US3184313A - Silver halide emulsion desensitized with a tetraalkyl thiuram disulfide - Google Patents
Silver halide emulsion desensitized with a tetraalkyl thiuram disulfide Download PDFInfo
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- US3184313A US3184313A US238751A US23875162A US3184313A US 3184313 A US3184313 A US 3184313A US 238751 A US238751 A US 238751A US 23875162 A US23875162 A US 23875162A US 3184313 A US3184313 A US 3184313A
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- United States
- Prior art keywords
- silver halide
- halide emulsion
- photographic
- thiuram disulfide
- desensitized
- Prior art date
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- 239000000839 emulsion Substances 0.000 title claims description 31
- -1 Silver halide Chemical class 0.000 title claims description 29
- 229910052709 silver Inorganic materials 0.000 title claims description 27
- 239000004332 silver Substances 0.000 title claims description 27
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 title claims description 7
- 230000005855 radiation Effects 0.000 claims description 11
- 230000035945 sensitivity Effects 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 9
- 239000010410 layer Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 150000002019 disulfides Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002601 radiography Methods 0.000 description 3
- 229940090898 Desensitizer Drugs 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- QOTYLQBPNZRMNL-UHFFFAOYSA-N bis(2-methylpropyl)carbamothioylsulfanyl n,n-bis(2-methylpropyl)carbamodithioate Chemical group CC(C)CN(CC(C)C)C(=S)SSC(=S)N(CC(C)C)CC(C)C QOTYLQBPNZRMNL-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KRALOLGXHLZTCW-UHFFFAOYSA-L calcium;2-acetyloxybenzoate Chemical group [Ca+2].CC(=O)OC1=CC=CC=C1C([O-])=O.CC(=O)OC1=CC=CC=C1C([O-])=O KRALOLGXHLZTCW-UHFFFAOYSA-L 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- PSXRWZBTVAZNSF-UHFFFAOYSA-N hydron;quinoline;chloride Chemical compound Cl.N1=CC=CC2=CC=CC=C21 PSXRWZBTVAZNSF-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/16—X-ray, infrared, or ultraviolet ray processes
-
- 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
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/36—Desensitisers
Definitions
- This invention relates to photographic elements for use in radiography, and more particularly, to X-ray sensitive elements which have materially reduced sensitivity to visible radiation.
- photographic silver halide emulsions can be usefully employed in radiography, and that these sensitive elements can be provided with an opaque or light impervious overcoat, which is removed during or after processing to a radiographic image.
- protective layers have many drawbacks in that they cause contamination of the photographic treating solutions, or they require a separate step to remove them from the surface of the photographic element.
- it is frequently difi-lc-ult to disperse uniformly the light reflective or light absorptive pigment throughout the overcoating layer with the result that uniform protection is not aways provided.
- radiographic elements which comprise a protective overcoat containing chrome yellow, Venetian red, or the like, and these pigments do have the advantage of allowing the element to be handled in ordinary ordinary daylight or room light, but it is necessary to remove them prior to photographic development, and this development must then necessarily be carried out in a darkroom.
- photographic silver halide emulsions designed for use in radiography be substantially desensitized to visible radiation without materially affecting their sensitivity to X-rays.
- the disulfide compounds useful in our invention are known as thiuram disulfides and they are characterized by marked desensitizing action toward silver halide emulsions, insofar as their sensitivity to visible radiations is concerned (particularly those beyond the blue region of the spectrum), yet retaining substantially the sensitivity of the emulsions to X-rays.
- the thiuram disulfide desensitizers which can be effectively employed in our invention include those represented by the following general formula:
- R and R each represents an alkyl group, such as methyl, ethyl, propyl, butyl, isobutyl, etc. (e.g., an alkyl group containing from 1 to 4 carbon atoms), an aryl group, such as phenyl, tolyl, etc., or together R and R represent the atoms necessary to complete an azine ring, such as morpholine, piperidine, etc., or, alternatively, a pyrrolidine ring, for example.
- the thiuram disulfide compounds are characterized in that the nitrogen atoms thereof are tertiary nitrogen atoms. Typical compounds included by the above general formula are, for example, the following:
- the quantity of thiuram disulfide compound employed in our invention can be varied, depending upon the particular silver halide used in the emulsion, the amount of gelatin or other colloid binder, etc. In general, we have found that quite useful results can be obtained at concentrations as low as 2 mg. per mole of silver halide, while amounts as high as mg. per mole of silver halide can be used without affecting the X-ray sensitivity too seriously.
- Different types of silver halide e.g., silver chloride, silver bromide, silver chlorob'romide, etc., can be employed, although we have found that iodide-containing emulsions are especially useful.
- Emulsions which form the latent imageespecially within the silver halide grain can be usefully'employed in our invention.
- the preparation of such internal latent image emulsions is described in Davey and Knott US. Patent 2,592,250, issued April 8, 1952.
- the amount of desensitizer employed will obviously depend somewhat upon the type of silver halide emulsion used. 7
- a small amount of alight-absorbing organic dye can be employed either in the emulsion or in an overcoating layer.
- invention may retain some sensitivity in the blue region of the spectrum, ithas been found that many azo dyes, such astartrazine, can be usefully employed.
- Other visible-light absorbing dyes which can be employed in such arrangements are 2-(2'-methoxy styryl)quinoline hydrochloride, the condensation product of two molecular proportions of quinaldine methosulfate and one molecular proportion of 4,4 diphenyl dialdehyde pyridine, 4,4-
- Lippmann-type emulsions can conveniently be em- 1 Since the'silver halide emulsions of ourv
- the silver halide can be dispersed in any of the conventional hy-drophilic, Water-permeable; binding materials, such as gelatin,alburnin, polyvinyl pyrrolidone,
- EXAMPLE 1' treated with varying amounts of:bis('dimethylthiocar5 bamyl)disulfide at the concentrations indicated in the following table. One portion of emulsion was untreated and this served as a control. Each of thealiquot portions.
- Kodak Safelight Filter Wratten Series OA transmits visible radiation principallybetween about 540 and 680 m with maximum transmission at about 575 m (Density of'about 0.76 at this point.) .Kodak Safelight Filter 'Wratten Series CC transmits radiation principally between about 560 and ,660 m l. ,with. maximum transmittance at (Density of about'0.92 .at this point.)
- Kodak Safelight Filter Wratten-Series 00 transmits subfour strips which were-separately exposed to a 100-watt bulb equipped with a Kodak Wratte'n Filter as indicated in the table at a distance of 14 inches.
- Each'sectio'n offilm was then-developed for 5' minutes in an ordinary MQ developer, -i.e., a developer'containing hydroquinone and N-methyl-p-aminophenol sulfate, such as KodakDe veloper DE-19b to which had been added a small amount oialkalito increase the pH toab'out 11.0.
- an ordinary MQ developer -i.e., a developer'containing hydroquinone and N-methyl-p-aminophenol sulfate, such as KodakDe veloper DE-19b to which had been added a small amount oialkalito increase the pH toab'out 11.0.
- the strips were then fixed, washed
- Kodak'Safelight Filter Wratten Series 6B transmitsradiation between about 565 and 660 m with maximum transmittance at about 595 ma. 7 (Den- Th'efamount of desensitlzing compound used can be varied cons'iderably as shown in the above examples.
- a photographic silver halide emulsion which has been substantially desensitized to visible radiation by the addition thereto of from 2 to 75 mg. per mole of silver halide of a tetraalkyl thiuram disulflde.
- a photographic element comprising a transparent, flexible support having coated thereon a photographic silver halide emulsion having substantially reduced sensitivity to visible light by the addition thereto of from 2 to 75 mg. per mole of silver halide of a tetraalkyl thiuram disulfide.
- a photographic element comprising a transparent, flexible support having coated thereon a photographic silver halide emulsion having substantially reduced sensitivity to visible light by the addition thereto of from 2 to mg. per mole of silver halide of bis(dimethylthiocarbamyl)disu-lfide.
- a photographic element comprising a transparent, flexible support having coated thereon a photographic silver halide emulsion having substantially reduced sensitivity to visible light by the addition thereto of from 2 to 75 mg. per mole of silver halide of bis(diisobutylt'hiocarbamyl)disulfide.
Description
United States Patent Office Patented May 18, 1965 This invention relates to photographic elements for use in radiography, and more particularly, to X-ray sensitive elements which have materially reduced sensitivity to visible radiation.
It is know that photographic silver halide emulsions can be usefully employed in radiography, and that these sensitive elements can be provided with an opaque or light impervious overcoat, which is removed during or after processing to a radiographic image. It is obvious that such protective layers have many drawbacks in that they cause contamination of the photographic treating solutions, or they require a separate step to remove them from the surface of the photographic element. Furthermore, it is frequently difi-lc-ult to disperse uniformly the light reflective or light absorptive pigment throughout the overcoating layer with the result that uniform protection is not aways provided.
Other radiographic elements have been suggested which comprise a protective overcoat containing chrome yellow, Venetian red, or the like, and these pigments do have the advantage of allowing the element to be handled in ordinary ordinary daylight or room light, but it is necessary to remove them prior to photographic development, and this development must then necessarily be carried out in a darkroom.
It has also been suggested that photographic silver halide emulsions designed for use in radiography be substantially desensitized to visible radiation without materially affecting their sensitivity to X-rays. However, as a practical matter, it has been difficult to discover desensitizing compounds which effectively reduce the sensitivity of these emulsions to visible radiation without materially reducing the sensitivity of the emulsions to X-ray.
We have now found a class of disulfide compounds which can be effectively employed to reduce the sensitivity of X-ray emulsions to visible radiations so that they can be handled easily under ordinary safelights. These disulfides of our invention have the advantage of only slightly lowering the sensitivity of these emulsions to X-rays.
The disulfide compounds useful in our invention are known as thiuram disulfides and they are characterized by marked desensitizing action toward silver halide emulsions, insofar as their sensitivity to visible radiations is concerned (particularly those beyond the blue region of the spectrum), yet retaining substantially the sensitivity of the emulsions to X-rays. The thiuram disulfide desensitizers which can be effectively employed in our invention include those represented by the following general formula:
wherein R and R each represents an alkyl group, such as methyl, ethyl, propyl, butyl, isobutyl, etc. (e.g., an alkyl group containing from 1 to 4 carbon atoms), an aryl group, such as phenyl, tolyl, etc., or together R and R represent the atoms necessary to complete an azine ring, such as morpholine, piperidine, etc., or, alternatively, a pyrrolidine ring, for example. The thiuram disulfide compounds are characterized in that the nitrogen atoms thereof are tertiary nitrogen atoms. Typical compounds included by the above general formula are, for example, the following:
(1) Bis (dimethylthiocarbamyl) disulfide The above compounds can be prepared according to techniques which have been previously described in the prior art, and any of these well known processes can be used to prepare these compounds.
In the copending application of A. H. Herz, Serial No. 147,766, filed October 26, 1961, now Patent No. 3,144,336, there is described a method of sensitizing photographic emulsions by a combination of two sulfurcontaining compounds, neither of which is a sensitizer in its own right. As indicated in this application, one of these sulfur-containing compounds can be a thiuram disulfide. However, it is imperative in the sensitizing. combinations of US. application 147,766, now Patent No. 3,144,336, that a sulfinic acid compound be present.. However, in the present invention no sensitization occurs since no reaction occurs between a sulfinic acid compound and the decomposition products of the thiuram disulfide compounds.
The quantity of thiuram disulfide compound employed in our invention can be varied, depending upon the particular silver halide used in the emulsion, the amount of gelatin or other colloid binder, etc. In general, we have found that quite useful results can be obtained at concentrations as low as 2 mg. per mole of silver halide, while amounts as high as mg. per mole of silver halide can be used without affecting the X-ray sensitivity too seriously. Different types of silver halide, e.g., silver chloride, silver bromide, silver chlorob'romide, etc., can be employed, although we have found that iodide-containing emulsions are especially useful. These typically include silver bromoiodide, silver chloroiodide, silver chlorobromoiodide, etc. Emulsions which form the latent imageespecially within the silver halide grain can be usefully'employed in our invention. The preparation of such internal latent image emulsions is described in Davey and Knott US. Patent 2,592,250, issued April 8, 1952. The amount of desensitizer employed will obviously depend somewhat upon the type of silver halide emulsion used. 7
In order to decrease still further the sensitivity of the silver halide emulsions of our invention to visible radiation, a small amount of alight-absorbing organic dye can be employed either in the emulsion or in an overcoating layer. invention may retain some sensitivity in the blue region of the spectrum, ithas been found that many azo dyes, such astartrazine, can be usefully employed. Other visible-light absorbing dyes which can be employed in such arrangements are 2-(2'-methoxy styryl)quinoline hydrochloride, the condensation product of two molecular proportions of quinaldine methosulfate and one molecular proportion of 4,4 diphenyl dialdehyde pyridine, 4,4-
methenyl-bis-( l-naphthyl 3 methylpyrazolone 5), etc.
Other light-absorbing dyes are described in' D'ostes and Pfafl? US. application Serial No. 83,709, filed January 19, 1961. The amount of'light-absorbing dye used to reduce the sensitivity of our photographic elements can vary as described in Serial No. 83,709. Instead of using a dyed silver halide emulsion layer or a dyed overcoating layer to protect further the radiographic sensitive layer, it is possible to use a light-absorbing silver halide emulsion layer which has very low sensitivity to visible radiation. Lippmann-type emulsions can conveniently be em- 1 Since the'silver halide emulsions of ourv The silver halide can be dispersed in any of the conventional hy-drophilic, Water-permeable; binding materials, such as gelatin,alburnin, polyvinyl pyrrolidone,
polyvinyl alcohol, hydrolyzedflcellulose'acetateyetc.
The following exampleswill serve to illustrate more fully the manner of practicing our'invention:
EXAMPLE 1' treated withvarying amounts of:bis('dimethylthiocar5 bamyl)disulfide at the concentrations indicated in the following table. One portion of emulsion was untreated and this served as a control. Each of thealiquot portions.
80 kilovolt X-rays and the other half was'divided into about 585 -m,u..
. V 4 the strips which had been exposed through Wratten filters was measured. The following results were obtained:
Table I Addenda, Rel. Gross D (7 mins. Exp.) Coating mgJmol. Speed AgX to X-rays 6B 00 0A 00 EXAMPLE 2 An ordinary photographic 'bromoiodide emulsion of the type described in Example 1 was treated with compounds as identified in the following table at the amount shown and strips of film coated with these emulsions were exposed either to kv. X-rays or to a 15-watt darkroom lamp mounted 4 feet above the film plane and equipped with either a Wratten Series OA or Series 00 Filter. The safelight exposure was for 6 minutes. The strips were then developed in an MQ developer, fixed, washed and dried, as described in Example 1. The following results were obtained:
Table II 80 kv. Safelight Exposure Direct 7 Addenda X-ray Ex- Coating (mg/mole AgX) posme,
' el. Spd Gross, Density,
at D =0.85 0A 00 above fog 100 0. 56 3. 0 25 mg. Compound 93 0. 12 0. 68 25 mg. Compound 2 0.18 1.62 40 mg. Compound 2 93 0.14 1. 21 75 mg. Compound 2 50 0. 12 V 0. 68 25 mg. Compound 3 107 0. 12 '0. 72 35 mg. Compound 3 0. 12 0.59 50 mg. Compound 3 95 0. 12 0. 52
Potassium bromide Water to make 1 liter.
For use in thepresent invention, this developer was found most effective when the pH was raised slightly to 11.0 by the addition of additional alkali. V
Kodak Safelight Filter Wratten Series OA transmits visible radiation principallybetween about 540 and 680 m with maximum transmission at about 575 m (Density of'about 0.76 at this point.) .Kodak Safelight Filter 'Wratten Series CC transmits radiation principally between about 560 and ,660 m l. ,with. maximum transmittance at (Density of about'0.92 .at this point.)
: Kodak Safelight Filter Wratten-Series 00 transmits subfour strips which were-separately exposed to a 100-watt bulb equipped with a Kodak Wratte'n Filter as indicated in the table at a distance of 14 inches. Each'sectio'n offilm was then-developed for 5' minutes in an ordinary MQ developer, -i.e., a developer'containing hydroquinone and N-methyl-p-aminophenol sulfate, such as KodakDe veloper DE-19b to which had been added a small amount oialkalito increase the pH toab'out 11.0. After develop-.1 ment, the strips were then fixed, washed and'dried in the f usual manner. The-relative-speedsof the 'coatings which had been exposed to' 80 kv.,X-rays were thenmeasured fat'a density of;0,85 .above,fog' and the gross density of 75 claims;
stantially all wavelengths beyond about 530 m (Density of 0.8 at about 5 30.) Kodak'Safelight Filter Wratten Series 6B transmitsradiation between about 565 and 660 m with maximum transmittance at about 595 ma. 7 (Den- Th'efamount of desensitlzing compound used can be varied cons'iderably as shown in the above examples.
f be effected within the spirit and scope of' the invention as described hereinabove and'as defined in-the appended What we claim as our invention and desire secured by Letters Patent of the United States is:
1. A photographic silver halide emulsion which has been substantially desensitized to visible radiation by the addition thereto of from 2 to 75 mg. per mole of silver halide of a tetraalkyl thiuram disulflde.
2. A photographic emulsion according to claim 1 wherein said disulfi-de is bis(dimethylthiocarbamyl)disulfide.
3. A photographic emulsion as defined in claim 1 wherein said disulfide is bis(diisobutylthiocarbamyl)disulfide.
4. A photographic element comprising a transparent, flexible support having coated thereon a photographic silver halide emulsion having substantially reduced sensitivity to visible light by the addition thereto of from 2 to 75 mg. per mole of silver halide of a tetraalkyl thiuram disulfide.
5. A photographic element comprising a transparent, flexible support having coated thereon a photographic silver halide emulsion having substantially reduced sensitivity to visible light by the addition thereto of from 2 to mg. per mole of silver halide of bis(dimethylthiocarbamyl)disu-lfide.
6. A photographic element comprising a transparent, flexible support having coated thereon a photographic silver halide emulsion having substantially reduced sensitivity to visible light by the addition thereto of from 2 to 75 mg. per mole of silver halide of bis(diisobutylt'hiocarbamyl)disulfide.
References Cited by the Examiner UNITED STATES PATENTS 2,759,821 8/56 Jones et al 96-109 2,927,899 3/60 Goldwasser 260567 3,017,270 1/62 Tregillus et al. 9629 NORMAN G. TORCHIN, Primary Examiner.
Claims (1)
1. A PHOTOGRAPHIC SILVER HALIDE EMULSION WHICH HAS BEEN SUBSTANTIALLY DESENSITIZED TO VISIBLE RADIATION BY THE ADDITION THERETO OF FROM 2 TO 75 MG. PER MOLE OF SILVER HALIDE OF A TETRAALKYL THIURAM DISULFIDE.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US238751A US3184313A (en) | 1962-11-19 | 1962-11-19 | Silver halide emulsion desensitized with a tetraalkyl thiuram disulfide |
| DEE25874A DE1244574B (en) | 1962-11-19 | 1963-11-16 | Photographic recording material for radiographic use |
| FR954081A FR1374842A (en) | 1962-11-19 | 1963-11-18 | New desensitized emulsion |
| GB45558/63A GB1061964A (en) | 1962-11-19 | 1963-11-19 | Photographic silver halide emulsions and sensitive materials prepared therewith |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US238751A US3184313A (en) | 1962-11-19 | 1962-11-19 | Silver halide emulsion desensitized with a tetraalkyl thiuram disulfide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3184313A true US3184313A (en) | 1965-05-18 |
Family
ID=22899154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US238751A Expired - Lifetime US3184313A (en) | 1962-11-19 | 1962-11-19 | Silver halide emulsion desensitized with a tetraalkyl thiuram disulfide |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3184313A (en) |
| DE (1) | DE1244574B (en) |
| GB (1) | GB1061964A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3276950A (en) * | 1965-05-10 | 1966-10-04 | Du Pont | Method for controlling arachnids |
| US3510348A (en) * | 1966-03-11 | 1970-05-05 | Eastman Kodak Co | Direct positive recording film |
| DE2640655A1 (en) * | 1975-09-10 | 1977-03-17 | Minnesota Mining & Mfg | PHOTOGRAPHICAL RECORDING MATERIAL WITH SENSITIVITY IN THE ULTRAVIOLET SPECTRAL RANGE, SENSITIZED HALOGSILVER EMULSION, X-RAY RECORDING MATERIAL AND A PROCESS FOR PRODUCING A SILVER-EFFECTIVE EMULSION EMULSION WITH A MINIMUM OF 50 MOLTH |
| US4061831A (en) * | 1976-04-13 | 1977-12-06 | Bard Laboratories, Inc. | Thermal recording system |
| US4539291A (en) * | 1982-12-24 | 1985-09-03 | Fuji Photo Film Co., Ltd. | Direct positive silver halide photographic materials |
| US4788126A (en) * | 1987-05-20 | 1988-11-29 | The Mead Corporation | Radiation dosimeter and method for measuring radiation dosage |
| US5356770A (en) * | 1992-05-29 | 1994-10-18 | Eastman Kodak Compamn | Color photographic materials and methods with stabilized silver chloride emulsions |
| US5576154A (en) * | 1994-06-28 | 1996-11-19 | Sterling Diagnostic Imaging, Inc. | Photographic recording materials for medical radiography |
| EP0775936A1 (en) | 1995-11-08 | 1997-05-28 | Eastman Kodak Company | Silver halide photographic elements containing dioxide compounds as stabilizers |
| US6280922B1 (en) | 1998-12-30 | 2001-08-28 | Eastman Kodak Company | High chloride silver halide elements containing activated precursors to thiolic stabilizers |
| US9304395B2 (en) | 2014-04-30 | 2016-04-05 | Eastman Kodak Company | Conductive element precursor and conductive pattern formation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2759821A (en) * | 1952-06-04 | 1956-08-21 | Eastman Kodak Co | X-ray film |
| US2927899A (en) * | 1955-09-28 | 1960-03-08 | Lever Brothers Ltd | Detergent germicidal compositions and process of making the same |
| US3017270A (en) * | 1958-03-31 | 1962-01-16 | Eastman Kodak Co | Photographic silver halide diffusion transfer process |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE348661C (en) * | 1920-12-30 | 1922-02-13 | Kranseder & Co G M B H | Process for the production of X-ray plates |
| US2090607A (en) * | 1934-07-25 | 1937-08-17 | Baldsiefen Walter Dewey | Selective desensitizer |
-
1962
- 1962-11-19 US US238751A patent/US3184313A/en not_active Expired - Lifetime
-
1963
- 1963-11-16 DE DEE25874A patent/DE1244574B/en not_active Withdrawn
- 1963-11-19 GB GB45558/63A patent/GB1061964A/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2759821A (en) * | 1952-06-04 | 1956-08-21 | Eastman Kodak Co | X-ray film |
| US2927899A (en) * | 1955-09-28 | 1960-03-08 | Lever Brothers Ltd | Detergent germicidal compositions and process of making the same |
| US3017270A (en) * | 1958-03-31 | 1962-01-16 | Eastman Kodak Co | Photographic silver halide diffusion transfer process |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3276950A (en) * | 1965-05-10 | 1966-10-04 | Du Pont | Method for controlling arachnids |
| US3510348A (en) * | 1966-03-11 | 1970-05-05 | Eastman Kodak Co | Direct positive recording film |
| DE2640655A1 (en) * | 1975-09-10 | 1977-03-17 | Minnesota Mining & Mfg | PHOTOGRAPHICAL RECORDING MATERIAL WITH SENSITIVITY IN THE ULTRAVIOLET SPECTRAL RANGE, SENSITIZED HALOGSILVER EMULSION, X-RAY RECORDING MATERIAL AND A PROCESS FOR PRODUCING A SILVER-EFFECTIVE EMULSION EMULSION WITH A MINIMUM OF 50 MOLTH |
| US4061831A (en) * | 1976-04-13 | 1977-12-06 | Bard Laboratories, Inc. | Thermal recording system |
| US4539291A (en) * | 1982-12-24 | 1985-09-03 | Fuji Photo Film Co., Ltd. | Direct positive silver halide photographic materials |
| US4788126A (en) * | 1987-05-20 | 1988-11-29 | The Mead Corporation | Radiation dosimeter and method for measuring radiation dosage |
| US5356770A (en) * | 1992-05-29 | 1994-10-18 | Eastman Kodak Compamn | Color photographic materials and methods with stabilized silver chloride emulsions |
| US5576154A (en) * | 1994-06-28 | 1996-11-19 | Sterling Diagnostic Imaging, Inc. | Photographic recording materials for medical radiography |
| EP0775936A1 (en) | 1995-11-08 | 1997-05-28 | Eastman Kodak Company | Silver halide photographic elements containing dioxide compounds as stabilizers |
| US6280922B1 (en) | 1998-12-30 | 2001-08-28 | Eastman Kodak Company | High chloride silver halide elements containing activated precursors to thiolic stabilizers |
| US9304395B2 (en) | 2014-04-30 | 2016-04-05 | Eastman Kodak Company | Conductive element precursor and conductive pattern formation |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1061964A (en) | 1967-03-15 |
| DE1244574B (en) | 1967-07-13 |
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