US3647458A - Solarization of silver halide photographic emulsions - Google Patents
Solarization of silver halide photographic emulsions Download PDFInfo
- Publication number
- US3647458A US3647458A US14454A US3647458DA US3647458A US 3647458 A US3647458 A US 3647458A US 14454 A US14454 A US 14454A US 3647458D A US3647458D A US 3647458DA US 3647458 A US3647458 A US 3647458A
- Authority
- US
- United States
- Prior art keywords
- emulsion
- silver halide
- solarizing
- agent
- aldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 70
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 33
- 239000004332 silver Substances 0.000 title claims abstract description 33
- -1 silver halide Chemical class 0.000 title claims abstract description 32
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 20
- 150000002576 ketones Chemical class 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 238000011282 treatment Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical group OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical group OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 claims description 3
- 229910052736 halogen Chemical group 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 108010010803 Gelatin Proteins 0.000 description 8
- 229920000159 gelatin Polymers 0.000 description 8
- 239000008273 gelatin Substances 0.000 description 8
- 235000019322 gelatine Nutrition 0.000 description 8
- 235000011852 gelatine desserts Nutrition 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BTQAJGSMXCDDAJ-UHFFFAOYSA-N 2,4,6-trihydroxybenzaldehyde Chemical compound OC1=CC(O)=C(C=O)C(O)=C1 BTQAJGSMXCDDAJ-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- BULLHNJGPPOUOX-UHFFFAOYSA-N chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- MNQZXJOMYWMBOU-UHFFFAOYSA-N glyceraldehyde Chemical compound OCC(O)C=O MNQZXJOMYWMBOU-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- HDZHNYWSJFVZIO-UHFFFAOYSA-N 2,3-diaminophenol;hydrochloride Chemical compound Cl.NC1=CC=CC(O)=C1N HDZHNYWSJFVZIO-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- VPMMJSPGZSFEAH-UHFFFAOYSA-N 2,4-diaminophenol;hydrochloride Chemical compound [Cl-].NC1=CC=C(O)C([NH3+])=C1 VPMMJSPGZSFEAH-UHFFFAOYSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- 108010082495 Dietary Plant Proteins Proteins 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/485—Direct positive emulsions
- G03C1/48515—Direct positive emulsions prefogged
Definitions
- ABSTRACT Silver halide is solarized by treatment with an aldehyde having more than one carbon atom or a ketone to provide direct positive photographic emulsions.
- the present invention relates to photographic emulsions of the direct positive type and to a method for the preparation of such emulsions.
- a solarized silver halide emulsion i.e., an emulsion which has attained this reversal point, yields directly a positive image of a subject which is photographed, and accordingly is called a direct positive emulsion.
- One known solarization process involves exposing to a light source of suitable intensity a photographic emulsion obtained by precipitating silver halide in a gelatin solution. This process is performed prior to spreading of the emulsion on a support, and is difficult to carry out on an industrial scale because of the difficulty of uniformly exposing all the silver halide grains.
- Another process comprises heating a silver halide emulsion in the presence of materials which promote fogging of the emulsion, such as AgNO decomposition product of animal or vegetable proteins, thiazoles, and photographic developers such as hydroquinone, paraphenylene diamine, amidol (diaminophenol hydrochloride), etc.
- materials which promote fogging of the emulsion such as AgNO decomposition product of animal or vegetable proteins, thiazoles, and photographic developers such as hydroquinone, paraphenylene diamine, amidol (diaminophenol hydrochloride), etc.
- Such treatments may cause hydrolysis of the gelatin emulsion since, for example, the emulsion may require heating at 100 C. for half an hour or at 45 C. for -24 hours.
- the present invention provides a solarization process for silver halide which comprises treating silver halide with a solarizing agent selected from the group consisting of an aldehyde having more than one carbon atom and a ketone.
- Such aldehydes and ketones may be aliphatic or aromatic, and may contain one or more aldehyde or ketone functions.
- the aldehydes and ketones of the aliphatic series are generally more effective and hence are preferred.
- those aldehydes and ketones which contain hydroxyl or halogen (e.g., chloro) substitution since such substituted aldehydes and ketones have been found to be especially effective in solarizing silver halide emulsions.
- Glycol aldehyde for example, is more effective than acetaldehyde, and monochloro acetone is more effective than acetone.
- the aldehydes of the present invention can be used also in the form of their bisulfite derivatives.
- Aliphatic aldehydes which may be used in the present invention include, for example, acetaldehyde, chloral, glycol aldehyde, glyceraldehyde, glyoxal, glutaraldehyde, ribose, etc.
- Aromatic aldehydes include benzaldehyde, salicylaldehyde, terephthalic aldehyde, 3,5-dioxybenzaldehyde, 2,4-dioxybenzaldehyde (resorcylic aldehyde), 2,4,6-trioxybenzaldehyde (phloroglucinaldehyde), o-chloro-benzaldehyde, ooxy-p-chlorobenzaldehyde, etc.
- the aldehyde or ketone groups may also be found in a macromolecule, for example, the oxidized starch commercially available under the name of Sumstar" and manufactured by the Miles Chem. Co., Division of Miles Laboratories Inc. (U.S.A.).
- Ketones useful in the present invention include acetone, monochloroacetone, acetylacetone, diacetyl (i.e., 2,3-butanone), sorbose, benzophenone, phenylacetone, 2,4-dihydroxy-benzophenone, etc.
- the amount of solarizing agent which is utilized depends upon the method of preparation of the emulsion and upon the desired solarization effect. ln general, the contrast of the solarized emulsion increases as the amount of solarizing agent is increased.
- the solarizing agents of the present invention preferably are employed in an amount of from about 0.2 to about 500 mg. of solarizing agent per gram-atom of silver.
- the solarizing treatment of the present invention wherein silver halide is contacted with a solarizing agent, may be carried out at any stage of preparation of the emulsion.
- the solarizing agent maybe added all at once or in successive stages in the course of emulsion preparation.
- the solarizing agent is added in solution during the silver halide precipitation step of the emulsion preparation.
- the silver halides employed in the present invention include the chloride, the bromide, the iodide and mixtures thereof.
- the silver halide emulsions of the present invention may contain any of the hydrophilic, water-permeable colloids suitable for this purpose such as gelatin, hydrophilic polyvinyl copolymers, acrylamide polymers, polyvinyl alcohol. etc., and may contain the usual photographic additives such as coating aids and the like.
- the emulsions. may be coated on a wide variety of supports such as cellulose triacetate film, poly (ethylene terephthalate) film and other films, glass, paper, metal, etc., to provide photographic elements.
- the present invention may be more easily understood by reference to the following illustrative examples.
- the graphs referred to in the examples are sensitometric curves for various emulsions wherein the ordinate D represents optical density and wherein the abscissa log E represents the logarithm of the exposure.
- the mass is stirred for additional 10 minutes at 65 C. and then the emulsion is adjusted to a pH of 3.0 by the addition of 45 percent sulfuric acid solution while cooling the whole to 30 C. At this point the silver salts and the gelatin are precipitated by the addition of a saturated solution of sodium sulfate.
- the precipitate is washed with water and is redissolved at about 50 C. in a solution of 30 g. of gelatin in 600 ml. of water. After addition of the usual coating additives, the emulsion is spread on a transparent support and dried.
- Curve 1 After exposure and development in a photographic developer for 5 minutes at 20 C a characteristic curve is obtained which is shown as Curve 1 in FIG. 1.
- Curve ll of FIG. 1 represents data for the same emulsion prepared without the glycol aldehyde
- Curve lll represents data for this emulsion (without glycol aldehyde) prepared at 80 C.
- the solarization effect afforded by the glycol aldehyde far surpasses the effect afforded by preparing the emulsion at 80 C., thereby providing for higher maximum densities with less risk of hydrolysis.
- Example 1 The whole is kept at 60 C. for minutes and the pH is adjusted to a value of 3.0. The emulsion preparation is then continued as in Example 1.
- Curve I of FIG. 2 represents the characteristic curve obtained with this emulsion.
- Curve II OF FIG. 2 represents the characteristic curve obtained from the same emulsion prepared without the use of glyceric aldehyde.
- Curve No. VIII refers to the emulsion prepared without the addition of solarizing agents.
- Example lO-benzaldehyde for the emulsion (Curve I)
- Example I I-salicylaldehyde for the emulsion (Curve II)
- Example l2-phloroglucinaldehyde for the emulsion (Curve III)
- Curve IV refers to the emulsion prepared without the addition of solarizing agents.
- a silver halide emulsion is treated with a solarization agent the improvement wherein, said material is selected from the group consisting of an aldehyde having more than one carbon atom and a ketone.
- the step which comprises treating silver halide during preparation of said emulsion with a solarizing agent which is an aldehyde having more than one carbon atom or a ketone.
- said solarizing agent is an aldehyde having more than one carbon atom and which contains a halide or hydroxyl substituent.
- the step which comprises treating silver halide during preparation of said emulsion with a solarizing agent selected from the group consisting of an aldehyde having more than one carbon atom and a ketone, said solarizing agent containing hydroxyl or halogen substitution.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT3562569 | 1969-03-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3647458A true US3647458A (en) | 1972-03-07 |
Family
ID=11242046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US14454A Expired - Lifetime US3647458A (en) | 1969-03-11 | 1970-02-26 | Solarization of silver halide photographic emulsions |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3647458A (https=) |
| JP (1) | JPS4920088B1 (https=) |
| BE (1) | BE747040A (https=) |
| CH (1) | CH533849A (https=) |
| DE (1) | DE2011072A1 (https=) |
| FR (1) | FR2037724A5 (https=) |
| GB (1) | GB1305423A (https=) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4259438A (en) * | 1978-07-03 | 1981-03-31 | Polaroid Corporation | Method for preparing photosensitive silver halide emulsions |
| US5814123A (en) * | 1991-08-02 | 1998-09-29 | Ecologel Usa, Inc. | Method for improving survival of plants in conditions of reduced watering |
| US9877434B2 (en) | 2013-05-30 | 2018-01-30 | Ecologel Solutions, Llc | Granular compositions and methods for drought mitigation |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE977553C (de) * | 1963-07-19 | 1967-02-02 | Bundesrep Deutschland | Schutzvorrichtung in Form sogenannter Graetings fuer OEffnungen an gepanzerten Objekten |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1221407A (fr) * | 1959-03-25 | 1960-06-01 | Kodak Pathe | Nouvelle émulsion photographique positive directe et procédé pour sa préparation |
| FR1405108A (fr) * | 1963-08-28 | 1965-07-02 | Ilford Ltd | Matière photographique fournissant directement des images positives et son procédé de fabrication |
-
1970
- 1970-02-26 US US14454A patent/US3647458A/en not_active Expired - Lifetime
- 1970-03-04 CH CH315370A patent/CH533849A/it not_active IP Right Cessation
- 1970-03-06 FR FR7008071A patent/FR2037724A5/fr not_active Expired
- 1970-03-09 JP JP45020043A patent/JPS4920088B1/ja active Pending
- 1970-03-09 GB GB1123170A patent/GB1305423A/en not_active Expired
- 1970-03-09 BE BE747040D patent/BE747040A/xx unknown
- 1970-03-09 DE DE19702011072 patent/DE2011072A1/de active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1221407A (fr) * | 1959-03-25 | 1960-06-01 | Kodak Pathe | Nouvelle émulsion photographique positive directe et procédé pour sa préparation |
| FR1405108A (fr) * | 1963-08-28 | 1965-07-02 | Ilford Ltd | Matière photographique fournissant directement des images positives et son procédé de fabrication |
Non-Patent Citations (1)
| Title |
|---|
| Mees, The Theory of Photographic Process, 3rd Ed. ed. 1966, Macmillan Co. * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4259438A (en) * | 1978-07-03 | 1981-03-31 | Polaroid Corporation | Method for preparing photosensitive silver halide emulsions |
| US5814123A (en) * | 1991-08-02 | 1998-09-29 | Ecologel Usa, Inc. | Method for improving survival of plants in conditions of reduced watering |
| US9877434B2 (en) | 2013-05-30 | 2018-01-30 | Ecologel Solutions, Llc | Granular compositions and methods for drought mitigation |
| US10798885B2 (en) | 2013-05-30 | 2020-10-13 | Ecologel Solutions, Llc | Granular compositions and methods for drought mitigation |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1305423A (https=) | 1973-01-31 |
| FR2037724A5 (https=) | 1970-12-31 |
| BE747040A (fr) | 1970-09-09 |
| JPS4920088B1 (https=) | 1974-05-22 |
| CH533849A (it) | 1973-02-15 |
| DE2011072A1 (de) | 1970-10-08 |
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