation method of sensitizer as claimed in claim 5, it is characterized in that: described water soluble inorganic substance is sodium acetate, sodium nitrate, potassium acetate, potassium nitrate, ammonium acetate, ammonium nitrate, nitric acid acetyl ammonium, sodium sulphate, sodium sulphate and sodium acetate potpourri, sodium sulphate and sodium nitrate mixture, nitric acid acetyl ammonium and ammonium acetate potpourri or nitric acid acetyl ammonium and ammonium nitrate mixture.
7. the preparation method of sensitizer as claimed in claim 5, it is characterized in that: the particle diameter of described manganese sulfide nanoparticle is less than 10 nanometers.
8. the preparation method of sensitizer as claimed in claim 5, it is characterized in that: described hydrophilic macromolecular compounds is gelatin, polyglycol, polyvinyl alcohol (PVA), polyacrylate, poly-methyl acrylate or starch.
9. the preparation method of sensitizer as claimed in claim 5, it is characterized in that: water-soluble manganese salt is manganese nitrate or manganese acetate.
10. the preparation method of sensitizer as claimed in claim 5, it is characterized in that: water-soluble sulfocompound is sodium sulphide, ammonium sulfide, potassium sulfide, thioacetamide or sodium thiosulfate.
11. the purposes as any described sensitizer of claim 1-4 is characterized in that: this sensitizer is as the sensitizer of silver halide microcrystal emulsion.
12. the purposes of sensitizer as claimed in claim 11 is characterized in that: 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 emulsion, hollow or how empty crystallite emulsion or non-galactic nucleus crystallite emulsion.
13. the purposes as claim 11 or 12 any described sensitizers is characterized in that: described silver emulsion comprises silver chloride emulsion, silver bromide emulsion, silver iodide emulsion, chlorine silver bromide emulsion, chlorosulfonylation silver emulsion, silver bromide emulsion or silver chloroiodobromide emulsion.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01130688 CN1196975C (en) | 2001-08-20 | 2001-08-20 | Manganese sulfide nano particle sensitizer and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01130688 CN1196975C (en) | 2001-08-20 | 2001-08-20 | Manganese sulfide nano particle sensitizer and preparation method and application thereof |
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|---|---|
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| CN1196975C CN1196975C (en) | 2005-04-13 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665270B (en) * | 2009-09-27 | 2011-08-31 | 武汉理工大学 | Preparation method of manganese sulfide nano-rod |
| CN102583555A (en) * | 2012-03-07 | 2012-07-18 | 陕西科技大学 | Preparation method of stable state octahedron alpha-MnS microcrystal |
| CN109748322A (en) * | 2018-12-15 | 2019-05-14 | 河南大学 | The synthetic method and application of α-MnS nanoparticle and α-MnS/rGO composite material |
| CN110828802A (en) * | 2019-11-07 | 2020-02-21 | 吉首大学 | Preparation method of high-power aqueous zinc ion battery positive electrode material |
-
2001
- 2001-08-20 CN CN 01130688 patent/CN1196975C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665270B (en) * | 2009-09-27 | 2011-08-31 | 武汉理工大学 | Preparation method of manganese sulfide nano-rod |
| CN102583555A (en) * | 2012-03-07 | 2012-07-18 | 陕西科技大学 | Preparation method of stable state octahedron alpha-MnS microcrystal |
| CN109748322A (en) * | 2018-12-15 | 2019-05-14 | 河南大学 | The synthetic method and application of α-MnS nanoparticle and α-MnS/rGO composite material |
| CN110828802A (en) * | 2019-11-07 | 2020-02-21 | 吉首大学 | Preparation method of high-power aqueous zinc ion battery positive electrode material |
| CN110828802B (en) * | 2019-11-07 | 2023-05-23 | 吉首大学 | Preparation method of high-power water-based zinc ion battery positive electrode material |
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| Publication number | Publication date |
|---|---|
| CN1196975C (en) | 2005-04-13 |
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